Semiconducting Polymers

Georges Hadziioannou, Paul F. van Hutten (Eels.
)
Senticonducting Poly01ers
Chemistry, Physics and Engineering
Editors:
Prof. G. Hadziioannou
Departmc'l.t of Polymer Chemistry and Ma.termls Science Centre
Univcrsi.ty of Groningen
Nijenborgh 4
NL-9747 AG Groningen
The Netherlands
Or. P. F. van Huucn
Oepartmen1 of Polymer Chen1istry and Materials Science Centre
University of Groningen
Nijenborgh 4
'The Ne.therlam.ls
1111:. book carefully prut.luccU. Ncvcrthclc:..". wthor., , ooitor.. <llld puhlishcr do nul warmnl the
information con.taincd lhcrcin to be fn:c or error... Rev.Jer:. arc advscd lu l.cc1> 111 mind tllu l>tatc-
menls, data. illus.tr.tlioru;, proccdur.tl delails or other may ina.Jvcncntly be inaccur.ue.
ubrary of Congress Card No. applioo for.
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Preface
When wnttng about a subject from a r:tpidly evolving research area, one is
templed into dealing with the latest results, those th;,tt still fascimtte. This is dan-
gerous, however, for such findings may not h;,tve a lasting value. They may not
be sufficiently unambiguous, enlightening, or novel to deserve their place in a re-
ference work.
We h:tve invited our colleagues to write ;,bout their licld or expc11ise. and put
dowtt on paper the thi ngs lhat they arc really cumfort<tble with, <tnd c.:onlillent of.
Fonun<ttcly, we found llluny willing to contribule in this vein. With their help, we
have been uble to eollecl much of the base or knowledge that hus been gathered
in " dt:c<tde of rese;.srch on semiconducling polymers. It is recognized, of course.
that research in thi s ticld coulll build on wh<tt had been learned about conducting
polymers in the preceding decade.
We like to thank those who collabor.ttcd in this book project. This includes all
uuthors, as well as the people at Wiley-VCH who offered us the opportunity and
m:tde it become a reality.
Georges Hadziioamwu
Paul van Huuen
Groningen, September 1999
Foreword
The science and technology of conducting polymers are inherently interdisciplin-
ary; they fall at the intersection of three established disciplines: chemistry, physics
and engineering; hence the name for this volume. These macromolecular materials
are synthesized by the methods of organic chemistry. Their electronic structure
and electronic properties faiJ within the domain of condensed matter physics. Effi-
cient processing of conjugated polymer rnatcri<.tls into useful forms and the fabri-
cation of electronic and opto-electronic devices require input from engineering;
i. c. materials science (more specificaiiy, polymer science) and device physics.
With the emergence of semiconducting and mewllic polymers <.ts an interdisci-
plinary field, a host of new concepts h;we evolved which are of broad and funda-
mental importance. The licld originated in the 1970s with an initial focus on n-
type and p-type doping of conjugated polymers. Reversible doping of semicon-
ducting polymers was the early highlight with associated electrical conductivity
values that span the full range from insulator to metal. The unique electrochemis-
try of conducting polymers was subsequently discovered and remains as an active
area of science and technology.
The opportunity to synthesize new conjugated polymers with improved proper-
ties began to attract the attention of a larger number of synthetic chemists in the
1980s. Equally important was the subsequent development of stable, processible
metallic polymers. As a result of these efforts, we now have a class of materials
which exhibit a unique combination of properties: the electronic and optical prop-
erties of metals and semiconductors in combination with the processing advan-
tages and meclumicallnvperties of polymers.
Because of the progress toward higher purity, proccssiblc semiconducting poly-
mers, these materials are now av<tibble for usc in "plastic electronic" devices. In
this context, the discovery (at Cambridge University) of elcctroluminescence from
semiconducting, conjugated polymers, was of particulm importance. More gener-
ally, however, plastic electronics devices include diodes, photodiodes, photovol-
taic cells, sensors, light-emitting diodes, lasers, field effect transistors and <til-poly-
mer imegrated circuits - und the list is growing. Thus, the emergence of electron-
ic and opto-electronic devices fabricated from semiconducting polymers has been
a principal focus of the 1990s.
Despite the scientific progress and the demonstmtion of novel device concepts,
there was considcmblc skepticism that semiconducting polymers would ever reach
the levels of purity required for long-lifetime commcrci;.tl devices. ln the context
of the l;.tst 50 years of semiconductor physics, conjugated polymers were often
VIII Foreword
considered as "dirty" and poorly chamcterized materiuls. Therefore, the recent de-
monstration of high-brightness polymer emissive displays with opemting lifetimes
of 10000-20000 hours was a particularly important step; it is now clear that
semiconducting polymers c:m be used to fabricate consumer product-; that meet
commercial specifications.
As a result of the remarlwble p1Vgress in the clzemiscry, physics uml c:11gi11eer-
ing (device physics) of semiconductillg and metallic polymers, we are now witnes-
sing the beguwing of a revolution in "Plastic Electronics".
The field of semiconducting and metallic polymers remains vital; again and
again the science anc technology have moved into new directions. Specific exam-
ples of recent advances (within the I 990s) of special importance include the fol-
lowing:
Metallic polymers which are stable, soluble and processible, and therefore suit-
able for industrial applications;
e The science and technology of high-efficiency light emission from polymer
light-emitting diodes and polymer light-emitting electrochemical cells;
Ultrafast photoinduced electron transfer in semiconducting polymers mixed
with controlled amounts of acceptors; this phenomenon has opened the wuy to
a variety of applications including high-sensitivity plastic photodiodes, and efti-
plastic solm cells;
Semiconducting polymers as mate&ials for solid-state lasers.
This book, "Semiconducting Polymers - Chemistry, Physics and Engineering",
edited by Georges Hadziiounnou and Paul van Hutten of the University of Gro-
ningen (The summarizes progress in areas of current activity wi thin
the field. The various chapters, all contributed by leading researchers, provide a
summary and review of the field that wi ll be useful and important to anyone seek-
ing a strong buckground in the basic interdisciplinary science and an up-IO-d4tte
"snapshot" of the current status of research. Emphasis is on the basic physics and
chemistry of conjugated polymers as electronic and opto-electronic materials <111d
on the performance (status, opportunities and limitations) of the electronic and
opto-electronic devices that are responsible for the on-going revolution in "Plastic
Electronics".
Alnn 1. Heeger
Professor of Physics & Professor of Materials
Institute for Polymers and Organic Solids
University of Califomia, Santa Barbam
and
UNIAX Corporation
Sunta Barham, CA
Contents
J
1.1
1.2
1.2. 1
1.2.2
1.2.2.1
1.2.3
1.2.4
1.3
1.3. 1
1.3.2
1.3.2.1
1.3.2.2
1.4
1.4. 1
1.4.2
1.5
1.6
1.6.1
1.6.2
1.6.3
1.6.4
1.6.5
1.7
Poly(arylenc vinylcnc)s - Synthesis and Applications
in Semiconductor Devices I
Michael M. Murray and Andrew B. Holmes
lntmduction
Poly( I ,4-phcnylenc vinylcnc) <md its Derivati ves 2
The Basic Polymer LED Device Architecture 4
Substituted Poly(phenylene vinylene)s 6
Poly( <nnhry lencvin y lcnc )s I 0
Step-Growth Routes to PPV Dcriv;nivcs 10
PPY Copolymers II
Relining the Properties of PPV - Multiluyer Devices 13
Multilayer Devices: The Incorporation
of Charge-Tr.mspo11ing l<tyei'S 14
Electron-Deficient Polymers - Luminescent Tnmspo11 l<tyers
Other Electron-Dclicicnt PPV Derivatives 19
Electron-Delicient ArOm;ttic Systems 19
Full Color Displuys - The Scurch for Blue Emitters 21
lsolmed Chromophores - Towards Blue Emission 21
Comb Polymers wi th Chromophorcs on the Side-Chain 22
Chiral PPV - Polarized Emission 23
Poly(thienylenc vinylene)s -
A Stable Cl<tss of Low-lli!nJ-Gap Materials 24
Organic Field EITect Tmnsistors (f.ET.-;) 25
Synthesis 26
Aldol Route 27
Ring-Substituted PTV Derivatives 27
Yinylene-Substituted PTV Derivatives - Tuning the Gap 30
Conclusions <md Outlook 31
Acknowledgements 32
References 32
16
X
2
2.1
2.2
2.21
2.2.2
2.2.3
2.3
2.4
2.4.1
2.4.2
2.4.3
2.5
3
3.1
3.2
3.3
3.4
3..5
4
4. 1
4.2
4.3
4.4
4.4. 1
4.4.2
4.4.3
4.5
4.6
Conlents
Oligo- a nd Poly(phenylene)s 37
Ullrich Scherf and Klaus Mullen
Introduction 37
Polymers 37
Oxidative Condensation of Benzene Derivatives 38
Transition Metal-Mediated Couplings 39
Other Routes to Poly(p-phenylene)s 48
Oligomers 50
Dendtitic and Hyperbranched Poly(phenylene)s 55
Hyperbranched Poly(phenylene) Derivatives 55
Oligo(phenylene)s Composed of Orthogonall y Arranged Arms 56
Dendritic Poly(phenylene)s and Giant Polyaromatic Hydrocarbons
(PAHs) 57
Conclusion 60
References 61
Disorder and Solitons in Trans-Polyacetylene 63
Jasper Knoester and Maxim Mostovuy
Introduction 63
The Peierls Instability and Solitons 65
Disorder: The Auctualing Gap Model 71
Disorder-Induced Kinks 76
Concluding Remarks 82
Acknowledgements 83
References 84
Gas Phase to Solid State Evolution of the Electronic
and Optical Properties of Conjugated Chains:
A Theoretical Investigation 87
Jerome Comi/, Donhelli A. dos Santos, David Beljumw,
Zhigang Shuai, and Jetm-Luc Bredas
Introduction 87
Theoretical Met hodology 89
Wavefuncti on An<tlysis of the Excited States in PPV Oligomers 90
lntcrchain Interactions 94
Absorption Properties of Highly Symmetrical Complexes 94
PholOiuminescence Properties of Highly Symmetrical Complexes 99
The Influence of the Number and Relmive Orientations
of the Interacting Molecules 103
Clusters of Sexithienyl Molecules 107
Conclusions ~ n d Outl ook Ill
Acknowledgements Ill
References lt 2
5
5.1
5.2
5.2. 1
5.2.2
5.3
5.4
5.4. 1
5.4.2
5.5
5.5. 1
5.5. 1.1
5.5. 1.2
5.5.2
5.5.2. 1
5.5.2.2
5.5.3
5.5.3. 1
5.6
6
6. 1
6.2
6.3
6.4
6.4.1
6.4.2
6.5
6.5. 1
6.5.2
6.5.3
6.6
6.6. 1
6.6.2
6.6.2. 1
6.6.2.2
6.7
Electronic Structure of Surfaces and Interfaces
in Conjugated Polymers 115
Michael LiJgdlund and William R. Salaneck
Introduction 115
Photoelectron Spectroscopy 116
X-Ray Photoelectron Spectroscopy 119
Ultmviolet Photoelectron Spectroscopy 120
Theoretical Approaches 12 1
M<!lerials 122
Electronic Structure of rrans-Polyacetylene 123
Charge Stomge States in Conjugated Polymers I 25
Polymer Surfaces <tnd Interfaces 128
Poly(p-phenylenevinylene) 128
Comeuts
Interface Formmion Between Aluminum ;.md PPV 130
Interrace Formation Bclwccn C.tlcium and PPV 132
Polythiophene 134
lmerface Fornmtion Between Aluminum <md Polythiophene 135
Interface Formation Between Copper and Polythiophene 137
Polyaniline 139
Polyaniline on Indium Tin-Oxide 140
Summary 144
Acknowledgements 145
References 146
Electronic Structure and Energy Tr<msfer
in Solid u-Sexithicnyl 149
Carlo Talia11i. Fabio Biscariui, and Michele Muccini
Introduction 149
Experimental 151
Excited Electronic States in Isolated T
6
152
Single-Crystal Electronic Structure 154
Davydov Splitting 159
Herzberg-Teller Yibronic Coupling 160
Thin Films 164
Growth in High Vacuum 164
Thin-Film Morphology 165
Sc<tling Behavior of Surface Roughness 169
Disorder Enect on Energy Tmnsfcr 174
Single-Crystal Fluorescence 174
Thin-Film Fluorescence 177
MoqJhology-Dcpendcnt Polarization or Fluorescence
and Eleclroluminesccnce I ~ I
Morphology-Dependent Energy Transfer 184
Conclusions 185
Acknowledgements I g(J
Rclercnccs I g7
XI
XII
7
7.1
7.2
7.2. 1
7.2.2
7.2.3
7.2.4
7.3
7.3. 1
7.3.2
7.3.3
7.3.4
7.4
7.4.1
7.4.2
7.4.3
7.5
7.5.1
7.6
8
8. 1
8.2
8.3
8.4
8.4. 1
8.4.2
8.5
8.5. 1
8.5.2
8.5.3
8.6
8.7
8.8
Con/ellis
Spectroscopy of Photoexcitation$ in Conjugated Polymers 189
Paul A. Lane, Sergey V. Frolov. and Zev V. Vardeny
Introduction 189
Experimental Techniques 190
CW Photomodulation Spectroscopy I 90
Optically Detected Magnetic Resonance 193
Transient Photomodulation Spectroscopy 196
Non-Linear Optical Spectroscopy 199
Poly(para-phenylene vinylene) 202
Absorption and Photoluminescence 202
Transient Photomodulation 204
Non-Linear Spectroscopy (TPA and EA) 208
CW Photomodulation 21 1
Polythiophcnc 2 14
Linear and Non-LinC<lr Absorption 214
Tr<msient Photomodulation 21 5
CW Photomodulation 220
Fullerene-Doped DOO-PPV 226
Transient Photomodul<ttion 226
Summary 232
References 232
Photophysics of Methyl-Substituted Poly(para-Phenylene)-Type
Ladder Polymers 235
Guiglielmo Lanza11i, Sandro De Silvestri, Giulio Cerullo,
Salvatore Stagira, Mauro Nisoli, Willi Gruupner,
Gunther Leising, Ullich Scherf, and Klaus Mullen
Introduction 235
An Overview of Previous Results 236
Optical Properties 237
Experimental 239
Conventionu1 Pump-Probe 239
Field-Assisted Pump-Probe 240
The Primary Photoexcitations in m-LPPP 241
Overview of the Experimemal Results 242
A Model for m-LPPP Electronic Structure 243
High Excitation Density Scenario 247
The Emission Process in m-LPPP 248
Charge Photogenemtion in m-LPPP 250
Conclusions 256
References 257
9
9. 1
9.2
9.3
9.4
9.5
9.5. 1
9.5.2
9.5.3
9.6
9.6. 1
9.6.2
9.6.3
9.6.4
9.6.4. 1
9.6.4.2
9.6.5
9.7
9.8
JO
10. 1
10.2
10.3
10.4
10.5
lJ
11.1
11.2
11.2. 1
11.2.2
11 .2.3
Comems
Solid-State Aspects of Conjugated Semiconductors 259
Wilhelm Grmqmet; Stefan Tasch, and Giinther Leising
Introduction 259
260
Functionalities in Devices 262
Order in Conjugated Semiconductors 264
Excited-State Spectroscopy 268
Excited States 269
Neutral Photoexcitutions 271
Charged Photoexcitations 274
Electroluminesccnce Devices and Models 282
EL Devices from Conjug<tted Polymers
with a High Defect Concentr<ttion 283
EL Devices from Conjugated Polymers
wi th a Low Defect Concentration
from an Elcctruchemical Cell 286
Carrier Injection and Charge Transpon 287
Thermal Emission 288
Field-1ntluced Injection 288
Charge Recombination und Efficiency 295
Highly Excited Conjugated Films 297
Conclusions 303
References 303
Lasing in Conjugated Polymers 309
Uli Lemmet; Anclreus Hcwgenedet; Christian Kullinger.
and Joc:hen Feldmunn
Introduction 309
Stimuluted Emission in Organic Materials 310
G<tin NmTowing in Cunjug<ttcd Polymer Thin Films 3 17
Lasing in Conjug:ucd Polymers 321
Outlook 325
Appendix I 327
Appendix II 328
References 328
Physics of Polymer Light-Emitting Diodes 333
I. H. Ccunpbell and D. L. Smith
Introduction 333
Thin Films of Electroluminescent Polymers 335
Electronic Energy Stna.:turc 336
Electrical Tmnsport Properties 338
XIII
XIV
11.3
11.3.1
11.3.2
11.4
11.4.1
11.4.2
11.5
11.5.1
11.5.2
11.5.3
11.6
12
12.1
12.2
12.2. 1
12.2.2
12.3
12.3.1
12.3.2
12.4
12.4.1
12.4.2
12.4.3
12.4.3.1
12.4.4
12.4.5
13
13. 1
13.2
13.2.1
13.2.2
13.2.3
13.2.4
13.2.5
Contents
Device Electronic Structure 339
Internal Photoemission Measurements
of Schouky Energy Barriers 340
Buill-In Potentials in Device Structures 342
Single-Layer Devices 345
Single-Carrier Suuctures 346
Two-Carrier Structures 352
Multi-Layer Devices 355
Blocking Layers 356
Transport Layers 359
Two-Carrier Multi-Layer Devices 361
Conclusion 362
References 363
Charge Transport in Random Organic Semiconductors 365
Heinz Biissler
Introduction 365
Charge Carrier Injection 367
Concepts 367
Comparison with Experiment 373
Space Charge Limited (SCL) Currents 379
The Concept 379
Experimental Results 381
Charge Carrier Transport 384
Concepts 384
Transport in the Presence of Extrinsic Traps 390
Charge Carrier Transport in Conjugated Polymers 398
Time-of-Flight Studies 398
Transient Absorption of Radical Cations 403
Some Remarks Concerning the Nature
of Charge-Carrying Moieties 406
References 408
The Chemistry, Physics and Engineering
of Organic Light-Emitiing Diodes 411
John Campbell Scott and George G. Ma/liaras
Introduction 411
Materials 413
Conjugated Polymers 413
Small Molecules 416
Molecularly Doped Polymers and Polymer Blends 419
Self-Assembled Layers, Langmuir-Biodgeu Layers,
and Liquid Crystals 420
Electrodes and Interface Modification 421
13.2.5.1
13.2.5.2
13.2.5.3
13.2.5.4
13.2.5.5
13.3
13.4
13.4. 1
13.4.2
13.4.3
13.4.4
13.4.5
13.4.6
13.5
13.5. 1
13.5.2
13.5.2. 1
13.5.2.2
13.5.2.3
13.5.3
13.5.4
13.5.5
13.6
13.7
13.7. 1
13.7.2
13.7.3
13.7.4
13.7.5
14
14.1
14.2
14.2.1
14.2.1.1
14.2.1.1.1
14.2. 1. 1.2
14.2.1.1.3
14.2. 1.2
14.2.2
14.2.2. 1
14.2.2. 1.1
Anodes 421
Cathodes 422
Electrode Modification 423
B<trrier Layers 423
Transparent Cathodes 424
Device Structures 424
Characterization 427
Device Characteristics 428
Figures-of-Merit 429
Built-in Potential 430
Barrier Heights 432
Ch<trge Tr.lllsport 433
Photoluminescence 434
Device Physics 435
The Elemelll<try Processes 436
Analytic Theory 438
Numerical Simulmions 439
Expcriment<ll Studies 440
Multilayer Devices 443
Electrochemical Cells 443
Microcavities 444
Degrad<ttion 445
Application of OLEOs in Fhtt-Panel Displays 449
Display Engineering Units and Conversions 449
Pixels. Patterning, and Drivers 450
Color 453
Encapsulation 455
Outlook 456
References 457
Physics of Organic Field-ElTcct Transistors 463
Gilles Horowitz
Introduction 463
Basic Principles 464
Junctions 464
Mewl-Semiconductor (MS) Junction 464
Formation of the Junction 464
The Junction al Equilibrium (Zero Bias) 465
Current-Voltage Characteristic 466
Met<tl -lnsulatur-Semiconductor (MIS) Junction 467
Ficld-EITect Transistors 471
Metal-Insulator-Semiconductor FET (MISFET) 472
Principle of Operation 472
Coments XV
XVI Contents
14.2.2. 1.2
14.2.2.2
14.2.2.3
14.2.2.3.1
14.2.2.3.2
14.2.2.3.3
14.2.2.3.4
14.3
14.3. 1
14.3.2
14.3.2.1
14.3.2.2
. 14.3.2.2.1
14.3.2.2.2
14.3.3
14.3.4
14.4
14.4.1
14.4. 1.1
14.4. 1.2
14.4.1.3
14.4.1.4
14.4.2
14.5
14.5. 1
14.5.2
14.5.2.1
14.5.2.2
14.5.2.3
14.5.3
14.6
14.6. 1
14.6. 1. 1
14.6.1.2
14.6.2
14.6.2. 1
14.6.2.2
14.7
15
15. 1
15.2
15.2. 1
15.2. 1.1
Current-Voltage Characteristic 473
Metal-Semiconductor FET (MESFE1) 475
Thin-Film Transistor (TFI') 476
Accumulation Mode, Linear Regime 477
Depletion Mooe 478
Accumulation Mode, Saturation Regime 480
Mobility Threshold 481
Charge Transport in Organic Materials 481
Localized Versus Dclocalizcd States 481
Hopping 483
Hopping Rate 483
Polarons 484
Polarons in Conjugated Polymers 484
Transport Mechanism of Polarons 484
Multi ple Tmpping and Release 486
Field-Dependent Mobility 487
Fabrication Techniques 488
Deposition of the Semiconductor 488
Elcctropolymeriwtion 489
Solution-Processed Deposition 489
Vacuum Evaporation 489
Langmuir-Blodgett 490
All-Organic Devices 490
Materials 491
Oligothiophenes 492
Other Molecules 495
Phthalocyanines 495
Pentaccne 496
n-Typc Semiconductors 498
Polymers 499
Models 500
Temper.llure and Gate Bias Dependence 50 I
Trap-Limited Tr.msport 501
Polaron and Hopping Models 504
Current-Voltage Characteristics 507
Short-Channel Effects 507
On-Off Current R:.1tio 508
Concluding Remarks 510
References 5 11
Conj ugated Polymer Based Plastic Solar Cells 515
Christoph J. Brabec and N. Serdar Sariciftci
Introduction 5 I 5
Conjugated Polymers as Photoexcited Donors 516
Linear Optic:.1l Propert1es 518
15.2. 1.2
15.2. 1.3
15.2.2
15.2.2.1
15.3
15.3. 1
15.3.2
15.3.3
15.3.4
15.4
15.4. 1
15.5
15.5. 1
15.5.2
15.6
15.6. 1
15.6.2
15.7
16
16.1
16.1.1
16. 1.2
16.1.3
16.2
16.2. 1
16.2.1. 1
16.2. 1.2
16.2.1 .3
16.2. 1.3. 1
16.2. 1.3.2
16.2. 1.3.3
16.2. 1.3.4
16.2.2
16.2.2. 1
16.2.2. 1.1
Cumems XVII
Photoinduced Absorption 521
Quenching of the Intersystem Crossing to the Triplet State 521
Photoinduced IRAV Studies 522
lime-Resolved Photoinduced Studies 524
Sensitiwtion of Photoconducti vity 525
Magnetic Properties 526
Light-Induced Electron Spin Resonance (LESR) 526
Pure Conjugated Polymer Photovoltaic Devices 528
Definitions 528
Basic Transport Properties 528
MetaUConjugated Polymer Contacts 53 1
Spectml Response 532 -
Conjugated Polymer Bi h1yer Devices 536
Conjugated Heterojunction PhOtodiodes 539
Conj ugated Polymer Bulk Heterojum:tion Dio<.les 545
Conj ugated Polymer/C<>o Bulk Heterojunction Photodiodes 545
Conjugated Polymer/Conjugated Polymer Bulk
Heteroj unction Photodiodes 549
Flexible, Large Area, Plastic Sol:.u Cells 55 1
Stability of Pl:.1stic Solar Cells 553
The Guest-Host Approach:
Blending with Convention:ll Polymers 554
Outlook and Strategies 555
References 557
A Model Oligomer Approach to Semiconducting Polymers 561
Paul van Hutten and Georges 1/ad-::.i.ioamwu
Introduction 561
Background 561
The Copolymer Approach to Controlled Light Emission
in Polymers 562
Oligomcrs as Model Compounds for Structure-Property Studies 563
Synthesis and Solution Properties of OPVs 564
Synthesis 564
Introduction 564
General Strategy 565
Synthesis or Model Compounds 566
Three-ring OVPs 566
Synthesis of u-OPV5 567
Synthesis of oct-OPV5 :md Ooct-OPV5 568
Synthesis of Cy;.mo-Substit uh!d OPV3s and OPV5s 568
Opt ical Properties in Solution 569
Comparison of Copolymers :md Related Oligomcrs 569
Three-Ring Chmmophorcs 569
XVIII Contents
16.2.2. 1.2
16.2.2.2
16.2.2.3
16.3
16.3. 1
16.3.1.1
16.3. 1.2
16.3.1.2.1
16.3.1.2.2
16.3. 1.2.3
16.3.1.3
16.3.1.3. 1
16.3.1.3.2
16.3. 1.3.3
16.3.1.3.4
16.3.1.3.5
16.3.1.3.6
16.3.1.4
16.3.2
16.3.3
16.3.3. 1
16.3.3.2
16.3.3.2. 1
16.3.3.2.2
16.3.3.2.3
16.3.3.2.4
16.3.3.3
16.3.3.3.1
16.3.3.3.2
16.4
16.4.1
16.4.2
16.4.2.1
16.4.2.2
16.4.2.3
16.4.3
16.4.3. 1
16.4.3.2
16.5
Index 615
Five-Ring Chromophores 572
Substitution Effects in OPV5s 573
About the Geometry of the Excited State 576
OPVs in the Condensed State 577
Single Crystals 577
Introduction 577
Crystal Structures of Five-Ring OPVs 579
Ooct-OPV5 579
Ooct-OPV5-CN' 580
Ooct-OPV5-CN" 581
Crystal Structures of Three-Ring OPVs 582
Ooct-OPV3 582
Ome-OPV3 582
Ooct-OPV3-CN' 583
Ooct-OPV3-CN" 583
Oct-OPV3 584
Oct-OPV3-CN" 584
Optical Properties of Single 585
Them1al Properties: Liquid-Crystalline Phases 586
Thin Films 588
Introduction 588
Thin-Film Structure 589
Ooct-OPV5 589
Optical Microscopy 589
X-Ray Diffraction (XRD) 589
Atomic Force Microscopy (AFM) 590
Ooct-OPV5-CN' 592
Ooct-OPV5-CN" 592
Ooct-OPV3 593
Five-Ring OPVs 593
Ooct-OPV3 597
Light Emission Applications of OPVs 598
Introduction 598
Light-Emitti ng Diodes 599
Influence of Morphology on Device Performance 602
Devices 603
Stimulated Emission 604
Single Crystals 604
Vacuum-Deposited Films 605
Summary and Outlook 608
Acknowledgements 6 10
References 6 10
List of Contributors
H. Biissler
Institute of Physical, Nuclear
;md Macromolcculm Chemistry
Philipps-Univers ity of
Hans-Meerwein-Stral3e
D-35032 Marburg
Germany
D. Bdjonne
Service de Chimie
des Matcriaux Nouveaux
Centre de Recherche en Electroni4ue
et Photonique Moleculaires
Univcrsite de Mons-Ho.tinaut
Place du Po.trc, 20
B-7000 Mons
Belgium
F. Biscarini
lstituto di Spenroscopht Molecolme
Consiglio Nazionale delle Riccrche
Via P. Gobeui, I 0 I
1-40129 Bologna
Italy
C.J. Brabec
Christian Doppler Laboratory
for Plastic Solar Cells
Physical Chemistry
Johannes Kepler University Linz
AltenbergerstraBe 69
A-4040 Linz
Austria
J.-L. Brcdas
Service de Chimic
ties Materi<tux Nouveaux
Centre de Recherche en Electronique
et Photonique Molcculaircs
Uni versitc de Mons-Hainaut
Place du Pare, 20
B-7000 Mons
Belgium
I. H. Campbell
Electronics Research Group
Los Alamos National Labomtory
Mail Stop 0429
Los Alamos
NM 87545
USA
G. Cerullo
lstituto Nazionale per Ia Fisica
della Materia
Dipartimcnto tli Fisica
Politccnico tli Mihmo
Piazza Leonardo da Vinci, 32
l-20133 Milano
Italy
J. Cornil
Service de Chimie
des Nouveaux
Cemrc de Recherche en Elcctronique
et Photonique Moleculaires
Universitc de Mons-H<tinaut
Plat.:e du Pm'C, 20
B-7000 Mons
Belgium
XX w t of Comributors
S. De Silvestri
Istituto Nazionale per La Fisica
della Materia
Dipartimento di Fisica
Politecnico di Milano
Piazza Leonardo <.Ia Vinci, 32
1-20133 Mi lano
Italy
D. A. dos Santos
Service de Chimie
des Materiaux Nouveaux
Centre de Recherche en Electronique
et Photonique Moleculaircs
Universite de Mons-Hainaut
Place du Pare, 20
B-7000 Mons
Belgium
J. Feldmann
Lehrstuhl fUr Photonik
und OptocleklrOnik
Sektion Physik und Center
for N;moScience
Ludwig-Maximilians-Universitat
Munchen
AmalienstraBe 54
D-80799 Munchen
Germany
S. V. Frolov
Bell Labor.ttories
Lucent Technologies
600 Mountain Ave.
Murr.1y Hill
NJ 0974
USA
W. Graupncr
Virginia Tech
Department of Physics
Blacksburg
VA 24061-0435
USA
G. Hadz.iioannou
Department of Polymer Chemistry
and Materials Science Centre
Nijenborgh 4
The Netherlands
A. Haugencder
Lehrstuhl fur Photonik
und Optoelektronik
for NanoScience
Ludwig-Maximilians-Universitat
Munchen
Amalicnstralk 54
Mi.inchcn
Germany
A. B. Holmes
University Che.nical L;tboratory
Department of Chemistry
Lcnslield Road
Cambridge CB2 I EW
United Kingdom
G. Horowitz
l.<tboratoire des Matcriaux Moleculaires
CNRS, ER 241
2 rue Henry-Dunant
F-94320 Thiais
Fr;mce
C. Kallingcr
Lchrstuhl rur Photonik
und Optoclcktronik
for NanoScience
Ludwig-Maximili;ms-UniversiUit
Munchen
AmalienstraBe 54
D-80799 Munchen
Genn<111y
J. Knoester
Institute for Theoretical Physics
Nijenborgh 4
The Netherlands
P.A. Lane
Department of Physics
and Astronomy
University of Sheffield
Sheffield S3 7RH
United King<.lom
G. Lanz.u1i
lstituto Nazionale per Ia Fisica
Mutcria
Dipartimemu <.li Fisica
Politccnico di Milano
Piau.a Leonardo d<t Vinci, 32
L-20 133 Mi lano
Italy
G. Leising
lnstitut fi.ir Festktirpcrphysik
Technische UniversiUit Graz
Petergusse 16
A-go 10 Gr.1z
Austria
U. Lcmmer
Lehrstuhl fUr Photonik
und Optoelcktronik
Sektion Physik

Munchcn
Amalienstr.1Be 54
0 -80799 Munchen
Germ<111y
M. Uigdlund
Labomtol'y M;.mager
IMC+IOF
Brcdg<ttan 34
S-602 2 1 NoJTkoping
Sweden
Ust of Comributors
G. G. Mal Iiams
Department of Matenals
and Engineering
Cornell University
332T Bard H;tll
lthuca
NY 14853- 1501
USA
M. Mostovoy
Institute for Theoretical Physics
an<.l Materials Science Centre
Nijenborgh 4
The Nethcrlunds
M. Muccini
X>
lstituto di Spcnroscopi;t Molccol;uc
Consiglio Nazionale delle Ricen:he
Viu P. Gobeui, I 0 I
1-40 129 Bologna
lwly
K. Mullen
Max-Planck-lnstitut
fur Polyme1forschung
Ackl!nnannweg I 0
D-55128 Mainz

M. M. Murray
Eli Lilly S. A.
Dunderrow
Kinsule, Co. Cork
Ireland
M. Nisoli
C.E.Q.S. E.-C.N.R.
Politccnico di Milano
Piazza Leon;.trdo da Vinci, 32
1-20133 Mi lano
ltuly
XX:ll List of Contributors
W. R. Salaneck
Department of Physics. IFM
Linkoping University
S-581 83 Linkoping
Sweden
N. S. Sariciftci
Christian Doppler Laboratory
for Plastic Solar Cells
Physical Chemistry
Johannes Kepler University Linz
Altenbergerstra8e 69
A-4040 Linz
Austria
U. Scherf
Max-Pianck-lnstitut
fur Polymerfon;chung
Ackermannweg 10
D-55128 Mainz
Germany
J.C. Scott
IBM Research Division
Almaden Research Center
650 Harry Road
San Jose
CA 95120-6099
USA
Z. Shuai
Service de Chimie
des Materiaux Nouveaux
Centre de Recherche en Electroniquc
et Photonique Molcculaires
Universite de Mons-Hainaut
Place du Pare, 20
B-7000 Mons
Belgium
D.L. Smith
Electronics Research Group
Los Alamos National Laboratory
Mail Stop 0429
Los Alamos
NM 87545
USA
S. Stagira
Istituto Nazionale per Ia Fisica
della Materia
Dipartimento di Fisica
Politecnico di Milano
Piazza Leonardo da Vinci, 32
I-20133 Milano
Italy
C. Taliani
Istituto di Speuroscopia Molecolare
Consiglio Nazionale delle Ricerche
Via P. Gobetti. 101
1-40 129 Bologna
Italy
S. Ta.,ch
Instttut fur Fcstkorpcrphy:-.ik
Tcchnisdu; Univcrsitat Gr.tz
Petcrga:-.se 16
A-8010 Graz
Austria
P. F. van Huuen
Department of Polymer Chemistry
Nijenborgh 4
The Netherland-;
Z. V. Vardeny
Department or Physics
University of Utah
Salt Lake -City
UT 84112
USA
j
II
List of Abbreviations
c
AFM
AOM
ASE
BDAD
BEH-PPV
BuEH-PPV
CB
CEO
CP
CPG
CTE
cw
DASMB
OAT
DBR
DFB
DH6T
DHPPV
DJA
000-PPY
DOS
DOS
DOYS
DPOP-PPY
DSC
DT
DTA
EA
ECC
ED
EDC
EL
ESCA
ESR
FET
dielectric constant
Atomic Force Microscopy
acousto-optic modulator
amplified spontaneous emission
bis-( 4' -diphcnylaminostyryl)-2,5-dimethox ybenzene
poly(2,5-bis(2'-ethylhexyloxy)-para-phenylene vinylene)
poly(2-butyl-5-(2' -ethylhexyl)-1 .4-phenylene vinylenc)
conduction band
coupled electronic oscillator
conducting polymer
charge photogenemtion
charge-transfer excitons
Continuous Wave
diphenylaminostyi)'Ibenzcne
di-para-anisyl-para-tolylamine
distributed Bragg reflector
distributed feedback
dihexyl-substituted 6T
poly(2.5-diheptyl-para-phenylene vinylene)
doping-induced absorption
poly(2,5-dioctyloxy-para-phenylene vinylene)
distribution of states
density-of-states
density of valence states
poly( I ,4-phenylene-1 ,2-diphenoxyphenylvinylene)
DiiTercntial scanning calorimeuy
diflercntial transmission
di-para-tolyl-pam-anisylaminc
clcctroabsorption
cxtcmal color conversion
electron ditrraction
energy distribution curve
Elcctroluminescencc
Electron Spectroscopy for Chemical Application
electron spin resonance
licld-cffect transistor
XXIV List of Abbreviations
FGM
FN
FTO
FWHM
GP
GPC
HOMO
H-T
HV
ICC
IGFET
INOO
IPCE
!RAY
ISC
ITO
LB
LCD
LEC
LED
LESR
LPPP
LUMO
MBE
MEH-DSB
MEH-PPV
MeLPPP
MIM
MIMIC
MIS
MISFET
m-LPPP
MNDO
MOSFET
MS
MSA
MSM
MTR
NBS
NTCDA
ODMR
OFET
OGM
OLEO
OMA
OMBD
Fluctuating Gap Model
Fowler-Nordheim
fluorine-doped tin dioxide
full width at half maximum
geminate pair
Gel Permeation Chromatography
highest occupied molecular orbital
Herzberg-Teller
high vacuum
internal color conversion
insulated gate FET
Intermediate Neglect of Differential Overlap
incident photon to converted electron
infrared active vibrational modes
intersystem crossing
indium-tin oxide
Langmuir-Blodgett
liquid crystal display
light-emitting electrochemical cell
light-emitting diode
Light-Induced Electron Spin Resonance
laddered poly(para-phenylene)
lowest unoccupied molecular orbital
molecular beam epitaxy
2 -methox y-5-(2' -ethyl hex y loxy )-1 ,4-bis( 4-styry lstyry I )benzene
Poly(2-methoxy-5-(2' -ethylhexyloxy)-1 ,4-phenylene vinylene
methyl-substituted poly(para-phenylene)-type ladder polymer
a metaVinsulator/metal
micromolding in capillary
metal-insulator-semiconductor
metal-insulator-semiconductor FET
methyl-substituted poly(pam-phenylene)-type ladder polymer
Modified Neglect of Diatomic Overlap
silicon metal-oxide-semiconductor FET
metal-semiconductor
tris(p-methoxystilbene)amine
mctaVsemiconductor/mctal
multiple trapping and thermal release
N-bromosuccinimide
naphthalene tetracarboxylic dianhydride
optically detected magnetic resonance
organic field-effect tmnsistor
oriented gas model
organic light-emitting diodes
optical multichannel analyzer
organic molecular beam deposition
OPY
P3HT
P30T
PA
PADMR
PAH
PAni
PB
PBD
Pc
PD
PDA
PDOT
PTCDA
PEOOT-PSS
PEDT
PEOPT
PES
PF
PHP
PIA
PLQY
PLDMR
PM
PMMA
PP3YE
ppp
pppy
ppy
PS
PSD
PT
PTFE
PTV
PVK
r.m.s.
RS
SCI
SCLC
SE
SF
Si-PPV
STM
TAA
oligo(phenylcnc vinylene)
poly(3-hexylthiophene)
poly(3-octylthiophene)
photoinduced absorption
PA-Jetected magnetic resonance
polyaromatic hydrocarbon
polyaniline
photobleaching
Lisr of Abbni(llious XXV
2-(4-biphenyl)-5-( 4-tert-butylphenyl)-1 ,3,4-oxadiaz.ole
Phthalocyanine
photodiode
personal digital assistant
poly(dodecyloxy-terthienyl)
perylene tetracarboxylic dianhydride
poly(3,4-ethylencdioxythiophene)-poly(styrenesultonate)
poly(ethylcnedioxythiophcne)
poly(3-( 4' -(I " ,4", 7" -trioxaoctyl)-phenyl)thiophene)
photoelectron spectroscopy
Poole-Frenkel
para-hexaphcnyl
photoinduced absorption
photoluminescence quantum yield
PL-detected magnetic resonance
photomodulation spectroscopy
polymethylmethacrylate
copolymer containing phenylene, vinylene and non-conju-
gated ethylidene units
poly(para-phenylene)
poly(phenylphcnylene vinylcne)
poly(pam-phenylenc vi nylene)
polystyrene
power spectral density
polythiophene
polytetmt1uoroethylene
poly(2,5-thienylcnevinylene)
polyvinylcarbazole
root mean S(JU<Ife
Richardson-Schottky
single configuration interaction
space charge limited current
stimulated emission
supcJt1uorescence
poly(dimetltylsilylcne-!'llm-phenylcnevinylene-(2,5-di-''-oc-
tyl-pam-phenylcnc)-vinylene-pam-phenylcne)
sc;mning tunneling microscopy
tri -para-a11isylaminc
XXVl List of Abbreviations
TCNQ
IDAE
TE
TEM
TFf

TOF
TPA
TIA
UHV
UPS
uv
VB
VEH
XPS
XRD
tetracyanoquinodimethane
tetrakisdimethylaminoethylene
transverse electric modes
transmission electron microscopy
thin-film transistor
transverse magnetic modes
time of flight
two-photon absorption
tri-para-tolylamine
ultra-high vacuum
Ultraviolet Photoelectron Spectroscopy (UPS)
ultraviolet
valence band
Valence Effective Hamiltonian
X-ray photoelectron spectroscopy
X-Ray Diffraction
1 Poly(arylene vinylene)s - Synthesis
and Applications in Semiconductor Devices
Michael M. Murray and Andrew B. Holmes
1.1 Introduction
Polymers have traditionally been considered as insulating materials by
and physicists alike. Indeed a conventional application of polymers is the safe iso-
lation of metallic conductors. The serendipitous discovery of highly conducting
polyacetylene, however, marked the birth of a new tidd Ll ]. The study of
new class of comtx>Unds is often termed .. molecular electronics" and the area
proven to be highly interdisciplinary in nature. Chemists, physicists and theorist'
alike arc continually exploring new materials and devising novel technologies.
Early studies focused on improving the conductivity of organic poly1ners upon
doping, but it has been generally accepted that most real devices are likely to ex-
ploit the intrinsic semiconductive prope11ies of these materials.
Poly(arylene vinylene)s form an important class of conducting polymers. Two
representative examples of this class of materials will be discussed in some detail
here. There are poly( I ,4-phenylene vinylene) (PPY) I, poly(l ,4-thienylene viny-
lene) (PTV) 2 and their derivatives. The polymers are conceptually PTV
may be considered <IS a heterocyclic analog of PPV, but has a considerably lowe1
band gap and exhibits higher conductivities in both its doped and undoped states.
The semiconducting properties of PPV have been shown to be useful in the
manufacture of clcctroluminesccnt devices, whereas the potential utility of PTV
has yet to be fully exploited. This account will provide a review of synthetic
approaches to arylcne vinylene derivatives and will give details an how the struc-
ture of the mate1ials relate to their performance in real devices.

n

n
1 2
Scheme 1-1. Structures of PPV and PTV.
2 1 Poly(arylt!lle vinyle11e)s - Symhesis alld Applicutio11s u1 Semiconductor Devices
Poly(1,4-phenylene vinylene) and its Derivatives
Eectrolumi nescence was first demonstrated for conjugated polymers (e.g. PPV 1) at
Cambridge in 1990 12]. PPV is the cheapest and simplest poly(arylene vinylene),
comprising of alternating benzene and vinylene units. The material is highly fluores-
cent and is bright yellow in color. Its emission maxima are in the yellow-green re-
gion of the visible spectrum and two distinct emission peaks are readily idemified: at
551 nm (2.25 eV) and at 520 nm (2.4 eV). The synthesis of PPV was first described
in the 1960s but the final material obtained was insoluble, infusible, and difficult to
process. The high crystallinity of conjugated polymers is believed to arise from
strong interchain n- n stacking interactions. Solution processing is a highly desir-
able chamctcristic as it allows the matclial to be coated cheaply and incorporated
into EL devices; PPV fonns excellent transparent films when cast from solution
or upon spincoming. Synthetic routes have been developed to allow thcmtal conver-
sion to PPV from a variety of soluble precursors. Wessling and Zi mmennan intro-
duced (3, 4] the sulfonium precursor route to PPV. '01e route has subscyucntly been
adopted and modified by other research groups 15-7]. It has also been used to good
effect in the synthesis of several de1ivati vcs of PPV.
The chemistry behind the synthesis of parent PPV is relati vely straightforward
and is outli ned in Scheme l -2. A sultide such as tetrahydrothiophcne is reacted
a
3
6

n
1
Scheme 1-2. Synthesis of PPV 1: a) tetrahydrothiophene. MeOH, 65"C; b) NaOH, MeOHI
H20 or Bu4NOH, MeOH, O"C; c) neutralization (HCI); d) dialysis (water); e) MeOH, soc;
f) 220"C, HCI(g)/Ar, 22 h; g) 220- 300"C, vacuum, 12 h.
1.2 Poly( 1,4-pheuyleue viuyle11e) tmd its Derivatives 3
wi th a,a'-dichloro-p-xylene 3 to yield a bis-sulfonium salt 4. Dimethyl sulfide has
also been used but dimethylsulfoniurn groups were found to under<.;o deleterious
side-reactions in subsequent steps 15). Dissolving the monomer 4 in methanol and
treatment with a4ueous sodi um hydroxide at 0-5 C results in polymerization 1ia
the quinomethide intermediate 5. Considerable research ellort has determined that
the optimal results arc achieved if slightly less than one equivalent of base per
mole of monomer is used. Excess base promotes d iminution to highl y colored
conjugated material, whereas insufficient base lowers polymer yield. The reaction
is best condud ed under inert atmosphere and is temtinated by the adpition of di-
lute hydrochloric acid. Low mok-cul;.u weight impurities and salts are removed by
dialysis to afford almost colorless solutions of precursor polymer 6. The molecu-
lar weight of the precursor polymer may not be easi ly detennincd by gel-permea-
tion chromatography (GPC) because it is insoluble in conventional GPC solvcms
such as chl urofom1, TI IF, and toluene. llte material may, however, be rcll uxcd in
methanol. where upon the sulfonium group is replaced by a methoxy substituent.
The resultant neutral polymer 7 is soluble in common organic solvents its
number-average molar mass M, has been determined to be at least 100000 g/mol.
The mechanism of this polymerization has been extensively investigated. lltc
high molecular weights and rapid rate of polymerization poim to a radical mecha
ni sm 1ia a yuinomethide intermediate. It has been shown that radical trappi ng
agents such as molecular oxygen lower the polymer's molecular weight 14.
Further studies by VanderL.ande lend support to this hypothesis [9], and reccm
work appc;m to have ruled out anionic propagation.
Thin lilms of the polymer precursor 6 Jmay be convea1cd into fully conjugated
PPV 1 by heati ng within the temperature range 180-300"C for 12 hours un<.lea
vacuum (2, 6). lltcse conditions favor the removal of the reaction's by-products
tetrahydrothiophene and hydrogen chloride. There are reports that the presence ol
oxygen during the conversion has a deleterious effect on the luminescence quan
tum efticiency of the final tilm. It is believed that oxygen promotes the fonn;Jtior
of carbonyl groups which quench luminescence [ 10-12]. The conversion tempera
ture may be reduced to l OOoC by using the bromide rather than the chloride sah
of precursor polymer 6, allowing the preparation of LEOs on flexible polymer foi
substrates (e.g., ITO-coated PET). Langmui r-Blodgett techniques have also bcea
used to deposit PPV I 13]. It has recently been demonstrated that well-aligned thia
fi lms and fibers of PPV may be formed by pre-ordering the precursor polymer (
in a lyotropic liquid crystall ine phase before thennal conversion. Such a nanocom
posite has potential appl ications for polarized emission [1 4].
There have been a number of other routes to PPV reported in the literature, bu
the resulting device li feti mes and v:uy considerably. The Wessling routl
has been modi fied by employing a sullinyl group instead of a sulfonium grout
I I 5-17 ]. The pol ymerization is believed to proceed by the same quinomethidc in
termediatc and affords PPV upon thermal conversion. lltc route is complemental'\
to the Wessling method as the polymer is soluble in organic
Galvin et a/. I 18 I reported that a xanthate precursor route aflords higher devict
etliciencics than the standard route. PPV may also be synthesized by chcmic;a
vapl>r deposition of dihalogcnatcd p-xylcnes 3 and 9 1 191 or of the chlorimltCl
4 1 Poly(arylene vinylene)s- Synthesis and Applications in Semic01uluctor Devices
3

8
c
X=CI, Br
n
10
-o-""
Ph#CH2 _"
c1e c,e
e

n
11
Scheme 1-3. Alternative synthetic routes to PPV 1: a) 500-700C, 0.01 rnbar; b) 580"C,
10 Pa; c) 800-000''C, O.Q1 rnbar. then 60"C, 0.1 rnbar: d) 200c. vacuum; e) CH
3
CN, 5.5 v.
cyclophane 8 [20]. In each case the intermediate a-halo precursor polymer 10 is
thermally converted to PPV at 200C under vacuum (Scheme 1-3). These meth-
ods yield PPV with low (0.002%) device efficiencies [ 19, 21 j.
A xylylene-bis-phosphonium salt 11 gave films of PPV 1 upon clectropolymer-
ization. The absorption and emission spectra of the resultant material were blue-
shifted with respect to PPV produced by other routes, suggesting that the electro-
polymerized material has a shorter effective conjugation length, possibly because
of incomplete elimination of phosphonium groups [22).
A potential drawback of all the routes discussed thus far is that there is linle
control over polydispersity and molecular weight of the resultant polymer. Ring-
opening metathesis polymerization (ROMP) is a living polymerization method
and, in theory, affords materials with low polydispersities and predictable molecu-
lar weights. This methodology has been applied to the synthesis of polyacetylene
by Feast [23), and has recently been exploited in the synthesis of PPV. Bicyclic
monomer 12 [24] and cyclophane 13 [25) afford well-defined precursor polymers
which may be converted into PPV 1 by thermal elimination as described in
Scheme 1-4.
1.2.1 The Basic Polymer LED Device Architecture
The simplest polymer-based EL device consists of a single layer of semiconduct-
ing fluorescent polymer, e.g., PPV, sandwiched between two electrodes, one of .
which has to be u-ansparent (Fig. 1- 1). When a voltage or bias is applied to the
material, charged carriers (electrons and holes) arc injected into the emissive layer
and these ca1Tiers arc mobile under the influence of the high (> 10
5
V cm-
1
) dec-

a
-
12
1.2 Poly( 1,4-phenylelle vi11yle11e) aiiCI its Derivatives 5
b
n n
Scheme 1-4. ROMP routes to PPV 1: a) [Mo(=NAr)(:::CHCMe
2
Ph)(OCMe
2
(CF
3
))
2
}; b) Bu
4
NF;
c) HCI(g). 190c: d) 108"C; e) 280 C.
8
(f)
Fluorescern
t polymer film

tl.
Figure 1-1. S.:hema1ic of " single-layer clet:lroluminescenl device. An applied eleclric lidtl
lcac.ls lo injec1ion of hole' (posilivc charges; I he majuniy carriers in polymers su.:h as Pl'V)
anc.l ci<."Clrun' (usually lhc minuri1y dlilfgC carriers ) into lhc lighl-cmiuing !Xllymcr film from 1hc 1wo
elcclroc.lc conlacls. Fmmalinn nf an ck'ClrOal hlliC pair wilhin 1he polymer m:ty then resul! in 1hc emi,-
sion ur a pholnn. Siu.:c huk:s much murc easily 1hmugh PPV !han clcclmn-huk
rccumbimniun lakes in !he vicinily of lhc <.:alhuc.le.
tric field. Some of these carriers may recombine within the emissive layer yield-
ing excited electron-hole pairs, termed excitons. TI1ese excitons may be produced
in either the singlet or uiplet states and may radiatively decay to the ground state
by phosphorescence (PL) or fluorescence (FL) pathways (Fig. 1-2). An important
figure of merit for electroluminescent materials is the number of photons emitted
per electron injected and this is termed the internal quantum etliciency. It is clear.
therefore, that the statistical maximum internal efficiency for an EL device is 25%
as only quarter of the excitons <Ire prodm.:ed in the singlet state. In pmcticc.
this maximum value is diminished funher because not all of the light generated i!>.
6
a)
I Poly(arylene vinylene)s - Synthesis ami Apfllicaticms in Scmiccmduuor Dt!vicc.1
LUMO C=:J c=:=:J
hY , hY'
C
- --!..
- -+-
c=:=:J
AaOocal
anaoo
Singlet
excited slate
Sdaglel
exoted state
hv'
Figure 1-2. a) Irr.H.Iiatiun of a nuun:M:cnt polymer an ckctruu frum IIOMO In LUMO. In a
typical conjug:aloo pt>lymcr, two new energy an: geueratcJ upon rclaxatllm wllhiu the original
HOMO-LUMO enc11;y gap anc.l arc each lillcJ with om: cle.:trun ur llJlJl'l'itc (singlet cx.:itcc.l
slate). TIIC cxcitc..-J polylllcr may 1hcn relax to the gruunc.l >IOIIe with emi"mn of light at a longer wave-
lcnglh than lhat absorbcc.l (phololumiucsccncc). b) In a (l\llymer LED. arc aujc4:tcc.l into the
LUMO (to form anions) :mJ holes into the HOMO (Ill Conn r.ac.lical cations) of the a:lcctmlumi-
nescenl p.>lymcr. lhc ch:ugcs migraJc from polymer chain to polymer ch:tin under the inllu-
of the applicc.l chxtric Iield. When a mc.lical anion ant.! a r.ac.lical cation a:ombtnc on a conju-
gated anc.l triplet excitet! slates arc formcc.l, of whicll the can emil lighl.
visible to the viewer. Some of the photons emitted are reflected by the polymer
itself and the external efficiency, therefore, is a factor of 2n
2
smaller than the in-
ternal efficiency, where 11 is the refractive index of the polymer (typically '' = 1.4 ).
Typical external quantum efficiencies for this class of materials is 0. 1- 2% [26).
1.2.2 Substituted Poly(phenylene vinylene)s
Conjugated polymers in general have.! a propensi ty to aggregate or s tack as a con-
sequence of their extensive n-delocalization. This is a limitation of PPV itself as it
requires thermal processing during device fabrication. LEOs fabricated from PPV
derivatives that arc soluble in the conjugatc.:d fonn were first reported by Ohnishi
et ul. at Sumimoto [27] and by Hceger and Bmun at Santa Barbam [28, 29]. The
solubility of the materials results from the presence of long alkyl chains which af-
ford some conformational mobility to the polymer chains. As a consequence, the
materials tend to have lower glass transition temperatures than PPV itself. Further-
more, the sulfonium precursor polymer 6 is soluble in methanolic solvenL-;,
whereas almost all soluble PPV derivatives are in solvl!nts that do not
cause swell ing of PPV or its sulfunium precursor 6. Multilayer or sandwich type
1.2 Poly( / ,4-plrenylene vinylene) ancl its Derivatives 7
structures comprising of different polymers (e.g. PPV and substituted PPV) may
be fabricated, and these exploit this difference in solubilities [30, 31 ].
Poly[2,5-diatkoxy- 1,4-phenylene) vinylene}s with long solubilizing alkoxy
chains dissolve in conventional organic solvents such as chloroform, toluene, or
tctmhydrofuran l27, 28, 32-36]. Their emission .and absorption spectm are red-
shifted relative to PPV itself, and the polymers' fluorescence and electrolumines-
cence quantum yields are greater than parent PPV. This benefit may be a conse-
quence of the long alkyl l:hains isolating the polymer chains from each other.
The sulfonium precursor route may also be applied to alkoxy-substituted PPVs,
but a dehydrohalogenation--condensation polymerization route, pioneered by
Gilch, h; favored 137}. The polymerization again proceeds via a quinomethide in-
tcnncdiatt:, but the synthesis of the conjugated polymer requires only two steps
and proceeds often in improved yields. Till! synthesis of the much-studied polyl2-
methoxy-5-(2-ethylhexyloxy)- 1,4-phenylene vinylenej, MEH-PPV IS is outlined
in Scheme 1-5 133. 35). The.! solubility of MEH-PPV is believed to be enhanCI!d
by the branch!.!d nature of its side-chain.
14
oy

MeO n
15
Scheme 15. Preparation of MEH-PPV 15: a) 2-ethylhexyt bromide, KOH, EtOH, reflux, 16 h;
b) HCHO, cone. HCI, dioxane. 20' C, 18 h, reflux, 4 h; c) KOtBu, THF, 20"C, 24 h.
4-Methoxyphenol is alkylated and then chloromethylated to yield the bis-chlor-
omethyl derivative 14 [28, 32- 351. Polymerization and elimination to fully conju-
gated matl!rial is promoted by the addition of a 1 0-fold excess of a base such a.-;
potassium terr-butoxide in tctrahydrofuran. The concentration of base and mono-
mer must be carefully controlled to prevent cross-linking and gelation. TI1e resul-
tant MEH-PPV is bright red-orange.! in color. A single layer elcctroluminescence
device (ITO/MEH-PPV/Ca) achieves illl eiTiciency of 1.0% [28, 38, 39]. The
etliciency may be improved four-fold by the incorpomtion of a thin
hole-blocking layer of poly(mcthyl methacrylate) deposited by Langmuir-Blodgcu
techniques and by using aluminum as a cathode.
Other poly(2,5-dialkoxy- l ,4-phenylcne vinylenc)s have been prepared in a sim-
ilar fashion [34, 35, 40, 41 ). Ahl!mativcly, a soluble a-halo precursor polymer 17
may be obtained by using less than one.! equivalent of base (Scheme 1-6). This
may then be conve11ed into fully conjugated material 16 by them1al trcatml!nt.
This halo-precursor route may be preferred if the fully conjugated mate1ial has
limited solubility ur if incomplete conversion is desired.
8 1 Poly(arylene vinylene)s - Synthesis and Applications in Semiconductor Devices
OR
OR
H,C-P-CH3
a

-
X
X
R = Ct;H1s. CeHe
X= OR, Br, Cl, F3
1 b
OR
OR

c

X n X n
16
17
Scheme 1-6. The Halo-precursor route to substituted PPVs: a) NBS, CC!.t. hv; b) KOtBu,
THF; c) 160-220"C, vacuum, 4 h.
a
c
20
(Cti:!lnH n
23
Scheme 1-7. Preparation of DP-PPV derivative 23: a) H-cs C-{CH2)n-H; b) UAIH4;
c) SOCI
2
; d) KOtBu, 2.2.
1.2 Poly( /,4-phenylene vinyle11e) UIU[ its Derivatives 9
Control of gelation and polydispcn;ity has recently been improved by the use
of a benzylic halide 22 as a terminator (Scheme 1-7) [42]. The halide serves as a
non-polymerizable acidic additi ve, and high molecular weight PPV derivatives 23
with relatively small polydispersities can be attained. A hexyl-substituted deri va-
tive 23a, DP6-PPV, shows a remarkably high photoluminescence quant um effi-
ciency of 65% in the solid state. Its emission maximum (490 nm) is in the blue-
green region of the spectrum. The synthetic route is versatile and utilises the
Diets-Alder reaction as a novel way of appending alkyl groups onto the benzene
ring.
The effects of the length and degree of bnmching of the alkoxy side chain on
EL etliciency have been examined by a number of research groups (Scheme 1-8)
[27]. Efficiencies pass through a maximum with increasing size of side chain be-
fore falling off tor very large substituents such as cholestanoxy, e.g. 26 [40, 43).
Il may be envisaged that such lar<Je substituents diminish the semiconducti ng
nature of the material by deleterious twisti ng of the polyrne backbone, and also
by increasing the insulating chamcter of the film. The introduction of a sterically
demanding silyl group as in DMOS-PPV 25 widens the HOMO-LUMO gap and
green light is emi ucd 144-47 ). External EL efficiencies of 2.1% have been
reported by Philips usi ng a dialkoxy-substitutcd PPV derivative 24 148] and an
28
Scheme 1-8. Examples of soluble, dialkoxy-substituted PPV derivatives.
10 1 Poly(arylene vinylene)s - Symhesi.1. w1d Applications ill Semiconductor Dcvias
Qrdered dialkoxy PPY derivative has been prepared by Yoshino e1 u/. r49l.
vinylene) 27a fonns a nematic liquid-crystal-
line phase upon 1nelting. TI1e material retains its order upon cooling to room tem-
perature, and its band gap (2.08 eY) is measurably smaller than in an unoriented
sample. Oriented clectroluminescence may be achieved by rubbing a thin film of
the material to induce molecular orientation [50].
1.2.2.1 Poly(anthrylene vinylene)s
The scope of Wessling route has been extended by Mullen and co-workers to de-
velop a soluble precursor route to poly(anthrylene vinylene)s (PAYs) [51). It was
anticipated that the energy differences between the quinoid and aromatic reso-
nance structures would be diminished in PAY relative to PPY itself. An optical
band gap of 2. 12 eY was detem1incd for 1,4-PAY 29, some 0.3 eY lower than the
value observed in PPY. Interestingly, the 9, I 0-bis-sulfonium salt does not poly-
merize, possibly due to steric cftccts (Scheme 1-9).

l<=5 Jn l<=5 Jn
;,9
A
A
a
-
29
Scheme 1-9. Synthesis of PAV 23: a) Et.NOH, CH
3
CNIH
2
0; b) 290 .. C.
1.2.3 Step-Growth Routes to PPV Derivatives
Substituted soluble PPY derivatives may also be synthesized by step-growth poly-
merization methods. Arylene-bis-phosphylidenes may be condensed with ter-
ephthaldehydes in a Willig fashion to yield alternating PPY copolymers [52). An
aJkoxy-substituted PPY derivative 28 (Scheme 1-8) prepared in this fashion emits
in the orange (..(""'" = 585 nm) region of the spectrum [52).
Palladium-mediated catalysis has only been exploited relatively recently in the
synthesis of substituted PPY derivatives. The use of aryl dibromides as monomers
is particularly useful as it allows the synthesis of PPYs substituted with alkyl
mther than alkoxy sidcchains. The Suzuki )53, 54], Heck (55], and Stille )56) re-
actions have been used in the synthesis of new PPY derivatives, but auaining
high molecular weight PPY derivatives by these methodologies has proved
problematic. A phenyl-substituted PPY material PPPY 31 was synthesized by a
Suzuki coupling (Scheme 1- 1 0) of dibromoethenc and bis-boronic acid 30. Its ab-
sorption U'max=385 nm) and emission (}.
111
.. "=475 mn) maxima were strongly
Ph
(HOhS-6-B(OHh
30
+
1.2 Poly( 1.-1-p/umylene inylcne) and its Deri1utiel' II
Ph
a
-

31
Scheme 1-10. Synthests of PPV 25 by Suzuki coupfing; a)
toluene,
60' C.
blue-shifted relative to PPY itself. The molecular weights of this material were
moderate: M,=3900 and Mw= 11930.
1.2.4 PPV Copolymers
PPY and its alkoxy derivatives arc p-typc conductors and, as a conset(UCnce. hole
injection is more fac.:ilc than electron injection in these materials. Efficient injec-
tion of both types of charge is a prerequisite for efficient LED oper.1tion. One
approach to lowering the banier for electron injection is the usc of a low wor"-
functi on metal such as calcium. Encapsulation is necessary in this instance, how-
ever, as calcium is degraded by oxygen and moisture. An alternative approach is
to match the LUMO of the polymer to the work function of the cathode. The usc
of copolymers may serve to redress this issue.
it has been found that statistical copolymers often exhibit improved EL proper-
tics relative to their homopolymer analogs. This was demonstrated initially in a
copolymer or PPY and poly((2,5-dimethoxy- 1,4-phenylcnc)vinylencJ [57). A vari -
ety of copolymers with interrupted conjugation have subsequently been investi-
gated by the Cambridge group )58, 591 and elsewhere r60. 61 1.
The of such copolymers is relatively straightforward. A mixture of
monomers 4 and 32 is polymerized in a water-methanol mixture using sodium hy-
droxide as base (Scheme 1- 11 ). The ratio of the units in the resulting copolymer
may be manipulated by changi ng the feed ratios of monomers 4 and 32. The sul-
fonium groups arc replaced by methoxy substituents, and this substitution occurs
faster at benzylic carbons adj acent to activating alkoxy groups. As a consequence,
the resulting copolymer 33 consists of many sulfonium groups adjacent to pheny-
lene units and mostly methoxy substituents next to dimethoxyphenylene units.
Sulfonium groups may be readily removed with heat treatment of polymer thin
films, whereas methoxy groups are only pat1ially eliminated under these condi-
tions. A polymer with interrupted conjugation 34 may be readily produced. Com-
plete removal of mcthoxy substituents is achieved using thermolysis under acidk
conditions to yield the fully conjugated material 35.
The composition of the copolymer determines its clcctroluminesccnce effi-
ciency. Optimal efficiency (0.3%) was achieved in system 34 when the ICed ratio
of monomer 4 to monomer 34 was 9 : I. This rcprc.-;cnts a 30-fold improvement in
luminescence elliciency relative to PPV in the same device conligumtiou
(AIAI
2
0_Jpolymcr/AI) 158. 6:!). Copolymer 33 has found uses as waveguide.'> and
12 1 Poly(wylt!l1e vinylene)s - Synthesis and Applications in Semiconductor Devices
la,b,c,d
OMe
34
1'

MeO n
35
Scheme 1-11. Synthesis of partially conjugated PPV copolymers: a) MeOH;
b) MeOH, 50C; c) 300C, vacuum, 12 h; d) 220C, HCI(g)/Ar, 22 h.
lithographically patterned copolymers [58, 59). High EL efficiencies have also
been demonstrated in alkoxy- and alkyl-substituted poly(phenylene vinylene)s
with interrupted conjugation. These systems may also be synthesized by the base-
induced dehydrohalogenation method [61 ].
The efficiency of PPV may also be mised by introducing disorder into the
polymer chains. The crystallinity of PPV may be lowered by employing a modi -
tied Wessling method utilizing a xanthate leaving group 163]. PPV produced by
this method is believed to contain a mixture of cis- and trans-alkene units. The
efficiency of the material is 0.22% when employed in a single layer device with
1.3 Refining the Properties of PPV - Multilayer Devitc:s
R R

36
Roo R
Y=NC6Hs.O
9
0
37
R = H. C
6
H
5
, p-CJ-14F
38
a
38
1-12. Synthesis of PPV derivatives incorporating triarylamines: a) KOtBu, toluene.
aluminum calhodc.:s; this may be.: improved to 2% when a doublc.:-layer device em-
ploying an electron-transporting layc.:r is employeq (see Section 1-3).
Triarylamines have been employed in arylenc.: vinylene AB copolymers 38 by
Horhold et a/. using a Horner polycondensation route of aldehydes and ketones
36 with /Jis-phosphonate 37 (Scheme 1-12) 164 ]. Phenylamines have remarkably
low redox potentials and their charge tr.msport properties have been investigated
extensively 165). EL devices comprising triarylamines have demonstrated low
driving voltages.
1.3 Refining the Properties of PPV - Multilayer Devices
Any commercial applications of polymer-based LEOs require maximum bright-
ness, high power efliciency, and extended device lifetimes. The.-:;e requiremenL-;
necessitate the need for light emission at low driving voltages. The simple single
layer device architecture described thus far is limited in this respect, and notable
auempts have been made to improve the performance of PPV-based EL materials
by the creation of multilayer devices. Such refinements in device architecture may
pave the way for organic displays that can compete effectively with their inorgan-
ic counterparts in terms of cost-effectiveness.
16 1 Poly( urylene vinylene)s - Synthesis and Applications in Semiconductor Device.s
43
Scheme 1-14. Examples of a oxadiazole- and a quinoxaline-containing electron-transporting
polymer.
A hyperbmnched polymer 42 compnsmg oxadiazole subunits has been synthe-
sized, but defect formation in such a structure appears to limit its use as a hole-
blocking material [74].
Other electron-deficient heterocyclic systems have also been as
electron-transporting materials. In particular, devices employing poly(phenyl qui-
noxaline) 43 as an ECHB layer have shown improvements in device efliciency
when used in conjunction with an emissive PPV layer [75).
1.3.2 Electron-Deficient Polymers - Luminescent Transport Layers
It would be preferable to incorporate both fluorescent and electron transport prop-
erties in the same material so as to dispense entirely with the need for elcclron-
tmnsport layers in LEOs. Raising the aflinity of the polymer facilitates the use of
metal electrodes other than calcium, thus avoiding the need to encapsulate the
cathode. It has bt:en shown computationally [76] that the presence of a cyano sub-
stituent on the aromatic ring or on the vinylenc portion of PPV lowers both the
HOMO and LUMO of the material. 1l1e barrier for electron injection in the mate-
rial is lowered considerably as a result. However, the We.-;sling route is incompati-
ble with strongly electron-withdrawing substitucnts, and an alternative synthetic
route to thi s class of matCJials must be employed. 1l1e Knocvcnagcl
1.3 Refining the Properties of PPV - Multilayer Devices
45 46
47
Scheme 1-15. Synlhesis ol CN-PPV 41: a) NaOAc; b) KOH, EtOH; c) pyridinium chlorochrc
mate; d) NaCN; e) KOtBu or Bu
4
NOH, tBuOH, ll-IF, SO"C.
177.1 utilized in the synthesis of CN-PPV 47, a dialkoxy-substituted PP\
dcnvat1ve wnh a substituent on the vinylene position. TI
1
e reaction in
.the of a tcrephthaldehyde 45 and a benzene- 1,4-diacetonitrilt
46 Ill the of a base such as tetrabutylammonium hydroxide o
1
potasstum in a solvent mixture of tetrahydrofuran and tert-butano
(Scheme l.-1.)) [78 ). Both monomers arc readily available from the dichloride 44
The may be puril}ed by precipitation. CN-PPV is a highly fluo-
rescent, bn!hant red matenal and Its band gap [590 nm (2.1 eV)) is very similar rc
other PPY derivatives. The molecular weight of the polymer is mod-
. albell lor step-growth polymerizations of this nature. The polymc
1
ts _soluble 111 such as chloroform, by virtue-of its long alkoxy side
chams. 1 He nature of the material is exemplified by cyclic vol-
tammetry studtes. These demonstrate that the cyano substituent reduces the onsc1
of reduction by 0.6 V relative to dialkoxy PPV (74].
In contrao;t with .L"O_njugated polymers, such as PPV, devices employing CN-
PPV 47 _as the enusstve layer can achieve respectable intemal erticiencies (ca.
wllh both and aluminum electrodes. EL elliciency may be further
unproved by cmploymg a hole-transporting layer such as PPV in COilJunction wi th
14 1 Poly(ary/eJ1e vi11ylene)s- Sy111hesis and ApplicaJions in Semiccmductur Devices
1.3.1 Multilayer Devices: The Incorporation
of Charge-Transporting Layers
To maximize light output. it would be ideal to create roughly equal amounts of
both charge carriers, i.e., electrons and holes. Most devices described thus far
have been single-layer devices where the semiconducting polymer is sandwiched
between the cathode and anode. It has already been mentioned that PPV has a
higher barrier for electron injection than for hole injection, and holes are preferen-
tially injected in a single-layer device. It is common. therefore, to use additional
layers of materials to enhance electron injection. These layers arc termed electron-
conducting/hole-blocking (ECHB) layers, and the configuration of a typical de-
vice incorpor.uing such a layer is depicted in Figure 1-3. To work efficiently, the
electron affinity of the ECHB layer must be higher than that of PPV. In such a
case charge carrier recombination takes place away from the polymer metal inter-
face, which is known to act as a quenching site. EL efficiency may thus be con-
siderably improved relati ve to single-layer devices.
The earliest ECHB materials studied were the oxadiazolcs. These are electron-
deficient materials and 2-( 4-biphcnylyl)-5-( 4-te rt-but ylphcnyl)- 1 ,3,4-oxadiazole
(PBD) 39 was the first member of this class of compounds to be used success-
fully in a sublimed film EL device [66, 671. The material is available in high pur-
ity, and may be sublimed or spin-coated as a dispersion in poly(mcthyl methacry-
late) (PMMA) (68]. It may also be blended to good effect with electroluminescent
polymers [47, 69, 70], although it is preferred to disperse PBD in an insulating
polymer such as PMMA to overcome potential problems with phase separation.
An increase in device thickness is llil inevitable consequence of this approach,
and this manifests itself as a ri se in driving voltages in an ITO/PPV/PBD-PMMA/
Ca device. This disadvantage, however, is outweighed by a ri se in EL efticiency
from 0. 1% (for an .ITO/PPV/Ca device) to 0.8% (for ITO/PPVfPBD-PMMA/Ca).
8
hv
Figure l-3. In improved bilayer dcvi<.-c fur a polymer LEO an cx1r.1 ECHU layer
bc.:n inserted bclwccn the PPV thc calhudc metal. The ECIIB tllalcrial euham:o the llow of cltt-
ln.ms bu1 rcsisb mdoalion. Elcclrons and holes 1hen ac.:umula1e ncar lhe I'PV/ECHll layer imcrfaa:.
Charge rccomhina1ion and phlllun gencrutinn lX:cur.. in 1hc PPV layer and ;away fnnn the culhude.
1.3 Reju1ing the Properties of PPV - Multilayer Devices 15
Scheme 1-13. Examples of oxadiazole-<:ontaining electron-transporting materials.
Electron-hopping is the main charge-transport mechanism in ECHB materials.
There is precedence in the photoconductivity licld for improved charge tr.msporl
by incorporating a number of redox sites into Lhe same molecule. A number of at-
tempts to adapt this approach for ECHB materials have been documented. Many
usc the oxadiazole core as the electron-transport moiety and examples include
mdialenc 40 and dendrimer 41. However, these newer systems do not offer signif-
icant improvements in electron injllction over the parent PBD.
An alternative approach utili l.Cs polymeric analogs of PBD. The oxadiazoh:
unit may be in the polymer main chain or attached as a side chain. A reasonable
device perfonnance has been demonstrated in poly(aromatic oxadiamle)s [71- 741.
18 1 Pvly(uryle11e - am/ in Seminmcluctor Dnic't'.\'
OMe
49
51 50
Scheme 1-16. Color range available for CN-PPV derivaiJves.
the highly electron-deficient CN-PPV. The insolubility of PPV may be readily
exploited in this context: CN-PPV may be spin-coated onto a layer of PPV and a
two-layer device (ITO/PPV/CN-PPV/cathode metal) functions with very high
(4%) internal efficiencies [79, 80). Unlike other two-layer devices discussed pre-
viously, emission in PPV/CN-PPV two-layer devices appears to occur exclusively
from the CN-PPV layer. It may be postulated that CN-PPV behaves a-. a sink lor
excitons and charge carriers; emission from the PPV layer is an unfavoured conse-
quence.
The Knoevenagel condensation route to CN-PPV may be easily tailored and
several derivatives of u-cyano PPV have now been synthesized (Scheme 1- 16)
(61, 81]. Many of these also show high EL efficiencies when used in a double-
layer device configuration with PPV [82, 831. A representative example is MEH-
CN-PPV 48, which exhibits very high EL device efficiencies in the red/omnge re-
gion of the spectrum. A double layer device ITO/PPV/48/Al produces red-omnge
(600 nm) light with a luminous efficiency of 2.5 hn w- [61, 81 ]. The emission
color may be altered by modifying the substituents on the polymer backlxme.
Bulky substituents such as the isopropyl group of 49 cause a twisting of the poly-
mer backbone, inducing a blue shift in its emission spectrum (peak wavelength at
5 I 0 nm). An alternati ve method of reducing the effecti ve conjugation length in
these systems is the incorporation of meta linkages. Polymer 49 emits in the blue
region of the spectrum. Substitut ion of one benzene ring with a thiophene as in
50 reduces the band gap of the polymer to 1.75 cV (740 nm). Emission in the in-
fr..l red was first demonstrated in an ITO/PPV/50/AI LED [84]. The emission max-
imum may be red-shifted further by the replacement of the second benzene ring
with a thiophene. Polyll'lcr 51 has a band-gap of 1.56 eV (800 mn) (X I, 851.
1.3 R(/iuing tftt l'mpt'rtit., of PPV - Multi/ay<r J\)
1.3.2.1 Other Elcctron-Dclicicnt I,PV Oc&iv<ativcs
Attachment of dectron-withdr..1wing groups directly onto the aromatic ri ng repre-
sents an alternative approach to polymers with a high electron affinity. 1l1e Wess-
ling procedure may be exploited to yield polymers 52 and 53 with alkoxy and
halide substituent-; on the ring (861. The group at Cambridge has synthesized
hokblocki ng derivatives such as 53, synthcsiwd by a bromo-precursor route 1871.
or 54, derived from a Homer polycondcnsation (88). The halogen-substituted
PPVs 52 and 53 emit light in the red region of the spectrum (emission maxima
620-630 nm) (86), whereas the trifluororncthyl derivative 54 was fol)nd to emit
yellow light (540-570 nm). However, the PL and EL quantum eHiciencies were
poor in these materials. A double-layer device employing PPV ac; a hole-i njecting
layer and AI a-; a cathode achieved an internal EL efficiency of only 0.0 I% [87.
89].1! is likely, therefore, that these materials will be more useful as ECHB layers
than as emissive layers.
54
Scheme 1-17. High-electron-affinity PPV derivatives with electron-withdrawing groups on the
aromatic ring.
1.3.2.2 Electron-Delicicnt Aromatic Systems
Pyridine is considered by organic chemists to be an electron-poor aromatic system
and pyridine analogs of PPV such ao; 55 represent an alternative approach to r.1ising
the electron affinity of conjugated systems (Scheme 1-18). The material may be
synthesized by a palladium-mediated Stille coupling of I ,2-bis-(uibutylstannyl)-
ethylcne and 2;5-dibromopyridine 190(. The polymer is yielded as an orange pow-
der and is soluble in m-crcsol. It emits in the red region of the visible spectmm
(590 nm). 1l1e materi al may be alkylatcd or protonatcd at nitrogen to yield soluble
polymers 56 and 57 respectively. N-alkylation induces a blue shift in emission to
540 mn. When a butyl group is appended to the 5-posilion of 2,5-dibromopyri-
dine, the rcsultana p()l ymer poly(J-u-hutyl-J' pyridylvinylenc) 58 is soluble in con-
ventional organic solvents [91, 921. Its emission spectrum i:; red-shifted consider-
ably to 630 nm and a device wit h the configuration r rO/Bu-PPyV/AI has an exter-
nal quantum clllcicncy of 0.02% 1921.
Polymer 55 exists as three different regioisomers: head-to-head, hcad-to-hc<td.
and random. The various isomers have been synthesized, and it has been found
they have dilkrcnt absorption. PL. and EL spectra (931. The efl"cctivc conjugation
20 1 Poly(aryleue viuylene)s - Synthesis and Applicmions in Semiconductor Devices
55
Bu
Kht
n
56
57 58
Scheme 1-18. Pyridine-based analogs of PPV.
a
-
Cl...._ _ f N\ __

59
b
-
Q.. ;=N,

cr S+
60
/
Xfr.
d
-trOt
d

---
n
!J n
62 55 61
l d
/
M{!Ot
!J n
63
Scheme 1-19. Wessling route to PPyV 49: a) NCS, CC4; b) tetrahydrothiophene, MeOH,
sooc; c) aq. NaOH, MeOH; d) heat; e) 0.98 eq. KOtBu, THF; f) heat, MeOH.
length of the head-to-head isomer is found to be the longest. Its emission spec-
trum is maximal at 605 nm, whereas the head-to-tail and random isomers emit at
584 nm and 575 nm, respect ively 194].
Poly(pyridine vinylene) 55 may also be prepared by the Wessling route
(Scheme 1-19) (95]. Fully conjugated material may be obtained by thennal elimi-
nation of the sulfonium salt 61 or the halide 62. The method, however, does not
I .-J Full Color Displ<1ys - Tile Searclt for JJ/ue millers 2 1
yield a material of pa1ticularly high molecular weight (ca. 2900) as is evident i1
MALDI mass spectroscopy. The HOMO-LU MO band gap of the material is esti
mated to be 2.2 eV, whereas it emits in the orange-red region of the spectrum a
2. 1 eY. The solid state PL quantum efficiency (2%) is considerably lower thau oh
served in PPV (27%).
1.4 Full Color Displays - The Search for Blue Emitters
A multi-color display requires the three primary colors - red, green, and blue -
and these colors need to fall within the parameters delined by the CIE
L96]. Blue EL hal> been the slowest in development, both in traditional inorganil
materials as well a-; in polymers. There are a number of different approaches to
suitable polymeric analog. It has al ready been discussed in Section 1-2 how th1
HOMO-LUMO gap of PPV may be raised by incomplete conversion to the full)
conjugated polymer. Furthermore, the band gap may be increased by
sterically demanding side groups onto the polymer main chain. The useful opto
electronic properties of phenyl-substituted PPV deri vati ves has already been dis
cussed (sec Secti on 1-2.2) 1421. The following section will enunciate a number o
other approaches to matc1ials that emit in the blue region of the spectrum.
1.4.1 Isolated Chromophores - Towards Blue Emission
An alternative pproach to tailori ng the band gap of a polymeric material
the use of polymer blends. 1l1e blend of a fluorescent dye in an inert polymc
matrix yields a polymeric EL material with useful luminescent charactetistics. h
practice, however, the fluorescent yield in such a blend is very low as a consc
quence of the low mole fraction of the luminescent species. Device
may be enhanced considerably by the use of an clectroacti ve polymer, e.g., poly-
(vinyl carbazole) 64. TI1e improvement in performance manifests itself even a1
very low concentrations of fluorescent species. Alternatively, the active chromo-
phore may be incorporated into the polymer backbone ito;elf and the light-emittinf
species can be separated by varying lengths of inert .. spacer'' units. This has beer
demonstrated in the preparation of copolymers such as 65. These are prepared h)
conducting a Willig condensation of a bis-ylidc in the presence of
amounts of saturated dialdehydes (Scheme 1-20) 197].
More precise control over the emission color may be achieved by
equimolar quantities of a his-phosphonium salt, e.g., 67 and a dialdehyde contain-
ing a flexible unit such as 66. This approach has been exploited by a number ol
researchers 19X- 1021. The emission wavelength of these materials is in the blue tc
hl ue-grcen region of the spectrum (470-495 nrn).
22 I Pol)(urylene vulyle11e)s - Symhesis and Applications i11 Semiconductor Devices
OMe OMe
n 0- (CH2}8
MeO m
64 65
Scheme 1-20. Poly(vinyl carbazole) and an example of a polymer with an isolated chromo-
phore.
OMe MeO
OHC-Q-0- (CH2}e -0-o-CHO
OMe MeO
66
+
67
I
MeO
OMe
68
Scheme 1-21. Synthesis of a blue-emitting copolymer with isolated chtomophore by Wittig
reaction: a) base.
1.4.2 Comb Polymers with Chromophores on the Side-Chain
The luminescent moiety may also be attached to the polymer backbone as a side-
chain, yielding a comb polymer. In this instance, the main polymer chain is often
non-conjugated, and classical approaches to high molecular weight polymers may
be employed. Distyrylbenzenc has proved to be a u:scful lumophore in this con-
text. It has been attached to polymethacrylates such as 69 bCaJing electron-trans-
porting diaryloxadiazole units [74, 103, 104]. A bilayer LED employing PPV as a
hole-transporting layer and 69 as an emitting layer showed emission in the blue
region (457 nan) of the spectrum with an efficiency of 0.037%. A tail into the yel-
low-green region of tl1e spectrum was observed, and this was attributed to emis-
sion from PPV itself.

0 'I
MeO
70
/ .5 Chiral PPV - Pulurized Emission
OMe
OMe
Scheme 1-22. Examples of electroluminescent polymers with side-ch,;n""' ho
... "'oromop res.
The precise control of ROMP methodolo has bee .
co-workers in the 1 , gy n cxploated by Schrock and
aW functionalized with a
. l n ca caum 1s used as a .. thod .
nal dev1ce efficiency of
0
J% . b . cd . . . ca e, an lnter-
(475 nm). .. IS o serv and the peak emission is in the blue
l.S ChiraJ PPV - Polarized Emission
Meijer and co-workers I 106j have recently re 011 d . . I I .
nescence (CPEL) . . h . P c cncu ar Y polanzed elcctrolumi-
. usmg a c lral 7H.:CmJugatcd PPV deriva( 71 S .. ,
such a system the absorebcd and emiued lioht hav' lrtl ave . ( 1-23). In
and ri oht (R) circularly ..,.
1
"'. d . o . c
1
c.:rcnt antcnsatiCS lor left (L)
o , . > auzc.: components To unpmvc >I b T
al and racemic monomers had to be c .I. . h' S Sl u a _aty pn>pcalles, char-
f
1

0
Pl> ymcn;rNU. mall ch1ral aggrc . t. .
orml-'"l Ill these matcriah. as a consequence of the rc<>iospll- .. b t . ga c.:s arc
o su s llutaon paucna
24
I Poly(arylene vinylene)s- Sy111hesis and Applicutions in Semicunductur Devices
R=CH3
71
Scheme 1-23. Chirooptical PPV derivatives.
of the enantiomcrically pure side groups on the chain. The conjugated polymer
obtained maintains its intrinsic chirality in both solution and solid state, and circu-
larly polarized emission requires no extemal macroscopic ordering of the chromo-
phores. Funhem1orc, it was found that the cin:ular polarization in absorption,
was larger in an aggregated solution than in a solid lilm, sugges_ting orderin_g
of polymer chains in an appropriate solvent. The dissymmetnc layer
a consequence of the polymer's constitution, the solvent and the proccss.ng condi-
tions employed.
1.6 Poly(thienylene vinylene)s-
A Stable Class of Low Band-Gap Materials
Polyacetylene is considered to be the prototypical low but its
potential uses in device applications have been hampered by senstllv_ty to both
oxygen and moisture in its pristine and doped states. Pol_y(thtenylene vmylene) 2_
has been extensively studied because it shares many ot the useful aunbutes ol
polyacetylene but shows considcr.1bly improved T_he low
band gap of PTV and its derivatives lends itself to potenttal apphcallons n both
its pristine and highly conductive doped state. Furthermore, the vinylcnc spacers
between thiophene uniL'i allow substitution on the thiophene ring without disrupt-
ing the conjugation along the polymer backbone. . .
Polymers such as PTV have potential applications as the acllve semtconductor
layer in thin-film transistors (TFTs).
1.6 Poly(thieuyleue vinylene)s - A Swble Class of Low Bcmd-Cup Mmerials 2:
1.6.1 Organic Field Efl'ect Transistors (FETs)
Organic materials have recently shown promise as the active layer in organic
based thin lilm tr,msistors (TFTs). Such devices have potential applications in th
switching element in flat panel displays and smart cards. Organic materials coul
have substantial cost advantages over their silicon counterparts if they can be de
posited from solution, as this enables the easy fabtication of large-area, tlexibl
displays. The geometry of a typical thin-film transistor device is depicted i
Figure 1-4. The current passing between two electrodes, the source and drain, i
controlled by applying a voltage to a third electrode, the gate. The semiconduc1
ing layer carries the current and the perfonnance of the device is very muc
dependent on the mobility, Jt, of the semiconducting material. Another figure c
merit is the ON/OFF r.1tio of the device; ideally the semiconducting layer shoul
have a low conductivity but a high field-eflcct mobility. Crystalline silicon has
mobility of 10-' cm
2
v- s- , whereas organics can only attain mobilities of th
order 1- 10 cm
2
v- s- but these values are sufficient for the intended applic<
tions. The best results to date have been achieved with discrete oligomers sue
as u-hexathienyl [107-112), C
60
fii3J and pentacene [114}. Mobilities as hig
a-; I cnl v- s- have been auained with ON/OFF ratios greater than lOll. bt
these results were obtained by sublimation of the semiconducting layer. An alte1
native approach utilizes low band-gap conductinf polymers; poly(thienylene vin)
lenc) 2 has yielded mobilities of 0.22 cm
2
v- s- 11151 but substantialtcchnologi
cal hurdles remain before these devices make it to market. Synthetic approachc
that yield well-ordered regioregular polythiophene or poly(thienylene vinylcm
derivatives may unlock the true potential of organic materials in semiconductl
devices.
Figure 1-4. Sc.:hcmalic.: dmwing of a 1Xllymer-basoo lhin film transi,lor device. A charge (usually pm
Jive) is injcclc:d imo the scmicunc.lucling layer from lhc source declroc.le anc.l Jhe charges
Jermcc.l polarons. arc swepl 1u 1hc dr.1in clcclrode under 1hc inlluenc.:e of a vollagc applied al a 1hi1
ch:t:m>dc. !he gale. In 'ueh a cunfJ!_!Uraliuu 1he device I S capable uf .:urrcnl amlllilkaliun. i.e .. sm.o
changes in til<: applic.J gale vuhagc can produce large in eurren1 passing bc1wccu lhc soun
and dr.1in. The clkt:liVCIICSS of lhC dcvit:c is lillliiCd hy !he :1lJili1y Of !he s.;miconducling layer I
tmnspurt charge, a parmnelcr 1ermcc.l Ute lielc.l ctTccl mobili1y.
26 1 Poly(wylene vinylene)s- Synthesis cmd Applications in Semiconductor Devices
1.6.2 Synthesis
In common with PPV 1, however, parent PTV is insoluble and infusible. The mate-
rial was first synthesized in powder fonn by Kossmehl using a Wittig polycondensa-
tion methodology [ 116). The first example of PTV synthesized by a soluble precur-
sor route was published by Elsenbaumer and co-workers [ 117). Once again, the
Wessling method was exploited (Scheme 1-24): 2,5-(Bis(tetrahydrothiophenonium,
methyl)thiophene chloride 73 was treated with one equivalent of water at O"C
and rapidly fonned a thick polyelectrolyte. The material may be cast from aqueous
solution and converted into PTV by heating to l50C. The material exhibited a con-
ductivity of 60S em- when doped with 1
2
The watersoluble precursor polymer,
however, has a tendency to gel or precipitate during dialysis and storage. Further-
more, the soluble precursor is prone to elimination even at room temperature. 1l1e
route was modified somewhat by Murase [ 118) and Saito [ 119 J by treating the
water-soluble precursor with methanol. As a conscquenc.:e, the sulfonium groups
arc replaced by mcthoxy substituents rendering the pn.:cursor polymer 75 soluble
in organic solvents. Thermal treatment at 200- 250'"C affords a shiny material with
a large absorption centered arounu 2.3 (540 mu) and an optical banu gap of
1.8 eV. A considerable amount of effort has been devoted lo optimising this
protocol[l20j. lt has been found that the reaction is best carried out in water, anu
that low temperatures are benelicial for high monomer conversion and polymer
processibility. The optical anisotropy of PTV was examined by orienting thin
films of thickness 0. 1 f.un [ 121 ). A red-shift in the absorption peaks on the ma-
terial was observed upon stretching indicating more highly-ordered polymer films.
A drawback of the Wessling methodology, however, is that trace amounts of
acid catalysts are required to completely eliminate the methoxy groups. A conse-

a

cr cr
72
73

1 b
n
OMe
75
'Z_
ld

n

0
S n 74
2
Scheme 1-24. Wessling route to PTV 2: a) MeOH, tetrahydrothiophene; b) NaOH, H
2
0;
c) heat
/ .6 Puly(tlzieuyleue vinylene)s- A Swble Cluss of Law Bwzd-Cup Materials
27
.
quence is that this synthetic route is not particularly useful for semiconductor de-
vice applications. A route employing a xanthate precur.;or has been recently de-
scribed by the group at Lucent Technologies.
1.6.3 Aldol Route
Parent poly(thienylene vinylene) has also been synthesized by an
route [ 122). ln this method, 5-methyl-2-thiophenecarbaldehyde 76 ts treated With
a base and the monomer polymerizes yielding a precursor 77 which is soluble in
water. 1l1em1al treatment in an acidic solution at 80"C yields the fully conjugated
material. Alternatively, the solid polymer may be heated to 280oC to effect elimi-
nation of water. Fully conjugated matt:rial exhibits low conductivity (10-41 S em- ')
in its pristine stale.
H cJ[)-CHo
3 s
76
a
1 b

2
Scheme 1-25. Aldol route to PTV: a) KOtBu, DMF; b) heat.
1.6.4 Ring-Substituted PTV Derivatives
There have been a number of different synthetic 'approaches to substituted PTV
derivatives proposed in the last decade. Almost all focus on the aromatic ring as
the site for substitution. Some effort has been made to apply the tmditional base-
catalyzed dehydrohalogenation route to PTV and its substituted analogs. 1l1e
methodology, however, is not as successful for PTV as it is for PPV and its den-
vatives because of the grca1 tendency for the poly(u-chloro thiophene) precursor
spontaneously to eliminate at room tempcr.tture. Swager and co-workers at-
tempted this route to synthesize a PTV derivative substituted with a crown ether
with potential applications as a sensory material (Scheme 1-26) [123). The synthe-
sis employs a Fager condensation [ 1241 in its initial step to yield diol 78. Treat-
ment with a ditosylate yields a crown ethcr-funetionalized thiophene diester 79.
This may be elabor.1ll ... "<i to dichloride 81, but pure material could not be
and the dichloride monomer had to be polymerized in situ. The polymer Isolated
28
1 Poly(uryle11e vi11ylelle}s - Symhesis am/ Applicutiolls in SemicvtuluL'Ior Devices
a
78
d
-
Scheme 1-26. Attempted synthesis of a crown ether-functionalized PTV derivative 76:
K2C03, NMP; b) liAJH4, THF; c) SOCI
2
, pyridine, THF; d) KOtBu,
showed solvatochromic behavior, but could not be redissolved when solvent was
removed, and the material could only be chamcterizcd by IR spectroscopy.
The first substituted PTV deri vatives poly(3-methoxy-2,5-thienylcne vinylene)
poly(3-ethoxy-2,5-thienylene vinylene) 84 were synthesized by Elsenbaumer
10 the late 1980s [ 125 ]. The method employed was a step-growth condensation
a nickel-mediated cross-coupling reaction between a Grignard reagent and a
dtchlorocthene (Scheme 1-27). The materials obtained were deep blue solids, but
the majority of the sample was insoluble in common organic solvents. Endgroup
OR
OR

OR
d
a,b
b.c

s
"
S n
RO
82 83 84
A = Me, Et
BuO 06u

S n
85
Scheme 1-27_ Synthesis of alkoxy PTV derivatives and dibutoxy PTV 79: a) Bull,
MgBr2Et20; b) CICH::oCHCI (0.5 equiv.), NiCI
2
(dppp)
2
; c) CICH::oCHCI (1 equiv.), NiCI
2
(dppph.
1.6 Pol_r(tlliellylene Pinylene)s - A Stuble Cluss of ww Band-Cup Materials 2'
analysis of the insoluble proportion suggested that the number average molecula
weight M,, was over 9 100 g/mol. The soluble pl)rtion, however, showed in teres I
ing optoelectronic properties. It has an absorption maximum of 600 nm and it
band gap of 1.5 eV was significantJy lower than that of PTV itself. In additio1
the polymer could be cast into thin fil ms. The electron-donati ng groups arc lx
licvcd to reduce the ionisation potential of the polymer considcmbly compared t
unsubstitulcd fYTV. The material could be readily doped by FeC1
3
and pressed JX
lets of poly(3-cthoxy-2.5-thienylene vinylene) treated with FeCI
3
in nitromethan
solution exhibited conductivities of 1.8 S cm-
1
[ 126].
The same synthetic route was employed by Blohm and co-workers [1 27] in th
synthesis of poly(3,4-dibutoxy-2,5-thienylene vinylene) 85. The alkoxy chair
help to solubilise the polymer in conventional organic solvents, and this facilitat'
a rca.;onablc estimation of its molecular weight. GPC analysis of the polymer su:
gests M,= 12400, concsponding to a degree of polymetization of 49. The efll!t
tive conjugation length of this material is an improvement over poly(3-ethox:
2,5-thienylcne vinylene): the absorption maximum of poly(3,4-dibutoxy-2,5-th
enylcne vinylcne) 85 is red-shifted to 607 nm with a shoulder at 670 nm an
furthcnnorc, the color l)f the material could be reversibly changed from blue
nearly transparent in a doping-dedoping cycle. The measured conductivity of tl
doped material. however, was of the order I S em
1

The methodoll)gy has been further extended to hexyl-substituted P1V detivativo
by Shirakawa et ul. [ 12g]. A regioregular polymer consisting of alternating vinylet
and hexyl-substituted thiophene units 88 wa.o; prepared by a nickel-mediated eros
coupli ng (Scheme 1-27). The degree of polymerization was (M, == 360
and the ciTectivc conjugation length of the material .:t ..... =470 nm) was consi<ll
ably shorter than Observed in parent fYTV or its diaJkoxy-substitutcd dcriV<ttiVl
This is probably a consequence or the increased stcric repulsion between an alk
group and the hydrogen attached to the vinylic carbon.
The McMuny coupling route ha.; been utilised by lwatsuki and co-workers
the synthesis of PDBoxTV 8S (Scheme 1-29) 1129). Oialdehyde 90 is polyml
ized in the presence of tit anium tetrachloride and zinc dust. Molecular weights
35000 are reported and the polymer is freely soluble in solvents such as chlm
form. The repo11ed absorption maximum (605 nm) was close to that observed I
the Blohm route 1127 j .
The Stille reaction has been employed by a number or researchers in the sy
thesis of soluble PTV derivati ves [ 130]. Alkyl-substituted PTVs were symhesiz

0Cr,H,3

a. b b,c
I
b
s
S n

86 87 88
Scheme 1-28. Synthesis of dihexyl PTV derivatives: a) BuU, MgBr
2
Et
2
0; b) CICH=CH
NiCI
2
(dppph; c) BuU, MgBr
2
THF.
30 1 Poly(arylene vinylene)s - Synthesis and Applications in Semiconductor Devices
C4H110 OCHe
OHC)i_CHO
s
80
b
Scheme 1-29. McMurry coupling route to dibutoxy PTV 79: a) BuU, TMEDA, DMF; b) T1CI
4
,
Zn.
R R
0
s
a
R R
.--0-.
s
ll1
b
A R
,f-1 A '

ll2
Scheme 1-30. StUie route to alkyl-substituted PTV derivatives: a) 1
2
, HN0
3
; b)
8u
3
SnCH=CHSnBu
3
, Pd(PPh
3
)(0Ac).
by the reaction of 1,2-bistributylstannyl ethylene with a diiodothiophene 91
(Scheme l -30).
An attractive route to dialkoxy PTV derivatives has recently been reponed by
Elsenbaumer and co-workers 1131, 132). The method employs the thenual elimi-
nation of a sulfinyl group from <1 soluble sulfoxide precursor polymer (Scheme 1-
31 ). In addition, the authors claim the first isolation of the quinomethide inter-
mediate and characterised it by
1
NMR and mass spectrometry. Dibutoxy-PTV pro-
duced by this methodology exhibits a significantly smaller band gap (1.2 eV) and
higher molecular weight (M,. = 8700) than the san1e material obtained by other
methods. Poly(3,4-dimeJhoxy-2,5-thienylene vinylene) PDMoxTV was deep blue
in color (},,.,.,x = 680 nm) and exhibited a conductivity of 25 S cm-
1
when doped
with FeCI
3
This method is especially as it avoid:; the use of tmnsition
metal catalysts, which are potential contaminants for device applications.
1.6.5 Vinylene-Substituted PTV Derivatives - 1\ming the Gap
There have been very few examples of PTV derivatives substituted at the viny-
lene position. One example poly(2,5-thienylene-1 ,2-dimethoxy-ethenylene) 102
has been documented by Geise and co-workers and its synthesis is outlinctl in
Scheme 1-32 [133J. Thiophene-2,5-dicarboxaldehyde 99 is polymetized using a
benzoin condensati on; the polyacyloin precursor 100 was treated with base to
obtain polydianion 101. Subsequent treatment with dimethyl sulfate affords 102,
which is soluble in solvents such as chloroform, methanol, and DMF. The molar
mass of the polymer obtained is rather low (M,= 1010) and its band gap
(x= 2. 13 eV) is substantially blue-shifted rdative to PTV itself. Despite the low
effective conjugation, the mate1ial is reasonably conJuctive when doped with /
2
(o=0.4 S cm-
1
).
HO OH

s
78
a

s
93
MeO OMe

-=----
PhS S SPh
97
l f

98
8 8
96
1.7 Cundusimrs and Outlook
b
MeO OMe

HO S OH
94
d
MeO OMe

PhS S SPh
95
Scheme 1-31. Elsenbaumer route to dimethoxy PTV 92: a) Me
2
S0
4
; b) UAIH TI-
c) PhSH, Znl
2
; d) MCPBA, CHCI
3
; e)KOtBu, THF; f) 80 C.
0
s
a
OHC--0-CHo
s
99
b
-
d

OH
100
1 c

' -s on
101
Scheme 1-32. Synthesis of 96: a) Bul.i, TMEDA, DMF; b) KCN; c) Buli, KotBu; d) Me2S04
1.7 Conclusions and Outlook
This survey demonstrated that the licld of conjugated arylene vinylcnc pol
mers has matured considembly over the past thicny years. Several symhc
approaches to poly(arylene vi nylcne)s have been developed, and many routes m
allow solution casting of polymeric materials, thereby facilitating
32 I Poly(arylene vi11ylene)s - Symhesis wul Applicutions in Semico11ductor Devices
semiconducting polymers into real devices. The technology employing poly-
(arylene vinylene)s as the active layer in LEOs has advanced considembly over
lhe past Len years, and lhc impact of controlled synthesis on device properties can-
not be underestimuted. lL is perhups fair to say lhat PPV derivatives have had a
greater impact to date in the field of molecular electronics, but research effons arc
continuing to devise new synthetic approaches to PTV and its derivati ves. As a
consequence, it is anticipated lhat novel applications of such low band gap materi-
als in solid-state devices will be pursued with increased vigour in the next de-
cade.
Acknowledgemenls
We lhank the Engineering and Physical Sciences Research Council (UK), the
Commission of the European Community (Marie Curie Fellowship to MMM),
and Cambridge Display Technology for financial support. We acknowledge the
collaboration in Cambridge of our colleagues Prof. R. H. Friend, Dr. S.C. Moratti,
Dr. N.C. Greenham, and Dr. F. Cacialli and we thank Dr. A. Kraft and Dr. A. C.
Grimsdale for their interest in this work.
References
I. H. Shirakawa, E. J. Louis, A. G. MacDiannaid, C. K. Otiang, A. J. Heeger, J. Cleem. Soc. Cleenl.
UJ/IUIIUfl. 1977, 578.
2. J. H. Burroughcs, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. MacKay, R. H. Friend, L.
Bum, A. B. Holmes, Nmure, 1990, 347, 539.
3. R.A. Wessling, R.G. Zimmcm1ann (Dow Chemical), U. 3., 196!! [Chem. Ab.r1r. 1968, 69.
87735q).
4. R. A. Wessling, J. J>olynL Sci., l' nlym. S)mp. 1985, 72. 55.
5. R. W. Lenz. C.-C. Han, J. Slcngcr-Smith, F. E. Kar.1Sz, J. Polym. Sci., Polym. CheiiL 19MB, 26,
3241.
6. P. L. Bum, D. D. C. Br:Kllcy, R. ll. Friend, D. A. Hruliday, A. B. Holmes. R. W. Jackson, A. Kr.lft,
J. Chem. Soc .. Perl:i11 TrtUIS. I 1992. 3225.
7. R. O. GarJy, U. Baier. C. Bubeck. K. Mullen, Adv. Mllter. 1993, 5, 561.
8. F.R. Dcnlon, P.M. Lalui. F. E. Kam.Q. J. J>uly11L S(i .. Polym. ClteiTL 1992, JO. 2223.
IJ. A. lssaris, J. Gclan, D. Vanc.Jcr.tanc.lc, Symh. Me1. 11}1}7, 1997. 1149.
10. F. Papadimilrakopoolos, K. Konsladinidis, T. M. Miller. R. Opila., E. A. M. E. Gal-
vin, Chem. Mmer. 1994. 6, 1563.
II. F. Papadimitmk(>poulos. M. Yan. L. J. Rothberg, H. E. Katz, E. A. Chandross, M. E. Galvin, Mol.
Cryst. Liq. Cryst. 1994, 256. 663.
12. V.H. Tran, V. Massurdier, T. P. Nguyen, J. Davcnas. Polwner 1996.37. 2061.
13. Y. Nishikala, M. Kakimoto, Y. lmai, Tlli11 Solid Films 1989, /79, IIJI.
14. R. C. Smtih, W. M. Fischer, D. L. Gin, J. Am. Clu:m. Soc. 19'17, 119. 4092.
15. F. Louwel, D. Vandenande, J. Gelan, Sy111ll. Met. 1992. 52, 125.
16. F. Louwel, D. Vandenantlc, J. Gelan, Sy111ll. Met. 11}1}5, 69, 509.
17. F. Louwet, D. Vandcrzandc. J. Gclun. J. Mullens, Macromolecules 1995, 2X. 1330.
II!. S. Son, A. J. Lovinger, M. E. Galvin, Poly11L Muter. Sd. Eng. 1995, 72. 567.
19. E.G. J. Staring, D. Braun, G. L.J. A. Rikken, R.J. C.E. Dcmandt.. Y.A. R. R. Kcsscncr, M. Bouw-
mans, D. Broer, Sy11th. Met. I IJIJ4, 67, 71.
Rejere11ces 33
20. S. lwatsuki, M. Kubo, T. Kumcuchi. Clwm. U!u. 1991. 1971.
21. 0 . Schuler. A. Greiner, J. Pomrncrchnc, W. II. Vcs1welx:r, II. Y. Tak, H. Bassler, C.
Schmidl, G. Liissem. B. Schanel. V. S!Umpllcn, J. ll. Wcnum11', S. Spiegel, C. Moller, H. W.
Spiess, Mer. 1996. X2. I.
22. Chan!!. W.-T. Whang. P.-W. Lin. l'o/.1'111<'1' 199(>, .17. 1513.
23. W. J. Fca", J. Tsibouklis. K. L. Pouwcr. L. Grocnendaal. E. W. Mcij<!r. Polymer l iJ%, 37. 5017.
24. V. P. Couliccllo. D. L Gin. R.ll. Grubbs. J. Am. Chc'IIJ. Sac IIJIJ2. 114. 9708.
25. Y.-J. Miao. G. C. Bawn. J. AIIL Cllem. Sac. IIJIJ-4. 116. 9371J.
26. N. C. Gn.'Cnham. R. H. rrienc.J, D. D. C. Br.idlcy, Mater. 11}1}4, 6. 491.
27. S. Doi. M. T. Nogudu, T. Ohnishi. Syutlt. Mtl. IIJIJJ, 57, 4174.
28. D. Braun. A. J. Hccgcr. Appl. J>l1ys. ul/. 1991, 5X. 191!2.
29. D. Braun, A. J. Hccgcr. H. Kr<JCmer, J. Elulrrm. Mlller. 11}1}1, 20. 945.
30. A. R. Brown. N. C. Grccuham, J. H. UurrougiiC:>, D. D. C. Br..KIIey, R. H. Friend. P. L Burn. A.
Kraft.. A. B. Chf!IIL Pllys. u/1. 1992, 200. 46.
31. N. C. Grccnham, A.R. Brown, J. H. Burroughes, D.D. C. Bradley, R. H. Friend. P. L Bum, A.
Kr.tfl, A. B. Holmes. Pmc. SP/1::: 11}1}3, 1910. I l l.
32. G. Gusta['l.'iOil, Y. Cao. G. M. Trcocy. r. Klavcner. N. Colancri, A. J. Hcegcr, Ncllurl' 11JIJ2, 357.
477.
33. A.J. Hcegcr. D. firaun (Uniax), P. I.P. A. W. 9 . IW31C/rem. Ab.1tr. 1993, /IX. 15740ljJ.
34. G. J. Samccki. P. L. Bum. A. Kraft. R. H. Friend. A. B. llohn.;,;, Syu11t. Met. 1993, 55. 914.
35. F. Wucll . P. M. Allemand. G. Snlanov, Z. Ne. D. Me Branch, ACS Syllll' Sc1: 1IJIJI , 455. 61!3.
36. D. Braun, E. G. J. Staring. R.C.J. E. Dcmandt . G. L.J. Rikkcn. Y. A. R. R. Kesscncr. A.H. J. Vcu-
ltuizcn. S\11111. Mt'l. 1994, 66. 75.
37. H. G. W. L. Wlu:clwrighl, J. J>o/ym. Sci.: 11- 1 1%6. 4. 1337.
31!. I. D. Parker. J. Appl. Plns. 1994, 75, 1656.
39. Y.-E. Kim. H. Park. J.-J. Kim, Appl. Plly.1. Lett. I IJ%, 69, 599.
40. F. Wudl, S. liiigcr. C. Zhang, K. Pakbaz, A. J. Hecgcr .. Po/ym. Pre11r. 11JIJ3, 34(1). 197.
41. N. N. D. J. Guerrero. ll.J. Olivos, Ferraris, Sy/1111. Met. l iJIJS, 75, 153.
42. B. R. H"'ich, Y. Yu, E. W. rol');ythe. G. M. Schauf. W. A. Feld, J. Am. Cltelll Soc. 1IJIJ8. 120.
231.
43. C. Zhang, H. v. Seggcm. K. Pakbaz. F. Wudl, A. J. J. lectm11. Mell er. 1993. 22, 413.
44. S. Hoger, J. J McNamam. S. Schricker, F. Wudl, Cluml Mllter. 1994, 6, 171.
45. D.-H. Hwang. 1.-N. Kang. M.-S. Jang, H.-K. Shim, T. Zyung, J>olym. Bull. IIJ%. 36. 31!3.
46. D.-H. Hwang. S. T. Ki m. H.-K. Shim. A. B. S. C. Momui , R. H. friend. Clrelll Com
1111111. 19%, 2241.
47. C. Zhang, S. Hoger. K. P..ikbaz. F. Wudl, A. J. Hccgcr, J. /ec:tronic Mmer. l iJIJ4. 23. 453.
41!. J. Salbc<:k. Ber. lllliiSt!IIJ:CS. Pl1ys. Cllem. 11}1)6, /00. 166<>.
49. M. Hamaguchi, K. Yoshino. Jp11. J. Appl. Pll)s. 1994, 33. L 1478.
50. M. Hamaguchi. K. Yoshino, Jpu. J. ApJ1I. Pltys. 1IJIJS. 34, L 712.
51. R. 0 . Garay. H. Naam1ann. K. Mullen. Mcutmrrtl/rculex 1994, 27. 1922.
52. Z. Yang. B. liu. F. E. Mucromoleculf!s 1995, 2X. 6 151.
53. F. Koch. W. Hciez. Mcummol. Pllys. 11}1}1, IY8. 1531.
54. Z. 13ao. Y. Chen. R. Cai , L Yu, Mocmmtl/enth.r 1993. 26. 5281.
55. A. Gn:inCJ, W. Heitz. J>oi)OII. Prl!pr. 1991, 32. 333.
56. Z. Bao, W. K. Chan. L. Yu., J. Am. Chem. Su(.'. 1995. 117. 12426.
57. P. L. Bum. A.B. Holme.-;, A. KmfL. A.R. Brown, D. D. C. Bradley, R.H. Friend, Ma1er. Rc-.1.
Soc Symp. PrtJc. 11}1}2, 247. 647.
58. P. L. Bum. A. B. Holmes, A. Kmft, D. D. C. Bmdlcy, A. R. Brown. R. H. Friend. R. W. Gyma.
Nalllrc 1992. 356. 47.
59. P. L Bum. A. Kraf1. D. R. Baigcnt. D. D. C. Uradlcy. A. R. Brown, R. H. Friend, R. W. Gymcr.
A. B. Holmes. R. W. Jackson, J. Am. Clu:m. Soc. 1993. 115. 10117.
60. E. Z. Famggi. H. Chayel, G. Cohen. R. Neumann, Y. Avny, D. Davidov. Adv. Me1ter. 1995. 7.
742.
61. E.G.J. Slaring. R. C.J. E. Dcenandt.. D. nraun. G. L. J. Rikkcu. Y. A.R. R. A.H.J. Vcu-
huiz.:n. M. M. F. v. Knippcnb<!rg, M. Bouwmans, Sy1111l . Mel. I IJIJ5, 71. 2179.
34 I Puly(wylene vinylene)s - Syntilesis ami in Semicmulucl()r Devices
62. A. KrJO, P. L Bum, A. B. Holmes. D. D. C. Bradley, A. R. Brown. R. H. Friend, R. W. Gymcr,
Symh. Met. 1993, 55, 936.
63. S. Son, A. Dodabalapur, A.J. Lovinger, M. E. Galvin, Science 1995, 269, 376.
64. H. Rost, A. Tcusdlel, S. Pfeiffer, H. H. Horhold. Symfl. Met. 1991, 84, 269.
6S. P.M. Borscnberger. L. Pautmcier. R. Richcn, H. Bll.\sler, J. Cflem .. Pltys. 1991, 94. 1!276.
66. C.W. Tang, S. A. Van Slyke,App/. Pltyl. Leu. 1981,51.913.
67. C. Adachi, S. Tokito, ' f. Tsutsui, S. Saito. Jp11. J. Appl. Phy.t. 1988, L269.
68. A. R. Brown. D. D. C. Bradley. J. H. Burroughes. R. H. Friend, N. C. Greenhum, P. L. Burn, A. B.
Holmes, A. Kraft, Appl. Phys. Leu. 1992, 6/, 2793.
(f). M. Yoshida, H. Kawahara. A. Fujii, Y. Ohmori, K. Yoshino, Jpn. J. Appl. Plrys. 1995, 34,
L l 237.
70. M. Berggren, M. GmnstrO!n, 0 . M. Andersson, Adv. Murcr: 1995, 7, 9CO.
71. Y. Yang. Q. Pci, J. Appl. Phys. 1995, 77. 4807.
72. E. Buchwald, M. Meier, S. Ka11;. P. resell, H.-W. Schmidt. P. Strohricgl, W. RK:."'" M.
Schwoerer. Adv. Muter. 1995, 7, 839.
73. M. Meier, E. Buchwald, S. Karg, P. Posch, M. Gn..-cwtiel, P. Strohricgl, W. Ru::.s, Symlt. Met.
1996. 76. 95.
74. X.-C. Li. A. Kmfl. R. Cervini, G. C. W. Spcnc.:r, F. Cadalli. R. H. Friend, J. Groner. A. U.
Holme.,, J.C. DeMello, S. C. Moraui. Mat. Nes. Stw. S)YIIJI. Pmc. 1996, 4/J, 13.
75. D. 0' Brien, M. S. Weaver. D. G. Litlzey. D. D. C. Bradley, Appl. Pltyl. Lett. 19'J6, 69. Ml\ 1.
76. J.-L. IJnidas, A.J. Heegcr, C/acm. Plty.f . Leu. 19').1, 217, 507.
77. H.-II. llorhold, M. Helbig. Mabtmwl. Cltt!m. Muarmw/. Symp. 1987. /2. 229.
78. N. C. Grcenhum, S. C. Momni, D. D.C. Bradley, R. ll. Friend, A. U. !;Iohnes. Noturl! 1993.365.
621!.
79. N. C. Grccnham, F. Cacialli, D. D. C. R. ll. Fricnd. S. C. Mor.tni, A. B. llolmcs, Mut.
Rc.f. Sac. Symp. Pmc. 1994, JZH, 351.
80. S.C. Momui. D. D. C. Bradley, R. H. Friend, N. C. Gruenham, A. B. Holmes, Mat. Ncs. Soc
Symp. Pmc. 1994, 128, 371.
81. S. C. Mor.llli, R. Cervini, A.B. Holmes, D. R. B:tigenl, R. H. Friend, N.C. Grecnham, J. Gruner.
P.J. llamcr. S>'"'' Met. 1995. 71, 2117.
82. D. R. Baigent. N. C. Gn.-enharn. J. Gruner, R. N. Marks, R. H. Friend, S. C. MurJUi , A. B.
S)111h. Met. 1994, 67, 3.
83. J. J. M. Halls, D. R. Baigcnl, F. Cacialli, N.C. Gruenham. R. H. Friend, S.C. Mmaui. A. U.
Holmes. Tlri11 St-,fid Films 1996, 276. 13.
84. D. R. Baigent, P. J. Hamer, R.H. Friend, S. C. Momui, A.B. Holmes, Sy11t/r. Mel. 1995, 7/,
2175.
1!5. S. C. Moraui, D. D. C. R. Cervani, R. l l. Friend, N. C. Grccnham, A. l3. I Iohnes, Pmc.
SPI 1994, 2144. 108.
1!6. R. M. Gurgc. A. P. M. Lahti , U. Hu, F. E. Kamsz. Mac:mmolt!ndes 1996, 2SI, 4287.
87. A. C. GaitnM.Iale, X.-C. Li, E Cacialli , J. Grtiner, A. B. Holmes, S. C. Montni , R. ll . FrtctuJ,
Sy11tlr. Met. 111'J6, 76, 165.
1!8. A. Lux. A. B. I Iohnes. R. Cervini. J. E. Davie:., S. C. Moraui. J. Gruner, E Cat:ialli, R. H.
Friend, Syntlr. Mt!l. 1997. 84, 293.
89. A. Lux, S. C. Momtli. X.-C. Li, A. C. J. F. Davie.'>. P.R. Kailhby, J. F. Cacial-
h. R. H. Fnend, A. U. Holmes. Po/)1/L Prupr. 1996. 37( I). 202.
90. M. J. Man.clla. T. M. Swager, Pol)>n. Prrpr. 1992, 3J(I}, 1196.
91. J. 1iun, C.-C. Wu, M. E. Thumpsun. J. C. Stunn, R. A. Register. M. J. M:u'l.Clla. T. M. Swager.
Adv. Mmcr. 1995, 7. 395.
92. J. 1ian, C.-C. Wu, M. E. n10mpson, J. C. Sturm. R. A. Regbter. Chtm. Mula I 995. 7. 21 'JO.
93. M.J. Mun.clla, O.-K. Fu. T. M. Swager. Adv. Mawr. 1995, 7, 145.
94. H. L. Wang, M. J. Marsella. O.-K. Fu, T. M. Swager, A. G. MacOi;umid, A. J. Epstein, Po/ym.
Mulu Sd. l::llf<. 1995, 73. 473.
95. X.-C. Li . F. Cacialli, R. Cervini, A. B. llolmc.,, S. C. A. C. Grimsdulc, R. H. Fticnd,
Symlt. Mrt. 1997, H-1. 159.
96. Colorimetry: 2nd ed.; CIE: Vienna, 191!6; Vol. Publit.:;uiou Nu. l5.2.
97. M. llay, F.L. Klavettcr, J. Am. Clwm. Soc 19')5, 117, 7112.
References
98. I. Sokolik. Z. Yang. F. E. Kar.!SL. D.C. Monon, J. AJIJII. P/ry:;. 1993, 74, 351!4.
IJ9. Z. Yang. I. Sokolik. F. E. Karas.t, Mu(wmo/ecu/es 1993. 26. 111!1!.
100. Z.. Yang, F. E. Kar.s.o;L.. H. J. GCISC, Macrmrw/ccules 1993, 26, 6570.
101. D.-II. Hwang. 1.-N. Kang. M.-S. Jang, 11.-K. Shim. Bull. Koll'ull Cltcm. Soc. 1995, /6, 135.
35
102. T. Zyung. 0 .-H. Hwang, 1.-N. Kang, H.- K. Shim. W.-Y. Hwang, J.-J. Kim. Mater. 1995.
7. 1499.
I 03. X.-C. Li . F. Cadalli. M. Gilo..-:-. J. Grilncr. R. H. Friend. A. B. l lolme!>, S. C. Moraui, T. M. Yon g.
Ada: Mtmr. 1995. 7. l!9K
104. F. Caciall i. X.-C. Li, R. H. Friend, S.C. Moruui, A.B. Holmes. Syllllt. Mct. 1995, 75. 161.
105. J.-K. Lee, R. R. Schrock. D. R. Baigcnt. R. H. Fricnd, Macnmwh(u/es 19115. 2H. 1966.
I 06. E. Pcetcr.., M. P. T. Christiaans, R. A. J;utsscn, H. F. M. Schuo. H. P. J. M. Dckkcrs, E. W. Meijer.
J. Am. Clrcm. Soc 1997. //9, 9909.
107. F. Garui.:r. R. Hajlaoui. A. P. Sriva.'>tava. Sl"icllce 1994. 265, 1684.
101!. E Gamier, A. R. Hajlauui. G. llunlwiiJ.. E IJdull"rc. B. Scrvct, S. Ries, P. Aluot. J. Am.
Clt<m. Sue 1993. 115. 11716.
Ill'). F. Gru11icr. G. Horowitz. X. Pen;!.. D. Fichuu. Ada: Mater. 1990, 2. 592.
110. A. Oodabala(lUI'. H. E. Ka11, L. R. C. Haddon. St:icJrcc 1995, 269, 1560.
Ill. L. Torsi. A. Dodabalupur. L.J. R<ltltbcr};, A. W. P. rung. H. E. Kau., Scit:IICI! 1996, 272, 1462.
112. A. L. Tursi , II. E. l<;.tl/., St"itrw<' 1995, Z6X. 270.
I D. R C. lbdduu. A. S. Pcr"CI. R. C. Murris. T. T. M. l'oabtm. A. F. Hcbanl. K. M. Fleming. AJIJ>I.
P/n.v. Leu. 1995. 67. 121.
114. C. D. A. R. Brown. A. l'ump. J. Appl. J>lty.v. 1996, XO. 2501 .
115. I I. Fuehigmui . A. Tsumum. H. Klll!t.ul-.a, Apf>l. Plry.v. Leu. 19'J3, 6J. 1372.
116. G. M. H;ulcl. G. Manccke, Maknmml. Clrem. 1970, /J/, 15.
117. K.-Y. Jcn, M. Maxfield. L. W. Sha.:klcuc, R. L. El..:ubaumcr, C/tl!lll. Soc. Clu:m. Cmmmm.
19M7, JO'J.
l iM. I. Mur.s.\C, T. Ohnbhi. T. N11guchi. M. Himul-.a. Commrm. I\IM7. 2H. 22\1.
119. S. Yamada. S. li1kitn, T. S. Saito, J. Clum. Suc. Clum. Ctmrmull. 19M7, 441S.
120. 11.-Q. Xic. C.-M. Liu. J.-S. Guo, w: l'ol.wrr. J. 1996. J2. 1131.
121. T. Tsutsui, H. Murata. T. Momii, K. S. Tokito. S. Saito, Syntll Ml!l. 1991,
327.
122. L Krcja. M. Kur1.aW.t. J. Kuu.awa. Mm-nrmol. Cltt!lll. l'lty.>. 1991, /9H. 643.
123. L. K. Uickndl. M.J. T. M. Swager. PoJ.wu. Prtp. Am. Clrem. S<w. Oil: Po/ym. Cflem.
1994, 35. 269.
124. E. W. J. Am. Otem. Soc. 1945. 67. 2217.
125. K.-Y. Jcn, R. L. Elscubaumer, L. W. Shuddo.:ue, SuiJsTiiiiU'd JYTVs t&ls.: K.-Y. Jcn, R.L Elsen-
baumer. L. W. 19M7).
126. K. Jcn, H. Eckhardt, T. R. Juw. L. W. Shucklcu.:. R. L. Elscnbaumcr, J. Cltcm. StK. Cmll-
mun. 198S, 215.
127. M. L. Bluhm. J. E. (>iekeu. 1'. C'. v<ut Dm1. Mtl<"tliiiHIII'ntlts 19113, 26, 2704.
12!!. R. Tuyushima. K. Akagi. H. Shimkawa. Sprllr. Ml'l. 1\197, X4, 431.
129. S. M. Kuhn, Y. ltoh. Clrcm. Ltu. 1993, IOXS.
IJO. A. M. C;uellatu. A. Mu....:u. R. l'nmdliui. Smt/r. Ml'l. 1993, 55- 57, 1255.
131. H. Otcng.. R. L J. Cltrm. Sac Cl11m. Co1111111111. 1995. I .t51.
132. H. R. L. I'MSJ-: 19%. 2JJ.
133. L. Pccrers. w. Ecvet"l>, M. van der fiurglu. S. II.J. GciJ>C, l'o/ym<'r 19'J3, J-1. 458'.1.
2 Oligo- and Poly(phenylene)s
Ulhich Scherf and Klaus Mullen
2.1 Introduction
The structural regularity and order in polymeric or oligomeric molecules play a
critical role in determining the physical properties of such electronically active
compounds. This creates an exciting challenge for the synthetic chemists; with the
emphasis on the physical function of such materials, their properties have to be
selectively engineered through synthesis and supramolecular assembly. A fruitful
design strategy is aimed at controlling both the microscopic and 1he solid-slate
macroscopic structure. On the microscopic level this concerns a homogeneous
chemical structure (conliguration, tacticity etc.) and, on the macroscopic level, the
solid stale morphology (disordered, amorphous arrangemem of the molecules or a
controlled supramolecular assembly).
The synthesis-driven approach towards material science can be applied to cre-
ate oligomcrs and polymers with optimized properties, e.g. maximized carrier mo-
bilities and electrical conductivities or high photo- and electroluminescencc quan-
tum yields. It becomes obvious, however, that the abili ty to synthesize structur-
ally defined n-architectures is the key to these high performance matetials.
Besides the classical' search for linear, one-dimensional electronically active
materials, synthetic approaches are now also focussed on the generation and char-
acterization of two- and three-dimensional structures, especially shape-persistent
molecules with a well-defined size and geometry on a nanometer-scale. It is there-
fore timely and adequate to extend concepts of materials synthesis and processing
to meet the needs defi ned by nanochemistry' since the latter is now emerging as
a subdiscipline of material sciences.
2.2 Polymers
A large part of organic and macromolecular chemistry starts with the chcmkal
functionalization or benzene, and benzene units serve as building blocks lor im-
portant polymers. Naturally, benzene-based aromatic materials also represent au
impottant sulx:hL'iS of n-conjugatcd an:hih.:dures. Despite some synthetic Jiflicul-
ties related to the gem:ration of structurally well-dctined oligo- and poly(phenyl-
38 2 Oligo- and Poly(phenylene)s
ene)s. both academic and industrial researchers have had constant interest in phe-
nylene-type materi als.
Poly(p-phcoylcne)s, PPPs. constitute the prototype of rigid-rod polymers and
are currently being intensively investigated [I]. The key role of PPPs follows
from their conceptually simple and appealing molecular structure, from their
chemical stability, and from their superior physical properties [2]. In tum, this
the result of important advances made in aromatic chemistry over the last few
years. The following section gives an overview of the most common methods to
generate poly(p-phenylene)s via different synthetic approaches.
ppp 1
Scheme 2-1.
Unsubstituted poly(p-phenylene) PPP 1 as a parent system of a whole class of
polymers is an insoluble and intractable material, available by a variety of syn-
thetic methods [3, 4}. The lack of solubility and fusibility hinders both unequivo-
cal characterization and the processing of PPP l . Moreover. the inuactabili ty of
unsubstituted PPP materials has thwarted any serious commercial development of
the polymer.
2.2.1 Oxidative Condensation of Benzene Derivatives
The first allempts to generate poly(p-phenylene) (l) were undertaken in the
1960s. Kovacic et al. [3) reported that the oxidative treatment of benzene with
copper(ll) chloride in the presence of strong Lewis acids (alumi num trichloride)
gives rise to a coupling of the aromatic rings. Duri ng the condensation reaction
radical cations are formed as reacti ve intem1cdiates. The maximum degrees of po-
lymerization are ca. The benzene subunits are preferentially connected in
the 1.4-position, however, crosslinking and oxidative coupling to polycyclic aro-
matic hydrocarbon building blocks occur as side reactions. Adapting the initial
procedures of Kovacic et a/. other 1,4-substitutcd benzene derivatives were
coupled to poly(p-phenylene)s.
Katsuya er a/ . [5 1 published the oxidative coupli ng (agent: copper( II) chloride/
aluminum chloride) of electron-rich benzene derivati ves such as 2,5-di methoxy-
benzene to poly(2,5-dimethoxy- 1,4-phenylene) (2). The resulti ng polymer is only
soluble in concentrated sulfuric acid, and is fusible at 32o<c. Ucda et al. 161 de-
scribed the coupling of the same monomer with iron(lll ) chloride/aluminum chlo-
ride. The polymers obtained by the authors were not thoroughly pam-linked.
2.2 Polymers
39
p
CuCI/ AICil
ft

MeO
or: f eCI,
0
n
Scheme 2-2..
Yoshino era/. [7 I prepared 9,9-substituted poly(fluorene)s 3, in which solubiliz-
ing alkyl substituents are auached at the methylene function. The soluble and fusi-
ble (3) are obtained by oxidative coupli ng
or w1th tron(ua) chloride and are characterized by number
M., or up to 5000. The longest wavelength absorption
Amax ol 3 IS centered at about 388 nm. Thereby, A
11
...,. is shifted batho-
chromlc<llly by about 50 nm relati ve to that of the parent PPP l structure due to
a partial planarization of the PPI, -typc polymer 3.
()---()

R: -alkyl
Scheme2-3.
Transition from the parent PPP 1 to the poly(Ouorcne) derivati ve 3 touches a
crit ical aspect of poly(phcnylenc) chemistry. Introducing alkyl or alkoxy substitu-
ems can dramatically enhance solubility while at the same time introducino inter-
ri ng tors ion and thu_s inhibiting extended n-conjugation. TI1e fluorcnylene can
be regarded as a bndged and planarizcd biphenyl moiety to which one can attach
substituents wi_thout creati ng steric inhibition of resonance. Further stmtegies
d1rcctcd at suppressmg the mutual distortion of aromatic subunits in substituted
poly(p-phenylcne)s wi ll be outl ined below.
2.2.2 Transition Metal-Mediatt-'<1 Couplings
Entries to the preparati on or structurally more dctincd PPI,s have evolved based
on synthetic. of organic <md organometallic chemistry. The
avatl ab1llly of more ellcct1vc, more recent methods for the aryl-aryl coupling or
small n_10lecules. an imponant drivi ng force in the development of new
synthetic stmtegtcs lor poly(p-phcnylenc)s and other poly(arylcne)s. In pa
1
1icular.
the Pu(O)-catalyzcd aryl-aryl coupling according to Su1.uki (arylboronic acid
40 2 Oligo- und Poly(l'lumylem! )s
plus aryl halide or -tosylate) and the nickei(O)-catalyzed or coupli ng ac-
cording to Yamamoto [9J (aryl halide or -tosylate plus aryl hahde or -tosylate)
have been most successfully employed.
Typically, such reactions were designed for the synthesis of low molecular
weight organic compounds and then, after having proven their synthetic potential,
applied to repetitive processes in the genemtion of macromolecules. This protocol
was shown to greatly improve the chemistry of conjugated polymers. Failure Ill
avoid side reactions such as dehalogenation or deboronation of the functionalized
monomers often creates, however. an unbalanced stoichiometry and limits the at-
tainable molecular weights.
Kaeriyama et al. [ 101 reported on the Ni(O)-catalyzed coupling of I ,4-dibromo-
2-methoxycarbonylbenzene to poly(2-methoxycarbonyl-1,4-phenylene) (4) as a
soluble, processable precursor for parent PPP 1. The aromatic polyester-type PPP
precursor 4 was then saponified to carboxylated PPP 5 and
latcd to 1 with CuO catalysts. However, due to the harsh reaction cond1t1tms 111
the final step, the reaction cannot be carried out satisfact01ily in the solid state
(film).
The strategy of Kaeriyama represents a so-called precursor route and_ was de-
veloped to overcome the characteri stic ol
abili ty) of previous PPP syntheses. The condensatton rcact1on 1s camed out w1th
solubilized monomers, leading to a soluble polymeric intennediate. In the linal
reaction step this intermediate is then converted, preferentially in the solid state
allowing the formation of homogeneous PPP films or layers, into PPP (or other
poly(arylene)s).

fd:1
Ni(O) ott
r
- -
!J
n

cue
-tot
-
!J
n

PPP 1
Scheme2-4.
As has been outlined above, a second, very fruitful synthetic principle for obtain-
ing structumlly homogeneous, processable PPP de.rivatives involves _the
of soluble PPPs via introduction of solubilizing s1de groups. The p10neenng work
here was canicd out at the end of the eighties by Schluter, Wegner, et a/. [II ,
12], who for the lirst time prepared soluble poly(2,5-dialkyl-1,4-phenylene)s 6.
'

Scheme 2-5-
R: ..alkyl, ..alkoxy
2.2 41
SchlUter et al. [ Ill were the first to describe the coupling of aromatic com-
pounds containing aryl magnesi um halide and aryl halide functions catalyzed by
Ni(O) compounds. Herein, the authors attached solubilizing side-chains at the 2-
and 5- positions or the benzene rings and in on.lcr to make soluble products. They
yicldt::d oligo(para-phenylene)s with maximum degrees of polymerization of 8-
10. The products arc chamctcrizcd by an exclusive 1.4-linking of the benzene
rings of the main-chain. However, the molecular weights were quite low.
Several authors developed the method further of Ni(O)-mediated couplings to
generate several derivatives (9, 13, 141. They described homocouplings of
various 1,4-dihalobenzene derivatives by means of nickci(II)chloride/triphenylpho-
sphine/zinc or the nil:kei(O)kyclooctadienc complex.
homocouplings of 2-substituted 1,4-phcnylcnebis(trillate)s have
been reported by Pcrcec et a/. [15] to provide substit uted poly(p-phenylene)s 7
containi ng alkyl, aryl or ester substitucnts in the 2- and 3-positions of the 1.4-
phenylenc skeleton. This method of preparation appears to be broad in scope.
especially due to the case of preparation of the bis(trillatc) monomers starting
from the con-csponding hydroquinone deri vatives.
Nl(O)
R: ..alkyl, 1)henyl, -COOMe
Scheme 2-6.
By means of a repetiti ve Suzuki aryl-aryl cross-coupling method, developed by
Schliiter, Wegner and co-workers, the synthesis of solubilized PPP's 6 with a dra-
matically increased molecular weight (number average up to 100 1,4-phenylcne
units) was possible (12j. 2,5-Dialkyl-substituted PPPs 6 were intensively studied
as prototypes of so-called ' hairy-rod' macromolccu!es, composed of a linear, rigid
PPI' main-chain and tlexible, ' hairy' alkyl side-chains. The individual, shape-per-
sistent macromolecules can be imaged by transition electron microscopy within
monolayers r 16]. Poly(2,5-di-n-dodecyl-1 ,4-phcnylene) 6 (R: -C I:!H:!:;) revealed a
sandwich-type structure with layers or aliphutie side-chains perpendicular and
layers or the PIP main-chain parallel to the substrate surface. Poly(2.5-di -n-uodc-
cyl-1,4-phenylene) of Mw 73000-94000 show a single anismropic liquid crystal-
line mesophasc in the molten state and macromolecules with Mw 44000-73000
gave coexisting isotropidanisotropic phases [ I 7 j.
Pd(O)
--
R: -alkyl, -alkoxy
Scheme2-7.
In addition to alkyl-substituted derivatives, soluble PPPs 6 are also known to-
day containing alkoxy groups as well as ionic side groups (carboxy ancJ sulfonic
acid functions) [l8j. Schliilcr cr a/. ~ t t n t l y described the gencmtion of soluble
PPPs decorated with densely packed stcrically demanding dendmns on the fomm-
tion of cylindrically shaped dendri mcrs, so-called cylinder dendrimers 119j.
Scherf er at. [20} reported the synthesis of the PI)P derivative Sa, which is
composed of chiml eyclophane subunits, by means of a Suzuki-type aryl-aryl
cross-coupling of the corresponding diboronic acid and dibromo monomers. The
monomers wi th the cyclic -0-C
11
,H
20
-0- loops can be resolved into the pure enan-
tiomers by preparative high pressure liquid chromatography on chi ral stationary
phases. The pure enantiomers were used to generate the corresponding stereoregu-
lar iso- and syndiotactic PPP derivatives 8b and 8c. Hereby, the isotactic deriva-
tive 8b is of special interest due to its main-chain chiral character [20].
Unsubstituted PPP 1 possesses a 23 twist between adjacent phenylene units
[2 I ). Since the n-overlap operates as a function of the cosine of the twist angle,
even at 23 there is a fair amount of conjugative interaction remaining. If one
places substituents along the PPP backbone (e.g. at the 2- and 5-positions as in 6,
7 and 8), the solubility is drJmatically enhanced, as discussed above, however.
the n-overlap is reduced. Twist angles of 60-80'' are reported for alkyl substitu-
ents in 2,5-positions [22j. Thus, for poly(2,5-dialkyl-1,4-phenylcne)s. only negli-
gible optical absorption can be detected in the wavelength region above 300 nm,
which is characteristic for delocalized n-n* tmnsilions.
The results described thus far sketch the synthetic demands for being able to
prepare processable. structurally defined PPPs, in which the n-conjugation re-
mains fully intact or is even increased as compared to that of the parent PPP 1
system. The key step in the realization of this principle is the prepamtion of a
PPP in which the aromatic subunits can be obtained in a planar or only slightly
twisted conformation in spite of the introduction of substituents.
One of the first examples was the above mentioned work from Yoshino er a/. PI
conceming the synthesis of poly(9,9-dialkylfluorene)s via oxidative coupling of
fluorene derivatives. Poly(9,9-dialkylfluorene) derivatives have been also synthc-
si:i".cd via Ni- and Pd-catalyzcd aryl-aryl homo- and cross-coupling reactions of sui-
Atactic PPP-Oerlvative Sa
lsotacllc PPP-Oerivative 8b
Syndiotactic PPP-Oerivative ~
Scheme 2-a.
2.2 Polymers 43
tably substituted monomers (2,7-dibromolluorene and fluorene-2.7-diboronic acid
derivatives. respectively) 123, 241. These reactions allow the synthesis or structu-
rully defined products possessing high molecular weights of up to 100000. Some
derivatives, e.g. the 9,9-dioctyl-substituted polylluorcnc form well-defined thermo-
II'Opic LC states and can be aligned on tubbed substmtes. These layers show a high
degree of orientation, both in absorption and photoluminescence {25].
The next allempt at these reactions were carried out by Yamamoto et ul. 1261.
They coupled 2,7-dibromo-9, I 0-dihydrophenanthrcne to give an ethano-bridged
pol y(p phcn y lene) <.Jeri v ali vc I pol y(9 ,10-d ih ydrophenanthrcne-2, 7 -di yl )I (9) by
way of low-valent nicl.cl complexes, which were used either stoichiometrically as
rc.tgent (Ni(CODh) or were generated electrochemically in the reaction mixture.
As a result or the insullicient solubilization of the ethano substitucnts only the oli-
gomer fraction with M .. < I 000 is soluble, the polymeric products precipitating out
as an insoluble powder. The value of A."'"" l(lr the soluble fr.tction of 9 is about
360 nm.
NI(O)
-
Scheme 2-9.
44 2 Oligo- a11d Poly(phe11ylene)s
Consequently, by combining the synthetic procedure of Yamamoto (26] with
the introduction of more extended solubilizing substituents, advantageous results
were expected. Accordingly, alkyl-substituted dihydrophenanthrenes or tetr-clhydro-
pyrenes offered themselves as starting monomers for the preparation of soluble
'step-ladder' PPPs of this type. 2,7-Dibrom<r4,9-dialkyl-4,5,9,10-tetrahydropyr-
encs (10) represent suitable starting monomers for the realization of this synthetic
route. These difunctionalized tetrahydropyrene monomers were first prepared by
Mullen et a/. and reacted in a Yamamoto coupling [27}.
Reaction of the dibromide 10 with Ni(CODh in DMF/toluene gave a poly(4,9-
dialkyl-4,5,9, 1 0-tetrahydropyrene-2,7-diyl) PTHP 11 as a completely soluble, new
type of PPP derivative, in which each pair of neighboring aromatic rings is doubly
bridged with ethano linkages [27j. The solubilizing alkyl substituents appear on the
periphery of the macromolecule so that they cannot cause twisting of the main-chain.
PfHP 11 possesses a relatively high number average molecular weight. up to
M
0
=45000, which com:sponds to coupling of about 100 THP units.
A further advantage of PTHP 11 is that distereomeric fom1s can be generated
which arc exclusively of cis- or lrcm.\-cunfigurcu monomeric TIIP
bui lding blocks. The stereochemistry or the substituents in 4- and 9-position (Ci.i,
trans) strongly intluences the solid state packing behavior of ll.
10
Scheme 2-10.
NI(O)
-
11
R: -alkyl
PTHP 11 possesses the longest wavelength absorption A"""' of 385 nm, almost
identical with the value for the polyfluorenes 3 of Yoshino et a/. [7}. Thus, inde-
pendent conlinnations exist for the correctness of this 'step-ladder' concept; the
introduction of solubilizing groups combined with simultaneous bridging of the
subunits guarantees an increao;ed degree of conjugative intemction.
In solution PTHP 11 exhibits intense blue photoluminescence (PL) with a rela-
tively small Stokes shift between absorption and emission <Ama absorption: 385
nm; Amax emission: 425 nm). PTHP 11 can be used as active component in light-
emitting diodes (LED) based on organic polymers, elcctroluminesccnce (EL)
quantum yields of 0. 1-0. 15% (single layer construction ITOIPTHP 11/Ca) of
blue-green LEOs were reported. Blue polymer-based LEOs represent an auracti vc
target, as blue cmilling LEOs based on inorganic semiconductor materials are not
easily accessible. As a result of their band gap energy of 2.7-3.2 eV, PPP deriva-
tives arc particularly suitable as blue emitters.
In contr.tSI to low molecular mass materials, polymcic emiucrs possess the ad-
vantage that they can be easily worked into tmnspurcnt tilms wi th a low degree
2.2 Polymers 45
of scauering. In addition, they show a higher morphological stability compared
with that of vapor-deposited low molecular weight compounds.
The logical continuation of the 'step-ladder ' stmtegy outlined above to mini-
mize the mutual distortion of adjacent main-chain phenylene units is the incor-
poration of the PPP-parcnt chromophorc into the network of a completely planar
ladder polymer. The perfect flallening of the conjugated n-system by bridging all
the subunits should then lead to a maximum conjugative interaction. As with the
PTHP ll systems, alkyl- or alkoxy side-chains should lead to solubilization of
the polymers. The realization of this idea culminated in 1991 in the first synthesis
of a soluble and conjugated ladder polymer of the PPP-typc by Scherf and MUl-
len [28]. This PPP ladder polymer LPPP 12 was prepared according to a so-
called classical route, in which an open-chain, single-stranded precursor polymer
was closed to give a double-stranded laducr polymer. The synthetic potential of
such a multi-step sequence wa."i doubted for a long time, and in the eighties syn-
chronous routes were strongly favored as preparative method for ladder polymers.
In a classical multi-step route the critical point is to conduct the ring closure
lfUant ilati vcly and rcgiosclectivcly. In the symlh.:sis of LIPJ. the pn:clll'Silf poly-
mer 13 is initially prepared in an aryl-aryl coupling from an aromatic diboronic
aciu and an aromatic dibromoketonc.
Pd(O)
-

LAH
R': -alkyl
R: -1,4-CaH -alkyl
Scheme 2-11.
The cyclization to structurally dclincd, soluble LPPI' then Iukes place in a
two-step sequence, consisting of reduction of the keto group followed by ring clo-
sure of the secondary alcohol groups of 14 in a Fricdcl-Crafts-type alkylation.
The resulting ladder polymer LPJ>J> 12 possesses a number average molecular
weight of 25000, which corresponds to the of 65 phenylene units.
No structure dcfce1s could be detected using NMR spectroscopy. LJ>PP 12 is
46 2 Oligo- a11d Poly(pltenylene)s
characterized by unusual electronic and optical properties; the absorption maxi-
mum undergoes a marked bathochromic shift as a consequence of planarization of
the chromophore, to a Amax value of ca. 440 nm (see Fig. 2- 1), depending some-
what on the substituents -R and -R'. In addition, the longest wavelength n- rc* ab-
sorption band possesses an unusually sharp absorption edge as an indication for
the fully planarized, geometrically fixed ladder structure.
The photoluminescence (in solution) of LPPP 12 is very intense and blue
(AnlaX emission: ca. 460 nm). The Stokes shift between absorption and emi ssion is
extremely small (ca. 150 cm-
1
); a consequence of the geometric tixation of the
chromophore in the ladder structure. The PL quantum yields are high in compari-
son to those of many other conjugated polymers; in solution values between 60
and 90% have been measured, in the solid state up to 40% [29). In comparison,
PPJ> 1, synthesized by the lCI-precursor route, shows a PL quantum yield of only
4% [30). Thus, the next step was to investigate the suitability of this new type of
material for application as an active component in organic materials-based LEOs.
Init ially, this led to the surprising result that although etlil:ient LEOs can be pre-
pared with LPJ>P. the color of the emission in the :-.olid state (lilm) is 111.:verthelcss
yellow (PL and EL). In addition to primary emission of the LPPP 12 chromo-
phore in the blue region, the PL and EL spcctm exhibit an additional unstruc-
tured broad emission band in the yellow region (ca. 600 nm) 13 11. The yellow
emission band could be unequivocally as aggregate emi ssion by
ious pieces of photophysical evidence (32-34j, and the occuncnce of excimer for-
mation unquestionably ruled out.
EL experiments showed that the yellow-emitting LEOs prepared from LPPP
12 exhibit quite remarkable chamcteri stics (single layer constructi on ITO/LPPP
12/Ca; quantum efficiency: ca. 1.0%, applied voltage: 4-6 V 135 J). These figures
are in the r.mge of the best values described hitherto for polymeric emitters in a
single layer arrangement. for example, poly(para-phenylenevinylene) PJ>V and
PI)V deri vati vcs.
4axlO

I
20(XX)
0
200

..
'
' ..
:
..
V\ LPPPU
.
,
--.................... .
400 600
Wavelength li'Vli
0
.Figur e 2-1. AbMlrplion and photuluaninc:;c\;flcc SJliX:Ira of LPI'I' 12 (solvent: dichluromclhanc,
-R: -11-Cc,H
4
C
10
ll2
1
; -R': -C.,Ho).
2.2 Polymers 47
From the perspective of the strategies aimed at fabrication of efficient blue
LEOs, the results outl ined above regarding yellow LPPP light emitting diodes
are, nevertheless, unsatisfactory. In order to prepare blue LEOs from LPPP
materials, it is necessary to efficiently mask out or suppress the dominant yellow
aggregate emission.
Suppression of the aggregate emission is possible in two quite ditl"erent ways.
At first, the aggregate emission could be almost completely shut out by simply di-
luting the LPPP 12 with a matrix polymer. LEOs with I% LPPP 12 in poly(9-
vinylcarbazole) PVK as emitter material are characterized by a pure blue light
emission with a quantum efliciency of ca. 0.15% in single-layer contigumtion
(ITO/I % LPPP 12 in PVK/Ca) 135).
If suppression of the aggregate emission in this first example was based on a
purely physical principle, chemical modification of the LPPP 12 structure towards
the same aim is also possible. 1l1us, one option is the introduction of additional sub-
slituems into the LPPP skeleton. Attaching an additional methyl group to the mellly-
lene baidge of LPPP 12, which can, indeed, easily be achieved by quantitative ad-
dition of methyllithium tu the precursor 13, in place of reduction of the keto groups.
yields ladder polymers Mc-LPI'I, 15. Their solid state PL spectra show only vcty
weak aggregate emissions; the solution- m1d solid state PL spectra are almost iden-
ticall361. The fact that the of the aggregate emission could be achieved
by molecular and supramolecular design is, indeed. a convinci ng example of the
above menti oned synthesis-driven approach toward electronic materials.
The suppression or aggrcgaae formation is accompanied by a dramatic increase
in the PL quantum efficiency to >90% for solution and up to 40% for the solid
state. This enom10us solid state PL quantum efficiencies favor Me-LPPP 15 as
emitter material lor solid state lasers based on organic mateaials. Leising er a/.,
Mahrt er a/. and Lemmer er a/. have independently demonstrated the potential of
Me-LJ>J>p as solid state laser material in seveml configumtions (waveguide con-
figuration, distributed feedback contiguration) l37-40J. The high molecular
weights of 15 (M .. up to 50000) allow lor the fabrication of thick lilms and strips
(up to 10 l-tlll). The devices are characterized by an extreme stability and lasing
was observed over a period of more than 10
7
pulses t40J.
Me-LPPP 15
R: -aryl, R': -alkyl
Scheme 2-12.
At this point it might be appropriate to comment on the conll icting require-
ments of the synthesis. The large interest which other conjugated polymers such
as polypyrrolc, polyaniline or poly(pam-phcnylcnevinylene) (PPV) have attracted
originates, tirstly, from their <tllractive physical properties, but also from the sim-
48 2 Oligo- and Pvly(phenylelle)s
pie fact that they are readily available in sufficient quantities - even in laborato-
ries without highly developed synthetic know-how. However, one must be aware
that each electrochemical formation of a polypyrrole or a precursor route towards
PPV provide individual samples whose performance in devices depends upon the
chemical conditions of materials synthesis. Thus. while one would not argue
against a 'practical' synthesis, two important aspects must be obeyed; (I ) a selec-
ti ve structure-property relationship necessitates a scrupulous definition of the mo-
lecular structure and of possible impurities, and (2) adequate synthetic solutions
for physical problems can require a higher level of sophistication and still remain
valuable, even from a practical point of view.
2.2.3 Other Routes to Poly(p-phenylene)s
Besides the oxidati ve and transiti on-metal-catalyzed condensation reactions discussed
above, several other syntheses were developed to generate PPP and PPP derivatives.
Marvel et a/. described [4 1] the polymerization of 5,6-dibromocyclohexa- 1,3-
? iene (16) to poly(5,6-dibromo- 1,4-cyclohcx-2-ene) 17 followed by a thermally
tnduced, solid state elimination of HBr on the formation of tPP l. The products,
however, display some indications for several types of structuml defects (incom-
plete cycliUttion, crosslinking).
-
-
16
11 1
Scheme 2-13.
Later on, Ballard e1 al. [42, 43) developed an improved precursor route starting
from 5,6-diacctoxycyclohexa-1,3-diene (18), the so-called ICI route. The soluble
precursor polymer 19 is finally aromatized themmHy into PPP 1 via elimination
of two molecules of acetic acid per structuml unit. Unfortunately, the polymeriza-
tion of the monomer does not proceed as a uniform 1,4-polymerization; in addi-
tion to the regular 1,4-linkages ca. 10% of 1,2-linkages arc also formed as result
of a 1,2-polymerization of the monomer.
Q--
I MoCOOOOC,...t
-
1ot.
MeCOO OCOMe
n
1 .1j
1
Scheme 2-14.
2.2 Polymers 49
Grubbs [441 and MacDiannid [45) et a/. described in 1992 and 1994, respec-
tively, an improved precursor route to high molecular weight, structurally regular
PPP 1 starting from the cyclohexa- 1,3-diene derivati ve 18 and leading to a stereo-
regular precursor polymer 20 via transition metal-catalyzed polymerization. The
final step of the reaction sequence is the thermal. acid-catalyzed elimination of
acetic acid to convert 20 into PPP 1. The authors obtained free-standing PPP
films of defined structure, however these tilms still contained large amounts or
the acidic reagent polyphosphoric acid. Nevertheless, in this work a reliable value
for the longwave absorption maximum Amax of PPP 1 could be obtained, at about
336 nm. This value is of utmost importance in the interpretation of the optical
properties of substi tuted PPPs.
Q , .. .... .,
MeCOO OCOMe l MeCJ----<OCOMe L
PPA
1ot.
n
1
R: F
1
ccoo-
Scheme 2-15.
As well as the polymerization of I ,3-cyclohexadiene derivatives. repetitive
Diels-Alder polyadditions wen.: widely used to prepare arylated PPPs. Stille and
co-worker"l' developed a set of suitable monomers (I ,4-diethynylbenzenc and 1,4-
phenylenebis(triphcnylcyclopentadicnone) derivatives) to gencr.lle phcnylateu
PPPs (e.g. 21) possessing molecular weights of 20000-100000 [46]. Unfortu-
nately, the repetiti ve polyaddition does not in a regioselective way; poly-
mers containing para- as well as meta-phcnylene units withi n the main-chain
skeleton are fom1ed.
+
-
Scheme 2-16.

h(H)
ll
n
Recently, Tour et al. [47) described attempts to use the Bergman cyclicll
produce PPP derivatives starting from substituted endiynes, e.g. pvi.: .
1.4-phenylene) 22 starting from 1-phenyl-hex-3-en-1.5-diyne or the structurally re-
lated poly(2-phenyl-1,4-naphthalene) 23 starting from 1-phenylethynyl-2-ethynyl-
benzene.
\J- -<J -idt. ld1
l 0 I.
n
Scheme 2-17.
2.3 Oligomers
Pamllel to the polymer synthesis, many activities have been directed towards solu-
ble. well-defined oligomers. Such oligomers are important to optimize the poly-
mer synthesis and to understand structure/property relations in the class of PPP
and other poly(arylcne) materials. The key approach, thereby, is a study of physi-
cal properties as a function of chain length. The problem of oligo(phenylene)s is,
as mentioned above, the low solubility of the compounds. The solubilities of flflfl
oligomers in conventional organic solvents decrease dramatically with increasing
chain length and reach, e.g. for octaphenylene, the negligible value of less than
10 ng/1 in toluene at 25 oc. In view of this, all attempts to synthesize and charac-
terize longer unsubstituted flflfl oligomers by direct couplings are inappropriate.
The first series of soluble oligo(para-phenylene)s OflVs 24 were genemted by
Kern and Wirth [48) and shortly after by Heitz and Ulrich [49]. They introduced
alkyl substituents (methyls) in each repeat unit and synthesized oligomers 24 up
to the hexamer. Various synthetic methods, like the copper-catalyzed Ullmann cou-
pling, the copper-catalyzed condensation of lithium aryls, and the twofold addition
of organometallic species to cyclohexane- 1,4-dione, have been thereby investigated.
The authors developed two gencml concepts for the synthesis of these mono-
disperse, defined oligomers. The oligomers can be built up in a stepwise fashion,
e.g. via addition of organometallic species to cyclohexane-1 ,4-dione followed by
aromatization to the oligo(arylene) (e.g. for 25).
The alternative stmtcgy involves the generation of oligodisperse mixtures of
seveml oligomers of different chain lengths, e.g. by copper-catalyzed couplings of
mono- and dilithioaryls, followed by a chromatographic resolution of the oligotlis-
perse mixtures into the monodisperse components 24 of defined chain lengths. In
2.3 Oli gomers 51
..
Scheme 2-18.
this way. oligomers 24 up to a duodeciphenylene derivative have been by
preparative thin-layer chromatogmphy.
..
Scheme 2-19.
.! MeA rtel
,-v-u-r
Recently Rehahn <!I a/. (501 presented the synthesis of constitutionally homoge-
neous oligo(phcnylene)s 26a/b with 2,5-alkyl substituents, located on the centml
aromatic ring, genemted via the cross-coupling reaction according to Suzuki. They
arc exclusively linked in para-positions and constituted of 3- 15 benzene rings.
All the above oligomers are characterized hy the presence of solubilizing alkyl
groups, resulting in an increased solubility. However, the electronic properties of
the 1r-system arc disturbed by the mutual distortion or the phenylenc units in-
duced by the substituents. Compared to the parent PPP-system with its 23"' twist
between adjacent building blocks, the substituted deri vatives display distortion an-
gles of 60-XO"", which minimizes the conjugative interaction within the conjugated
backbone. One possibility to overcome this drawback is the substitution only at
the terminal rings as pcrfonncd by Liillkc eta/. 1511. They generated oligo(phenyl-
enc)s 27 with tat butyl substituents at the tenninal 3- and 5-positions using a
52 2 Oligo- and Pvly(phenylenc)s
Scheme 2-20.
Grignard coupling us the key step. However, longer oligo(phenylene)s 27 are not
available fo llowing this approach, since the compounds become also insoluble
when reachi ng chain lengths of more than 7 aromatic buildi ng blocks.
Scheme 2-21.
As described for the corresponding polymers, a powerful strategy to achieve
soluble oligomers with maximum conjugative interaction is to incorporate the
PPP backbone into a step-ladder (or ladder, see Section 2.2) fr.unework in combi-
nation with the attachment of solubili zing side groups onto the bridging function-
alities. Following this, it was possible to generate short-chain tetrahydropyrene
oligomers via separation of polydispersc mixtures into their (monodispersc) indi-
vidual components 28 with the aid of preparative gel permeation chromatogmphy
[52j.
28 (n: o -8)
n
R: -alkyl
Scheme 2-22.
2.3 0/igomer.s 53
With such a series of oligomer.; 28 available, the convergence of optical proper-
ties with increasing chain length can be monitored and the conj ugation length in
the corresponding polymer YfHP 11 can be determined as comprising of about
10 monomer building blocks (i.e., 20 aromatic rings) [53j.
The above approaches to synthesize oligomer.; (i.e. stepwise synthesis, chroma-
togmphic resolution of oligodispersc mixtures) have more recently been comple-
mented by repetiti ve modular stmtcgies. Such concepts involve the repetition of
directed protcction/couplingldcprotection sequences in a convergent process to
minimize the number of reaction steps necessary to genemte the extended oligo-
mers. Such a stmtegy was developed e.g. for linear poly(para-phenyleneethynyl-
ene)s PPEs by Tour eta/. 154j. Using a similar approach, Schluter et a/. [55] dc-
:.cribed the synthesis of monodisperse oligo(phcnylene) rods 29 with up to 16
phcnylcne rings and with well-defined functional end groups. The synthesis is
based on a convei"Jent (exponential) growth using the Suzuki reaction as the cou-
T ~
R
/
+
~
l Pd(O)
1
Zl!. n: 2,4,6,8
R: -n-hexyl
Scheme 2-23.
54 2 Oligo- und Poly(phenylene)s
piing step. The key principle rests upon the significantly faster coupli ng of iodoar-
yl functions as compared to the corresponding bromoaryls in the aryl-aryl cross-
coupling reaction according to Suzuki. Accordingly, building blocks containing
both iodo and bromo functions undergo the coupling with an arylboronic acid pre-
ferentially at the iodo side, leaving the unreacted bromo side for subsequent
chemical derivatization, such as conversion into a boronic acid function.
Ladder-type LPPP oligomers J O (56] were also synthesized following a so-
called 'oligodisperse approach'. The two bifunctional (chain forming) monomers
of the polymer (20) synthesis were co-reacted with a monofunctional (end cap-
ping) monomer to produce an oligodisperse mixture of 'end-capped' molecules of
differing chain lengths. These mixtures were resolved into their monodisperse
components by means of liquid chromatography; preferentially by size exclusion
chromatogmphy. Following this protocol, LPPP oligomers 30a, J Ob, and JOe
were achieved containing three, five, and seven I ,4-phenylene units within the
planar ladder-type main-chain.
R:--0+
R': -n-hexyl
Scheme 2-24.
Using UV-VIS measurements of this series of monodisperse, oligomelic model
compounds JO the effecti ve conjugation length of the corresponding polymer
LPPP 20, i.e. the convergence limit or absorption and PL properties, be
identified as compri sing about II phenylene units (53). While a plot of the physi-
cal properties as a function of chain length and a determination of the effecti ve
conjugation length has no sound theoretical background, it is a remarkable out-
come that the convergence of the optical absorption energy with increasing chain
length occurs much more mpidly in the planar u >pp 20 molecule than in non-
bridged PPP detivutivcs or in the partially bridged step-ladder polymer PTHP 11.
2.4 Dendritic ond H)perbmnclred Poly(plreny/ene)s 55
'
2.4 Dendritic and Hyperbranched Poly(phenylene)s
The results presented up to here concem only one-dimensional oligomers and
polymers of the PPP-type. This section is mainly focussed the electJ"?nic
et1ies or extended n-chains and on the morphology of sohd PPPs usmg cham-
stiffness as a structure-fonninu principle for supmmoleeular architectures.
b .
The transition from one- to two-, and three-dimensional PPP-structures gtves
access to novel spectrum of attractive properties. The n-conjugated cl}amcter of
1,4-disubstituted phenylenes drJws in the background, such 2D- and
of the PPP-type represent, moreover, a unique, novel class of shape-perststent .
nomaterials. Their bmnched backbone, which is exclusively composed of ngtd
phenylene units, causes the above mentioned stinness of the whole molecule. En-
ormous synthetic <K:hievements in this field open opportunities for a contro!lcd
molecular and supramolccular design. 2D-Structures can be, e.g. processed mto
monomolecular absorbatc layers on surfaces. 3D-Dendritic structures are available
with a size and shape which can be systematically vatied. The shape-persistent na-
noparticles can carry well defined chemical functions and can act e.g. as caniers
for biologically active principles (tracers, drugs etc.). Moreover, the 3D nanomole-
cules can be further tmnsrormed into planar, giant polycyclic aromatic hydrocar-
bons (PAHs).
2.4.1 Hypcrbra nched J>oly(phcnylcnc) Derivatives
Kim and Webster (57] were the first to show that trifunctional benzene-based
monomers can also be used to synthesize poly(phenylene)s, in this case hypcr-
bmnched structures Jl based on 1,3,5-trisubstituted benzene cores. They self-con-
densed 1,3-dibromophenyl-5-boronic acid leading to the formation of soluble,
hyperbnmched PPI)-type macromolecule Jl .
Pd(O)
Scheme 2-25.
56 2 Oligo- and Poly(pheny/ene)s
The transfonnation of the hydrophobic periphery composed of bromo substitu-
ents into a hydrophilic wrapping of carboxylic acid functions was achieved by re-
acting 31 with (i) n-butyllithium and (ii) carbon dioxide. The polymer-analogous
tmnsfom1ation provides water soluble, amphiphilic derivatives of 31 which consti-
tute useful covalently bonded unimolecular models for micellar struciUres.
2.4.2 Oligo(phenylene)s of Orthogonally Arranged Anns
Star-shaped molecules with oligophenyl arms derived from 9,9-spirobifluorene as
the central unit have been synthesized by Tour et al. [58] and Salbeck et al. [59]
and have been suggested as potential emitter materials for blue LEOs.
+
Scheme 2-26.
The authors used a synthesis of 9,9-spirobifluorenes 32 which was developed
by Clarksen and Gomberg [60J and which includes the addition of biphenyl-2-yl-
magnesium iodide to fluorenone and subsequent cyclization with protic acids. To
obtain 2,2,'.7,7'-arylated 9,9-spirobifluorcnes 33, 9,9-spirobifluorenc (32) was
tetrabrominatcd [58] to yield 34 followed by a Suzuki-type aryl-aryl cross-
coupling with various oligoaryl and oligoheteroaryl boronic acids to obtain the
2,2',7,7'-tet.r.:tarylated derivatives 33.
32
Scheme 2-27.
B
+
R-B(OH)
2
r Pd(O)
-
2.-J Dtntlritic uml Hypabmucltecl Paly(pltenyleuc )s 57
The star molecules 33 are characterized by a drastically increased solu-
bility when compared to the corresponding unsubstituted PPP oligomers. The
spiro compounds 33 are non-polymeric organic glasses with high thennal stability
and unusually high glass transition temperatures (59. 61]. TI1ercfore, high quality
amorphous films can be with these spiro compounds by vapor deposi-
. tion or spin coating. Derivatives of 33 composed or two orthogonally arr.mgcd
oligophenyl chains, e.g. sexiphenyl anns (R: - 1.4-C<>H
4
-C<>H
5
), display an efficient
photoluminescence, which makes them promising materials to be used as emitters
for organic light emitting diodes LEOs.
2.4.3 Dendritic Poly(phenylene)s and Ghmt Polyaromatic Hydrocarbons
(PAHs)
More recentl y, Mullen et a/. have worked out very ellicient procedures to gener-
ate highly arylatcd, branchal oligo(phenylcne) and related oligo(arylene) deriva-
ti ves following di fferent synthetic approaches.
A first milestone was the development or a novel intmmolecular Oiels-Alder
cydiwtion or terphenyl monomers 35 and 38 containing both 4-phenylbutadienyl

Scheme 2-28.
58 2 Oligo- and Poly(pllenylene)s
and styryl functions. The formation of the 14+2) cycli:zation adducts 36 and 39 is
then followed by a simple aromatization of the eyclohexene moieties 162]. In this
way, the phenylatcd, two-dimensional arylene structures 37 and 40 based on a
tetmbcnl.oanlhmccnc cure and possessing a hithc11o unknown topology were
achieved.
The branched oligo(arylene)s 37 and 40 can undergo a further oxidative cycliza-
tion with copper( II) chloride or triflate/aluminum trichloride leading to the formation
of large, hitherto unknown polycyclic aromatic hydrocarbons PAHs 41 and 42.

Scheme 2-29.
The large polycyclic aromatic hydrocarbons (PAHs) 41 and 42 are character-
ized by their extremely high them1osUtbility. They can be sublimed at tempera-
tures of 550-650C under ultrahigh vacuum (UHV) conditions. Such a sublima-
tion step is of crucial importance to obtain pure compounds because the solubility
of the reaction products in organic solvents is very low. The sublimation proce-
dure can be used to grow densely packed monomolecular absorbatc layers. Such
organic absorbate layers can be chamctcrized by means of electron diffr.1ction
(LEED) or scanning tunneling microscopy (STM). It was possible to get a molec-
ular resolution of the rhomboid PAH 41 with STM 163]. Fommtion of mono-
molecular absorbate layers of giant PAHs is also possible by physisorption from
solution if the disc-type molecules arc made sulliciently soluble by suitable alkyl
substit ution. The large size of the molecular gr.tphite models such as 41 and 42
also allows one to achieve a submolecular resolution in STM and thus to record
current-potential curves for single molecules. h follows that the tonnation of or-
dered surface absorbates from adequately designed PAHs is a challenging starting
point to enter the field of molecular electronics.
In a second novel approach, Mi.illen and co-workers further developed ;m inter-
molecular repetitive Diets-Alder procedure for the gener..ttion of dendritic and hy-
pcrbranched poly(phenylcne)s. Hereby, they applied the concept of reacting A2B-
typc monomers, in this case monomers containing both cyclopcntadienone (dicn-
2.4 0("11(/riti und Hypabrcmdttd Poly(plu!llylene)s 59
ophilc) and ethynyl functions (sec 1461). Simple polyaddition of the monomers
yield-; hyperbranchcd poly(phenylcne)s.
If the polyaddition is carried out (i) starting from suitably substituted core mol-
ecules containi ng. llucc. four ur six cthynyl fum:tiuns. ami (ii) with
mers containing TMS-protccted cthynyl functions, a facile divergent synthesis of
monodispersc dendritic poly(phenylene)s becomes possible. 13y selecting the cen-
tml (core) unit and di- (A
2
B-) or tetrafunctional monomers, dcndrimers of
different size (genemtion) and topology were accessible by applying a directed,
repetitive !4+2) cycloaddition/dcprotection sequence. Within the synthetic se-
quem:e, the authors made usc of the ditlcrent reactivity of protected and depro-
tected ethynyl functions within the key (4+2] cyctoaddition step. The largest
phcnylcne dendrimcrs generated via this procedure contain more than 140 ben-
zene rings (dian1eter up to 50 A) and surpass all previously known exan1ples of
phenylene nanoparticles 161 J.
In this way. Mullen and co-workers have, e.g., gencmted 43 starting from a
3.3',5,5'-tctmcthynylsubstitutcd biphenyl core and 44 164).
TMS
+
1
= TMS)-
Scheme 2-30.
+44
60 2 Oligo- and Poly(pflcnylcnc)s
This modular concept allows for the synthesis of monodisperse dendritic phen-
ylene dendrimers of the fi rst (43a, 22 benzene rings) and second (43b, 62 ben-
zene rings) generation f651. Due to the dense packing of the pht:nylene rings,
shape-persistent nanostructures result. Several of these large phcnylene-type den-
drimers (e.g. 43a) can be further cyclized to giant polycyclic PAHs.
2.5 Conclusion
This article has been focussing on poly(phenylene)s with 1,4-(para-)phenylene
units since these polymers play a key role in the synthesis-driven search for elec-
tronic materials. From this article it hao; become clear that poly(phenylene) chem-
istry has not restricted its attent ion to linear ( I 0 -) structures. but has more re-
cently developed into 20- and 3D-structures as well, the Iauer serving as
tional shapt:-persistcnt nanoparticlcs.
The versatility of poly(phenylcne) chemistry can also be seen in that it consti-
tutes a platfonn for the design of other conjugated polymers with aromatic build-
ing blocks. Thus, one can proceed from I ,4- to I ,3-, and I ,2-phcnylene com-
pounds, and the benzene block can also be replaced by other aromatic cores such
as naphthalene or anthmcene, heterocycles such as thiophene or pyridine a<; well
as by their substituted or bridged derivatives. Conceptually, poly(phenylene)s can
also be regarded as the parent structure of a series of related polymers which arc
obtained not by linking the phenylene unit-. directl y, but by incorpomtion of other
conjugated, e.g. olefinic or acetylenic, moieties.
The careful control of electronic properties is, of course, a key motivation of
such structural changes; the so-called band-gap tuning being a particul arly impor-
tant concern. Etliciency of synthesis and structural homogeneity of the products
are essential ingredients of such an approach since failure to achieve e.g. quantita-
tive transformation of precursor polymers or to couple benzene units exclusively
in a para-fashion inteiTUpts the extensive n-conj ugation and hampers a reliable
structure-property-relation.
On the other hand, it has also become clear that a materials-oriented synthcsis
of conjugated poly(phcnylene)s cannot narrow its attention to properties of mole-
cules only in sol ution, but has to include aspects of processing and supmmolecu-
lar ordering as well. The rigid-rod chamcter of PPPs therefore suggests the use of
chain stillness as a structurt:-fom1ing principle in the design of supramolecular
motifs.
This article, while not being intended to provide a full account of poly(arylcne)s,
emphasises the synthetic aspects. The synthesis of conjugated oligomers aud poly-
mers is, however, always part of an interdiscipli nary approach with their active
physical function being a key conccm. In that sense the research being revi ewed
above concentmtes on physical properties rather than playing with exotic chemical
structures.
Refaem:es 6 1
References
1. J. M. Tour, Adv. Mma 19'J4. 6, 190; A.D. Sdllut.:r, ami G. W.:gncr, Acw Polymtr 1993. -1-1. 59.
2. A.-D. Sdlluh.:r in Hmullnmk oj Polymtrs, 2ml '-"-' (Eo.: T. A. Skothcim, R. L Elscn-
haumcr, J. R. Reynolds), Marccl Dekker. N.:w Yuli<. Ba.'ICI, tlong Kong l 99S, Oaptcr 8, 209.
3. P. Kovad.:. M. B. Juno .. .,._ Cht!m. Rt: am. 87. J57.
4. R. H. Baughman. J. L Un.:Oas. R. R. Chance, R. L Ebenbaumcr, and L W. Shaclletlc., Chem. RC'a:
l 'Jl!2. 82, 209.
5. M. Kalsuya. T. T.:shirugi. N. anll T. J. Polym. &f., Pui)'IIL Cllem. 1995,
23, 1259.
6. M. lktlos. T. Abc, and H. Awano. Mammwletu/c.v am, 25. 5125.
7. M. Fukuda, K. Sawada, and K. Yoohi no. J. Polym. Sd. A 1993, J/, 2465.
8. M. Miyaum, T. Yanagi. and A. Suzuki, S.vu/11. Commrw. 198a, //,513.
9. T. Kanbar.l, N. Saito. T. Y:.unamoto, and K. Kuhota, MucrcmroiC'nriC's 199a, 24, 5883; T. Y:una-
muto, A. Morita, Y Miy;v.aki, T. Maruyam:a. II. Z. Zhou, Y. T.
S. Sasaki. :md K. Kubota, Mmmmolet1rles 1992, 25, 12 14.
10. V. C'h:uurv ... 'tli, S. T:maka. and K. Kacaiyama, a993. 26, 2607.
II. M. Rehahn, A.-D. Sdllutct. G. Wegner. and W. J. l'caSI. Pnlymtr 1989, JU, 1054.
12. M. R.:hahn, A.-D. Sdlliiter, G. Wegn.:r. and W. J. Fc:L,t , l'olyma 19H9, .W. Jl)(>()_
13. T. Y:nn:unutn. Y. llay:tshi, and A. Yam:nnolll, /Ju/1. C//C'III. Sue )[Ill. 197M, 51. 2091; A. Noll. N.
Si.:gliehl, W. H.: itz. Mttknmwl. Chmr .. Rapid Cmmmm. a9'JO, II . 41\5.
1*. M. Ucda, F. khikawa, McwrcmwiC'mlts 1990. :?3, IJ26: M. Ucd<t, Y. Miyaji, and T. Ito, Muem
mnltmlts t991. 24. 2694; I. Colun, G.T. Kwiatkowki. J. Po/ym. Sd. A 1990, 28, 367.
15. V. Pere<-"C, S. Okita. and R. Weiss, Mm-rouwltmlts tiJ92. 25, IIH6.
16. J. H. Wu. G. Lieser. and G. Wegner. Atil: Mttttr: 1996 . 151.
17. T. r. lf. Wiuclcr, T. and G. Wegner, I \I'J5, 28. H350.
18. T. Vahlcnkamp. G. W<.'-IICr. Ma.-rrmw/. Phy.<. 1994. IY5, 19J3; Wallow. 13.M. J.
Novak. J. Am. C/r,m. Soc l 'J'Jl . 1/J. 7411 ; A. D. Otild, J. R. Reynolds. MtrcnJmo/emlts 1994,
27. 1\175; J.U. Rau, M. Rc.:hahn, Acllr Po/yml'l' a\194, 45. 3; R. Rulk.:ns, M. Schult/.C. and G.
Wcg,aJCr, Macnmwl. Rapid C'cm11111111. a994, 15. 669.
l<J. 13. Kamkaya. W. Claussen. K. Gessler. W. Sacng.:r. and A.-D. S.:hliit.:r. J. Am. C/rC'm. Soc. 1997,
1/IJ, 3296.
20. J. Huber. U. Schcrf. Mtwmmol. Rtrt>id Co1111111111. 19'J4. 15, 1!?1; R. J. Huller. U. Apcl. V.
Enkclmann. R. HcnL,chkc. U. Schaf, antl K. Mucrrmml. Clwm. Pl1ys. 1997. IYH, 262J.
21. R. L. L W. ShackkUc: in HwrdiHHik of CmuluttiiiK Pnlymers (Ell.: T.A. Skolheim)
Vol. I , Mar.:el Dekker. New York l 9H6, 01. 7.
22. K.C. LR. Dotkl. K. U:von, and T. K. Kwci, Macmmolt!t"lllt!s a9%, 29.7149.
23. Q. t>ei, Y. Yang. J. Am. Clrcm. Sac. a9'J6, 1/8, 7416.
24. M. Ranger. D. Rnmlcau. and M. Lcdcrc. Manrmrnlemlrs am. 30. 7686.
25. M. Grell, D. D. C. Bmdley. M. lnb:Lo;ckar:.nl, and E. P. Woo. At/a. Matur. 19'J1, 9, 79l!.
26. N. Saito. T. Kanbar.t. T. Sato. :.uw T. Yamanwto. Polym. /Jrr/1. (Jtt[H.III) a993. 30, 285.
27. M. E U.:k.:n. and K. Mullen, a995, 28, 4577.
28. U. Scherf. K. Mullen, Makmmol. C/rt'/11., Rapid Cmmmm. a991. / 2, 489.
29. J. W. Gr.wpncr. G. U:ising, IIlli U. J. Lumf11. a995, 63, 117.
Jll. S. A. Niku, G. U:ising, :md U. SciJCrf. Appf. Lt.u. 19%, 68. 1090.
Jl. J. Huller. K. Miilkn. J. Salhc.:k, H. S.:hcnk. U. Sdtct1', T. Stdtlin, R. St.:m, t\clll
l'JY4, 45, 2M.
_,2. R. E Mahrt, U. Sicgne r. ll. M. llulliiiCicr, U. S.:hcrf. S. lknn, E.O. Giibcl. K. Miillcn.
aaw H. ua.,skr, Clrem. 1'/ry.v. Lm . I'J95. 240, :n.l.
J3. w. Gr:IU(liiCr. G. Lciing, G. Lan:.'ani. M. NiMIIi. s. IIC Sihcstri, antl u. C/ttm. Pily.v. uu.
l'J'J6, 246. 95.
.l4. A. Khhkr. J. Griincr. R. H. friend. K. Miillcn. and U. Scherf. Cl!tm. 1'/rys. u'/1. I!J95. 24.1. 456.
J5. J. Gruner. H. F. Wittmann. P. J. It II. Frictu.l, J. llubcr, U. Scherr, K. Mullen, S. C. Morat-
ti. ant! /\. B. llulmes . .'i,\'11//r. Mt/. I"""* 67. I X I.
62 2 OHgo- and Poly(plumylem:)s
36. W. Graupncr, S. Eder, S. TaliCh, G. Leising, G. Lanzani, M. Nisoli, S. de Silvcsui, and U. Scheff,
J f1uaresce11cc 1995, 7, 195.
37. G. Kmnzelbinder, W. Gr.tupncr, G. Leising, M. Nisoli, S. de Silvestn, K. Milllen, U. Schert.
Appl. Phys. Leu. 1997, 71, 2725.
38. B. Schweitzer, G. Wegmann, D. Hertel. H. GiCl;Scn, U. Scherf, K. Milllen, W. W. Rilhlc, H. BiiB-
Ier, and R. F. Mahrt, Appl. Phys. Leu. , 1998, 72, 2933.
39. C. Zenz, W. Graupner, S. Tasch, G. Leising, K. Mullen, and U. Scherf. Appl. Phys. Leu. 1997,
71, 2566.
40. C. Kmlingcr, M. Hilmer, A. M. Pemer, W. Spirkl, U. Lemmer, J. U.
Scherf, and K. Mullen, Atlv. Mater., 1998, 10, 920
41. C.S. Marvel, G. E. Hanzell, J. Am. Chem. So<". 1959, 81,448.
42. D. G.H. A. Courtis, I.M. Shirley, and S.C. J. Chem. Sl1c . Chem. Comm. 1983,
954.
43.
44.
D. G. H. A. Courtis, I.M. Shirley, S.C. Macromolecules 1987,21. 1787.
D. L. Gin, V. P. Conti.:ello, and R. H. Grubb:., J. Am. Chem. Sue. 1992. 114, 3167.
45. D. L. Gin, J. K. Avtyanuv. ;uut A. G. M;od)iannid. Symh. M<l. 1994. 66. Ul9.
55.
56.
1
57.
58.
159.
60.
1
61.
62.
63.
G. K. Noren, J. K. Stille, Rto. 1971, 5, 3S5.
J. M. Tour, J. A. John, Polym. Prepr. (Am. Clrcm. Sue., Div. Polym. CIIL'm.) 1993, 34(2), 372; J.A.
John, J.M. Tour, J. Am. Clrem. Soc. 1994. 116, 5011.
W. Kem, M. Seibel, and 11.-0 . Wirth, Malmmwl. Chem. 1959, 29, t64.
W. Heitz. R. Ullrich, Makmmol. Clrem. 1%6, 98, 29.
P. GaJda. M. Rehahn. Synthesis 1996, 614.
H. Gerll3rdt, PlrD Thesis, Gcorg-August-Univcrsillit Giiuingcn 1984.
M. Kreyenschmidt, PhD Tiresis, Johanncs-Gutenberg-Universitat Main: 1995.
J. Grimme. M. Kreyenschmidt, F. Uckert, K. Mullen, md U. Scherf, Adv. Mm<l: 1995, 7, 29i.
J.S. Schumm, D. L. Pearson, and J. M. Tour. A11gen: Clrcm. 1994, /06, 1445; A11ge: C/rem. l111.
EJ. l:.'llgl. 1994, JJ, 1360.
P. Liess, V. Hensel, and A.-D. SchlUter, Licbigs Amr. Chem. 1996, 614.
J. Grimme, U. Scherf, MaLmmol. Clwm. P/lys. 1996, 197, 2297.
Y. H. Kim, 0 . W. Webster, J. Am. Chem. Soc. 1990. //2, 4592.
R. Wu, J.S. Schumm. D. L. Pcar.;on, and J.M. Tour, J. 0,-g. Cllem. 1996, 61, 6906.
J. SaJbeck, Ber. /lrmse11ges. Plr.v.\. ChtmL 1996. 100, 1667.
R.G. Clarkson. M. Gomberg, J. Am. Clrcm. Soc. 1930, 52, 2881.
J. 5mbeck, F. Wcissortel, and J. Macromol. Syml' 1998, 125, 121.
M. Muller, M. M. Wagner, V. Enkchnann, K. Mullen, Ange11c Cllem. 1995,
107, 1151;AugCiv. Clwm. lm. EJ. l:.i1gl. 1995,34, 1583.
M. Miille.-, J. Pelerscn, R. C. Gilnther, N. and K. Miillen, Angeov. Clll!m. 1996,
/08, 947; Angev. Cllcm. Int. &1. Engl. 1996, )5, 886.
64. F. Morgenroth, C. Kilbel, and K. Mullen. J. Mat. Cllcm. 1997, 7, 1207.
65. F. Morgenroth, E. ReulhCJ, and K. Mullen, Augeov. Chcm. 1997, lOY, 647; Augew. Clrem. /111. Etl.
EngL 1997,36, 631.
3 Disorder and Solitons in Trans-Polyacetylene
Jasper Knoester and Maxim Mostovoy
3.1 Introduction
The elcctronit: and optical properties of conjug.ated polymers have received con-
tinuous <tllcntiou over the past two Jc.:adcs. From a h.:dmulogiGtl point of view,
the semiconducting nature and the large optical non-lincarities of these materials
are of great interest, while, li-om a fundamental point of view, the unusual excita-
tions in these quasi-one-dimensional many-body systems have stimulated much
research ll j . Undopcd polymer chains arc half-filled Pcierls systems:
their ground state is dimerized, which means that along the chain the carbon-car-
bon bonds have altemating length. In chemical structures, this alternation is seen
ac; an <tlternation of single (long) and double (short) bonds. This Peierls dimcriza-
tion contributes to the gap in the electronic excitations. Another contribution to
this gap originates from the electron-electron intcr..tctions and is refen-ed to as the
Mott gap [2).
Trcms-polyacetylene is one of the most studied conjugated polymers and in
model studies it is often considered as the generic example. The Pcicrls instability
of a half-filled tnms-polyacetylcne chain results in the appcar..tnce of two degener-
ate ground states, which only ditl'cr in the sign of their dimerization (+ and -
phase; see Fig. 3-1 ). As a result, topological excitations of trcms-polyacctylene ex-
ist in which one or more domain walls occur that interpolate between the two de-
gener..tte phases (Fig. 3-2). The possibility of such domain walls (also called soli-
tons or kinks) wa-; noted as early as 1962, by Pople and Walmsley (3). The real
breakthrough in the interest in solitons, however, did not occur until 1979, when
Su, Schriefter, and Hecger presented their SSH Hamiltonian [4). Using a varia-
tional approach, they found the energy and the size of the domain wall. In the
weak coupling limit their variational solution becomes exact 15. 6). It appeared
that the energy of a charged soliton wac; lower than the energy of electron or hole
excitations. Thus, the idea was put forward by Rice l71 and Su, Schrielfer, and
Hecger (4, gl that in char<Jc may be tr..tnsported by charged
solitons, mther than by electrons and holes. It should be notcu that solitons in
one-dimensional systems with a dcgcncr..ttc ground state also received much atten-
tion from high-energy physicists when the importance of topological objects in
yuantum field theory was recognized 19- 11 ).
The most interesting aspect of solitons is their charge-spin relation ll). Charged
solitons arc spinlcss, while neutral solitons have spin 1/2. Titis property provided
a natural explanation for the fact that in doped /mm-polyacetylene the electrical
3 Disorder and Solitons in Trans-Polyacerylene
H H H H H
H H H H II
Figure 3 1. Perfectly dimeri"L.Cd murs-polyacctylcne chain. Double and singk correspond to
hort and long bouds, respectively. The two ground state (b) arc IJ.:gcncr<IIC,
H H H H H
!Fq:ure 3-2. Solilon: a domain wall between the 1wo diiTcrcnt dimcrizcd pha.'leli shown in FigUI'C 3- 1.
dot indicates lhc unpaired electron which is localized nc-dJ' lhe domain wall in C>tsc il is neutr.ll.
rises much faster than the Paul i susceptibility (1 2, 131: adding charge
I
to a half-lilled chain creates charged solitons. Also, the ESR detection of neutr.tl
1
free spins in pristine tnms-polyacetylene [14, 151 could be understood on the ba-
sis of the soliton picture: neutml solitons may occur as defects, resulti ng from an
incomplete cis-trans isomerizati on (16].
Monte Carlo simulations [ 17, 18], the valence bond approach I 19, 20], and
g-ology [21-24) indicate that the Pcierls instabili ty in half-filled chains survives
the presence of electron-electron interactions (at least, for some r.lnge of intemc-
tion paJameters). This holds for a variety of different models, such as the Pcicrls-
Hubbard model with the onsite Coulomb repul sion, or the Pariser-Parr-Pople
model, where al so long-mnge Coulomb interactions are taken into account 12]. As
the dimcrization persists in the presence of inter,u:tions. also the
soliton concept survives. An important difference with the SSH model is that neu-
3.2 The Peierls Justubility and Solitons 65
tral and charged solitons no longer have the same energy: the neutral soliton is
lower in energy [25, 26].
Solitons are usually associated with excited or doped states, because in regular
chains their energy is too high ( - I eV) for thennal population in the ground
state. Conjugated polymer chains, however, in general are far from regul ar. One
important type of disorder is conformational disorder, which leads to disorder in
the electron hopping amplitudes along the chain. The si mplest way to treat such
disordered Peierls systems is a n'lCanfield treatmem, where the lattice dimerization
is assumed to randomly Ouetuate along the chain around some average value (the
so-called Auctuat ing Gap Model, FGM [27J). Using this approach, disonJer sup-
presses the dimeri zcd phase by localizi ng the and filling the Peierls gap
with clcctmn states.
If, instead, one allows the lattice to respond to the electronic disorder, one
finds that disorder induces a linite density of neul.-.al solitons in the ground state
of a single chain [28- 30]. These solitons destroy the long range order, unless they
arc suppressed hy suiTiciently strong inlen:hain intenu.:tions. 1l1e disorder-induced
solitons also affect the opt ical and magnetic properties or tmns-polyacctylene. In
the limit of weak disorder, we t'Ccently studied the creation of solitons by disorder
by using a mapping on the random ticld Ising model 131, 32}.
In this contribution, we review our recent work on disordered ttuasi-one-dimen-
sional Peierls systems. In Section 3-2. we introduce the b<L'iic models and con-
cepts. In Section 3-3, we discuss the localized electron states in the FGM, while,
in Section 3-4. we allow fM lauice relaxati on, leading to disorder-induced soli-
tons. Finally, Section 3-5 contains the concluding remarks.
3.2 The Pcierls Instability and Solitons
As noted in the the Peierls instability of a half-lillcd
kne chain results in the appearance of two degenemte ground states, in which the
lengths of carbon-carbon bonds altcmate (sec Fig. 3- 1 ). The Pcierls order parame-
ter fl (dimerization). dctined as the difference between the electron hopping am-
plitudes on neighboring even and odd bonds. has opposite sign in these two
states: fl =flu. The minima l energy inhomogeneous lattice configuration ll,. (x)
that satislies the boundary conditions
{
+A, for x ....... +oo
fl_,(x) -+ - AI
Lll for x ....... - oo
(3. 1)
nccc.-;sarily contains a domain wall separating regions with opposi te sign of fl.
This wnliguration is rcfened to as a soliton (ur a kink). The lallicc configumtion
fl, (x) =- fl., (x), satisfying the boundary conditions op[X>sile to Eq. (3. 1 ), is called
an antisoliton (anli kink).
66 3 Disorder a11d Solitons in Trans-Polyacetylene
The soliton lattice configumtion is characterized by the soliton position Xo and
the width of the domain wall which, quite genemlly, is of the order of the cor-
relation length <o in the uniformly dimerized chain. The soliton energy (counted
from the energy of the uniformly dimcrized ground state) is finite, since the en-
ergy density is concentmted in a region of size <s near Xu The soliton energy is
!independent of its position Xu. which makes solitons mobile objects capable of
l tmnsporting the charge or spin that is localized near the domain wall, along the
chain. (Actually, lattice discreteness results in a periodic dependence of the soliton
1
energy on xo, that is, however, r.llher weak and can be neglected [4, 8].)
I
In a seminal paper [4], Su, Schrieffer, and Heeger discussed the energetics of
solitons using a simple model of free electrons interacting with the Janice de-
scribed by the Hamiltonian:
(3.2)
where
f/d = - L
1
, ., 11 (c:!, . r.nc,.n + c!,.nc,1 l .n)
(3.3)
n,n
and
K ( )2]
f/laJ = 2M+2 Un+l - u, .
(3.4)
In the context of tran.\-polyacetylene ct
0
and c .o are, respectively. the creation
" n
and annihilation oper.nors of an electron with spin projection a in the n-orbital of
the nth carbon atom (n= l , . .. ,N) that is perpendicular to the chain plane (sec
Fig. 3-3). Furthem10re, u, is the displacement along the chain of the nth CH unit
I
from its position in the undimcrizcd chain, P, denotes the momentum of this unit,
and M is its mass.
I The electron-lattice intemction is introduced through the dependence of the
electron hopping amplitude on the carbon-carbon bond length:
t,_, ... = lo + a(u,- u,.H) . (3.5)
l'igure 3-3. A schcm;uic pi.:lurc uf a mms,lOiyacctylcnc ch01in. showing the 2tl: cle.:lrunic orbilill,,
which arc rcJ>emlicular to the plane funn . "tl hy the n-bontls (soliu lines).
3.2 Tile Peicds Instability cmd Solitous 67
The Coulomb intemction between the n-electrons is neglected. 11te standard
trtms-polyacetylene parameters are t
0
=2.5 eV for the hopping amplitude in
the undimcrized chain, C1=4. I cV/A for the electron-phonon coupling, and
K=2l eV/A
2
for the spring constant[!, 4, 8l
The SSH model (Eq. (3.2)) is, essentially, the model used by Peierls for his dis-
cussion of the clectron-Jauice instability [331. lls ground stale is characterized by
a non-zero expel:lation value of the operator:
(3.6)
and by a periodic lattice distortion wave with wave vector
1l1e undoped
tnms-polyacetylene chain contains one electron per site (half-filling), so that the
disto1tion wave vector 2kF equals rr/u (a is the length of a C-C bond in the umlis-
torted chain), which corresponds to alternating shifts of the CH units:
u, = (- )"un. (3.7)
The alternation of the bond lengths results in an ahemation of the electron hop-
ping amplitudes:
(

t,J, 1 1 = tu + - -;;- . (3.8)
with the Peierls order parameter .1
0
=4au
0
. 1l1e lattice dimerization opens a gap
in the spectrum of the single-electron excitations equal to 2.1o. In tmns-polyacety-
lene
eV.
An imp01tant property of the electron Hamiltonian (Eq. (3.3)) is that for arbitrary
hopping amplitudes tll.ll.+l the spectrum or the single-electrons states is symmetric
with respect to t:==O; if f/1, is the electron amplitude on site 11 of an eigenstate with
energy c, then the slate with :unplitudes (- )"f/1
11
is also an eigenstate, with energy -1:.
In particular, in the uniformly dimerizcd state, the gap between the empty conduction
and the completely filled valence banJs mnges from

to

The ground stale of a (sufficiently long) t:hain with an odd number of units,
N == 2 L+ I, and periodic boundary conditions, obviously, cannot be uniformly di-
merized and must contain a soliton (the same is true for an odd chain with open
boundary conditions). In this case, because of the symmclry of the density of
slates, the energy of one electron state is exactly zero. For a half-filled chain (one
electron per carbon atom) the solitonil: ground state is neutral. It has. however,
spin 1/2, which is the spin of the singly occupied zem-energy level (the L doubly
occupied valenl:e states have total spin 0). If we now add another electron to the
zero-energy levd, the solimn ch:trge will be - l' and its spin will be zero. Similar-
ly, by removing one electron from the zero-energy state, we create a spinless soli-
ton wilh charge +e. In the free del:tron model the charged and neutral solitons
have the same energy, as they diller only by the occupation of the zero energy
state.
68 3 Disorder and Solitons in Tra11s-Polyacetyle11e
In Ref. [4], the soliton lattice configuration and within the SSH model
were found numerical ly. Analytical expressions for these quantities can be ob-
tained in the weak-coupl ing limit, when the gap

is much smaller than the
width of lhe n-clectron band 4t
0
. At this point it is useful to define the lattice cor-
relation length:
e _ VF _ 2ato
o- 6o- 6o.
(3.9)
In the weak-coupling limit eo becomes much larger than the length of the unit
cell a (<
0
-7 a for trans-polyacetylene) and the Peierls gap has a strong effect
only on the electron states close to the Fem1i energy F=O, i.e., states with wave
vectors close to The interaction of these electronic states with the lattice may
then be described by a continuum, model [5, 6]. In this description, the electron
Hamiltonian (Eq. (3.3)) takes the form:
(3.10)
where the real order parameter at x,=2na is defined by
= l2J,- 1,211 - l2n.2Jr+ l (3. 11 )
Furthermore, a
1
and a
3
are Pauli matrices and
'I' (x) = ('I' Ra(x))
o 'l'u(x)
is the fermionic field operator. The first tem1 in the Han1iltonian Eq. (3. 1 0) de-
scribes the free motion of the electrons and the two amplitudes 'I'
11
(x) and 'II L (x)
correspond to particles moving, respectively, to the right and to the left with the
Fcm1i velocity v,.. The second term in the Hamiltonian descri bes the backward
scallering of electrons from the lattice distortion wave.
Momentum conservation impl ies that the wave vectors of the phonons, intcmct ing
with the electrons close to the Fermi surface, are either small (forward scattering) or
close to 2k.F=nla (backward scattering). In Eq. (3. 10) forward scattering is ne-
glected, as the electron inter.lction with the acoustic phonons is weak. Neglecting
also the weak q-dependcnce of the optical phonon frequency, the lattice energy reads:
I I [ I )
2
2
]
H..,, = A.nvF dx Q 2 Dr '
(3.12)
where A.=
is the dimensionless electron-lattice coupling constant and

Q =
bare optical phonon frequency at q=nl1.

3.2 The /nswbility aud Solitons 69
The continuum model with the Hamiltonian equal to the sum of Eq. (3. 1 0) and
Eq. (3.12), describing the interaction of electrons close to the Fermi surface with
the optical phonons, is called the Takayama- Lin-Liu- Maki (TLM) model [5, 6].
1l1e Hamiltonian of the conti nuum mollcl retains the important symmetries of the
discrete Hamiltonian Eq. (3.2). In particular, the spi!Cttllm of the single-particle
states of the TLM model is a symmetric function of energy.
By minimizing the chain energy
one obtains the self-consistency equa-

tion for
nA.v
1
.. " t
= -
2
- L.)'l'o(x) a, f11
0
(x)) ,
a
(3.13)
where ( ... ) denotes the average over the many-electron ground state for the lat-
tice configumtion (x).
The x-independent solution of Eq. (3. 13) for the uniformly dimerized chain

is:
(3. 14)
Here, W is a cut-off of the order of the n-band width, illlroduccd because the
right-hand side of Eq. (3.13) is formally divergent. As in the discrete model, the
spectrum of eigenstates of H.,. for has a gap between

and

sepamting the empty conduction band from the completely filled valem:e band.
The inhomogeneous soliton solution with boundmy conditions Eq. (3. 1) has the
form of a hyperbol ic tangent [5, 6):
"()A (X-Xu)
u, x = <->t1 lauh ""T, . (3.1 5)
with eo as defined in Eq. (3.9). For the soliton configuration, the spectrum of the
single-electron states also contains, apart from the valence band with highest
energy

and the conduct ion band with the lowest energy one state with
zeru energy (sec Fig. 3-4):
(3.16)
where
I I
C/>u(x) = (Tu)
(3. 17)
and

70 3 Disorder and Solitons in Trans-Polyacetylene
-...
X
---------- =0
-.o..
Figure 3-4. nlC onJer par.unc1cr 6,, (x) for I he solilon soiUiion (lhick line) mKI lhc clccuvn
IIJI
0
(x)l
2
for 1hc in1r..1gap slaiC uccomp;.mying 1hc solilon (c.loucd line) arc :.hown 10 1hc lcll. To lhc
righ1 lhc spectrum of singlc-dcclron SI<IICS for lhc solilon lauicc configur.tlion is cJcpic1cu.
denote the eigenvectors of a
2
with eigenvalues I . This state is known as the
"midgap" state. Its wave function has the spatial extension

and is local ized
near the soliton position x
0
. The energy of the soliton is of the occu-
pation of the midgap state, i.e., charged and nculml solitons have identical ener-
gies, given by:
2
Es = - 6o.
7r
(3. 19)
The single-electron spectrum for the antisol iton solution, is exactly
the same as for the soliton, except that now the wave function of the midgap state
is given by
'llo(x) = o(x)l+} (3.20)
The existence of a stale with zero energy depends only on the topology of (x),
i.e., on how (x) behaves at x-+ co, and not on its precise fonn (34 ). .
Up until now we have only discussed the situation where the Coulomb intemc-
tion between the electf?ns is neglected. As we mentioned in the Introduction, the
soliton concept does survive electron-electron imemctions, although the energetics
differ from the above. We will rclum to this in Section 3.4.
3.1 Dismrler: Tire F/uctullling Gt1p Model 71
3.3 Disorder: The Fluctuating Gap Model
So far, we discussed perfect trm1s-polyacetylene chains. In pr..tctice, however,
polymer materials sutler from various kinds of disorder: confom1ational defects,
cross-links, impurities, etc. 12). Within the SSH model (Eq. (3.2)), effects of disor-
der were studied by introducing randomness in the on-site puLcntials or in the
hopping amplitudes (see, e.g., L35, 361). It was noted in Ref. l37) that the effect
of non-magnetic impurities in Peierls systems is similar to that of magnet.ic impur-
ities in superconductors. Based on this analogy. the existence of a gapless dimer-
izcd stall! was predicted for sulliciently stmng disorder )37. 38). We note that,
though the eflect of disorder on the Pcicrls state is, indeed, titrong, the analogy is
not exact, since the scauering from impurities, apart from "pair-breaking" tenns,
also results in (r.mdom) "pairing" terms. Most importantly, however, the eflect of
disorder on the electron motion in 4uasi-onc-dimensional materials cannot be de-
scribed satisfactorily by the Abrili.usov-Gorkov theory of superconuuctors with
magnetic impurities [39). because of the strong electron localization. Strictly
speaking, even in superconductors the gap is tilled wi th electron states lor an arbi-
trarily weak conccntmtion of magnetic impurities l40). These states are localized
near the regions where the concentmlion of the impurities is high and the super-
conductivity is locally destroyed. In this section we show that the disordcr-in-
uuccd state1> that Jill the Pl!ierl s gap arc localized ncar the regions where the di-
meri zation changes sign. We also discuss the encct of these stales on the opt ical
properties of disordered Peierls chains.
If the random variations in the hopping a mplitudes and the on-site potentials
arc small compared to l u. the disonler may be deseribeu using the continuum
model. In this case, the density of slates can be found an:1lytical ly 127, 4 1). Here.
we concentmte on disorder in the electron hopping amplitudes (off-diagonal disor-
der). As the Peierls order parameter is related to the ahemating part of the hop-
ping amplitudes, off-diagonal disorder results in random lluctuations of the order
pammeter in the clcct.ron Hamiltonian (Eq. (3.10)) around some average
value
= 6o + 1/(x) , (3.21)
where '1 (x) is the fluctuating part, which is assumed to have a Gaussian corrclator,
{IJ(X)IJ(y)} = AJ(x - y) . (3.22)
This model, which is sometimes referred to as the Fluctuating Gap Model (FGM)
142]. has been used to study various aspects of quasi-one-di mensional systems.
Examples arc the thermodynamic properties of quasi-one-dimensional organic
compounds (NMP-TCNQ, TIF-TCNQ) 127), the effect of disorder on the Peicrls
tranl>ition 143. 441. and 1hc erti:c1 of quantum lallice llucluations on the oplical
of Pcicrls materials 141, 45, 46).
72 3 Disorder and Solitons i11 Trans-Polyacelylene
As we saw in Section 3.2, in the absence of disorder
the electron spec-

m has a gap between the energies and e=+6o. Disorder gives ri se to the
ppearance of electron states inside the gnp, although for weak disorder a pseudogap
till exists. Using the "phase fonnalism" (47], Ovchinnikov and Erikhman derived a
losed expression for the integrated average density of states p(c')dt!) of the
GM at arbitrary disorder strength [27]. The average density of states, p(c), that
y be obtained from their result, is plotted in Fig. 3-5 for three values of the dimen-
ionless disorder strength g = A/( vF6o). For small di sorder, one clearly observes
pseudogap. Close to the center of this pseudogap (lei the energy depen-
dence of the density of states is approximately given by [27]
(3.23)
ere and below we assume e to be positive, which is sufficient in view of the
ymmetry of p (e) for the Hamiltonian Eq. (3.1 0). For g < 2 the density of states
as a pseudogap (the Peierls gap filled with disorder-induced states). For g > 2 the
seudogap disappears and the density of states becomes divergent at c=O.
From Eq. (3.23) it is clear that at weak di sorder (g I) the density of states close
to the middle of the pseudogap is strongly suppressed. The reason for this is that a
large fluctuation of (x) is required in order to create an electron state with energy
This makes it possible to apply a "saddle-point" approach to study the typ-
,.....__
w
..._,
a.
3
2.5
2

a
Figure 3-S. Disordcr-avcrag!XI density of st:11cs p(1:) in the FGM for three of the dimcnsiunlc....s
disorder strength: g=O. i.e., no disorder (curve a). g=0.25 (curve b). g=4 (curve c). 1l1c fn:c <!lcctron
density Of SI:IICS was CI IU unity.
3.3 Di.wmler: The Flucllwting G11p Ma(/(/ 73
ical electron states occurring at these low energies and to calculate disorder averages.
This method, which gives much additional insight into the nature of the states deep
inside the pseudogap, was used in Ref. [48]. In that paper, we showed that the "sad-
dle-point" disorder fluctuation determining the most probable form of the low-en-
ef'_;y electron states, has the form l>f a soli ton-anti soliton pair, where the scpar..ttion
between the soliton and the antisoliton depends on the energy r. of the state. The
wavefunction of the electron state induced by this lluctuation contains two peaks,
whidl are localized near the two kinks of the fluctuation. Away from the kinks,
the electron wave function falls oiT exponentially on u length scale

In the remai n-
der of this section, we will describe these results in somewhat more detail and dis-
cuss the average density of states and the average optical absorption spectrum that
may be obtained in thi s way.
1l1e ''saddle-point" disorder fluctuation [49- 5 1] (also called the optimal fluctua-
tion) IJ(x) is the least suppressed one among the required large lluctuations. It can
be found by minimizing.
(3.24)
The first term in this equation describes the suppression of the probability of the
fluctuation with the corrclator Eq. (3.22) (the weight pl1l(x)J of the disorder con-
figuration is exp (- J d.nl (.x)) ). while the second term stems from the (:ondi-
tion that the energy c+[IJ(.x)J of the lowest positive-energy single-electron state for
the disorder realization IJ(X) equals 1:. 1l1e 11 is a Lagrange multiplier. It can
be shown that the disorder lluctuation 1/(X) that minimizes A [1J(x)J has the form
of the soliton-antisoli ton pair contigumtion described by [4H):
IJ(x) = -v,.K [tanh ( K (x- x0 (K (.x- , (3.25)
where x
0
describes the position of the disorder fluctuation in the chain, R is the
distance between the soliton and the antisoliton, and K is determi ned by
v,.K =

tanh (KR) . (3.26)
1l1c instanton is shown in Figure 3-6 by plotting = 6t
1
+ 1j(x) . The spectrum
of single-electron states for this is well-known fmm studies of polaron states
within the SSH H;unillonian 152, 531 and is also plotted iu Figure 3-6. lt consists
of a valence band (with highest energy - L1
0
), a conduction band (with lowest en-
ergy 6t1), and two localized intmgap states with energies (R), where
c (R) - 6tt
+ -cosh (KR)
(3.27)
Thus, the soliton-antisoliton scpamtion R is fixed by the condi tion c+(R)=c.
74 3 Disorder and Solitons in Trans-Polyacetylene
- - - - - - - - - - - - - - - - -
Figure 3-6. The sohlon-uuisolilon lauicc coofigurauon (lhick line) and 1hc clccuvn
IIJI+(x)J
2
= lrp_(x)J
1
li.lr lhc corrc!>ponding slate> (doucd line) are shown to 11..: lcfl . To lhc
righ1 Ill<! of singlc-clc.:rron si<IIC> for 1hc sol ilon.utlisolilon cunligumliun is dcpiclcd.
The two intragap states ll':a:(x) arc the symmetric and antisymmetric superposi-
tions of the midgap states localized ncar the soliton :.md the antisoliton:
I ( .fKl2 .fKl2 )
ll':t(x) = J2 cosh (K(x - cosh (K(x '
(3.28)
where 1} are defined by Eq. (3.18). :1: (x) is schematically plolled in Fig-
ure 3-6.
The energy splilling 2 between the intragap states decreases exponentially
with the soliton-antisoliton scpar..ttioo, so that for e 6o.
(3.29)
with

the correlation length dctincd in Eq. (3.9). The suppression factor
Eq. (3.24),
I 2 226o
A[17(x)] ::::: - (2.6o) R :::::-ln- ,
2A g I;
{3.30)
also depends logarithmically on energy, so that the weight of the saddle-point con-
figuration is
(3.31)
Comparing this result to Eq. (3.23), it is seen to give a good estimate for the
shape of the density of states inside the pseudogap at g I.
1.3 Di.wrclc:r: Tire Fluctuuting G11p Model 75
A more detailed calculation requires peri"om1ing the Gaussian integration over
the disorder realizations close to the "saddle-point" eonfigumtion Eq. (3.25). One
then finds the following expression for the average density of electron states per
unit length,
{p(c)} = _ e_ ( ec ) : -
ngvF 26o
(3.32)
For g I, this agrees with Eq. (3.23), confim1ing the validity of the "saddle-point" ;
approximation at small energies and weak disorder. The easiest way to get the result
Eq. (3.32) is to use the correspondence between the averaging over disorder realiza-
tions 17 (x) and the quantum-mechanical averaging over the ground slate for a certain
double-well potential I 54!. 1l1e .. saddle-point" disorder fl uctuation then corresponds
to the instanton tunneling the wells 155, 56).
The form Ey. (3.28) for the most probable disorder-induced electron states can
also used to calculate. in a relatively su-aightfurward way, the optical absorp-
tion cocllicient fur a half-filled chain at photon energy w 26
11
and g I .
Again, only a large disorder 11111.:tuation can make the energy uificrence between
the empty and tilled electron levels small. With the highest probability the photon
absorption will induce a tmnsition from the highest occupied to the lowest unoc-
cupied electron state. Due to the particle-hole symmetry, the energy of the lowest
unoccupiL'Ci state at half-tilling should equal +w/2, while the energy of the highest
doubly occupied state should equal - w/2. Hence, the saddle-point" disorder con-
figuration, whose probability largely detennines the absorption r.lle, is given by
Eqs. (3.25), (3.26), and (3.27) with r.+(R)=w/2.
Thus, in the saddle-point'' approximation, the absorpti on coefficient is the
product of the averaged density of states (which is essentially the probability to
find the necessary disorder fluctuation) and the osci ll ator strength of the optical
tr.msition between the two intr..tgap levels:
{3.33)
Here, d is the dcctric dipole operator, 111
1
(.r) arc the wave functions of the intmgap
states with energies w/2, and Cis an w-indepcndent coenicicnt (for small w, we
can neglect the weak w-dcpcndence of the real pan of the dielectric constant).
From Eq. (3.28), one finds that the oscillator strength is proportional to the
square of the soliton-antisoliton separation R. Using this, Eq. (3.33) reduces to the
tullowing lurm for the average absorption codlicicnt at low photon energy:
{3.34)
Altemative evaluations of the absorption spectrum (or the optical conductivity) of
Peicds systems within the FGM have been rcpo11ed in Refs. L451 and l46J. In those
76 3 Disorder tJnd Soli1011s in Tmlls-PolytJce/ylt'ne
papers, however, the factorization approximation, ( GG} = (G) (G). was used to eval-
uate the disorder average of the product of two Green functions. From the above, it is
clear that this approximation is not valid at low photon energies, as it results in the
optical conductivity (as well as the absorption coefficient) being proportional to the
second powcrofthc weight Eq. (3.31), ratherthan the lirstlcf. Eq. (3.33)1. Of course,
at weak disorder the absorption at photon energies w is small anyhow, but the
factorization approximation makes it even much smaller.
3.4 Disorder-Induced Kinks
In the previous section we a..o;sumcd that disorder results in random fluctuations of
the order parameter around some avemge value
Such an approach is, essen-

tially, a mean field treatment of the lattice. It re4uire:-. suflicicntly strong inter-
chain interactions, whose role is to establish a coherence between the phases of
the order pammeter in dilkrent chains.
In this section we consider the opposate case of very weak inkrchain interac-
tions .. In a first approximation, we neglect them entirely and study the effects of
disorder in isolated Pcierls chains. In this approach we no longer assume the
chain lattice to be uniformly dimcrized. Instead, for a given disorder realization,
we have to find the lattice configuration that minimizes the chain energy. In a
Peierls chain with a doubly degenerate ground state, even weak disorder can then
produce significant changes in the chain's lattice configuration. Numerical study
of the minimal energy lattice configumtion of a half-filled chain described by the
SSH model indicated that disorder in the electron hopping amplitudes can induce
kinks in the lattice dimerization l28, 29). In Ref. l30) we showed, independently
of the model of the Peierls chain, that the density of the disorder-induced kinks is
approximately proportional 10 the disorder strength. Furthcm1ore, if the Coulomb
interaction between the electrons is taken into account, the kinks are neutral and
have
For explicitness. let us assume that off-diagonal disorder is caused by chain
twists. which randomly diminish the overlap between the rr-orbitals of neighbor-
ing carbon atoms (see Fig. 3-7). The electron hopping amplitudes that depend
both on the interatomic distances and on the relative orientation of the electronic
orbitals on neighboring atoms can then be wriuen in the form:
1,,,H 1 = to+ a(u,.- u, ... . ) + c)r,,, +J . (3.35)
Here, the second term describes the change of the hopping amplitudes due to the
displacement of the atoms parallel to the chain [cf. Eq. (3.5)} and the third term is
a mndom contribution resulting from the conformational disorder (chain twists).
While the lattice displacements 11, arc dynamic variables, the lluctuations
due to disorder <lfe assumed to be frozen ( .. 4ucnched" disorder).
: .
:--...........
3.-1 Di.mnler-lndun:d Kinks 77
l.<' igurc 3-7. A simplifJC<.I pK:turc of a trcm.-polyacetylcnc chain with conformational <.lisor<.ler: the right
part uf the chain rotated with to its left over the angle "' The clcctron hopping ampli
tude on the twistc<.l bond is reduced by a factor of cos</'
The Peicrls order parameter is the alternating pa.1 of the hopping amplitudes
bee Eq. (3.11) I and now consists of two parts
(3.36)
The first part is the lauice dimerization,
{3.37)
which describes the alternating part of the hopping amplitude determined by the
shifts u, of the atoms and is the usual order parameter of the SSH model. The
second term in Eq. (3.36) describes the disorder
1J(2na) = Jt2, - 1.'211 - c512,.2, t l . (3.38)
Note that, while the mndom chain twists always decrease the hopping amplitudes
(all c5t,J,+I are negative), IJ(x) can be both positive and negative, as it is the alter-
nating part of the tluctuations. As in the FGM, we consider white noise disorder
with a correlation function given by Eq. (3.22). 1l1is corresponds to independent
random variations of the hopping amplitudes c5t on differclll bonds.
llte diflcrencc between Eq. (3.36) and Eq. (3.21) i:-. that in the FGM the lattice
was assumed to be uniformly dimerizcd, Llaa
1
{x) = wherea..o; now it has to be
found by minimizing the chain energy:
{3.39)
In the Hamiltonian Eq. (3.39) the first term is the harmonic lauice energy given
by Eq. (3. 12). It depends only on 6
1
;,., i.e., the part of the order parameter that de-
scribes the lattice disto11ions. On the other hand, the electron Hamiltonian Hc1 de-
pends on il(x), which includes the changes of the hopping amplitudes due to both
the lattice disto11ion and the disorder. llte free electron part of is given by
Ell. (3. 10), to which we ;Jlso add ;a term . .-. th;at describes the Coulomb interac-
78 3 Disorder and SCJiiiOilS in Trans-PCJlyacety/ene
tion between the electrons. Actually, the precise form of HcJ.cl will not be needed
for the following consideration, as long as the interaction between the electrons is
sh011-rangcd and does not destroy the dimerized state, i.e., we assume that in the
absence of disorder the (half-lilled) dl<lin reaches iL-; minimal energy in either one
of two unifom1ly dimerized configurations:
(x)=L\,. In particular, the on-site

Coulomb repulsion satisfies these criteria (17, 19, 20]. As we shall shortly see,
the existence of two degener.ttc ground states, which also implies the existence of
kink solutions, is crucial for the appearance of disorder-induced kinks, while the
precise form of flc
1
.c
1
is only important to the extent that it determines the value
of Ao and the kink creation energy Es.
An important property of the dimeri zcd Peierls state is the existence of gaps in
the spectra of spin and charge excitations. For free electrons both gaps
are equal, while in the pre..'ience of Coulomb repulsion the spin gap is smaller
than the charge gap 123. 241. In what follows, we wi ll assume the temperature to
be much smaller than these two gaps, so that we can neglect electronic excitations
and replace flc.l6(x)] by its ground state expectation value.
Next, we argue that the minimal-energy lattice configuration in the presence of
disorder may contain kinks. At zero temperature the lattice conligumtion, i.e.,
6 1a1(x), has to be found by minimi zing the total chain energy (Eq. (3.39)) with re-
spect to

(x) at a given disorder realization 'I (x). This makes 6
1
., (x) implicitly
dependent on YJ (x).
In the absence of disorder the total energy of a half-filled chain ha<;, apart from
the two minima for 6(x)=6
0
(corresponding to the two degcnemte uniformly
dirnerized configurations), infinitely many nearly perfect extrema. These are the
multikink configur.ttions, in which a sequence of kinks and antikinks interpolate
between and +llo and vice versa (see Fig. 3-8). A kink is locally stable, i.e.,
the chain energy increases, when its form is perturbed. The energy of a multikink
configuration can be decreased only by changing the distances between the kinks.
However, when the sepamti on between neighboring kinks is large compared to
their size (which is of the order of the correlation length

= v,.-f the change
of the energy caused by shifts of the kinks is exponentially small, so that the en-
ergy of the configumtion with N kinks is approximately
- 6 :
0
.
.
Figure 3-8. A mullikink cunfigur.uiun.
(3.40)
1.4 Di.wrrler-lllduce(/ Kinks 79
Here, . is the kink creation energy and
0
is the chain energy in the absence of
kinks. As discussed in Section 3.2, kinks can be either charged and spinless or
neutral with spin In the SSH model
both types have the same en-

ergy Ill; if the repulsion hctwccn dc'-t mns is wkcn into account. the
neut r...l soliton has lower energy (25, 26(. In in the limit U 4tu (U is
the on-site Coulomb repulsion), the charge excitati ons have a gap U-4t
0
and the low-energy physics is described by the intcrJCtion between the Janice and
the spins of the electrons (the so-called spin-Peicrls model [57, 58]). In this case,
the energy of the neutral soliton is of the order of the gap in the dimcrized spin- .
Peierls chain, while the energy of the charged soliton U is much larger. Since
the on-site Coulomb repulsion in trtms-polyacetylene is appreciable [2), only neu-
tml kinks are induced by disorder in trans-polyacctylenc chains.
Let us now consider the change in the energy of a multikink configur.uion due
to weak di sorder. We will denote the lattice conli guration containing N kinks,
whose positions arc described by the N-dimensional vector z = (z
1
, z2, ... , ZN ), by
6N(xlz). To first order in fJ (x), the correction to the energy of the configuration
reads,
(3.41)
where the extremum condition for the con11guration 6N(xlz) at zero disorder was
used.
For instance, the change in the energy of the uniformly dimerizcd configuration
(6(x) = llo) due to di sorder is
. 26o J (
c>Eo = - --
1
dXIJ x) ,
TCAVt-
(3.42)
while for Lhe configuration with an antikink at ::
1
and a kink at z
2
, such that the
whole disorder fluctuation lies between ::
1
and z
2
, the change of energy equals
o2=-<5o. because between Z1 and Z2 6 2(xl::.,z2):::::: - 6o. We thus sec thal, in
the disordered chain, the conligumtion obtained by the perturbation of a kink-anti-
kink pair is energetically favorable to the perturbed uniform configur.ttion if
(3.43)
Here, we introduced
(3.44)
which for free electrons (SSH model) equals I [sec Eq. (3. 19)). Since the fluctua-
tions in d..n7(x) grow with the chain size L, for a suiTiciently long chain the in-
equality Eq. (3.43) can certainly be futritlcU, no maHer how small the disorder is.
80 3 Disorder cmd Solitons in Trans-Polyacetylene
The creation of kinks by off-diagonal disorder is illustrated in Figure 3-9. The
thick line is the ground state order parameter lln = 6(2an) = I2Jr- l ,2n - t
21
,,a+l for
a discrete chain of 160 carbon atoms. obtained by numerically minimizing the
total energy for one particular realization of the disorder. In this example, we ne-
glected the Coulomb repulsion and used standard SSH parameters [I]. It is dearly
seen that the order parameter fluctuates ncar a soliton-antisoliton pair configura-
tion. The disorder realization that was used ru; input is visualized by the thin line,
which gives The thin line in
fact directly represents the order parameter along the chain if we neglect the lat-
tice relaxation (the order parameter in the FGM model). In that case, no Janice
kinks are created.
It is not difficult to estimate the density of solitons induced in the chain by
weak disorder [30]. As for weak &-.order the distances between neighboring kinks
on the chain are large compared to the kink size c;
0
, the order parameter in a mul-
tikink configuration (Fig. 3-8) may be considered to take only two values:
6(x)=6o. This allows one to replace the order par.1meter by an Ising variable.
Then, Eqs. (3.40) and (3.41) describe the energy or (the continuum version ol) the
one-dimensional random-field Isi ng model. In this mapping, solitons take the role
of spin-flips, while the disorder IJ(x) is the analog or the random magnetic field.
As was first estimated by lmry and Ma (59], the balance between the cost
of spin-flips and the energy gain that may be obtained by orienting the spins par-
allel to the local magnetic field, lead to an average density of spin-flips (or soli-
tons in our case) given by:
I A
n=-= 2
L (r.,A.v,.-)
(3.45)
This estimate, which is based on simple scaling arguments, may be substantiated
by calculating the free energy of a disordered Peierls chain, as we did in
Ref. [3 1]. Treating the lattice vibrations classically, the final result for the kink
density is

e
<l
20 40
m
60 80
flgurc J.\1. The numerically obLainC\1 onlcr par.unctcr along a pulyacctylcnc chain of 80 pairs of car-
bon a1oms for one panicular (bul lypi.:al) realizalion of off-()iagonal disonlcr. 1l1C lhin lioc does not
account for lauic.:c relaxation, lhc 1hic.:k line (adaplc(] frotn Rcf. l 301}
3.4 Di.mrder-lncluCl'd Kinks 81
A I
n(A, T) =
2
.,
(y,J.vF) (I+
(3.46)
where T
0
is a temperature that is propot1ional to A
112
and which generally is much
smaller than E_ It can he argued and shown hy comparison to numerical simula-
tions [31 J, that the continuum model at T
0
behaves within a good
approximation as the discrete Ising model at zero temperature. Titus, (3.46)
gives corrections to the estimate by Imry and Ma that arc of the order A
31
If the
lattice vibmtions arc treated quantum-mcchaniclly, which prob<lbly is more
propri ate in view of the typical vibmtion frequencies of I o K, the result is very
similar in fom1 to Eq. (3.46); the lowest-order corrections then are of the order
A7ts [541.
Finally, we discuss the consequences of the disorder-i nduced solitons for the
optical and magnetic properties. In the absence of elcctron-clcctron interactions,
the finite density of kinks le<1ds to the appeamnce of a peak in the single-particle
densi ty uf st<1tes at t:=O, because each kink carries an electron state with zero en-
ergy (Section 3.2) [ IJ. At weak disorder this peak is sharp since the distances be-
tween the kinks arc large. so that the splitting of the energies of the electron
state.<> localized ncar diflcrent ki nks due to their mutual interaction is very small
( rv exp ( - t,)). The peak in the density of states should result in a midgap peak
in the optical absorption spectrum. In undoped trluls-polyacetylene, however, this
peak is not observed. This could be ascribed to a small magnitude of the di:;order,
but this is unlikely, because the: avcmge (presumably disorder limited) conjugation
length of trans-polyacetylene is known to be of the order of several tens of car-
bon atoms [60).
Because the on-site Coulomb repulsion decreases the neutral soliton energy
(25, 261 (y, < l ), it increases the kink density (Eq. (3.45)). At the :mme time, how-
ever, the Coulomb interaction shifts the absoavtion peak resulting from the neutml
kinks toward.'> higher cncr<.;ies [25, 261. where it may merge with the peak result-
ing from interband tmnsitions. This may explain the absence of a clear midgap
peak in the absorption spectrum, but it does not reconcile the theory with mag-
netic measurements. The neutral disorder-induced kinks have spin 1/2 and should
contribute to the magnetic susceptibility. However, the observed Curie susceptibi l-
ity for undoped trans-polyacctylcne corresponds to only one free spin per 3000
carbon atoms [ 14), which is much smaller than the avemge conjugation length.
These contradictions between theory and experiment indicate that the consid-
cr.Jtion of totally isolated chains of trans-polyacetylcne, which we restricted our-
selves to in this section. is too strong an approximation. Even if the interchain in-
temctions resulting from interchain electron hopping (611. Coulomb repulsion be-
tween electrons in different chains (62), and exchange by three-dimensional pho-
nons, arc not strong enough to bring us in the limit of the FGM (Section 3.3),
they still play a crucial role in suppressing the creati on of isolated kinks. The in-
terchain interactions tend to favor a coherence between neighboring chains, in
which, for instance, the double bonds on neighboring chains arc aligned. Thus, in-
terchain remove the degneri.lcy of the two uniformly dimcrizcd stales:
82 3 Disorder and Solitons ill Trans-Polyacetylene
The creation of kinks in one particular chain results in the appearance of a string
with the "wrong'' sign of the dimerization (as compared to the nei ghboring
chains) between the kink and the antikink. The energy cost of such a stri ng is pro-
portional to its length r, resulti ng in a linear potential.
V(r) = Kr, (3.47)
that tends to bind kinks to antikinks. The coefficient K measures the strength of
interchain interactions and may be called the string tension.
In order to create a kink-antikink pair in the presence of interchain interacti ons.
the disorder should not only compensate for the creation energy of the kink and anti-
kink, but also for the energy of the stri ng. Therefore, interchain intemctions suppress
the creation of disorder-induced kinks. The thermodynan1ics of interacti ng disor-
dered Peierl s chains and the dependence of the densi ty of kinks on the disorder
strength and the temperature were studied in Refs. 132, 63, 64]. Although. qualita-
ti vely, these models explain the above noted contmdictions between theory and ex-
periment, a quanti tati ve comparison is hard to make: estimates for the interchain in-
temctions have large error bars and, moreover, an independent measure for the dis-
order is not known. As in the above picture the Curie-like part of the magnetic sus-
ceptibility of trans-polyacetylene is given by the susl:eptibil ity of the disorder-in-
duced kink-antikink pairs, a calculation of this quantity and a comparison to experi-
ment may shed more light on the actual situation.
3.5 Concluding Remarks
In this contribution, we discussed effects of disorder on the electronic propet1ies
of quasi-one-dimensional Peierls systeJTL<;, like the conjugated polymer
acetylene. Since polymer materi<1 ls generally are mther disordered and the effect
of disorder on any quasi-one-dimensional system is strong, a proper descri ption of
these materials requires consideration of such effects.
As we have seen, disorder in the electron hopping amplitudes suppresses the di-
merized Peierls state. The mechanism of the suppression, however, depends on the
strength of the interchain interactions. For strong interactions, disorder decreases the
average value of the dimcrization by filling the Peierls gap with localized electron
states. We showed that the most probable fom1 of the wave function of the electron
states lying deep within the Peicrls pscudogap contains two peaks. The "saddle-
point" disorder lluctuation, which induces such a state, has the form of a solitou-
antisoliton pair and the peaks of the wave function are localized ncar the two kinks
of this fluctuation. The "saddle-point" approach allows for a relatively easy calcula-
tion of the low-energy density of states and the absorption coellicicnt.
While for strong interchain intemctions large deviations of the order pammcter
from its avcmge value arc unl ikely, for weak interactions the minimal-energy lat-
tice configumtion of disordered chai ns contains a linitc density of kinks and anti-
3.5 Cvucluding Remarks 83
kinks. These tend to destroy the long-range order of the Peierls state. The inter-
chain interactions bind nearest kinks and anti kinks into pairs and the transition
from the ordered into the disordered state occurs at the tempcmture at which the
pairs dissociate into free ki nks and antikinks. l11e disorder-induced kinks arc neu-
tml and have spin Even when they are bound, they strongly affect the optical
and magnetic propenies of disordered Peicrls systems.
We note that in this contribution, we have treated the lattice motion classically.
In lrtms-polyacetylene, however. the eflect of lattice quantum fluctuations is
rather important, because the CH units are relatively light l65]. In pat1icular, it is.
well-known that the quantum nature of the lattice adds a "subgap" absorption
wing to the low-energy side of the rigid-band absorption spectrum 166, 67]. Sev-
eral authors have modeled the eiTect of quantum Janice lluctuutions by static dis-
order. which was then tn:atcd wi thin the FGM H5. 461. 1l1e underl ying reason for
this view is the relative slowness uf the lallice motion. II should he noted. how-
ever. tl1<1t the strong dCJ1Cndem.:e of the lauice dynamics on the occupation of the
single-electron levels makes it impossible to descri be the quantum lauicc before
and after the absorption process hy one ;md the same static disorder. Incorporat-
ing the quantum lattice effects through disorder gives a fi nite absorption codll-
cient down to zero photon energy. A correct quantum treatment of the lattice,
however, should lead to a finite absotption threshold, given by the energy of a so-
liton-antisoliton pair (46.,/n wi thin the SSH mudd).
For long (infinite) uwu-polyacetylenc chains, the treatment of quantum lattice
fluctuations is very complicated, because many lattice degrees of freedom couple
in a non-linear way to the lowest electronic tr..Jnsitions. We have recently shown
that for chains of up to 70 CH uniL.;, the amount of relevant lauicc degrees of
freedom reduces to only one or two, which makes it possible to calculate the low-
energy part of the absorption spectrum in an essenti ally exact way [681. It re-
mains a challenge to study models in which both disorder and the lattice quantum
dynamics arc considered.
Note added in proof:
A recent theorctic;l analysis of the temperature dependence of the magnetic re-
sponse of neutral disorder-induced solitons 169], has revealed that these solitons
may explain the low-temperature deviation from Curie behavior that is observed
in experiments on Durham tran.v-polyacctylcne l70]. A more stringent test of the
theory would involve extending these experiments to even lower temperatures
(down to I K or lower).
A< k II (I, ,., ('{ lg {'1/1 ('Ill.\"
We would like to thank M. T. Figge and Professor D. I. Khomskii l(>r useful dis-
cussions. This work is pan of the resemch programs of the "Stiehting Scheikun-
dig Ondcr.wck in Nederland (SON)" and the .. Stil:hting vuor rundamcntccl On-
derwck der Materie (FOM)" which arc financially supported by the "Nedcrlandsc
Organisatic voor Wctenschappclijk Onder.wck (NWO)".
84 3 Disorder and Solito1zs ilz Truns-Polyucetylene
References
I. See for n review A. J. Heeger, S. Kivelson, J. R. Sehricffer, W. P. Su. Rev. Mod. Plrys. 19111!. (;(), 781.
2. See, e.g., D. Baeriswyl, D. K. Campbell, S. Mawmdar in Cu11jugated Couduc1ing Polymers, (cd.:
H. Kics), Springer, Berlin, 1992.
3. J. A. Poplc, S. H. W:!lmslcy, Mol. Phys. 1962. 5, 15.
4. W.P. Su, J. R. SchricfTer, A. J. Heeger, Plrys. Rev. u ti. 1979. 42. 1698.
5. S. A. Sov. P/rys. JETP 1980, 51, 342 (ZII. Ekst' Teor. Fiz. 1980, 78, 677).
6. H. Takayama, Y. R. Lin-Liu, K. Maki, Plrys. Rev. H 1980, 21, 231!8.
7. M. J. Rice, Phys. ull. A 1979, 71, 152.
8. W. P. Su, J. R. SchricfTe.r, A. J. Hccger, Plrys. Rev. H 19110,22, 2099; ibid. 1983,28, 11 38.
9. S. Coleman, AIUr. Plrys. (N. Y.) 1976, /01, 239.
10. R. Jackiw, C. Rebbi. Plry.r. Rev. V 1916. JJ, 339!!.
II. R. Shankar, E. Willen, Nttcl. Plrys. IJ 19711. 141. 349.
12. S. lkchata ('/ al., Plry.Y. R: Lt!ll. 19110, 45, 1123.
13. A. J. Epsteinet a/., Mul. Cryst. Liq. Cry.>t. 191!5. 117. 147.
14. H. Shimkawa, I. Ito, S. Ikeda. Mucmmol. Chm1. 19711. 179, 1565.
15. M. Schwoerer. U. Lauterbach, W. Muller. G. Wegner. Clrtm. i>lry.v. uti. 19110, 69, 351).
16. W. P. Su, Sulid Swte Ct"'"'"'" 1980. 35, 1!99.
17. J. E. Hir.lch, Plrys. Ht!l. u11. 1983, 51, 296.
18. O. K. Campbell, T.A. DeGmn<.l, S. Mazum<.lar, J. Stu/. Pllys. 191!6. 43. 1\03.
19. S. Mazumdar, S. N. Dixir, Pllys. Utv. u11. 19113, 51, 292; Plry.v. Hn. lJ 191!4. 21J, 1824.
20. E. Jeckelmann. D. Baeriswyl. Symlr. Mel. 1994, 65. ::! I I.
21. S.T. Chui, T. M. Rice, C. M. V.mnu, &1/id Swtt' Cuurr11utL 1974, 15. 155.
22. B. Horovitz, J. S61yom, Phy.f. Rev. H 1985. 12. 261.!1 .
23. V. Ya. Krivnov, A. A. Ovchinnikov, llr. Eksp. Teor. Fiz. 1986. 90, 7W [Suv. Plrys.-JI:.TP 19116, 6.1,
4 141.
24. J. \\>it, H. J. Schulz., Plry.f. Rev. 8 19118, 17. IOO<iS.
25. S. Kivelsoo, D. E. Heim, Phys. Ht!V. H 1982, 26. 4278.
26. O. K. Campbell, T. A. DeGrand. S. Mazumdar, Plrys. Rev. uti. 1984, 52. 17 17.
27. A.A. Ovchinnikov, N. S. Erikhman, llr. Eksp. Tlrcor. Fiz. 1977. 73, 650 [Sov. P/ry.r. JETP 1977,
46. 340).
28. K. lwano et a/., J. Plrys. Soc. lU(NIII 191!9, 58. 4048.
29. Y. Wada 1!1 a/., Symh. Mewls 1989, 28. 0447.
30. M. V. Most.ovoy, M. T. Figge, J. KnocsLer, Eumplry.Y. uu. 1991, JX, 687.
31. M. V. Mosrovoy, M. T. Figge, J. Knoestcr. Plrys. Rev. H 19911, 57. 21!61.
32.. M. T. Figge, M. V. Mostovoy. J. KllOCSlcr, Plrys. Rev. B 1991!. 58, 2626.
33. R.E. Pcierls, Quantum17rt!of) of Solids. Clarcmlon Pn:ss, Oxfunl. 1955.
34. E. Wiuen, Nuc/. Phy.f. H 191!1, Ill!!, 5 13; ibid. 191!2, 202. 253.
35. S. R. Phillipot, D. Bacriswyl. A. R. Bi.shop, P.S. LunKlahl. Phys. H 1987. 35, 7533.
36. 0 . Gromer, P. Rcinckcr, S)ntlr. Mrwls 1994. 64. 281.
37. H. G. Schu!>ter, Solid Swte Commun. 1974, /4, 127.
38. K. Journ. Phys. C 19117. 2/, 5361.
39. A. A. Abrikosov. L.P. Gorkuv, llt. Ek.ffl. T/r(tJr. f 'iz. l %tl, 39, 171!1 IStv. Plry.<. JEI'P 1961, /2,
1243[.
40. A. V. Balntl>ky. S. A. Trugman. Pllys. Rev. Le11. 1997, 79. 3767.
41. R. Hayn, J. Mcns.:hing, Plly.Y. Rev. 8 1996, 54. R5 199.
42. L. V. Zlr. Eks(l. '11u.'or. Fit. 1963, 45, 364 JSov. Plrys. JEI'P 1964. 18, 2531.
43. B. C. Xu. S. E. Trulinger, Plly.<. Rev. l.ell. 191!6, 57, 3113.
44. R. Hayn. II.J. Fischbcck, Z. Plry.<. lJ 191!9, 76, 33.
45. K. Kim, R. H. McKenzie, J. H. Plrys. Rt'v. Leu. 1993, 7/, 40 15.
46. B. Starke, J. Mcrt>;ehing, Symlr. Ml!t. 19%, 76, 2 17.
47. Sec, e.g., I. M. Lifshits, S. A. Grcdcskul, L.A. P..tslur. lnmxlucticm w tit< '/1wory of Di.wm.kred
Sy.fU'ms, Wiley lntcrscicnce, New York, 19118.
References 85
48. M. V. Moslovoy, J. Knocster, Plrys. Leu. A 1997, 235, 535.
49. B. li;Jiperin, M. Lax, Plrys. Rev. 1%6. 148, 722.
50. J. Ziuar1z., J. S. Plrys. Rev. 1966, 148, 34.
51. I. M. Lifshitz, Zh. 17u!ar. Fiz, 1%8, 53, 743 (Suv. Phys. JETP 1961!, 26. 462j.
52. S. A. Bmrovskii. N. Kimva, Sm: JETP u u. 1981, 33, 4.
53. D. K. Campbell, A. R. Bishop. Phys. Rtl: H 1981, 24.41!59; Nud. Plrys. H 1982.200, 297.
54. M. V. Mos tovoy. SulittmJ' cmd l11stm11mu iu (Still } Ptierls S,\'.lttm.. Ph. D. thesis. University of
Groningen, 1998, M. V. Mo:.tovoy, J. Knocstcr, 1111. J. Mml. Pllys. lJ 1\!99. /J, 16 11.
A. M. Polyul..ov, Gaugl' wul stri11gs, liurwood Acatlcmic Chur, 1987.
56. Sec, e.g . S. Coleman, of .vymmetr): Cambridge Press, Cmnbridge, 19tlll.
57. LN. Bulacvskii. A. I. Bu:Win. D. I . Khomskii. &lui State Ctmmw11. 19711, 27, 5.
58. M. C. D. S. Fisher, Plrys. Ret! lJ 1979. /9, 402.
59. Y. lmry. S. K. Ma. Phy$. Lt!11. 1975, 35. 1399.
60. R. Silbcy. in Polymer.f wrd Rl'lml!d Mmt!rials (&Is. : W. R. S:tlalll."Ck et t1/. ). Oxfortl
University Oxford, 1993.
6 1. D. B<JCriswyl. K. Maki . l'lly:r. Rn: lJ 191111. 28, 206!!; ibid. 191111. 38. 1! 135.
62. S. Jeyadcv, l'llys. Rtl: H 19t0, 28. 3447.
63. D. Khum.,l..i i, W. Gccnstna, M. C:<'dr. Joum. ofl'lry.<. 1996, -16. Sup1l. S 6. 3229.
64. M. Mostuvoy, D. Kh11m:-.kii. Z. l'lly.ik lJ 1991. 10.1. 209.
65. W. V. Su, Solitl Sllltl! Cmrrmwr. 19112. -11. 497; J. E. llirsh, E. R<' l: 1.1!11. 19112. -19,
.
60. 1\ . Aucrhlch. S. Kivd -..m. J>h.' Ht: II 191!6, .1.1. Kl71.
67. Z. Su. L. Yu. /'lrys. Htl : IJ I'JIU. 27. :'iiW.
6K. M. V. Mustuvoy, J. l'hy.v. Ut'l: lJ 1991'. 5.1, 1::! 1157; i/Jirl. 1996 . . 'i-1. 971\4.
69. M. T. Figge, M. Mu:-.rovy. J. Kuuc:-.h:r, Plry.r. Nt!1: H 1999. 5<), L\K!\2.
70. P. J. S. Foot. N. C. Billingham, P.O. Calvcn, S,11rtlr M<'t. 19116, /6. 265.
4 Gas Phase to Solid State Evolution
of the Electronic and Optical Properties
of Conjugated Chains: A Theoretical Investigation
Jerome Comil, Donizetti A. dos Santos, David .Beljonne,
Zhigang Shuai, and Jean-Luc Bredas
4.1 Introduction
At the end of the seventies organic conjugated polymers emerged as very aUr.JC-
ti ve materials after the discovery that their electrical conductivity could be in-
creased by seveml orders of magnitude upon chemical or clcctrochemical treat-
ment referred to as doping in to the physics of semiconduc-
tors) [I j . Extensive theoretical and experimental studies initially addressed the
properties of trcms-polyacetylene [2] and then shifted towards more environmen-
tally stable conjugated chains such as poly(pam-phenylene) (PPP), poly(para-
phenylene vinylcne) (PPV), polythiophcne (PT), poly aniline (see Fig. 4-1 ),
which incorpomte aromatic rings into their backbone [3]. In 1990, the first report
of electroluminescencc from PPV [4} renewed the interest in conjugated polymers
and opened the way to the of electro-optic devices by exploiting their
semiconducting propea1ics and high luminescence yield. Ellicient organic light-
emitting diodes (LEOs) [5- 7] now available in the whole UV-VIS range [8-
1 0) and they are almost into the commercialization stage. Conjugated polymers
arc also used as acti ve clement in light-electrochemical cells I II], photodiodes
[12, 13], and solid-state lasers [ 14-16}.
In spite of outstanding achievements in the field of device fabrication, a full
understanding of the intrinsic electronic and optical properties of the conj ugated
chains is still far from being complete [1 7 j . This is partly due to the fact that the
experimental results strongly depend on the purity and/or morphology of the sam-
ples; hence, much caution h;.ts to be exercised when comparing different sets of
data. In this context, the theoretical techniques of quantum-chemistry can prove to
be useful in order to improve the understanding or the electronic and optical prop-
erties of the chains, for instance to chamclcrizc the nature of the excited states
playing an essential role in the electro-optic devices.
Accordi!lg to a large number of experimental studies, the most stable photogcn-
erated in the lowest excited states of conjugated chains are electron-hole
pairs bound by Coulomb attraction and associated to a local deformation of the
backbone, i.e., polaron-excuons [ I g j. A good insight into the properties of these
species be provided by quantum-chemical our rccen1 theoretical
88 4 Gas Phase to Solid State Evolt11io11 of the Electronic uud Optical Properties
N
n
u IU IV

n
v
Figure 4- 1. Chemical Slruclure of: (I) trwu-polyacclylcnc (II ) poly(paru-phcnylcnc vinylcnt:); (Ill)
poty(puru-pbcnytcnc); (IV) potylhiophcnc; uno (V) poly;milincs.
studies on the lowest excited state in PPV oligomers (i.e., the state acting as
source of light emission in LEOs ami lasers) have all owed us to describe the ab-
sorption [ 19] and photoluminescence (20) spcctm of various PPV oligomers and
to chamcterize the nature and chai n-size evolution of the relaxation processes tak-
ing place upon photoexcitation [21]. The choice of tinite-sire systems to mimic
the properties of actual polymer samples can be justi fied in many instances by the
reduced degree of delocalization o.1 long the chains, resulting from the presence of
physical or chemical impuriti es (22]. To further demonstrate the suitability of the
oligomer approach, we show in Section 4.3 that a detailed analysis of the wave-
function of those excited stales that are optically coupled to the ground state in a
long PPV oligomer, provides complementary information on the geometric and
electronic propenies of the electron-hole pairs. Furthcnnore, we demonstmte that
the photocurrenl action spectra measured for PPV and substituted derivatives can
be rationalized on the basis of the results of these calculations 1231.
We emphasize that some issues, such as the exciton bi nding energy, still remain
controversial; thi s pammeter, which we detinc as the difference between the energy
of a fully relaxed polaron-exciton and that of two separated polarons of opposite
sign, has been estimated in recent theoretical and experimental studies lo be in the
range of 0.0 to 1.0 eV 1241. Si nce the geometric relaxation effects are very similar
for an exciton and two separ.ued polarons l24J, the amplitude of the exciton binding
energy in the solid state results from a fine balance between: (i) the Coulomb aurae-
lion between the electron and hole and (ii) the polarization ell"ecLo; stabilizing the free
carriers (which have been largely overlookell in the past). A unitied picture explicitly
taking these two dominant contri butions into account is still lacking.
Calculations performed on isolated chains appear to be fully consistent with a
number of experimental data. However, many recent experimental studies have
clearly demonstmted that interchain effects can play an important role [25- 32). In
Section 4.4, we rcpon the results of COITclatcll calculations investigating the way
.J.2 Therm:tic:ul Methodology 89
effects modulate the absorption and emission characteristics with re-
spect to isolated PPV chains.
When the chains arc isolated (i n highly dilute solutions or in inert host ma-
trices), the luminescence (which originates from the lowest excited state, as stated
by Kasha's rule [33)) competes with seveml non-mdiative decay channels. In this
case, time-resolved studies reveal that the dynamics of the lumi nescence are iden-
tical to those of the picosecond photoinduced absorption features; this indicates
that intrachain excitons are the only photogenemted species (2&-29]. In the solid
state, various manifestations of interchain couplings have been observed, among
them: (i) a significant increase in the radiative lifetime without any substantial
los.'> in quantum efticiency (28j ; (i i) a lack of correlation between the dynamics of
the luminescence and those of the fast photoinduced peaks (25, 32j; and (iii) a
signilicant decrease in lluoresccnce quantum yield (26). These studies indicate
that intcrchain species present in conllcnsed media even though their nature
and origin is still unclear. Therefore by means of quantum-chemical calculations it
is of interest to try and uncover the nature of photogenerated species
and to mtionali re the somewhat contradictory experi mental observations. Deeper
understanding of the intcrchain ciTects in the licld of organic LEOs and solid-state
lasers should provide new guidelines towards the design of devices with enhanced
efficiencies.
In Section 4.5, we discuss the optical pmpcnies of clusters formed by scxi-
thienyl molecules adopting the herringbone structure characteristic of their crystal
structure (34). The theoretical results arc compared to corresponding experi mental
mcasu remcnlo;.
4.2 Theo1etical Methodology
The ground-state geometry of isolated and intemcting PPVoligomcrs (denoted here-
after PPVn, where 11 is equal to the number of phenylene rings so that 11 = 2 corre-
sponds to the stilbene molecule) arc optimized by means of the semiempirical Har-
tree-Fock Austin Model I (AM I) technique (351. 1l1is met hod is known to provide
geometric parameters in very good agreement with experimental X-ray data 1361.
The chains arc set to be planar, in view of the weak torsions reponed in the solill
stale (371. Note that the grounll-state geometry of the unit cells constit uti ng the var-
ious complexes is found not to be affected by intermolecular interact ions. We deter-
mine the equilibrium geometry in the lowest excited state of isolated ;md interacting
PPV chai ns by coupling the AM I Hamiltonian to a limi tell Configun.llion lntemction
(AM 1/CI) scheme (38), as implementell in the AM PAC package (39). In the case of
scxithienyl molecules, the geometry used is that provided by X-ray data.
On the basis of the optimized grounll-state geometries, we simulate the absorption
spectra by combining the semiempirico.1l Ho.ulree-Fock Intermediate Neglect of Di f-
ferential Overlap (INDO) Hamiltonian lo a Single Conligurution Interaction
90
4 Gus Phase to Solid State Evolution of tlte Electronic a11d Ot11ical Properties
scheme. We use the INDO parametrization developed by Zemer and co-workers [40]
and express lhe electronic repulsion term via the Mataga-Nishimoto potential [41].
In order to avoid any size inconsistency, we systematically involve all the occupi ed
and unoccupied n-levels when generating the singly excited configumtions. The
emission spectra arc simulated on the basis of a very similar approach, except that
the starting geometry is the one opti mized for the lowest excited state in ito; rel axed
confom1ation [20]. It is important to stress that the excited states we refer to are sui -
tably described by the SCI approach; however, a much more elaborate treatment of
the correlation etTects would be required for a complete characterization of the ex-
cited states (including two-photon states) of a conjugated system [42, 431.
Excited-state wavefunction analyses are carried out in the framework of the Inter-
mediate Neglect of Diflcrential Overlap/Single Configumtion Interaction (INDO/
SCI) technique to chamcteri ze the properties of the photogenerated electron-hole
pairs. The SCI wavefunction writes:
cl>sct = r/>o + L C;' r/>i' (4. 1)
i,u
where
0
corresponds to the SCF solution, i' denotes the configuration formed by
promoting one electron from the occupied molecular orbital X; to the unoccupied
molecular orbital x.,; and C/ is the interaction expansion coefficient. For a given ex-
cited state k, we calculate = J ), which represents the probability amplitude in
finding an electron on a given site x,. assuming the hole is centered on the si te x11 = I.
Within the LCAO approximation, this probability is given by L45J:
= 1) = L C;'(k)Z;(l )z..(x .. )
(4.2)
i,u
where Z;(/) [z..(x.,)] is the LCAO coefficient associated to molecular orbital i [a]
on site l Lx .. ].
4.3 Wavefunction Analysis of the Excited States
in PPV Oligomers
The main goal of these calculations is to shed light on the intrinsic properties of
lhe electron-hole pairs generated in those excited states of PPV oligomers that arc
optically coupled to the ground state (i.e . observed in linear absorption spectra).
On that basis. we also aim ut rationalizing the lineshape of the experimental
photocurrent action spectra meu.o;ured by the Cambridge group for PPV and MEH-
PPV, poly(2-methoxy-5,-(2' -ethylhexyloxy-p:.mlphenylenc vinylene) [461. A typi-
cal plot of the frequency dispersion of the short-circuit photocurrcnt recorded in
air and conected for the incident photon tlux shows: (i) a one-to-one correspon-
4.3 Wuvefunctimt Anctlysis of tlte fcited Swus ill PPV 0/igomers 91
dence between the absorption features and the photocurrent peaks; and (ii) a large
increase in the photocurrent around the third absorption band that cannot be re-
lated to changes in the absmvtion coefficient [46].
In order to understand the origin of the large photocurrcnt mea<;ured at high
photon energies, we have simulated the absorption spectrum of a PPV oligomer
containing eleven rings, as shown in Fig. 4-2. We have also computed the wave-
function of excited states located in each of the absorption bands, assuming lhat
the hole is located near the middle or the oligomer backbone, i.e., on site x,,=34
(the sketches and the site labeling are reponed in Fig. 4-2). There is actually
manifold of similar excited states contributing to the total intensity of bands 111:
IV, and V but it suffices here to discuss the lowest in energy.
Figure 4-3 allows us to distinguish between two types of excitations. On the
one hand, we cakulate electronic distributions wi th a Gaussian lineshape that are
centered on the hole position and extend over a few repeat units. This is observed
for states involved in lhe first, second, and liflh absorption bands; there, the
photogcnemtcd electron and hole arc thus signilicantly bound by Coulomb attrac-
tion. These states arc mainly polarized along a direction parallel to the long chain
axis, in agreement with previous theoretical and cxperimcnial data [47, 48]. From
the results, we estimate the coherence length of the exciton in the lowest excited
state (peak I) to be on the order of 5 phenylene rings ( "' 30 A), as also reported
120
100

80
c
::l

.e 60
:::
' (jj
c
2
40
Il l
IV
c
20
0
3 4 5 6 7
Energy (eV)
l; igure .a-2. INOO/SCI-simulalo:tl lim:m ahsorptiun Sl"li!O.: Irum ol' I he dcvcn-1i ng PI'V oligomer. 'lliC vcr
tk ;1l lines n:pl\:scm the uscillal<>r uf tho.: lr.m,iliuns lhal an: tk::.cril"ll!d; lhc silc labeling u:.c<l
for lhc wavcfun..:tiun analyses is 'huwn un lOp.
92
0.40
0.30
,..
-o.20
0.10
a
0.40
0.30
"o.20
0.10
b
0.40
0.30
,.
-o.20
0.10
4 Cas Phase to Solid Stute EvoluJion of the Electrollic and Opricul Properties
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64
Carbon site number
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64
Carbon site number
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64
c C<!rt>on site number
0.40
0.30
,. 0.20
0.10
0
0.40
0.30
,. 0.20
0.10
4.3 Wuvefuncricm Analysis of rite Excirnl ill PPV 0/igomcrs
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64
Carbon site number
0.00
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64
c Carbon site number
93
Figure 4-3. AbSt>lute of the INOOISCI-cak;ulatco cle.:tron wavcfunctions IV'(x_,.K,, = 34)1 cal-
culated for lhc eleven-ring PJ>V uhgomcr as a funclion or cmoon site (hole fix cO on siLc 34) for the cx-
citcO stales corrcspontling LO: (a} the Cir..t Jlcak (3.0 eV}; (b) the set:ono absClrption peak
(3.1! cV); (c) tbc thiro.l absorption Jl<:ill. (5.h cV}; (til Jiurth Jl<:ilk (b.J cV}; u.O (c) the
fifth absorption peak (7.0 cV). The cnct'gies given parentheses rcli:r to the theoretical values.
by recent calculations based on U1e coupled electroni c oscill ator (CEO) representa-
tion (49]. The delocalization of the electronic wavefunction of the excitons is cal-
culated to be larger than the width or the lattice relaxations (on the order or 20 A
according to recent AM 1/CI calculations (20(): this is a typical feature in conj u-
gated chains. A detailed analysis of the configuration interaction expansion of the
excited states reveals that they originate from excitations between the same type
of molecular orbitals, i.e . either between fully delocalized levels (peaks I and II )
or between localized levels (peak IV). characteri:ocd by nodes on the pcmr carbon
atoms of the phcnylenc rings and hence cunlined on the armnatic cycles (50).
94 4 Gas Phase lo Solid Swle Evolution of the Elecltvnic and Oplicu/ Ptvperties
On the other hand, in the third and fi fth absorption peaks, we observe charge-
transfer states, for which there is a fi nite probability of finding the electron and
the hole separated by a few phenylene rings. Such states are polarized mostly per-
pendicular to the long chain axis and are described at the Cl level by a mixing of
excitations taking place between a delocaliz.ed level and a localized level. Recent
picosecond time-resolved measurements have shown that the decay of high-lying
excited states is extremely fast [5 1, 52]. 1l1e data indicate that the emission is es-
sentially from the lowest excited state within I ps; therefore, the probability of
charge tnltlsfer is intimately related to the ability of electron and hole to sepantte
at shoa1 ti mes. Under these conditions, the charge-tmnsfer character observed in
the absorption bands Ill and V is a favorable element for a fast dissociation of the
exciton. This dissociation, however, remains an extrinsic phenomenon since it is
believed to be linked to the presence of impurities; the external agents could for
instance be oxygen molecules giving rise to photo-oxidation of the samples and
the appeamnce of carbonyl groups along the conj ugated chains [53- 551, or water
molecules forming van dcr Waals complexes with the chains, as suggested by re-
cent high-level ab initio calculations !56).
To summari ze, wavefunction analyses allow us to distinguish cxt.:ited slates
where the electron and the hole arc significantly bound by Coulomb attmction
from those where the two carriers are loosely bound due to an dlicicnt charge
separation. We consider that such charge transfer states constitute the origin of the
large photocurrent yields experianentally observed at high energies [46).
4.4 lnterchain Interactions
4.4.1 Absorption Properties of Highly Symmetrical Complexes
In the following section, step by step a qualitati ve picture is formed describing
the impact of intermolecular interactions on the absorption and luminescence of
organic conj ugated chains. The present calculations do not distinguish between di-
mers and aggregates (for which the wavcfum:tions of adjacent chains interact in
the ground state, due to, for instance, solid-state ctTects) and cxcimers (where
overlap occurs only upon photoexcitation) 129].
Firstly, we focus on cofacial dimers formed by stilbene molecules; in such con-
formations, the amplitude of intcrchain interactions is expected to be maximized
157]. Table 4- 1 collects the INDO/SCI-calculated transi tion energies and intensi -
ties of the lowc.;t two excited stales or stilhcne dimers ror an inlerchain distunce
ranging from 30 to 3.5 A.
For large interchain separations (8 A ::-:;; R ::-:;; 30 A), the LCAO cocllicients of a
given molecular orbital ure localized on a single chai n, as intuitively expected.
The lowest exci ted state of these dimers results from a destructive interaction of
the two intrachain tr.1nsition dipole moments, wherea-; a constructive interaction
prevails for the second excited state. This result is fully t'Onsistcnt wi th the molcc-
4.4 lnlerc:lwin lnlemctions 95
Table 4-1. tmnsilion energies, intensities, and Cl of lhe lowest two
ellCitcd St.ates (S1 and 5:?. re.pe.:tively) of a cofacial c.limer forme<.! by Jwo stilbcoc molecules for
various imcn:hain dislilOCes.
lnt .. n:hain st,lle Transition Cl
oil>lance energy (eV) (arb. units)
30 A s. 4.097 0.0 -0.7 H-. L+ l--0.7 H- 1- L
s1 4. 1()(1 2.5 0.7H -. L+ I 0.7 H-l - L
t 5A s, 4.01!7 0.0 - 0.7 H-. L+ 1--0.7 H- 1 ..... L
s2 4. 112 2.5 0.7 H _, L+l -0.7 H- 1 L
10A s.
4.()()jj 0.0 - 0.7 H -+ Lt-1-0.7 H- 1-+ L
s2 4. Ul 2.5 0.7 11 - L+l--0.7 H- 1 _, L
7A s. 4.0:\4 0.0 0.67 H _, L+l -0.66 H-I -> L
Ii- I _. L+l i-{1.21 H _, L
s2 4. 1(>4 2.5 0.6911- 1 _. L+0.69 H _, L+l
6A s. 4.014 0.0 H _, L-0.67 H- 1 _, L+l
H _. L+ I +11. 17 H- 1 _, L
4. 1XJ 2.5 0.69 H- 1 _, L+O.C>IJ H _, L+ I
sA s, 3.91!5 (1.(1 --0.71 H _. L+ll.61l H- 1 -+ L+ l
s! 4.2111 2.4 11.6<J U - L+ H 1.61l H- 1 _, L
4A s, .U!70 0.0 0.!17 H _, L-0.47 H- 1 _, L+l
s! 4.235 2.3 0.77 11- L+l - 0.56 H- I -> L
3.5A s. 3.437 0.0 omH- L
4. 161 1. 8 0.93 H _, L+l
Note thai, at 3.5 A. the lowest imcnsc optical tr.msition involves the fifth excited state.
ular exciton model developed by Kasha 158, 59]. In this weak coupling regime
the calculated optical propea1ies can thus be mtionalizcd by a simple dipole-dipole
interaction model. The energy splitting calculated between the lowest two excited
slates increases when the chai n separation is lowered, despite the fact that the
LCAO cocllicients of a given molecular orbital arc still localized on a single
strand. In this mngc of interchain distances, the Cl description of the lowest ex-
cited state indicates that the probability or linding the exciton on one chai n is the
same for the two stil bene units. However, due to low energy tmnsfer r.11es be-
tween adjacent molecules. the exciton is localized at any given ti me on a single
chain. Consequently, the luminescence signal is chamctcristic of an isolated mole-
cule ;md is not quenched hy 1he intcrdtain cllccts.
In it regime of stnmg interact ion hctween the chai ns no optical coupli ng hc-
twceat ground stale and the lowe!\! cM:iao:d occurs. The absence or cou-
pling, however, has a dillcrent origin. Indeed, below 7 A, the LCAO codlicicnts
start to delocalize over the two chains and the wavefunctions become entirely
symmetric below 5 A Jue to an cflicient exchange of electrons between the
chains. This delocalization of the wavcfunction is not taken into account in the
molecular exciton model, which therefore becomes unreliable at short chain scpa-
r.Jtions. Analysis of the one-electron structure of the complexes indicate.-; that the
96 4 Gas Phase to Solid State Evolution of the E1ectronic and Opticttl Properties
HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied
Molecular Orbital) have the same parity, as is also the case for the HOMO-I and
LUMO+l levels (see Fig. 4-4). The lowest optical transition is described by a
mixing of the H -+ L and H- 1 -+ L+ I excitations, and is forbidden according to
the selection rules; the whole intensity becomes concentmted in the second ex-
cited state originating from the intemction between the H-+ L+I and H- 1 -+ L
transitions. The energy splitting calculated between the two excited states in-
creases continually when going from 30 A down to 3.5 A, as illuslr'clted in Figure
4-5. It should be noted that, at short distances, the splitting is not symmetric with
respect to the optical tmnsition calculated for the isolated stilbene molecule.
The one-electron structure of the cofacial dimer also reveals that the splitting of
the HOMO and LUMO levels arc not equal (0.31 cV and 0.16 cV at 4 A, respec-
tively). This explains the reason why the H-+ L+l and H- 1-+ L transitions have
different Cl weights in the description of the second excited state at short inten:hain
distances. n1e lack of electron-hole symmetry rcllects changes in the of the
overlap between the levels; the LUMO can be rationalized by the
fact that there arc more nodal surfaces in the LUMO wavcfunction than in the
HOMO. Indeed, the overlap of the molccubr orhiwls is made up of the sum of
many atomic overlaps with a product of LCAO coeflicients; the larger the number
of nodal surfaces, the larger the possibility of cancellation of terms, due to the signs
of the products of coellicicnK By extmpolation, in a one-dimensional stack of inter-
acting chains, the valence band can be expected to be wider than the conduction
band. The present results arc highly relevant with respect to charge tmnsport proper-
E
au--.---- L
bg _ _._ ___ II
bg - --.---- L+l
J0. 16<V bu _ _._ __ _
L
au - --.---
Jo.lrcv
ag--'---
II
Hoi
figure 4-4. S.:hcmaaic rcpreM:ntaliun of the onc-<:lcctron struclun: uf a single Milbcnc molecule and
thai uf a dinlCr funned by rwo sca>ar.lloo by 4 A. 1111: JNOO-calcularcJ CIK.'Jl!.Y split of
the HOMO and LUMO when suing from lhc isul:uctl mulcculc lu rhc <linter au: ilbo given.
4.4 lnterc:lwin lutemc:tious 97
4.5 -r------ - - ----- -----,
4.2
>

>-
3.9-

Qj
c
Qj
c
0
:0::::
;;;
3.6
c

.._
3.3
2 4 6 8 10 12 14 16 18 20
lnterohain distance
J."igurc 4-S. INOOISCIGlk:ul<lh.'tl lr.Jit\ilion encrgil!!> or lhc IOWC!ol two uptical or a .:of:JCial
di mer hy lwo muk-.:ulcs a funcl ion uf Tile horironlal line rdi:l'l>
lo lhc lr.lllsiriun energy nf lhe iMllarcJ molc.:ulc. Nure tllal the upper value a1 3.5 A
lo rhe tr.snsilion In the riflh excircd stale, which lhc lowesr intense abMlrplion f.:.tlurc.
ties in the solid stare, since they are consistent with the typical observation that in
conjugated polymers holes arc more mobile than electrons.
We now address the way the properties, calculated for highly symmetric con-
fomlations, arc affected by the size or the intem,ting unit To do so, we have
built complexe.-; formed by two PPV oligomers up to 7 phenylene rings
and separated by 4 and 6 A, respectively. In general, the trends prevailing for in-
teracting stilbenes hold true for the longer chains. However, two main differences
occur:
(i) The critical distance connecting the regime of weak and strong interaction
depends on chain length; this evolution agrees with earlier theoretical studies
which have shown that mcxlels b;L-;cd on the dipole-dipole approximation break
down when the interchain di st<tnce is than the size of the interacting unit
[60-62]. Interestingly, this cri tical distance saturates around 14 A; this value can
be reasonably associated to the average separation between the electron and the
hole in the excited state;
(ii) the second main dillcrcncc is that the spliuing between the two lowest ex-
cited states, calculated al a given separation distance, tends to decrease non-linear-
ly with chain length, <L'i shown in Figure 4-6. Note that this evolution contrasts
98 4 Gas Phase to Solid State Evolutio11 of tile Elec:tr<mic: and Opti,a/ PIVperties
with the molecular exciton model which predicts !he splitting to be proportional
to the oscillator strength (hence, to increase with chain length). These results can
be simply rationalized from perturbation theory by the fact that: (i) the nonnalized
n-LCAO coefficients decrease with the number of sites L (as L-
112
); (ii) the rele-
vant matrix elements arc constituted by a product of four coefficients (thus pro-
portional to L-
2
); and (iii) the dominant matrix tem1s are diagonal and their num-
ber is proportional to L. Therefore, the sum of the dominant terms describing the
strength of the interaction is proportional to L-
1
Though reduced, the amplitude
of the splitting is expected to be significant for chains having a size correspond-
ing to the typical effective conjugation lengths encountered in polymer samples.
However, for polymers that can be effectively described as an infinite chain, such
as MEH-PPV in highly drawn and oriented polyethylene [631. the splitting could
become extremely small. In such a case, the interaction would lead to a red-shift
of the lowest optical transition, as suggested by recent highly-correlated calcula-
tions perfonned on intcmcting polyenes [601. Accordingly, the luminescence
would not be quenched by the mechanism proposed for finite-size systems. We
have also to bear in mind that the shifts and splitting discussed above become
larger when increasing the number of neighboring chains, as discussed below.
0.40
0.35
0.30
0.25
>

0.20

a.
(/)
0.15
--- -------------
-----
111' /
/
/
0.10

0.05
0.00
0.02 0.04 0.06 o.ea 0.10 0.12
1/n
Figure 44). Evolution of lhc INDOISCJ-cakulalcc.l bclwccn lhc lowest Jwu optical
of l'Ofacial l.lintCr.> fomtct.l by Jwo PPV chains as a funcliun of lhc inverse numhcr or ( 1/u)
along rhc conjugated backbone of 1hc oligomer. The lhcon:tical results an: reponed for intcn:hain c.Jj,..
lance:. of 4 A (open circles) :mc.l (l A (lillct.l circles).
4 . .J /mere/will lntemctimrs 99
At this stage, we can draw seveml important conclusions regarding the absorp-
tion and emission properties of cofacial dimers formed by two identical PPV
chains:
(i) the lowest symmetry-allowed optical transition involves the second excited
state (or a higher-lying state at short interchain distances, as shown in Table 4-1 at
3.5 A) and is blue-shifted with respect to the isolated molecule. Such an evolution
has been observed experimentally for stilbene molecules [64] and for other conju-
gated systems It should also be noted that the blue-shift expected from
our calculations could be masked by additional c!Tccto; such as confom1ational
changes upon interaction; for instance, an increase in the planarity of the conju-
gated backbone characteristic of a gas/liquid to solid phase transition could result
in a red-shift of the lowest optical transition;
(ii) due to the absence of optical coupling between the ground and the lowest
excited states, interactions arc expected to strongly affect the lumi-
nescence efficiency, however, more so in molcculur m<tleri als than in polymers
since the amplitude of the interchain effect-; decreases with increasing chain
length.
4.4.2 Photolumim.-sccncc Propeaties
of Highly Symmetrical Complexes
In the previous discussion, we have not considered Ulc possible influence of the
large electron-phonon coupling that is a trademark of conjugated systems; for in-
stance, the equilibrium geometry in the lowest exci ted state can differ signifi-
cantly from that in the ground state [20, 68, 69j. It is therefore of interest to in-
vestigate the role played by relaxation cll'ecLo; in the lowest excited state, assum-
ing there is enough time for them to occur.
As expected, the AM 1/Cl-optimizcd geometry of a cofacial dimer formed by
two largely sepamted stilbene molecules indicates that one chain possesses the
typical ground-state geometry of an isolated unit while the other strand presents
an equilibrium geometry characteristic of a si ngle stilbene molecule in its lowest
excited slate. When the imcrchain distance is lowered, the lanicc defomlations re-
main highly asymmetric; thi s is illustmted in Table 4-2 where we have collected
the C-C bond lengths in the two stilbene units at various separation distances.
Even though the chain, which is initially in the ground-state geometry, becomes
increasingly affected by the intermolecular inter.1ctions when the chain sepamtion
decreases, the major relaxation phenomena always take plat:e over a single chain.
The mostly intrachain ehamctcr of the exciton, also suggested by other theoretical
SlUdies [70, 71 ], can be understood as driven by the Coulomb anraction between
the electron and the hole, which is maximized when the two charge canicrs arc
on the same chain. Since there is an equal probability of finding the relaxed exci-
ton on each of the two ch<.tins, it is wm1h stressing that the most gencml solution
should be described beyond the Born-Oppenheimer approximation ao; a linear
combination of the asymmetric states ('f', = t/1
1
,.(R,.) and
100 4 Gas Plrase to Solid State Evolution of the Elect runic and Optical Pmperties
Table 4-2. Ground-stale and lowCSI-cxcitcd stale AM 1/CI-optimizcd C..{: bond lengths (in A) in a
cof:JCial dimer fonncd by two stilbene molccute.s separJJed by 3.5, 4.0, and 4.5 A, rcspa:livcly. Tite
geornctric-JI par.uncters for single molecules arc reponcc.l in the right-harld-snlc column.
IU

3.5 A 4A 4.5A co
Ground stale
R l 1.397 1.396 1.396 1.395
R2 1.3!18 1.390 1.391 1.392
R3 1.415 1.410 1.409 1.407
R4 1.394 1.394 1.394 1.394
R5 1.391 1.392 1.393 1. 394
R6 1.411 1.406 1.404 1.402
R7 1.432 1.442 1.447 1.453
R8 1.366 1.355 1.350 1.344
Lowest excited stale
Rt 1.401 1.403 1.403 1.404
R2 1.3!!3 1.3!11 1.3!!1 I.] I!{)
RJ 1.424 1.427 1.429 1.4:10
R4 1.394 1.394 1 .. 193 1.:193
R5 1.3lll! 1.3lll! 1.31!!1 1.3!17
R6 1.420 1.424 1.425 1.426
R7 1.412 1.406 1.404 1.403
R8 1.388 1.395 1.398 1.400
tfozr(Rc), where we have explicilly noted that the equilibrium geometry of the two
molecules is di fferent. However, when the dimer is put in a condensed phase, dif-
ferent solvent shifts of the two stales can occur and the correct description is ex-
pected to be VJ, and '1/b and notlVJ, 'llh/.../2]1571.
The self-localization of the electron-hole pair is also supported by a detailed
analysis of the wavefunction of the lowest excited state of a cofacial uimer
formed by two live-ring PPV oligomer'S. In analogy to what we have previously
described, we have computed the probability amplitude lv(x.,,x
11
= 16, chain 1)1 of
finding the electron on a given site Xc when lixing the hole on site 16 in the mid-
dle of chain I of the dimer (sec Fig. 4-7). The corresponding wavefunction repre-
sents a Gaussian lineshapc centered on the position of the hole. The probability of
finding the electron on chain II, i.e., of creati ng .an interchain exciton, is only
6.7% when the two oligomers are separated by 4 A. This probability evotves ex-
ponentially with the intermolecular dis lance R going from 28. 1% at 3.5 A down
to 0.6% at 4.5 A (inset of Fig. 4-7). We emphasize that charge tmnslcr-excitcd
stales are observed at hiohcr energies, the lowest of those being 0.88 cV above
b
the lowest exci ted slate for the two chains sepamtctl by 4 A. In these states, there
is a large probability of finding the electron on chai n II when the hole is tixctl on
chain I, as illustmtcd in Figure 4-8.
0.4
::::: 0.3
c:
ro
.s::.
0
cD
0.2
..-
II
><c.
><.
0.1
0.0
0.4

c:
0.3
ro

cD
..-
0.2
II
><c.
..

:r 0.1
4.4 fiiiCtt'fWill ftlii!YCICtiOIIS
chain II
30
A
25

A
....
ctto
5
A
0
A
....
3.5 4.0 4.5
R(A)
chain!
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Site
101
Figure 4-7. INDO/SCI simulation uf the li o.a cx.:iloo J.tatc wavcfum:lion in a cufacial dimcr
funned by IWO fiv<.'-f"ing PPV oligumcrs. hv(x., .fA = I fl. chain 1)1. an intcnuulccular distance
o.f 4 A. l111(.r,.'.r = 16. d':'in hi rcpec!\Cnls the pmbahility ampliluc.lc of linding an ckctrun on a given
SJIC x, a.'i.-.ummg the hole 1s t:cntc":d lHl l(i of chain I of the dimcr (the Ulhcr chain hcing rcfem:d
IO c.:hain II). Tile site labeling is rcpn:-cntcd in the lup panel. TI1e inset the evolution of the
pruhability lo L'I'Calc an inlcn:hain Cllc.:ilon, fl rr. a function ur ll1e intcnnulccular dbtancc N. The H
arc given in A.
The above results indicate that the selection rules are relaxed when the geome-
try modifications taking place upon photOt::xcitation arc considered. Although the
tmnsition dipole moment between the grounu state and the lowest exci teu state re-
mains small, the luminescence is no longer entirely quenched by U1c inten:hain in-
102 4 Gus Phase to Solid Swte Evolution of the Electronic und Optical Properties
0.4 .,.------------------,
chain II
-
0.3
.
Ill
.r:.
0
w 0.2
....
h
<:
)(
..

0.1
;t
0.0
0.4
chain I

c
0.3
'iii
.s::
0
<t5
....
0.2 II
<:
)(
..
)(

0.1
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Site
Fagur-e 4-8. tNOO/SCt sinJUialion of lhc wavcfun..:lion = 16. Ill of loc
lransfer-excilcd Slalc in a cofacial dimct formed by lwo live- nng PJ>V ohgomcrs separollcd by 4A.
IIJI('<-Ail = 16, chain I)J lhe probabilily ampliludc in an eiCCiron on a given sil.e X..
assuming the hole is ccnlercd on 16 of I. 1lle site labchng s the same as Uta! rcp!lf'led on
lop of Figure 4-7.
Leractions and is red-shifted wilh respecl to the emission of the single molecule.
This is illustr..lted in Figure 4-9 where we have reported the
absorption and photoluminescence spectra of a cofacial dimer by two stil-
bene molecules separdled by a huge distance and by 4 A. In the reg1me of strong
interactions, the results also show that the shorter the interchain di stance is, the
larger the red-shift of the emission peak. The optical coupling between the ground
stale and the lowest excited state is simultaneously reduced due to the fact that
the wavefunctions become increasingly symmetric for low chain scpamtions. The
red-shift and the attenuation of the emission signal predicted by our calculations
appear to be fully consistent with recent experimental measuremcnls the
luminescence properties of PPV chains as a function of an external apphcd pres-
sure, i.e., more or less as a function of intcrchain distance [72[.
4.4. lntcrdwin lntemctiuns
103
Emission
3.0 3.3 3.6 3.9 4.2 4.5
Energy(eV)
Figure 4-9. INOO/SCI-simulaled absorplion :111d emission spcclra of 1wo stilbene molecules wilh a
huge inlen:hain (solid lines) and lho.o;c of a cofacial dimcr fonned by lwo slilbenc chams scp-
aralcd by 4 A (dolled lines) .
!he main of this section is that intcrchain couplings have not neces-
to be to a substantial decrease in the lumi nescence quantum
y1eld. As a mauer of fact, a decrease in the r..1dia1ive decay rate increases the rela-
tive importance of multiple non-radiative decay routes. In contmst, the effective-
ness of these channels can be greatly limiled by the confinement of the excitons
due to, for example, the fonnation of cxcimers or 10 1he migmtion of the photo-
generalcd species towards regions where the chains arc strongly intcmcting (i.e.,
!he low-energy domain of the samples), as suggested by recem experimental stud-
Ies [30, 3 1). The actual luminescence thus result-; from I he balance of these contri-
butions. In this context, the significant increase in the mdiative lifetime of the lu-
mi nescence in recent studies [28, 73 I can be altributed to the joint in!lu-
ence of a process and of the weak optical coupling between the
ground stale and the lowest excited slate.
4.4.3 The Influence of the Numbea and Relative Orientations
of the I ntea-acting Molecules
n1e next step in our study is go to beyond the mere consideration of two mole-
cules in a highl y symmetric configuration and to adJress the changes occurring in
the calculated oplical properties when increasing the number of interacting units
and when modulating the relative orientations of lhc chains. In this context, we
have lirst investigated the propc11ics of one-dimensional slacks conlaining up to 5
104 4 Gas Phase to Solid State Evolution of the Electronic and Optic:al Pro{Jerties
stilbene molecules at various separations. For large interchain distances, we ob-
serve that a cluster containing n units gives rise to a splitting of the lowest ex-
cited state of the isolated molecule into n non-degenerate states. This leads to the
formation of an exciton band for an infinite array of units, as elegantly discussed
by Kasha [58, 59). The entire oscillator strength is concentrated in the
between the ground state and the highest excited state of band, leadmg to
an hypsochromic shift of the lowest symmetry-allowed optacal tmns1t1on. ln con-
trast, the lowest excited state is not optically coupled to the ground state
found previously for the cofacial dimers) and is with respect to sm-
gle molecule. The width of the exciton band With the number of _mter-
acting units but tends to saturate mpidly; this evolut1on the
Hucke! calculations would describe the formation of bands m terms of mtmcham
or interchain transfer integrals. The same picture also prevails in the regime of
strong interactions except that in some instances sevcml high-lying excited states
are cakulatcd to be optically coupled to the ground state.
Regarding the emission properties, AM 1/CI cakulati!>ns. performed on ... clus-
ter containing three stilb\!ne molu:ulcs separ..ttl!d by 4 A. show tha_t the mam
tice deformations take place on the central uni t in the lowest cxctl!tl slillC. It s
therefore reasonable to assume that the wavcfunction of the relaxed electron-hole
pair extends at most over three intcr.u:ting chains. The results further demonst:..1tc
that the weak coupling calculated !>\!tween the ground state lowest exCi ted
state evolves in a way very similar to that reported for cofactal duncrs.
In order to address the possible inlluencc of positional disorder, we have cho-
sen to analyze the way basic operations such as translations and rotations affect
the properties calculated for highly symmet_ric _configumt_ions. This_ approach could
provide guidelines to prevent the loss of sJgmficant opt1cal couph_ng the
ground stale and the lowest exci ted state, and hence the quenchmg of lummes-
cence in the solid state.
We start from a cluster formed by two or three intemcting stilbene units sepa-
rated by 4 A. Small tmnslalions of any unit along the chain axis or in direction
tmnsverse to the chain axis (see Fig. 4-10) is a very inefficient process to recover
a significant optical coupli ng. to _the this is
explai ned by the fact that the rclat1ve onentatJOns ot the transtlton dtpolc mo-
ments (which arc polarized along the chai n axis) are not changed. In all CilSCS, the
lowest optical tmnsition is weakly coupled to the ground and the energy
splitting between the lowest two excited states is di rectl y related to the overlap
between the wavefunctions of the two units.
The second set of opemtions involves rotating the molecules. Starting from a
coracial dimer consisting of two stilbene units separ..1ted by 4 A. one molu:ulc
was rotated: (i) in the stacking plane an axis perpendicular to the molecu-
lilr planes and passing through the center of the vinylcnc linkage; and (ii) around
iL'i long axis, thus breaking the pamllclism between the In the
Iauer case. the calculated properties arc very similar to those obtilJOed lor the co-
facial dimer because the relative orientations of the tr..lflsition dipole moments arc
still not modi fied. In the first case, we observe that increasing the angle between
the chain axes leads to a reduction of the splilling between the lowest excited
z

'tc
.
II
----.....
4.4 lnterclrui11 lnteractio11S

/ ------7 /
v
-X I>

105
Figure 4-10. Skcldl of applictl tn a cufacal dimcr funned by two Sl ilbcnc moJ.c:QJ Jcs
SCpar.liCd by 4_ A whcu invt.-stigati ng the role ur Jisonler. The an: induuxl by:
(I) the nf unc molco.:ulc along Jhc chain-axis clin:clion; (II) 1hc 1r.1nslatiun of one molt.'t:ulc
along the transvcr.;c axis: (I ll) the mtation of one stilbene uniJ around its long axis; ancl (tV)
the n>talu.Jil ol one sulbcnc molecule around the ux1s while keeping 1hc p;
1
rallclism between
the molecular
states, due to a _decrease in overlap clliciency. In addition a tmnsrcr, from
the second state to the lowest one, of the electronic coupling with the
ground state ts also observed, as shown in Figure 4-11. In such confom1ations
the intemctio.n two chains thus leads not only to an intense
band _wtth to the single molecule but to the
of a _weak red-sh1fte<..l pcil k (t.e., a t'\!d tai l in highly disordered samples). The cal-
a supramolccular architecture chamcterizcd by a perpen-
dicular ol the long chain axes tums out to be an efficient confi guration
to J'\!ducc lummcsccnc.:c quenching in the solid state. This is due to the fact that
the lowest two excited states then degenerate and that the whole osdllator
involved in absorption is conserved in emission. Such pc
1
pcndicular ori-
entattons are encoumcred li>r instance in spiro-conj ugated molecules 1741.
In summary, _over a lm-gc r..1ngc or intcrchain distances, the most stable species
111 excited Still e of clusters formed by m<>lu:ulcs
arc mostly_ wtth :m The al so show that po-
laron-pmrs. ill so rclcncd to iiS mtcn:hatn cxcitons (con-csponding to .. positive
106
4 Gas Phase to Solid State Evolllticm of the Electrcmic and Optical Properties
4.25 -.::-------------,
--- --0-
--
--'() ......
..........
..........-a..
4.20
> 4.15

.........
.........
.....Cl,.
......
4.10
Qj
c:
Q) 4.05
c:
0
4.00
..,

3.95
0 10 20 30 40 50 60 70 80 90
Rotational angle (degrees)
2.5
Iii

c:
2.0
:;) 1.5
.e
.!!.

c: 1.0

0.5
0 10 20 30 40 50 60 70 80 90
Rotational angle (degrees) . .
' .. I nnor "''rt ) an0 reJaJCd llltCru.l
Fi
4-ll INDCVSCI-calculatcd evolution ol the eucrg.cs ,u,.,- v- .
1
.... ol
agure 1 f ofacial Oimcr fom1cd by IWO .,.:nc
111

lies (bonum pan) of lowc.'l opufcahl "tx: lwccn the long molecular axes. when f l)-

1
. aralcO by 4 A a funcuon o I c uh...ur. o
11
1
, .. IV of
ocu cs scp I . . I . 0 the slacl>ing axis ;IIIJ keeping the muh:.:ular planes c ,ca>oe
aatmt: one 111\1 ccu e aruun . he S. s (S. _ s l tr.m,,llllll
4- 10). Open M!uafl:)o (doM.-d cir\:IC.\ ) to I .- 2 J I .
4.5 Clusters of Sexitltienyl Molecules 107
on on one chain in Coulomb aumction wilh a negative polaron on an adjacent chain)
can be generated in charge transfer-excited states. 1be latter are found at energies
higher than those of the lowest intr.1chain-cxcited smte. Since the average separation
between the electron and the hole in a polaron-pair is not expected to be significantly
different from that in an intrachain exciton, the polarization effects should not
strongly stabilize the energy of the charge transfer-excited stales with respect to that
of the lowest excited state. The fom1ation of polaron-pairs, observed in recent ex-
perimental studies [75 J, thus appears to have an extrinsic origin since it js related
to the presence of impurities giving rise to intcmctions between chains of different
nature and leading to a reversal in the ordering of intrachain versus interchain exci-
tations. Further theoretical and experimental studies :.u-e defi nitively required to un-
derstand the panu11eters governing the occurrence of charge and energy tmnsfer be-
tween intemcting chains in more detail. In actual samples, the decay in luminescence
is intimately to the concentmtion of intmchain excitons while the dy-
namics of the picosecond photoinduced absorption features results from the contri-
bution of both intmchain excitons and polaron-pairs; this rationalizes the fact that the
dynamics of the.'\c two processes is genemlly different. Depending on the nature of
the samples, the dominant photogenemtcd specie.-; could be either int r.1chain excitons
or polaron-pairs. 1l1is hus strong implications on the properties of the samples; as a
matter of fact, upon decreasing the interchain distance, the luminescence ctriciency
of chains supporting intrachain excitons is reduced whereas luminescence is ex-
pected to increase if polaron-pai rs arc mostly present since short distances would
favor their recombination.
Several strategies that could be followed to prevent a substantial decrease in lu-
minescence elliciency in condensed media emerge from the above results.
Approaches that can be suggested are: (i ) to minimize the splitting between the
optically-forbidden and optically-allowed excited states; this can be done either by
using long chains with highly dclocalized excitations or by separating the chains
with the help of bulky substituent-;; and (ii) to reduce the diffusivity of the exci-
tons to lumincl;Cence-qucnching traps, by fom1ing aggregation zones acting as
low-energy centers from which emission is allowed.
4.5 Clusters of Sexithienyl Molecules
We now turn to an investigation into the optical properties of dusters of u-scxi -
thicnyl molecules adopting the heJTingbone strut:ture. us determined by X-ray dif
fraction (sec Fig. 4- 12) 13ll. 1l1e theoretical results arc compared to relevant experi-
mental data, whit:h allows us to assess the reliability of our theoretical approach.
Various clusters comaining between 2 and 6 units are considered. We have tirst es-
timated the amplitude or the Davydov splitting as <1 function of configur:ation (this
splitting is dclined as the difference between the energy of the lowest excited state
and that or the higher-lying state strongly coupled to the ground state [761).
108
4 Cas Plrase w Solid State volr1tion of the Electrrmic wrd Optical Properties
a
c
b
Fi urc 4-l:Z. Sketch of the rclalivc orientatiuns of the scxithicnyl in the crystal and n:pre-
se!:taaion of the crystal axes a. b. and c discussed in the text. Note thai the layers arc Slacked along
the a
When consideri ng sexithienyl molecules located in the same layer no in-
temction between molecules aligned along the chain axis), the md1eate that
the Davydov splitting increases with the size of cluster but, m sys-
tems we have considered, tends to gel to 0.5 cV, as_
in Figure 4-13. For a cofacial dimer, the energy dtfterence IS _very scnstt1ve to the
interchain scpamtion; it evolves frotn 0.2 to 1.0 eV when gomg from 4 to 3.3 A.
In all cases, the lowest excited state is onl y weakly to the ground
due to the Jack of significant angles between the moments ol
units in the herringbone structure. Note that the amphtude ol the sph_t-
ting is largely dominated bj'
distances arc around 3.5-4 A) and 1s httle aflectcd by the mteract10ns_ between ad-
jacent layers, which are by A. We also obscr-.:e F!g, 4-1_3) that
the lowest charge transfer-excited state IS located the h1gh-lymg
state, as suggested by previous calculations and conlmncd by clcctroabsorpt ton
spectra rccordi!U on a scxithicnyl crystal 177].
4.5 Clusters of Sexithienyl Molecules
3.2
3.0
2.8

>-

Q)
c
w 2.6
2.4
IT --
- e:, . .... .
[), ........... 6
---
--
....a---
-a----0
2.2 -t---.-----.---r----r---.----!
2 3 4 5 6 7
Size of the aggtegate
109
folgurc 4-13. Evolution with the sit.c ul the scxithicnyl dust.: of the excitation cncrg1<.-s frum the
ground to the lowest exci ted laic (open cin:les}. lu the high-lying excited Slate stl'\lngly coupled
to the ground (open MJuan-). and lu the luwcst tnmsfcr-cx.: itcd stiltc (open triangles). In
all .:uses. unly intr-.tlaycr into.:ra.:1iom have l:x."Cn .:onsK.k:ro.:d.
The dominant features of the experimental optical spectrum of the scxithienyl
crystal is an absorption onset at 2.28 e V, pola1i:ocd along the b axis, and an in-
tense vibronic progression at higher energy wi th the 0-0 peak at 2.60 cV [76j, po-
larized along the c axis. We report in Figure 4- 14 the theoretical absorption spec-
trum of a complex containing six units on top of each other within the same
layer. The main goal of this simulation is to reproduce the overall shape and the
main absorption chamctcristics of the sexithienyl crystal; consequently, we have
not taken into account the HerLbcrg-Tcllcr coupli ng (i.e. , vibronic borrowing) pro-
viding intensity to the low-lying excited states. Our approach is based on the dis-
placed harmonic oscillator modd where the Fnmck-Condml factors fm a given
mode arc applied only to the states si:;nificantly coupled to the ground state and
expressed for cxcitons by [20, 781:
(4.3)
and for dtargc-transl'cr cxciaons by [791:
llO 4
Gas Phase to Solid Stute vol11tioll of the Electro/lie wtd Optical Properties
-:-
::l
4000
3500
3000
c polarization
b polarization
.!!. 2500
c
0
a
0
2000
1/)
J:l
l!l
n;
G)
X 50
--
c
1500
...
:.:;
1000
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
Energy (eV)
F. 4-1
4
. JNOOISCI-sintutalcd absorpt ion spcctrJ of a cunta.ming six top of
e!'h other within the same layer. for polarizations along the b (dOlled hnc) anc.l c lmc) axes.
(4.4)
In these expressions.
11
is the vibmtional quantum. number in the exci ted state,_ bu
represents the displacement parameter a'isociated wtth the mode for a neutral
f on (b"f/l = S is the corresponding Huang-Rhys factor); b+ and b_ the parameters
lor the positive and negative polarons fof1!ling the charge transfer :me
l . based on the usc of the single dommant mode at 0. 18 eV observl!d 10 Raman
(80}; the displacement are _taken a., adjustabl_:
chosen to match the experimental vibrontc (bu= 1.18, b+-:-b_- 0.55
10
. ) nd the line broadening is fitted to the expenmental rcsolutton. .
our case, a d F. 4- 14
1
char
The INDO/SCI-simulated absorption spectrum reportc m 1gure . s -
acteri:t.ed by a weak absorption at 2.24 eV polari:t.ed along the axts and a
tron vibronic prooression with the 0-0 feature at 2.58 eV, polanzed I c _c
s - gThese results
0
are in remarkable agreement with the correspondmg
data; they also provide a Davydov spliUing cV the
of the first band and the 0-0 peak of the mtcnse v1bromc progresston, wh1lc ,a
.
1
f 0 31 eY is obtained experimentally (761. Our rcsuiL'i cast doubt on other
va ue o .
1
- 1 v 11
recent experimental estimates of the Davydov sp attmg, > e -
4.6 Concl11sio11s u11d Outlook Ill
4.6 Conclusions and Outlook
In this chapter, we have tried to demonstrate that the computational methods of
quantum chemistry are useful tools to provide an understanding of the intrinsic
electronic and optical properties of isolated and interacting conjugated chains.
First, we chamcteri:t.ed the electronic properties of photogenerated electron-hole
pairs in isolated PPV oligomers, through a detailed analysis of the wavefunctions
in the excited states. This study gives access to how the electron distributes
around the hole in a given excited state.
In the second step, we went beyond the mere considemtion of isolated chains and
started investigating the properties in supramolecular architectures. We showed that
the changes occurring in the absorption and luminescence properties when going
from an isolated molecule to a duster containing several intemcting units can be
unmveled with the help of quantum-chemical cakulations. A geneml picture de-
scribing the inlluence of intennolecular inter:u.;tions was provided on the basis of
calculations by varying in a systematic way the sire, the number, and the relative
orientation of the conjugated chains; str.uegies were suggested in order to avoid a
substantial decrease in lluoresccncc quantum yield in condensed media. The reliabil-
ity of our thl.'Oretical approach was fut1hcr established by the remarkable agreement
observed between the calculated properties of clustl!rs torrned by sexithienyl mole-
cules and the corresponding experimental data. This reintorces the accuracy of our
melhod in using an INDO/SCI approach to shed light on the absorption prope11ies or
interacting systl!ms, provided that the relevant excited states arc suitably described
by single excitations (note that thl! interest or such calculations is rcinlorccd by
the fast satumtion of the I!Uiculatcd properties when increasing the size of the clm-
ters and their applicahility to a large class or compounds). We have also pointl!d out
that the chemical impurities are expected to play a major role in the dynamics of the
excited states, by inducing the formation of charge-transfer excitons. Although dis-
sociation processl!s ure highly desirable for the opcmtion of photodiodcs, much has
still to be learnt on the parameters governing the occu1Tence of charge transfer be-
tween adjacent chains. This is without any doubt a new challenge for futurl! joint
experi mental and theoretical studies.
Ackno1vledgements
This work has been partly suppmted by the Belgian Prime Minister Oflice or
Science Policy (SSTC) 'Pole d' Attmction lntcruniversitairc en Chimie Supr- .lluolc-
culaire el Catalyse Supramol&:ulairc (PAl 4/1 1 )', and the European Union Tmin-
ing and Mobility for Rl!scarchers (TMR) network program on Synthetic Electroac-
tive Organic Architectures (SELOA), the Belgian National Fund for Scicntitic Re-
search FNRS/FRFC, and an lBM Al:adcmic Joint Study. JC is Charge de Re-
cherches and DB is Olerchl!ur Qualilic or the FNRS. We ackMwlcdge stimulat-
ing discussions and collahomtions with R. H. Fril!nd, A.J. Hccgcr, A. Kohler, E.
Lunedci, M. Muccini, R. Silbey, and C. Taliani .
112 4 Gas Pltuse to Solid State Evolution of the Electmnic and Optical Pmperties
References
1. H. E. J. Loui s, A. G. C. K. A. J. Hceger, 1. Chem. Soc. Cllem.
CommwL 1977, 578.
2. A. J. Hecger, S. Kivclson, J. R. SchrieiTer, W.P. Su, Nev. Mod. PIJy.r. 1911S, 781, 1981!.
3. Handbook of Conducting Plllymers. 2
00
Edition (Eds.: T. A. Skotheim. J. R. Reynolds, R. L
Elsenbaurner), Dekker. New York 1997.
4. J. H. D. D. C. Dr.!dley, A. R. Brown, R .N. Marks., K. Mackay, R. H. Friend, P. L
Bum, A. D. Holmes, Nature 1990. 147, 539.
5. R. W. Gymcr, R.H. Friend. A. D. Holmes, E.G. J. Stating. R.N. Mark..;, C. Taliani , D.D. C. Drnd-
ley, D. A. dos Santos, J. L. Dredas, M. LOgdlund, W. R. Salancck, Nature 1999, 197, 12 1.
6. R. W. Gymcr. E11dcawmr 1996, 20, 115. . .
7. J. R Sheats, H. Antoniallis, M. Hoeschen. W. Leonard. J. M1llcr, R. Moon. D. Rullman. A. Stocl..-
ing. Scie11cc 1996, 273, 1!&4. .
8. M. Bcrggn:n, 0 . lngan!i.,, G. J. Rasmusson, M. R. Andersson, T. HJcnbcrg, 0 . Wcn-
ncc:ilrtim, Nuwrc 1994, 372. 444.
9. R.E. Gill, G. G. J. Wildeman, G. Had1.iioannou. Ad1. Mota 1992, 4, 36.
10. S. Tasch, C. F. Meghdadi, G. G. Fruycr. L. Athoud, Mlll<'l: 1997, Sl,
33.
II. Q. Pci, C. Yu, Y. Zhang, A. J. Hccgcr, Sdt'l"'" 1995, 26Y. IOX6.
12. N.S. Sariciflci, L. Smilowitz, A. J. liecgcr, F. Wudl, Scit'll t:e 1992, Z5H, 1474.
13. J. J. M. Halls, C. A. Walsh. N. C. Grccnhalll , E. A. Marscglia, R.l-l . Friend, S.C. Moraui, A. B.
Holmes, Nature 1995, .l76, 498.
14. F. Hide, M. A. Diou-Garcia, B. Schw11tz. M. R. Q. Pci. A. J. Hccgcr, Scic11Ce 1996,
1811, 273.
15. N. Tessler. G. J. Denton. R. li. friend, Nllture 1996, 3112, W5.
16. S. V. Frolov. W. Gellermann, M. O.taki , K. Yoshino, Z. V. Vardcny, PIJy.r. Leu. 1997, 7/1,
729.
17. Primary PllmlH.'xdtatious in CcmjUJ:UId Pol)111er.1: Molecular E..rcil<m versus Semicmuluc/cJr
Bund Model (Ed.: N. S. Sariciftci) World Scienlilic, Singapore 1997.
18. R.H. Friend. G. J. Denton, J. J. M. Halls, N. T. Harrison, A. B. Holmes, A. KOhler, A. Lux, S. C.
Moro111i, K. Pi<:hler, N. Tessler. K. Towns, H. F. Wiumann, Solid State Conuuwt. 1997, 102, 249
and references therein.
19. J. Cornil, D. Beljonnc. Z. Shuai. T. W. Hagler. I. H. Campbell, K. Mullen, C. W. Spangler,
D. D. C. J. L. Clltm. P!Jys. Leu. 1995. 247, 425.
20. J. Comil, D. Bcljonnc, C. M. Heller, I.H. Campbell, B. K. Laurich, D. L. Smith, D. D. C. Bnxlh:y,
K. Mullen, J. L. Drt<las, ClleiiL Pllys. u11. 1997, 278. 139.
21. D. Beljonnc, Z. ShUili, R. H. Friend, J. L. 1. Chcm. Phys. 1995, 102, 2042. . .
22. EJectnmic Mlllerial - 11\e Oligomer ApfJTIJ(Jc/t G. Wegner, K. Mullen) VCH,
1998.
23. A. KOhler, D. A. dos D. Dcljonnc. Z. Shuai, J. L. Brooas, R. H. Friend, S. C. Muruni,
A. B. Syutla. Met. 1997, 84, C>15.
24. J. L. Br<ilas, J. Corni l, A. J. HL'Cger.lltlv. Mula. 1996. H. 447.
25. B. Schwanz. F. Hide, M. R. A. J. lh:cgcr. Cltem. I'IJys. Leu. 1997, 265, 327.
26. M Yan, L. J. Ruthbcq;. E. K. Kwock, T. M. Miller, Phys. He\ Leu. 1995, 75, 19\12; L.J. Rulh-
bcrg, M. Yan, F. Papadimilmkopoulus, M.E. Galvin, E. K. Kwuck, T.M. Mi ller, Syntll. Mel. 1996,
xo. 41.
27. W. G. Leising, G. Lan1..ani, M. S. De Silvestri, U. Scherf, Pllys. Nev. Lei/. 1996,
76, 1!47.
2!S. I. D. W. Samuel, G. Rumbles. C. J. Coll ison. PIJys. Hcv. 8 1995, 52, 11 573.
29. S. A. Jcnekhc, J. A Osaheni, Scitltt'e 1994, 265, 765.
30. J. W. Blatchford, S. W. Jessen, L. U. Lm. J. J. Lih, T. L. Gusrafssun, A. J. Epstein, D. K. Fu, M. J.
Marsell a, T. M. Swager, A. G. MacDianttid, H. PIJys. Nev. Leu. 1996, 76. 1513.
References
113
31. U. S. Heun, R. F. Mahn, U. Scherf, M. Hopmcier, U. Siegner, E. 0. Gobel, K. Mullen,
H. Bassler, Cllem. Ph_y.r. Leu. 1995, UO, 373.
32. S. V. Frolov, W. Gellcmtann, V. Vardcny, M. O.a!ki, K. Yoshino, SyntiL Met. 1997, 84, 493.
33. M. Pope, C. E. Swcnbcrg, /e.:tronic Processes in Orxanic Cnstals Oxford University Press.
New York 191!2. '
34. G. B. Bacher. A. Ya. .... o;ar, P. Lang. F. Dcntanze. J. L. Favc F. Ganticr Chtn u,
11
d,
1995. 7. 1337. . . ,., .
35. M. J. S._Dcwar. Zocbisch, E. F. Healy, J. J. P. Sr.cwan, 1. AnL Cllc111. Soc 1985, 107. 3')()2.
36. J. Conul. D. Bcljonnc. J.L BrCdas, 1. Cllem. PIJ1s. 1995, 103, 1!43.
37. G. J. E. Fischer, EE. Karnsz, M. J. 1. Clwm. Ph.'ts. 1993.98, 712.
38. J. Corntl, A. J. Hccl!cr. J. L Bn.'da.o;. Chem. Pllys. u11. 1997, 272. 463.
39. Ampa.: 5.0. I'J94, &'lnichcm, 7121:! Summit, Shawnee, 66216.
40. J. Ridley, M. C. Zcmcr, fl1cm'l!t. Cllim. Acta 1973 . .12. Il l.
41. N. Malaga, K.Z. Nishimoto, Z Plly.f. Cllem. 1957, IJ. 140.
42. D. Bcljumtc, J. _Comil. D. A. tJu, Santos, Z. Shuai. J. L. in Ref. 17, p. 559.
43. We. note thai h1ghly cakulations pcrfunncd on isolul<.'tl stilbene indicate that the
CXCII<.'\1 M:11c sl_rong.ly coupled lo the gruund laic b nut the IOWL"lol in energy, in L'Oilli"J-'1
h 1 the INDO/SCI l-41: however. emission place fmm the strongly coupled excited
s1.11e t-claxallon .:IT<.octs arc cottstdcr<.'tl; lhc tlrtlering of lhe lnwc:;t rwo excited
docs ntll the main cmtdu,ion' of our tudy.
-4. R:mt<L'e'l"' D. S. Galvao, S. Etemall, Phy.>. lJ 11193. 47, 1742.
45. R. S. Knox, lhtmy of Enilam, New York 1963.
46. A. Kiihkr. D. A. dus Sanlm. D. Bcljnnnc, Z. ShUili, J. L. lll'l!da,, R.li . Friend. S. C. Mor.JIIi, A. B.
A. K. Mullen. Numrc 1991$, .IIJl, \)(J3.
47. M. J. Rice, Y. N. G:u-stcin, PIJ.ts. Net: uu. 1994. 7.1. ::!.S0-1.
4!S. M. ... S. Mat.umJar. M. Lies. P.A. Lane, Z. V. Vartleny, M. H 1 K y; sh.
Plty.f. Ht: lJ 1991, 55. I.:IXC>. amaguc 11, . o: mu,
4\1. S. S. Trctial... T V. CheOiyill.. 1997, 277, 71!1.
50. J. Conn': D. Bd Jtllllll:. R. U. J. L. Brctla,, Clltm. Plty.f. U>u. 1994. 22.1. 1:12.
51. R. Kerst mg. U. Lemmer. K 1-'. Mahrt. K. U'(l, H. Kurt., H. li 0 . Gobel Plt)r He" ' -
11 1993, 70, 31!20. . . . . .._.. .
52. G. R. Haye..._ I. D. W. Samuel, R. T. Plly.f. Htt: lJ 1995, 52, 11569.
53. N. T. G. R. I-I ayes. R. T. Philipp,, R. B. Friend, Plty.r. Hel'. u11. 1996. 77, 181!1.
54. H. Antutu:xl'' L. J. Rothhcfl\, F. Pap:Kiintilrako(I\1\Jh-.:.. M. Yan, M. E. Galvin, M. A. Abkowir:r
Pity.,. Htv. lJ 1994. 50. 1-1911.
55. D. H._Cumpsltm. K. F. 1il'mlf ill Scit'l/1'1' 1996, 4, 151.
56. K. Xng. M. Falt lm:m, M. Uigdlun..t. D. A. do, S.uuo,, V. l".ucnrc. R. Lauaroni. J. L. 13r&la..., R
Gymcr. W. R. SaJancck, lldt: Matrr. 1996, S, 911.
57. J. Cumil, D. A. dos S:ullos, X. Crist>i n. R. Silbcy. J. L 1 A C'' S 1'""' 2
12M9. n.-ua!>, Ill. lll' IIL OC'. 7 7 0 , I 0,
58. JiG. McRae, M. J. J. Cltrm. Plly.,. 195H, 28. 721.
59. M. K:t,llil, Htuliation He.\iwrh 196..1. ZO. 55.
60. 'L G. Suus, G. W. Haytlcn, P. M. S. J. Elcm;KI, 1. Ch,m. Pllyl. 1990, SIJ.
61. D. A. C'uulson, L. Davu:s. l'tmuh11 Soc 1952. -IX. n1.
62. H. J. StcrnlichL. J. Chrm. Phy.,. JWw. 40, t'175.
63. W. .. K. F. A.J. Jlccgcr. Plty.f. Ht'l \ IJ 1\191. 44. 9-15.
64. F_. D. Lcwts, I. Wu. t::. L llun:h. 1). M. J. S. Y:mu, S. Schneider, W. J" R L
C
..
sutgcr, J. Am. htm. Soc 1995, 117. 1!71!5.
65. K. T. Kumta. S. Kuhut:J, II. Kuct.uka, 11111. 1. t\ppl. 1'111'-f. 1994, 32, LI 031.
6C1. M.S. r arahal, J. Pc11stcin, K. Y. l.mv. D. G. Whine,;, 1. Am. Chtm. Soc 1997, 1/IJ.
67. J. Gicrsdtner, II. J. Egclhaa f, D. Octkrug. Mtt. 1997. X.J, 529.
(II!. W. P. Su, J.R. A. J. Hccgcr, l' h.P. He1. I.A'/1. 1979, .J2. 1(19!!.
()Q. J. L. llrCdas, G. B. Stn.'t.'l. flee. Chtm. Ht.r. 191:!5, IX, 30'-J.
70. 1' . Guntcs da C'<t a, E. M. C'unwell, /'lt.rx. Ht' l'. II 199.l, -IS, 1993.
71. S. Ahc. Mtt. l9'n. 85. 11115.
114 4 Gt1s Phase to Solid SttJte EvolutiOII of the Electronic and Optical Properties
72. s. Webster, D. N. Batcheltler, Polymer 1996, 54, 13713. . R.H F ' entl
73. L. Magnani, G. Rumbles. J. D. W. Samuel, K. Murray, S.C. MoraU1, A. B. Holmes, n
Sylllh. Met. 1997. 84, 899. H Schenk H A
N. Johansson. D. A. t1os Santos, S. Guo. J. Comil, M. Fahlman, J. Salbeck, rwm.
74
' J. L. BrCdas, w. R. Salaneck, J. Chem. Phy.f. 1997. 107, . ,
75. M. Yan, LJ. Rothberg, F. Papadimitmkopoulos. M. E. Galvm. T. M. M1ller. Phyl. Rev. Leu. 1994,
72
M MJI04._ E L tl D BelJO ' nne J Comil J L OrCdas C. Taliani, J. Clltm. Plrys. 1998.
76. . ucc1m, . une eJ,
109. 10513. Yutl' R z.a bo C1 m.
77. L. M. Olinov. S. P. Pallo, G. Ruani, C. Taliani, A.A. Tevosov, S.G. 111,
111 111

Phys. ull. 1995. 232, 401.
78. z. Shuai. J. L. Oredas. J. Che111. P/1y.f. 1992, 97. 5970.
79. P. Petclenz, V. H. Smith Jr., Chem. Pllys. 191!9 /J/, 409. .. . R T b'
80. G. Oongiovanni, c. Cotta. J. Comil, J. L Orooas, D. R. Ferro, A. Mura, A. P1agg1, u mo,
Clum. Phys. Leu. 1997,278. 146.
223
81. E DeloiTrc. F. Gamier. P. A. Yas.,ar, J. L. Favc. Met. 1994, 67,
5 Electronic Structure of Surfaces
and Interfaces in Conjugated Polymers
Michael LOgdlund and William R. Salaneck
5.1 Introduction
A description of the and chemical structure of pol ymeric and con-
densed molecular solid systems is an important ingredient in the field of organic
polymeric and molccuhtr materials in modern electronics applications. The investi-
gation of the interaction between conjugutcd polymer materials and various metals
has become an important issul.!, both for interfacial characteristics as well as for
doping-inclucecl effects. Studies on the interface characteristics arc of significant
importance in the connection with various device applications. Investigations of
initial stages of both metal-on-polymer and polymer-on-metal interface formation
are or importance in the context of how the interfaces may affect the actual de
vice performance. In other words, when a few isolated atoms of an active metal
are applied in some way to a polymer surface, they will react in a ve.ry different
way compared to the case where an isolated polymer chain is applied in some
way to the cle<.m surlace of an otherwise three dimensional metal substmte, with
or without the presence of an oxide layer (I). In this context, the single most use-
ful experi mental tool has turned out to be photoelectron spectroscopy (PES) (2).
Also, it has been shown that use of the results of appropriate quantum-chemical
calculations (3) in interpreting PES data in many cases provides a level of infor-
mation output which is larger than the sum of the two [4]. In this chapter, the
principles involved in the study of the electronic and chemical structure of conj u-
gated polymer surfaces and interfaces arc reviewed. Examples of materials system
arc included which demonstmtc information obtainable from photoelectron spec-
troscopy on both pristine and doped conj ugated polymers as well as the modifica-
tion of the electronic und chemical structure of conjugated systems induced upon
intcr..1ction with diflc rent metals such as aluminum and calcium. Also, the useful-
ness of the combinution of photoelectron spectroscopy und quantum-chemical cal-
culations is demonstr..tted with some examples. The theoretical models most com-
monly used arc only brielly outlined. More theoretical details are to be found in.
for example. Ref. (Jj .
This chapter is organi'l.Cd as follows: the experimental and theoretical tech-
niques are presented brielly in Sections 5.2 and 5.3. In Section 5.4 some materials
aspects and concepts arc introduced, where rnms-polyacetylcnc is used as an illus-
trative example.. A series of ill ustrative exampks on surfaces and intct1.uccs arc
116 5 Electmllic Structure of Surfa"e.\ cmtl lmerfcu:e.\ i11 Conjugutcd l'olynu:r.,
given in Section 5.5, including a brief discussion on some aspects of the ITO sur-
face and its interface with polyaniline, using indium-tin-oxide (ITO) as an elec-
trode in light-emitting devices. An up to date list of references are provided for
the interested reader to obtain further information. A basic knowledge of certain
principles of organic chemistry and solid state physics is presumed, but references
are also given here for more detailed information.
5.2 Photoelectron Spectroscopy
The use of soft X-my sources Jed to the development of X-my photoelectron
spectroscopy (XPS), originally known as Electron Spectroscopy for Chemical Ap-
plication (ESCA) [5}, indicating the applicabil ity of the method to surface chemi-
cal analysis. More or less simultaneous wi th the development of XPS, Ultmviolet
Photocle<.:tron Spectroscopy (UPS) 161. i.e., the usc of ultmviolct photon sources
in PES, was applied to studies of gases and bulk as well as electronic
structures of solids. The increasing use of the continuous spectral distribution of
synchrotron radiation [7, 81 as a photon source, however, has made the historical
terminology less meaningful. Today, PES has become a widely used tool for
studying the bulk and surface chemical and electronic structure of condensed m<tl-
ter, liquids, and gases. In particular, the method is very useful for studies of the
chemical and electronic structure of conjugated polymers and interfaces with poly-
mers because: (i) it provides a arutximum amount of chemical and electronic infor-
mation within a single technique, (ii) it is essentially non-destructive to most or-
ganic systems, and (iii) the method is extremely surface sensitive.
Although the purpose here is not to give a full undcrsl<mding of photoelectron
spectroscopy, it can be useful to discuss some of the specific features in a photo-
electron spectrum which can be helpful for the understanding of the diO'erent ex-
amples discussed in this chapter. The main emphasis in the background to PES
will be focused on the molecular solids aspect since this chapter deals with con-
densed conjugated systems. The interested reader can find a more in-depth discus-
sion on the technique, relative to organic polymeric systems, in Refs. [4, 9, IOj.
The fundamemal process in molecular photoionization is represented by
(5. 1)
where M
0
represents lhe isolated ncutml molecule, hv is the ionizing photon,
represents the positive molecular ion in the excited state, and e- is the photoelec-
tron which carries kinetic energy Ek- If Ek is sufficientl y large, then the escaping
electron and the molecular ion arc not strongly coupled. The energy balance ac-
cording to Eq. (5. I) is then given by
11 + /1 v = + E, , (5.2)
5.2 1'/wtol!ll!cflvll Spectm.n:opy
117
where Eo is the total energy of the neutral molecule in the ground state and *. is
the the molecular ion in an excited state. Thus, the b;;..,ic
equ ,' on used m mterprctmg photoelectron spcctrJ can be written as
(5.3)
photon '"' is known and the photoelectron kinetic energy distribution
IS measured m deduce the binding energy 1bc binding energy is thus
not equal to the bmdmg energy of the elect rons in the neutml ground state of the
molecule, bu.t corresponds to the energy diiTerencc between the initial ground
state and vanous final excited states. The electronic structures of M. and M are
usually. modeled in tenus of si ngle-electron st<lles, with as much ph
0
ysics buill in
as possible.
are possible single-electron molecular contigumtions, as shown
schem;all c<llly Ill Figure 5-l . In the neutral molecule in the ground state, repre-
sented as Mu. all of the electmns in the moh.."Culc ;arc occupying only the lowest
allowct.l energy levels { V,). while the V;' lcvds arc empty. The other panels illus-
(f)
_,(.)
v: wu
>o
I
wz

w
(.)
vi
z .
wu
...J(.)

w-'
a:!!;'
c,
Ow
u .....
Mo
-.
-- -
---
w
.....

uw

OjS
:!:(f)

...

wa::
ZC>
-

---
Zw

lrt-
<VJ
-'o
=>z
&b
-'0
Oa:
:!:C)
M+m M *
0
---
- - -
--
- - ..
-
- -
---
-- . -
---
--
..... _
0
w
t-
u. z
w
><wQ .....
W...Jt-
zO;'S
(.)
ox-
ww
-wu
...Jt-
a:>< OjS
sow :!:(f)

wWZ
55

W)(
zw
118
5 l;"'Jcc:trrmic: Structure? of Surfuces and llllcrfuc:el' in Conjuguted Polymcr.r
tmte the genemlized excited state of the (photo-ionized) molecular cation,
where an electron has been removed from the core-level, C;, but the remaining
electrons do not occupy the lowest possible single-electron states (the special case
of ionization from the HOMO level is illustmted as M .); and the optically excited
neutml molecule, Me; (where one elt:etron has been excited from the HOMO to
the LUMO in the illustration). The case of illustrates the phenomena of
shake-up, where an electron is excited across the band gap simultaneously with a
core-electron ionization event [5, 11- 13].
Most of the intensity in a photoelectron spectrum usually resides in one main
line, corresponding to a particular simple tinal excited state of the
which is fonned by the direct removal of a single electron from a spec1tic m1t1al
state of the molecule. However, all of the various possible final states, COITespond-
ing to a given initi al state, can in principle be observed, but usually they have
low intensities and can only be seen as weak satellites on the main line. In Figure
5-2. an idealized photoelectron spectrum, or energy distribution curve (EDC),
with the corresponding molecular levels is displayed. The most important feature
in thi s one-electron picture is that there is a one-to-one correspondence between
the peaks in a photoelectron spectrum and the one-electron molecular levels in the
neutral molecule. The small feature appearing on the low kinetic energy side of
the main peak, labeled C
2
in the idealized spectrum, COITcsponds to a _sa-
tellite; the escaping electron loses kinetic energy, 6 . a result of an
from an occupied level, V
3
. to an unoccupied level, V simultaneously wllh the
electron emission from a core-level, Cz.
During the photoelectron emission event there are electronic relaxation
occurring, which arc usually divided into it1tra- and inter-molccu_lar relaxatiOn ef-
fects. These effects can be mtionalized in a classical picture as lollows. An elcc-
BINDlNG ENERGY OF ELECTRONS

t
/ !

l
()

<<< <
c
-....
. c

r-() < r-c
,....
mo

m
<:n
:Z:m mg
<

m
o ;z:
{;;n
,....
U) o
m
c
'tl
n;
0
INTRAMOLECULAR
/
ELECTRONIC
j RELAXAnON
\ ._,
1
! ,/
'
'! o
...
INTERMOlECULAR
ELECTRONIC
RELAXAnON
KINETIC ENERGY MEASURED
(WIDE RANGE XPS SPECTRUM)
Jo'igun: S-2. An illcatizc<.l s pct:ll\llll wilh 1hc corrc.,puno.ling unl.O..Cil."t:lrun moh:cular levels.
5.2 P/totm!lectro/1 Spectroscopy 11 9
.

a photoelectron a molecule tXpically within about
I 0 s. The nuclear gcomctnc relaxation tune 1s around I o-
3
s (i.e., which corn:-
to _an optical phonoo frequency) while the corresponding electronic relaxa-
tion tune IS il!xlllt 10-
16
s 1141. Thus. the main line com:spontls 10 the binding en-
ergy of an electron in ;m ioni:t..ctl molecule where the electrons have hatl m
i.e.: the hole is fully scra!ned. but the nuclei are frozen during the process;
th1s 1s rekrrcd to as the adiabatic peak. The intra-molecular electronic-relaxation
effects occur in response to the creation of a hole-stutc in photoelectron spectros-
copy of an isolated molecule in the gas phase. In the solid state, there are also in-
ter-molecular relaxation etTects occurring due to electronic and atomic polarization
of the molecules surrounding the panicular molecule on which the hole-state is
created. The inter-molecular relaxation energy is given to the escaping electron
and thus the kinetic is increased, i.e., the corresponding peak in the photo-
spectra appcurs at a lower hinding energy compared to photoelectron
from the level in the gas phase. TI1is energy difference. i.e., the po-
larwttlon energy. 1s 111 the order of 1- 3 eV [15) throughout the valence renion.
The relaxation energy lor core-levels. however, can be much larger due to a hi"h-
er degree of localiL.ation of the core-holes 113, 14). b
5.2.1 X-Ray Photoelectron Spectroscopy
With XPS, as commonly carried out with Al(k,.) and Mg(k, ) labor-.atory sources, it is
possible to pcrfonn qualitative and even semi-quantitative anal ysis of chemical com-
posi tion in the ncar surface region of a solid sample. Changes in the valence electron
density will he rellected as small, but significant shifts in the core level bindino en-
ergies. so-called chemical shifts. although thc core electrons are not involved the
chemical bonds [51. Of course XPS can be (and has been extensively) used for stud-
ies of the valence band region, but the photoionization cross-section for the valence
photoelectrons in XPS arc approximately one ortlcr of magnitude lower than that for
the core which however IC<lds to more time-consuming experiments.
Also, the photo1onaz.at1on cross-sections are such that it is not very convenient to
study conJugated polymers, where interesl is in the states ncar the valence band
edge, which are very weak in XPS valence band spectrJ.
Another in PES spectra is the so-called shake-up structures, appeari ng
as weak satellites on the hi gh binding energy sitle of the main line. The shake-up
structure reflects the spectrum of the 1-clcctron-2-hole states "eneratcd in connec-
tion with photoionization, anti can give useful infonnation .iliout the valence TC-
elcctronic structure of a molecular ion.
The PES measurements arc pcrlonncd with reference to the Fermi level of the
photoelectron spectrometer, in solid as wi th here, by the way the
spectroscopy works. Thus, in case.<> when the Fcnni level shifts due to some
chemical of the sample, i.e . in the intercalation of gmphite or other
layered compound 1161 or in the doping of conjugated polymers [ 171. it is neces-
sa1y to account for the change in the Fermi energy level before interpreting spec-
120
5 Electronic Structure of Surfaces wul Interfaces in Coujugated Polymers
tra. This can be done, for example, by combining the XPS core-level spectra with
UPS valence band speclm . as described in more detail in the next section, or by
referencing to model compound (13].
5.2.2 Ultraviolet Photoelectron Spectroscopy
The most commonly used laboralory photon source for UPS is the_
lamp, although lhe use of synchrotron mdiation as a photon source 1s 111 extens1ve
use today. For valence band spectrOscopy, UPS has two over
First, the usual in-house photon sources have high energy resolutiOn, a full w1dlh
of half maximum (FWHM) of- 30 meV for the He lines, and second, the photo-
ionization cross-section for electrons is higher in the valence region for UPS.
However, the natur.tl line widths in condensed molecular solids, from both homo-
geneous and inhomogeneous broadening effects, can approach I eV at tem-
pemture ( 10, 1 g, 19 ). and a large fraction of the photon energy resol ut1on advan-
tage is not fully realized. . . .
As mentioned above, the PES measurements of sohd spccnnens arc pcrlormcd
relative to the Fermi level. ln some cases, however, it can be desirable to derive
the binding energies relative to the vacuum level from a photoelectron spectn:m
This is particularly important before interpreting ditTerent core-level ch_em1c:-'l
shifts induced upon, for example, doping or interaction with metals. In 111
some cases, the apparent binding energy shift can appear to be in the wrong d_lrec-
tion before the Fermi energy shift is taken into account [ 17, 20). en-
ergy shift can be deduced by measuring the position of kmettc energy
cut-off of the secondary electron distribution, as illustrated tn F1gure 5-3. The vac-
uum level can be located s imply by adding the photon energy to the secondary
electron cut-off energy; measuring down from the vacuum level energy to the.
known posi1ion of the Fcrrni energy (Ep) determines the work function (C/>.,) ol
the subst111te (21 j.
Au UPS Hel (hv:21.2 eV)

u.
c

..J
:l
u. w

_,
>
.e
> w w

>
..J

::>
w
:
0
::>
u
u
(/)
w
-4:
z V) >
w
1-

IW
Eco
BINDING ENERGY (eV)
0 Ev
J;"igure S-3. UPS spectrum uf Au 1hc 10 obtain level rcli:rcnccd s[><!<:lra.
5.3 Tlwuretical Approaches 121
It is also wo11h pointing out that the determination of the reference level, i.e.,
the Fermi level of the spectrometer, is done by performi ng a UPS measuremenl
on a metallic specimen in equilibrium with the S(X-'Clrometer, laking for instance
Au as in the example here. Si1ll"e, in equilibrium, the position of the Fermi energy
is conslant throughout the cross-section of the thin films under discussion in this
chapter, the position of the Fcnni energy on the UPS spectrum is equal in analyz-
er voltage to lhe location of the Fermi level in the metallic subslrate, as observed
prior to the deposition of the organic overlaycr. This positioning of the Fermi lev-
el, coincident with that in lhe substr.1tc, has been observed in all UPS studics re-
viewed in lhis work, us well us in other molecular overlayer systems, on both me-
tals and semiconductor substr.lles (4, 22-25].
Valence band spectra provide information about the electronic and chemical slmc-
ture of the syslem, si nce many of lhe valence electrons participate directly in chem-
ical bonding. One way to evaluate cxpcrimental UPS spectra is by using a finger-
print method, i.e., a compari son with known standards. Another important approach
is to utilize wilh the results or appropriate model quantum-chemical cal-
culations [41. The combi nation with quantum-chemical calculations allow for an m;-
signment uf the diffcrem in the elccuonic structure in terms of atomic or
molecul<lf orbitals or in terms of band slructure. The experimental valence band
spcclm in some or the examples included in this chapter mc interpreted with the
help of quantum-chemical cakuhct ions. A brief outline and some basic considem-
tions on theon:ti cal approaches are outlined in the next secti on.
5.3 Themetical App1oaches
During the last decade. the progress in thcoretical methods and the access to
quantum-chemical c;clculations has become more available. Nowadays, lhc use of
quantum-chemical calculations in the interpretation of experimental UPS valence
band spectra is a common approach [26-29].
Usually the interpretation of UPS spectra of molecular systems relies on the
one-electron picture of the neutml molecules. In this ca'ic a one-to-one correspon-
dence between the m<yor peaks in the photoelectron spectrum and the one-elec-
tron molecular orbitals exists, as illustmtcd in Figure 5-2. This approximation is
assumed to be valid for large molecules. The numerical values of the calculated
binding energies of the peaks are usually set to the Hartree-Fock eigenvalues of
the molecular orbitals in lhe neutral ground :>late of lhe molecule, e.g., employing
the Koopman's theorem. When relying on quantum-chemical calculations, it is im-
portant to consider the various relaxation eflccts that occur during a photoelectron
emission event. The.'ie relaxut ion effects often make it necessary to apply correc-
tions that account for di llerences between the molecular orbitals of the neutml
molecule and the molecular ion. Usually the theoretical model calculations are
pcrfonncd on isolated i.e., not laking into account any illler-molecular
122
5 Electronic Structure uf Surfaces wrd Interfaces in Conjugated Polymers
imemction. This is justified by the observation that for organic molecules there is
a one-to-one correspondence between the UPS valence band spectra of the molec-
ular solid and molecules in the gas phase, caused by the genemlly weak inter-mo-
lecular van der Waals interaction between the molecular species in organic molec-
ular solids; there is a rigid shift throughout the valence region in the order of 1-
3 eV [15, 30]. The shift is due to polarization of the surrounding molecules which
stabilizes the final ion state and leads to a decrease in binding energy [13).
The systems discussed in this chapter give some examples using different theo-
retical models for the interpretation of, primarily, UPS valence band data, both for
pristine and doped systems as well as for the initial stag_es of interface for"':'ltion
between metals and conjugated systems. Among the vanous methods used m the
examples are the following: semiempirical Hartree-Fock methods as the
Modified Neglect of Diatomic Overlap (MNDO) [31, 321 and Ausun Model I
(AMI) (33): the non-empirical Valence Effective Hamiltonian tVEH) pscudopo-
temial mcthod[3, 34); and ab initio Hartrcc-Fock techniques.
A common strategy for calculating the density of valence states for large conju-
gated systems. both for pristine and charged (doped) systems, is to usc a two step
procedure. The ground state geometry is first optimized by applying a semi-em-
pirical method (for example AM I or MNDO). The optimized geometries then
serve as input for electronic structure calculations perfonncd with the VEH meth-
od. The AM 1 and MNDO methods arc known to yield reliable geometries for
large organic molecules. The appl icability of the VEH model in interpreting
photoelectron valence band spectm of conjugated systems is well estnblished
35- 37]; the VEH parameters have been determined by fitting to double-zeta-quali-
ty ab initio results on model molecules [3, 34). When using ab initio I:Ianrec-
Fock. the calculations on conjugated molecules has, of course, to be restnctcd to
relatively small systems due to the dmmatic<tlly increased computational clT011s.
In some cases. however, one can gain reliable detailed infomlation for a particular
material system by performing calculations on an adequate model system. More
details on the theoretical approaches are to be found in the references themselves,
or in other chapters of this book.
5.4 Materials
During the past decade, a large effort in improved synthesis of soluble conjugated
polymers has led to an in. the quality . of samples by
venl techniques, and thus made 11 poss1ble to obt:un more dcta1led mformat1on
about, for example, the electronic structure through the use of photoelectron spec-
troscopy. The high quality of substituted conjugated polymers with vurious side
gmups allows for detailed investigations or the inll uencc o.f the srdc groups o.n
the electronic structure, as demonstrated by Fahlman et a/. Ill the case of subsu-
tutcd poly(p-phcnylcnevinylene) L38J. In order to demonstrate the level of inlor-
5.4 Materials 123
obtainable ti'Om PES (mostly UPS), sorrie of the most commonly used
polymers are presented below. The subset of polymers chosen for dis-
arc poly(p-phenylenevinylene). polythiophene. and polyani-
hne. The bas1c chem1cal structures or these different conjugated polymers are dis-
in Figure 5-4 for subsequent reference. In order to introduce conccpl.., and
tenmnology, the electronic structure of tralls-polyacetylcne and the various types
of charge-bearing species in conjugated polymers arc discussed in the next two
sections.
5.4.1 Electronic Structure of trans-Polyacetylcne
1bc gcomctrica! structure of .. :ctylcm:: (see Fig. 5-4) is particularly sim-
ple; a. planar z1g-z:1g configuration with ultt:rnating single und double bonds of
1.44 A and 1.36 A 139). The band structure is very simple and well suited for
demonstrating the relationship between band structure, density or valence Slates
(DOVS), experimental valence band spectra. The:: culculatcd energy band
structure of trmn-polyucetylcnc, c<tlculatt!d using the Valence Effecti ve Hamilto-
nian method [3, 34), is compared with the measured UPS spectrum in Figure
5-5. The energy scale is detennincd experimentally, i.e., with respect to the Fenni
level in the UPS spectra. The input geometry for the VEH calculations has been
from AM I optimizations on an oligomer of trans-polyacetylene.
010erences wht:n usmg experimental values instead are small and are not found
to <tlfcct any of the results. Normally, a band structure is presented with the en-
ergy vertically and the momentum vector k horizontally. The band structure in the
figure is rotated by 90", to enable a more direct comparison with the experimen-
tal spectrum. To facil itate the comparison between the UPS data ;md the calcu-
lated band structure, the density-of-valence states, p() (or DOVS), is included.
The highest occupied energy band is the n-band, which can be seen clearly as the
POL YACETYLENE
POL Y(p-PHENYLENEVINYLENE)
POLYALKYLTHIOPHENE
,r{ /s,

A
POL YANILINE
f(_)
y 1-y
5 ..... CtlCillll' ;Jt nr \tllllC uf lhc nmjugal.:l( 1>t.>lymcn. tli:.cuss.:J lll lhc .:haplcr
124
5 /ectromc Structure of Surfaces a11d brtcrftlces in Co11j11gated Polymers
-25 -20 -15 -10 -5
0
0
7<"
i!
.e

0
-25 -20 -15 -10 -5
BINDING ENERGY (eV)
Figure S-S. Valence baml spcclm of al
27 cV and 50 eV photoo energy, and the com:sponllmg DOVS llcnvcd from VEH cakulauuns. 1l1C
VEH band structure is shown in \he lower part of the figure (from Ref. )281).
band edge in the UPS spectra. The position of the n-band edge, changes
the electronic structure in the region of the edge, arc of central Importance m
studies of conjugated polymer surfaces and the early stages of formation of the
polymer-metal interface. Clearly, the UPS spectm, sensitive to only the top most
molecul es of the lilm, arc appropriate in such studies.
The electronic structure of trans-polyacetylene can be rationalizetl in the fol-
lowing manner (3). If the cartx>n-carhon bomls would be of et.JUUI in
the absence of dimerizmion, polyCJCetylenc would be a 'regular polyene , w1th a
unit cell consisting of a single (-CH-) group. At least within one-electron
three occupied valence bands would exist, corresponding, in localized bond orbi-
tal terminology, to approximately a C-C a-band, a C-H a -band and an-band, the
latter being derived from the remaining atomic orbital on each C-atom (the z-
axis being perpendicular to the molecular plane). occupied n-ba?d wo_uld be
only half filled, since there would be one eh.:ctron m each atom1c orbital
each C-atom, and the electronic structure of the polymer would have a mctalhc
5.4 Materials 125
character. However, due to a Peierls transition (or, equivalently in molecular ter-
minology, a Jahn-Teller distortion) and electron correlation effects, the system is
dimerized with altemating si ngle and double carbon-carbon bonds. This results in
a unit cell in trans-polyacetylene consisting of two carbon atoms, corresponding
to (-CH=CH-) units. Since the width of the one-dimensional Brillouin zone in the
unit cell wi th two C-atoms is onl y half of that for the regular polyene, each band
of the regular polyene is split into two bands, resulting in four occupied a -bands
and one occupied n-band. Due to the presence of dimerization, there energy
gaps at the Brillouin zone edge, ncar - 8 and - 15 eY in Figure 5-5, where each
pair of bands from the regular polyene structure is folded back to fonn the dimer-
ized-dmin band stmcture. 1l1e Peierls gap in the n-band, which occurs at the Bril-
louin zone edge, corresponds to the forbidden energy gap of approximately
1.5 eY in trcms-polyacetylene.
The details in the calculation allow for an assignment of the different peaks in
the UPS spcctr;.1 to dillcrenl calculated l>imds: Pe<tk A in the :spectra corresponds
to electrons from a band derived almost exclusivel y from C(2s) atomic orbitals.
i.e., the C-C' hackhune. Peak 13 is derived from the lhtt p011ion of a
2
band ne<tr
the zone center. Peaks (' ;uld 0 corrcspoml to from the ar ami a-'-bands
derived from cumbinalit)ns of C- C and C- H bands at points in the Brillouin zone
where there is u high density of states, i.e., at the zone center ncar - 9 e V and at
the zone edge ne.tr - 8 e Y. The broad peak E has its origin in the strongly dis-
persed n-band, which also contributes to peak D. The valence band edge corre-
sponds to the highest pot1ion of the occupied n-band, at the zone edge.
It can be instructive to follow the evolution of the a-bands when going from
the unit cell with one carbon atom to that wi th two carbon atoms. As mentioned
above. the a-bands can loosely be to as C-C and C- H. In polyethylene,
the upper bands arc essentially C-H and the lower C- C {3J. Because of the large
dispersion in polyacetylene, however, this separation in energy does not occur.
This is demonstmted in Figure 5-6 where the evolution of the two a-bands is
shown. The two a-bands cross at about - 15 eV, m; seen in Figure 5-6a. Upon
folding the bands into the tina Brillouin zone Figure 5-6b another band crossing
at about - 18 eY occurs. At the points where two a-bands of like symmetry intend
to cross, there is an band-crossing. In addition, energy gaps occur at the
Brillouin zone edges. When taking into account the avoided band crossings and
the energy spliuing <tt the Brillouin zone edges (Figure 5-6c), the actual a-band
structure of can be fully rationalized.
5.4.2 Charge Storage States in Conjugated Polymers
The intrinsic low dimensional geometrical nature of linear polymer chains, as well
as the general property of conjugated organic molt.."Cules that the geometric struc-
ture is dependent upon the ionic slate of the molecule (strong clcctron(hole)-lat-
Lice interactions), leads to the cxistem:c of unusual charge can-ying These
manifest themselves through either optical absoq>tion in the neutral
126
5 Electro11ic Structure vf Surfaces w1d Interfaces ill Co11jugated Polymers
>
.!!.
>-
C)
a:
w
z
w
(a)
-10
-15
-20
-25
0,0 0,5 1,0
K(n/a)
(b)
-10
-15
-20
-25
-30
0,0 0.5
K(n/a)
/
/

.-1
/I
/ I
'I
'(
I '
I '-..
-
I
\
\
\
\
\
\
\
\
'
'
'
.....
1,0
(c)
-10
/
,.

/
-
/
,.
I
-15 / I
I
'
I
..... .,
-20
/,. ___
I
I
I
-25
'
'
'
'
'
'
-30
'
,_
0,0 0,5 1,0
K(n/a)
tigure 54;. Illustration of the evolution of lhc two u-bands in mms -polyacctylenc.
tern or charge transfer doping, as self-localized elecu-onic states with energy
within the otherwise forbidden electron energy gap {40-44]. For m n-
type doping, although the very first single electron on the (any) lt"CliiS-
polyacetylene polymer chain goes in as a polaron {42, 431. po_larons rcad1ly
bine to form a lower energy state, that of the soliton, named alter the
which describes its behavior [40, 4 11. Although solitons must be funned m pmrs
[45j, usually a single species is sketched for <.-onvenicnce. An isolated
containi ng an excess electron, leads to the of a electromc stat_e
within the energy gap .. The schematic rcprcsentat1?ns of a pos1t1vely c ha'?ed soh-
ton (left), a neutral soliton (middle), and a negattvely charged sohton (nght) arc
shown in Figure 5-7 [43, 451. . . .
Some photoelectron spectroscopy studies of tram-po_lyacctylene m _the
t28, 46], p -type doped [47- 521 and doped l_52J lorms, can be lo_und m
literature. Although no new well del med sulJcture IS detected. dop111g, wh1ch
would correspond to doping induced soliton levels, the dens1ty ol state.<; close to
s+ -----

so - t-

'/1// /// / / //1
s
':'\ \ \\\\\.

Figu.rc S-7 .. Oanu dia&:lm of solilons with pol>llivdy n<.'"tltral, and negatively charged sys-
from lcl'l 111 right.
5.4 Materic1/s 127
0
w
Q..
0
0
:..::
-l
<:
a:
5
w
z
0
w
Q..
0
0
...
0
u
-14 -12 -10 -8 -6 -4 -2
BINDING ENERGY (eV)
Figure S-8. UPS valcm:c himd spct:lra or llupcu muu -pulyacctylcnc for K-uupcu, neutral, and CI0
4
-
<lopc<l fmm top lo holtonl (a<laptt..'tl rrum Ref. 1521).
the Fermi energy levd hilvc hcen reported for both 11-typc 1521 and p-lypc 151.
521 doped tra/1.\-polyilcetylcnc. It shoultl he kept in mind here th:..tt only tH ypc
doped spct;ies would he directly detectable in PES. As illustmtions of the cll.'c-
tronic structural changes induced upon doping, are UPS spectra shown in Figure
5-8 in the cases of potassium-doped (top) and perchlorate (CIO;j)-doped (bottom)
/ra/ls-polyacetylcne {521. The spectrum corresponding to the pristine polymer is
shown in the middle as a reference for the doped situations.
The evolution upon doping is cxpl:..tined as li.>llows: new mid gllp states arc
formed immediately at the initial stage of doping, with Fermi energy level shifts
towards higher binding ener<.;y in the case of pcrchlor.tte and to lower binding e n-
ergy in the case of potassium doping. These shifts arc in agreement with the re-
of electrons fmnllto the /ra/1.\-polyacetylcne chains upon the 1'-
typc/n-typc doping.. A filled mid gap band is expected for the 11-type doping
while the mid gap band is expected to he empty for a p-type doped situation.
Upon further doping, density of states appc<tr close to the Fenni level, as shown
magnified in Figure 5-8 .. This evolution is explained here a:; the of a
mew/lie state. The mechanism behind this fonnation of a metallic state is, how-
ever, not fully understood.
Also in the case of non-degenerate ground state polymers, the very first single
electron on the (any) isolated polymer chain goes in as a polaron .. However, the
individual polarons interact (combine) to form spinless bipolarons, which is a
lower energy configuration. Thus, in general, depending upon the symmetry of
the ground st;tte, the charge-carrying species arc charged polarons, spinless
chargl.-d solitons. or spinless charged bipolarons 140-43, 45. 531 .. The negatively
charged hipolitrun slalcs for poly(p-phcnylcncvinylenc), or PPV, <t
128 5 Electronic Struc:ture of Surface.v and lmcrfates in Conjugmed Polymers

BP- I
-!--1-
\\\\\\\\\\\\\\\
Figure S-9. Band diagram of ncgalivcly charged bipolarons (BP--) in PPV.
conjugated polymer, arc sketched in Figure 5-9. These species. solitons, polarons
and bipolarons, represent the lowest energy eigcnstatcs of the l:oupled electron
(hole)-lattice systems (54), <tnd arc responsible for the unusual electrical, magnetic
and optical properties of conjugated polymers.
5.5 Polymer Surfaces and Interfaces
In the following sections, results from various photoelectron spectroscopy studies
of poly(p-phenylenevinylenc), polythiophcne, and polyaniline, ar1d their intentc-
tion with ditferem metals will be discussed. The intention is not to cover the
whole existing Iitcmture, but still give a relatively extensive overview, and, where
appropriate, give references for further reat.ling.
5.5.1 Poly(p-phenylenevinylene)
In Figure 5-l 0, the experimenwl UPS Hcl and Hell valence band spectr.t of PPV are
compared with 1he results of a calculation of the band structure based on the VEH
modei[2H). The chemical structure of PPV is displayed in Figure 5-4. 1l1c excellent
agreement between experiment ant.! theory may be seen, there three
reasons that the experiment and theory might not agree al all bmdmg encrgacs: (I)
photo-ionization energies arc not included in the thcon:tical (2)
many-body effects, inherent in photo-electron spectroscopy, whach appear 111 the lO-
ner valence region ponion of the valence band in hydro-carbons; ant.! (3) the VEH
0
0
0
-25 -20
-25
-15 - 10
-15 -10
BINDING ENERGY (eV)
5.5 Polyma Surjllas ami lnterji.Jccs
129
-5
0
5 0
5-JO. _l-Ie I and II UPS valence band 'flllo:lra uf PI'V with DOVS derived from
VEH COJk:ulaiiOtl'>- Tile VEH band slruciUrc in lhc luwcr ll'lrl uf 1hc liguc (from Ref. 12!1J).
models have not been properly parameterized for states in the inner valence band
regi?n. _On the ot_her especially good agreement is expected and found, at low-
er bmdmg 111 the so-called frontier electronic slructurc region.
den_slly valence states, shown in direct comparison wi th the UPS spcc-
tm, IS lrom the band s_tructure which is shown al the bouom or Figure 5-
10. The port1on of the electronic structure which is of most interest the so-called
elccbonic structure, is at the low binding energy region, . to the right
ot the figure. at higher binding energies, peaks A, B and C, 01iginate
electrons _m d1ftercnt a-band'> while pe<tk 0 is built up from contributions
the four a-bands, the lowest n-band, and a small portion from tbc re-
latively tlat part ol the_ n-band. The two peaks at lowest binding energies,
peaks E and F, arc denvcd from the three topmllst n-bands. Pc;tk E is dominated
by next h_ighcst n-bmuJ, which is extremely llat, since it corresponds to elec-
levels lully localized on the bonds between onho carbons within the phenyl
nngs. In general, a llal band results 'in a high illlcnsity peak in the DOVS, since
there arc many slates per unit energy just ill the llat hanll. The larger dispersion of
130 5 Electronic Structure of Surfaces 011tl lnte1j'iKes i11 Coujugatetl Polymers
the top n-band results in a lower intensity in the UPS In studying
moms on the surfaces of the PPVs, the low energy electromc structure, as seen m
UPS, changes in particular ways, depending upon the nature of the interactions or
the metal atoms with the surface of the polymer. Also, this energy region is sensi-
ti ve to substituents as demonstrated by Fahlman et al. [38], where the fine details
in the low binding energy part of UPS spectra have been compared with VEH
calculations in a series of PPVs with different substituents such as alkyl chai ns,
me.thoxy groups, and cyano groups. Details such as the splitting between lhe two
topmost peaks (E and F in Fig. 5- l 0) and the position of the valence band
relative to the Fermi energy arc affected. The latter is consequence of a change m
the size of the optical band gap.
In the many reports on photoelectron spectroscopy, studies on the interface for-
mation between PPVs and metals, focus mainly on the two most commonly used
top electrode metals in polymer light emitti ng device structures, namely aluminum
[55-62] and calcium [62-67). Other metals studi<Xl include chromium [55, 68],
gold (69J, nickel [69], sodium [70, 71 ), and rubidium (72]. For of n_ick-
el, gold, and chromium deposited on LOp of the polymer surfaces, mtemct1ons
with the polymers arc reported [55, 68]. In the case of the between PPV
on top of metallic chromium, however, no interaction with the was
lected [55]. The results conceming the interaction between chronuum and PPV m-
dicates two different effects, namely the polymer-on-metal versus the metal-on-
polymer intertace formation. Next, the PPV inte1face lormation with aluminum
and calcium wi ll be discussed in more detail.
5.5.1.1 Interface Formation Between Aluminum and PPV
In connection with the progress made in the fabrication of light emitting diodes
(LEOs) from conjugated polymers, some of the most promisi ng results have
obtained with poly(p-phenylenevinylene) as the light emission medium, With
(hole-injecting) ITO-glass as the transparent substr.tte and with a calcium or alu-
minum electrode as the (electron-injecting) metall ic contact.
There are two more or Jess equivalent approaches when studying the chemistry
at an interface with the help of PES. One way is to build up a metal ovcrlayer on
top of the polymer using physical vapor with a full set. of
data recording between the vanous steps. Another posstbthty ts to grow a th1ck
metallic overlayer on top of the polymer and then, in a stepwise fa..-;hion, etch
away layer by layer using ion (e.g. Ar) bombardment. The latter been
by Nguyen et al. 155]. A set of XPS core level spectra, recorded dunng stepw1se
removal of the aluminum top electrode, are shown in Figure 5- 11 . Note the re-
verse order of the set of spectra in the case of the C(l s) peak (middle).
In Figure 5-12 is a set of core level spectra shown, which have been recorded
between successive steps during the growth of an aluminum metallic overlayer on
top of PPV [59]. The thickness o{ the aluminum layer for the lowest and highest
coverage correspond to 2 and 20 A, respectively.
In both of the above cases, the PPV lilms were prepared from precursor poly-
mers and converted at elevated tcmper ..uures wi th a minute amount of oxygen
5.5 Polymer Surfaces a/Ill lntetjaces
131
u.... ............. 1 ----.1 ......... ""- . _ ... ...........
536 532 528 288 284 280 76 72 68
BINDING ENERGY (eV)
Jolgure S-11. XI>S L' Ofl: lcvd S(X'\:Ir.. rc.:ot\k:d during n:mnvals olthc aluminum layer on
PPV (;nlaptcd from (S5J).
r- - ,- - I --. -
Q(1S)A C(ls)
20!/1A

534 532 530 288 286 284 76 7 4 72
BINDING ENERGY (eV)
5-12. Xl>s cure level rL'<.'ortlcd during dcpu,itiun of aluminum on PPV
(a<.laptet.l from IS9J). HJC Al(2p) spce1ro1 have lx-cn numlali,.._'<.l In L'l(ll:ll IIICI<II mmpuncnt intensity (at
abuol 72.5 eV).
contamination present on the polymer surtitccs (Konstildinidis reports slightly
more than 4 at.% of oxygen).
Some comm?n be seen in the (I) oxygen is present
thn>.ughout the mterractal rcgnm. extending <Jil the way to the outcnnost metalli c
surface; (2) two comtxmcms can be detected in the case of the aluminum signal;
and (3) the carbon peak shape remains essentially unchanged and the bindino en-
. . . b
posnto? c_onstant. The source of the relat ively high oxygen concen-
trations are m the uuerlace and in the metallic layer itself. The two component in
the Al(2p) spectra, at about 72.5 and 74.5 eV, originates from oxidized and metal-
lic aluminum, respectively. As can be seen in both cases, the feature related to
_uluminum has a relatively large intensity in the ncar polymer surface re-
gion, would expected in the case of oxygen-contaminated surfaces; oxy-
spcctes as carbonyl groups would be the primary reaction
sne for the vapor-deposited aluminum [591. In connection with point 3 above, it
_menti oned in similar work out by Ettedgui et ul. a succes-
SIVe shtlt, m the order ol 112 cV. was dclcctcd for the C( l s) peak, which has been
132
5 Electronic StruclUre of Surfaces cmd Interfaces in Colljugclled Polymers
b d be u1
8
at the ,ntcrface [57 58]. 1l1e core level shifts can,
d1scussed as a an '
111
. '
however, be explained in different tenns [73]. . . . h-
. . d b Dannetun et al . [561. using the same alummum lee
. In a stu y y d" .d. t I [59] i e UPS and XPS the fine detmls m Jhc va _ lence
mque as Konsta 101 IS e a . . . . t
and ed e of the UPS spectra, together wi th the evoluuon_of ur:
? h Cg( 1 ) XPS core level spectr.t. shows that Jhe imeracuon wllh alummum atoms
m t e s . tal ults are supported
strongly affects the frontier orbitals of PPV. The ex_penme? res PPY . d AI
b results obtained from theoretical studies of the mteracllon _between_ an .
y h . fi nd that AI preferentially w1th the vmylene mol-
atoms, w ere 1t was ou . . d . 1 odifies
eties, which have large contri butions to the frontier orbitals, an. yh ":, "d" -
the geometrical structure by the fonnation bonds and sp Y n za
lion, which leads to interruption of the 7t-eOnJugallon [74, 75).
5.5.1.2 Interface Formation Between Calcium and PPV
The low binding energy parts of the UPS He I (21.2 cY photons) valence band
spectm of poly(2,5-diheptyl-p-phenylenevinylene) recorded
different stages of deposition of calcium, are shown Ill Fgu.rc 5-1_3. !f1el cfty
. d hains on the phenyl groups do not contribute to the mtcnslY m l 1e
energy part, e.g., below eY 1661. The spectrum at the bollom corrc-
z
0
''
i=
Ui
c
0 J
(l.
e
2
w
0

Ill

(.)
<!) (j)
z
z
Ui w
.... c(

w
a:
(.)

-10 -8 6 4 -2 0
BINDING ENERGY (eV) . .
1 1 . H 1 UPS spectr.1 of DHJ>I>V rcl.'t>n.ku during succcsstvc
5-13. Low bmdutg .P'1
1
" rt
0
1
1

.. , (one Ca awm per munumcr) OIIPt>v with u

, . 1 of calctum 1l1c HlSCI s 1uw:. I lc u I""" . . .- .. . . (fm u
ucpust ton . . . I . b. k u to emphasize the calctum-ltluu..:u '
simplccstimah: of th.: c cctmn 'IC gmuu . .
Ret. (66J).
5.5 Polymer Surftlt'es wtd lmerfaces
133
sponds to pristine DHPPV. while the upper-most curve corresponds to the pres-
ence of about one Ca-atom per DHPPV monomer unit, as detennined from the
relative intensities of the XPS Ca(2p) and C(l s) core-levels. The energy scale is
relat ive to the vacuum level, determi ned <L'i described above, and the Fenni en-
ergy lor C<tch spectrum is indicated by black bars. The XPS bindi ng energy of the
Ca(2p) level indicates that the Ca atoms are in the ionic lonn. At the first stages
of Ca deposition onto the polymer surface, a complete doping of the top layer oc-
curs, as probed by UPS. and upon addi tional deposi tion satur.ttion doping is at-
tained in the surface region. The excess Ca <ttoms in the surface region :then dif-
fuse somewhat into the bulk. Finally, the C(l s) spectrum broadens and shifts
s lightly towards a lower binding energy as the deposit ion of calcium continues,
indicating charge tmnsler from the calcium to the carbon atoms. As a result of the
deposition of Ca, the work function of the sample changes from 4.0 (0. 1) to
3.0 eY, which is close to that of metallic calcium.
In the low binding energy parts of a UPS spectra, signatures of charge tr-clllsfcr
(doping) versus covalent chemical bonding can be distinguished. New features ap-
pear in the previous empty energy gap, which is more clearly shown in the inset
of Figure 5-13, where a simple subtmction of the inelastic electron background
signal has been carried out in order to the interpretation of the new in-
duced states in DHPPY. It can be seen that two new electronic states above the a-
band edge of the pistinc polymer. near -4.0 eV and - 5.8 eV relati ve to the vacu-
um k vd . arc induced upon doping. Details such as the position wi thin the other-
wise ' " ' dden energy gap, and the relative spliuing of the two new states, arc
similar to those in the case of sodium on PPV 1701 and sodium on cyano-substi-
tuted PPV 171), where two new (bipolaron) stales wi thin the gap were observed.
In both calcium and sodium doping of PPV, features corresponding to doubl y
charged species arc detected even al the lirst very low doping steps (66, 70. 7 1).
In the case of rubidium doping or PPV, however, an evolution from singly
charged species at very low doping levels to doubly charged species, correspond-
ing to a polaron to bipolaron tmnsition, can be detected as the doping level in-
crea'ics 172].
Some results from XPS studies of the interface formation between calcium and
PPVs have been reported by Gao and co-workers. The studies have been focused
mainly on the interface fonnalion with the lctmhydrothiophenium precursor PPV
162-65. 671. but <tlso on an oligomer of PPV containing six phenyl groups (761 as
well as some PPVs substituted with phenyl groups on the vinylene moieties (771.
A general result from these studies is that binding energy shins arc detected li.1r
both the C(ls) and Ca(2p) (as well as in the O( ls) when oxygen is present in the
sample:;), as the ovcrlayer grows. In the polymer C(lscs 162-65, 67. 771. the sur-
races showed an oxygen conlitmin;Hiun r.mging from 4 up lo 17 at.%, and in
some cases sulfur impurities remaining from the precursor, which are most
likely to act as re<tction sites for the vapor-deposi ted calcium. The shift in the
C( Is) peaks in the samples has been allributcJ lo a band bt'llding in the
C<tsc l(>r the polymers 162-(>5, 67
1
771 and to molemlar eua1:y h!l'el b<'nding in
the case of the PPV oligomer deposited onto a calcium surface 176). This is the
same inlerpl\!lation as in the: case of dc:pusilcd 0 1110 PPY as
134
5 kclronic Structure of SurftJces wullnterfaces ill Conjugated
above, where also a shift in the C( l s) peak was the same [57,
58). It is important to repeal here, that the core level sh&tts can be explamed m al-
ternati ve terminology [73].
5.5.2 Polythiophene
Polythiophene [78} is a promising .rr:ateriaJ for applica-
tions, due to its relatively high stabthty and. m the form
[79-81]. Upon substitution, with e.g. alkyl stde-chams [79, 80], ex-
hbt properties such as solvatochromism [82} and thennochromtsm [83j.
a large variety of substituted polythiophenes with various band gaps extsts
(for example sec Ref. 1811). .
Two Hc11 UPS spcctr.t of poly(3-hcxylthiophenc), or P3HT, compared_ the
DOVS derived from VEH band structure llBI. shown 111
5- 14. n
1
e geneml chemical structure.: of IS sketched. tn Flg_-
ure 5-4. The two UPS spectra, were rcconlcd at two_ dtlfc_rcnt
+190C and -60"C, respectively, and the DOVS wm. dcnved VEH
t" ons on a planar confom1ation of P3HT. Compared to unsubsut utcd polythto-
the main inOuence in the UPS spcdm due to the prcsence of the hexyl
+190C
.
--
UPS
...........
.. . : .
...
-
..
..
-60 c .. _.
VEH
-20 -15
-
. . ..-... .. .
:
.
,.. .,.
. . ....
. . , .
: .
. . .
. .
..
_ ..
-10
. .
. .......
., .___
-5
BINDING ENERGY (eV)
0
lo' igun: 5-14. He 11 UPS o f poly(J.Iw.:xyllhiuphcne). r.xuruc<l at ami +190"C, <. -ontpan:c.l
with DOVS derived from VHI calculattons (lrom Ref. 11131).
5.5 Polymer Suifaces ami l11teifaces 135
side-chains, is additional intensity in the energy region from about - 5 to - 12 eV,
as deduced by comparison with the fine details in the YEH calculations. The en-
ergy region below - 5 eY is derived entirely from electrons in the uppermost n-
bands. Thus, the frontier orbitals which are important in, for example, metal/poly-
mer intemctions, are unaffected by the hexyl-chai ns. From a spectroscopic point
of view, however, one problem with the side-chains is that the XPS C( l s) core-
level signal from electrons in atoms in the thiophene units will be obscured by
the signal from the carbon atoms of the side-chains. This effect will be discussed
in more details later in connection with the interaction between and
polythiophene. When comparing the fine details in the low binding energy part of
the UPS spectra with the calculated DOVS, it can be concluded that the spectrum
recorded Cit -60' 'C corresponds to " more planar situation than that recorded at
+190"C. This is in agreement with optical absorption spectroscopy. where it was
founll that the optical hand gap increases with increasing tcmpemturc [H2J.
5.5.2.1 I nterface Forma tion Between Aluminum and Polythiophene
The evolution of the XPS C(l s), S(2p). and Al(2p) core level lines, upon AI de-
position onto poly(3-octylthiophcnc) films (PJOT), is shown in Figure S- IS ll$41.
The S(2p) spt.-ctrum for the pristine polymer consists of two components. S(2p
1
d
and S(2p_v::! ). tlue tu spin-orbit coupling.
The main clkct upon AI deposition C<UJ be seen in the S(2p) core level, where
a new component is gradmtlly growing on the low binding energy side of the
peak. Also in the C( Is) spectrum, a small shoulder can be seen on the low bind-
ing energy side. However, for most of the samples, no shoulder was found on the
C(l s) level, and only a very weak shoulder could be found in some of the sam-
ples at the highest AI coverage, as seen in the C( Is) spectrum (to the left) in Fig-
ure 5-15. Since aluminum is expected to intemct preferentially with the carbon
S(2p).A Al(2p)
z
C(1s)
0
'
E
(/)
c 0
:>
t
I ll.
-e
I w

0

C(

(!)
u;
z
z
(j)
w <
1-

w

a:
0

290288-286284282-280 170168166164162160 80 -78 -76 14 12 70 -68
BINDING ENERGY (eV) BINDING ENERGY (eV) BINDING ENERGY (eV)
lo' illurc 5-15. XI'S C( Is). S(::!p). :Uitl Al(2pJ SI><XII"a of the AVP.lOT for AI ' :over-
age. ntc C( Is) anu S(::!p) spe<:tr.t of lhc pristine system is al lhc lx>llom and inc reas ing AI cuvcragc
(frnm Ref. 111-i iJ.
136
5 Electrollic Structure of Sutfuc:es and lllletfuc:es in Conjugated Polymers
atoms of the conjugated backbone [85), and the C(ls) spectrum of P30T is
nated by the aliphatic carbon :lloms of the side chains, . any _new carbon spectes
might be small in numbers, because not only do the ahphattc carbons
the major contribution to the C(ls) line, but also because a pru1 aro-
matic carbons are expected to be affected by the AI deposttlon. '!'he mrun hne . of
the Al(2p) shifts slowly towards a lower binding energy as the thackness of AI an-
creases which is consistent with cluster-like growth of AI on the surface. The
energy of the Al(2p) is - 74.0 eV at the lirst . AI and shifts
slowly to - 73.3 eV for an AI layer equivalent to a few A, _as stall somewhat
different from the bulk metal value of - 72.7 cV. A low mtensaty component ts
present on the high binding energy side of the Al(2p) peak (corresponding to AI
atoms where the electron densities arc lower relative to unaffected atoms). A small
amount of oxygen was detected in the P30T films, about one per ten thio-
phene rings, indicating that this component might conespond oxadazed
A complementary study of the inter.JCtion between alumanu_m and tht?phene
was carried out by using a model system consisting of a polythaophene oligomer,
namely a-sexi thienylcne (a-6T). The lack of aliphatic side chains that
the C( 1 s) signal from the carbon atoms in the bockbone, and the possabahty m
situ prepamtion of films, i.e., obtaining contamination (oxygen) free samples from
a-6T, allows for more detailed information. The C(Js), S(2p), and Al(2p) core lev-
els upon AI deposition onto a-6T arc shown in Figure 5-16 For AI on a-6!,
a shoulder apperu'S more clearly on the low binding energy sade the mam
line upon AI deposition. The evolution of the S(2p) line as to
the evolution of the S(2p) observed for the case of alummum deposated ont_o
P30T. The evolution of binding energy for the Al(2p) line is similar to what as
observed for AIIP30T, except for the fact that no high binding energy component
is detected, indicating that this feature seen in AI/P30T, indeed. is related to the
formation of AlO,. species.
S(2pA
z
C(1s) 0
E
'iii en
'E
0

Q.
:::
w
.e
0
C{

(!)
.. z
Ui
Ui
z <(

... w
a:
.
()

290288 286284 282260 170 168166 164 162 160 80 78 -76 74 72 -70 68
BINDING ENERGY (eV) BINDING ENERGY (eV) BINDING ENERGY (eV)
Figure 5-16. XPS C( ts). S(2p), and Al(2p) spcclm of the Allu.-6T inlcrfucc for incn:a.,ing AI cover
age. The C( Is) and S(2p) sp.:clra uf lhc prislinc syslcm is al lhc tx1IIUIII ant! AI ..:ovcr.,gc
(fmm Kef. 11141).
5.5 Polymer Swfaces am/ llllerfuus
137
From the experimental data presented above, the conclusion would be that AI
reacts with both the sulfur atoms and the carbon atoms in the backbone of the
thiophene units. However. the result') from both semi-empirical MNDO calcula-
tions on a aluminum/a-6T system, and ab initio quantum-chemical calculations on
a aluminum/a-trithienylene (a-3T), shows that the aluminum atoms preferentially
fom1 bonds wi th the a-carbons of the thiophene rings (86 J. The AI-C bond leads
to a redistribution of the charge density in the Al-oligothiophene complex relative
to the sepamte . pa11ners. The aluminum atoms become strongly positive, as ex-
peeled, and electron density is tmnsferred to the a-carbons and the adjace.nt sulfur
atoms, while the atomic charge of the fJ-carbons remains unaffected together with
the charges on the thiophene units without aluminum. Although the amount of
negative charge transferred from the AI to the C ru1d S atoms diffe.rs somewhat
depending upon the computational level, <til of the calculations point to a charge
lhl! AI 10 the a-carbon and the adjacent S, and only to U1cse sites.
On lonnallon of a bond AI and a a-carbon, the hybridisation of that car-
bon atom changes from sp
2
to sp:\ i.e . the conjugation is broken at these si tes.
1l1is selective bonding of the AI atoms to the a-carbons can be explained in terms
of the electronic structure of the lowest unoccupied states of the pristine mole-
cule. These states are lound to hybridize with the AI valence levels to lorm the
occupied states of the complex. Since these states obtain a large contribu-
llon lrom the a-cruixm. it is expected that the bonding ptdercntially takes place at
these si tes. Reaction of the AI, which is an electron donor. directly with the sulfur
atoms. is less likely, due to the inherently high electron density on those sites.
Thus. the combined expeaimental and theoretical results indicate that U1e chemi -
cal shift observed for the S(2p) core level, of about 1.6 eV, should be due to a
secondary effect from the allachmcnt of AI atoms to the adjacent carbon atoms.
Indeed, this is fully consistent with ab iuitio Hartree-Fock llSCF calculations of
chemical shifts in aluminum-oligothiophene complexes (87). From culcula-
hons on a Al2/a-JT complex, where the two AI atoms arc attached to the a-car-
bons on the ccntml thiophene unit, the chemical shift of the S(2p) level for the
sulfur atom is found to be 1.65 eV. which is in close agreement with the
value about 1.6 eV (84). It should be pointed out that although
seveml dtflerenl Al-thaophene complexes were tested in the llSCF calculations, no
stable structure, where a11 AI atom binds directly to a S atom, was found [87 j.
The spectra (not shown here) recorded upon AI deposition onto the conju-
gated thaophene systems shows only small visible changes in the positions of the
in the spectra [84]. 1l1e main ciTcct is a rapid decrease in intensity, which
mdacates that a metallic overlayer is formed since the cross-sections for the
Al(3p) or AJ(3s) are much lower than for the C(2p) or S(3p) orbitals. This is con-
sistent with the Al(2p) XPS spectm discussed above .
5.5.2.2 Interface Formation Between Copper and l)olylhiophcnc
The XPS S(2p) core level spectra recorded duaing the stepwise deposition of cop-
per onto poly(3 hcxylthiophcnc), or PJHT (S8J arc shuwn in Figure 5- 17. The
S(2p) spectrum at the top correspond to the pristine system. On increasinl' l'tlJlfX'r
138 5 Elearonic Structure of Surfaces tuul Jmerfaces in Conjugate'/ Polymers
168 166 164 162 160
BINDING ENERGY (eV)
Figure 5-17. XPS S(2p) spcc1ro1 of the Cu/PJ HT interface fa Cu covcmge. The S(2p) spcc-
uum of the pristine system ;11 the top and Cu downwards (adapted from Rcr.
)88)).
covemge, a new feature is growing up on the low binding energy side of the
S(2p). The new feature has a binding energy shift of about 2 eV towards lower
binding energy, indicating an increase of electronic charge on the sulfur atoms
due to the interaction with the copper atoms. As in the case of P30T discussed
above, the C( Is) spectrum of P3HT has a large contribution from the alkyl side-
chain. However, in the case of AVP30T, a weak signal on the low binding energy
side could be detected at a high level of aluminum coverage, while no visible
changes in the C(ls) signal occurs in the case of copper deposited on P3HT [88].
Thus, the results indicate a direct intemction between the copper atoms and the
sulfur atoms in the thiophene units.
This interpretation is supp011ed by the results from a combined experimental
and theoretical study by Ghijsen et a/. [89]; the copper on P3HT interface was in-
vestigated by photoelectron spectroscopy, using synchrotron mdiation as the
photon source, and combined with the rcsullc; from quantum-chemical calculations
performed using a density functional technique. The valence band spectra, re-
corded with 40 eV photons, shows no significant change in the low binding en-
ergy part of the spectra upon copper deposition, i.e., the frontier orbitals seem to
be unaffected by the copper atoms; the highest occupied n-band is delocalizcd
along the carbon backbone in the case of polythiophene. The calculations resulted
in a optimized Cu-S bond of about 2.2 A, indicating that a strong bond has taken
place between these atoms. Also, the geometric structure of the carbon backbone
is not significantly changed by the Cu-S bond, in agreement with the lacJ... of ob-
servable changes in the low binding ene1-gy pan of the experimental spectm (89J.
In addition to the Cu/P3HT system discussed above, Lachkar et ul. have re-
ported results from studies on the intemction between P3HT and Cr, V, Ti, Ag,
and Au [88, 90]. From the expe1imcntal results it was concluded that Ag, as in
the case of Cu discussed above, interacts exclusively with the sulfur atoms; Cr. V,
and Ti inteJ<tCI with both the carbon and sulfur atoms; Au does not interucl al all
5.5 Polymer Surfaces and Interfaces
139
with P3HT. In a separate theoretical investigarion of the interaction between thiu-
ph.ene. and the V, Cr . Cu. and Au, using a density functional technique, the
the. resul ts .ror the cases of copper and gold [91 ).
J..e., no .nh.:r.JdJon was found lor gold whrk copper was found to intemcl exclu-
WJih the atom:-; in the thiophene unils. However, in the cases of vano.t-
dJum and chrom1um. it was found that strong covalent bonds arc fonned between
the V the a-cart>ons in the thiophene unit, and similar, but weaker.
covalent occur between Cr and all the conjugated atoms in the
phcne umt (91 ). Thus, the changes in the S(2p) signal, detected upon deposition
of':' and Cr, could be attributed to a secondary effect, as in the case of the inter-
acLJon between AI and P30T discussed above.
5.5.3 Polyaniline
has past few ycaJ'!\ been considered for a number of applica-
such as optical tracers, COJTOsion inhibitors, and anti-
films texllles .. Pulyamhne has outstanding redox prope
1
1ies and a divcrs-
. through substitution. The geneml fonnula of polyani-

dtsplaycd m. F1gure 5-4. Three base (neutral) forms of polyaniline have

been the fully reduced leucoemeraldinc lorm (Y= I), the half oxidiz.cd
emeraldmc lonn 1/2): and the full y oxidized pemigraniline fom
1
(Y=O}.
the m the literature photoelectron spectroscopic studies of pol _
anthne can be found: (1) polyaniline in different oxidation states
the dopmg mechantsm [92- 971; (ii) the inte1face formation with metals or semi-
conductors and (iii) corrosion protection [102- 104).
The spectm of the ememldine base fom1 of polyaniline is
compared wJth VEH-dcnved OOVS in Figure 5- 18 J97 j. The DOVS were derived
from the VEH band structure cakulations shown at the botlom of Figure 5-18.
agreement between the experimental and theoretical rcsull-; in
par1tcular m the low binding energy region extending from - 10 to - 5 eV which
to the n-band region. allows for a detailed assignment of the differem
f'?'tures Ill the spec.trum. TI1e feature at - 5.5 eV 01iginates from the highest occu-
pied molec:ular orbual (HOMO) which corresponds to electronic states localized
on the ammo groups and the aromatic rings they sunound. The small feature at
eV. to electrons in the second and third highest occupied rnolec-
_.orbttal, HOMO-I a.nd respecti vely. The HOMO- I orbital is mainly
over the amme umts and the phenyl ri ng while the HOM0-2 is dclo-
cahzcd all. rings and units. The peak at - 8 eV originates from
m several llat ?ands whtch coiTcsponds to. electronic states completely
l?cahzed. on. the nngs. In the next section, the interaction between polyani-
hne and Jndum-tm oxtde will be discussed.
140
5 Electronic Structure of Surfaces and Jmerfuces ill Co11jugatcd
::j
d

u;
z
w
......

VEHDOVS
- 15 -14 - t3 -12 -11 - 10 -9 -8 -7 -6 -5 -4
1
B
.....
..!:.
II IIIII
-"'
0
-15 -14 - 13 - 12 -11 -10 -9 -8 -7 -6 -5 -4
BINDING ENERGY ( eV )
Flgure 5-18. UPS speclnlm of the emcr.lldinc ba.o;c form of polyanilinc is compared with the VEH cal
culaled band strudure (bouom) and lhc VEH DOVS.
5.5.3.1 Polyanilinc on Indium-Tin-Oxide
Concerning studies of metal/conjugated polymer interfaces, the main focus has so
far been on the interface fonnation between conjugated polymers and metals of
interest for electron injecting electrodes in polymer light emitting devices.
Although other transparent, high work function, _ exist,
(ITO) is so far the most commonly used hole mJectmg contact m LEOs. Cml?-
pared to metal-on-polymer interface formation, as discussed above_, muc_h ts
known abo ut the intcmction at the polymer-on-ITO interface. Befor-e dtscussmg
the actual interface formation between polyaniline and ITO, some aspects of the
ITO surface itself are outlined. .
One of the most important parameters of ITO, apat1 from the transparency,
the relati vely high work function. In a compamti vc photoelectron _
study of ITO from different sources, atld prepared hy diiTcrent tcchmques, a varm-
tion in the chemical composition and work functions are reported ( I 0 I, I 051. For
three carefully chosen types of ITO, the chemical composition and wort- functions
5.5 Polymer Surfaces und lllterfuces 141
were determined, using XPS and UPS, a.-; a function of sample-cleaning proce-
dures. After cleaning with acetone and isopropanol in an ultra-sonic bath, the
work functions vatied. by some tens of an eV, between the different ITO samples,
whilst treating the samples with hydrogen peroxide r"l:sulled in about the same
work function (4.60. 1 cV). In the Iauer case, it is interesting to note that both
the chemical composition (ln/Sn r.uios ranging from 7 to 9) and the morpholooy
varies between the different ITO sampl es [I 0 I]; the surface roughness, as
by atomic force microscopy (AFM), vatics over the range of 25 to 100 nm [101).
Also, when using the ITO substrates in LED devices the influence of the substr.uc
precleaning on the device pcd"om1ance ha.o; been studied (I 0 I, I 05). The hydrogen
peroxide treatment clearly improves the device perfonnance, which could be at-
uibuted to the increased ITO-workfunction. Most interesting is the fact that,
although an improvement in the device performance was found for the hydrogen
peroxide-treated ITO surfaces and that the work functions are the same, the pcr-
fonnancc varies. This demonstrates that both surface roughness and work function
have primary inllucnce in the hole-injection characteristics at the polymer-on-ITO
interface.
Although polyani line has not been used as the acti ve polymer itself in LEOs, it
has been used as an additional layer to improve the device performance. For ex-
ample, by usi ng a combination of doped polyat1iline atld ITO as the tmnsparcnt
anode of a polymer LED with MEH-PPV ao; the active layer, the volt-
age was lowered and the quantum eOiciency increased si!,'Tlificantly, compared to
devices using ITO alone as the hole-injecting atlOdc [106, 107). 1l1is effect was
attributed to a higher electronegativity of doped polyaniline as compared to ITO.
which then provides a lower batTier to hole injection into MEH-PPV ( I 08 J. In
multilayer LED devices based on poly(2,5-dihexadccanoxy phcnylene vinylene
pyridyl vinylcne), undopcd emer..tldine ba'ie has been used as an insulating layer
between the emissive polymer layer and the electrodes, resulting in a decrease in
the total resistance as the number of insulating polymer layers increases (109).
Thus the nature of the electrode/polymer interface plays a critical role in dctcnnin-
ing the device
Also, failure modes in LEOs due to the ITO substmtc, such as indium cJiO"usion
into the active polymer (IIOJ and oxidation (degmda tion) of the emissive poly-
mer, where the ITO acts as a source of oxygen f i ll, 1121. have been repor1ed. In
this context, coating the ITO-anode with polyaniline, ao; used in MEH-PPV-bascd
LEOs, was reported to stabilize the chemistry of the electrode-polymer interface.
In addition to a higher c urrent and brighter emission, the polyanilinc injection
layer lowered the rate of degradation ao; compared to uncoated ITO. This was <tt-
tributed to a reduced oxidation or the emissive polymer as the polyanil inc layer
pmvidcs a barrier for the passage of oxygen out of the ITO. In addition. an im-
provement in microscopic shot1 fonnation indicated a planati:t.ation of the anode
interface by the polyanilinc film f l l:! 1.
Ultra-thi n lilms of polyaniline may be spin-coated onto the ITO substmtcs. By
studying thick lilms, spct:tm of the polymer itself arc obtained. As the thickness
of the polymer overl;tycr is some of the subtle details of the intcrf;tcc be-
tween the very thinnest possible polymer l;tycr (essentially a mono-layer, in the
142 5 Elec1ro11ic Slruclure of Sutfaces a11d buerfac:es u1 Ccmjugaled Polymers
best case) and the substrate (ITO) may appear. In the best case, enough detail can
be seen to infer infonnation about the nature of the intemction of the polymer
with the ITO. Emeraldine base films of ditTerent thicknesses have been studied by
XPS, with particular attention made to the N(ls) core level spectra. One such se-
ries of spectra is shown in Figure 5-19. In the case of the thickest film (at the bot-
tom), the N( I s)-emission contains two components with spectral peaks at binding
energies of about 400.2 and 399. 1 eV, corresponding to the amino- and imino-ni-
trogens in the emcraldine base. Decreasing the film-thickness leads to a decrease
in the intensity of the main amino-component in the N(ls) spectrum, while a new
shoulder appears at higher binding energy. From an analysis of the data it may be
inferred that there is an imcraction between the amino-groups in emeraldine base
and the ITO-surface [101(. One complication with the interpretation of the N(ls)
spectra is that the commonly used solvent NMP, which can ditlicult .to remo.ve
from the emcrakline base, contains ni trogen. The N( Is) s1gnal assoc1atcd w1th
NMP would appear al the high binding energy side of the amino-component, at
about the same binding energy as the new feature appearing in the spectrum at
the top in Figure 5- 19, and adding intensity to this region. Thus, the dcacaM: in
intensity for the amino-nitrogen contti bution still indicates a reaction between ITO
and the amino-nitrogens.
In a complementary study of the intcmction between polyaniline and ITO, oli-
gomeric polyaniline model compounds, namely phenyl-cappc.d amino (PC2) .and
imino (PC20X) dimers [1 13, 114) have been used. The chem1cal shuctures of
polyanil ine oligomers arc displayed in Figure 5-20. Both substances arc soluble m
408 406 404 402 400 398 396 394 392 390
BINDING ENERGY (eV)
J'igure S-19. N(ls) XPS cmc lc"d spcc1r:1 uf cmcmlllinc_ ;ltl:""il. .. -d on ITO. The hlfl must
lrum corrcspum.ls hi uhr.Hhi n lihn (in 1hc munu layer rcgnnc) wlulc rho.: houum spccuum cum:SfXMIOs
to lhick film.
5.5 Polymer su,faces Gild llllerfaces
143
PHENYL ..CAPPED AMINO DIMER (PC2)

I - I -
H H
PHENYl-CAPPED IMINO DIMER (PC20X)
uf lho.: pulyanilinc mudd .:umpuunlls I'C2 pltenyl...:app..-d
an1lmc tluncr: illlllllO cumpnulltl) anti i'C20X (uxidi1.<--d phcnyl ...:oopf".'m solutions with dill'crcnt concentrations of the oli .. o-
mcrs in chloroform by spin-coating onto ITO-samples. The ITO surfaces
prcdcaned by ozone treat ment over a period of 5 min.
A. of XPS N(ls) core level spectra, recorded for different thicknesses of
the muno compound, arc displayed in Figure 5-2 1. In the case of the thick
PC20X-Iilm, the N( I contains a main component at a binding energy
of 397.8 eV, together wuh nunor peak components at 3'J'J.4. 401.6, atld 405.1 eY.
1l1e Iauer peaks arc auributed to shake-up tmnsitions and wi ll not be discussed
further. thickness decreases, a bmadcning of the N( 1 s)-emission to-
h1gher bmdmg occurs. This evolution is completed when only the
chen.llsorbcd 1s present on the ITO-surface, result ing in a broad, sym-
metnc N( I s)-emtss1on composed of the 01iginal component (slightly shifted to
eY) and an additional, high binding energy component at 399.3 eY. This
sphllmg of the N( l s)-emission indicates that there is an intemction between one
of the two imino-nitmgens in the model compound and the ITO-surface whereas
the imino-nitrogen docs not interact with the [I 14].
However, 111 the correspondmg scncs of spcctr.t for the! amino model compound
(not shown here), the N( I s)-emission cssemially remains unchanged at a bindino
energy of 9 .e Y, except for a small incrC<.Jse of the width of the peak. o
The low energy parts of the UPS-spectra for increasingly thinner layers
of both the compound (PC2) and the imino compound (PC20X) on ITO
me shown m 5-2:!. the case of the thick PC2-li lm, the low binding
energy electromc sllucture d1splays well resolved peaks at - 5.8, -6.9, -8. 1, and
- 9. 1 A, B, C atld D). Decreasing the film thickness in a gradual
ol peaks and B, until a broad, unstructured shoulder is observed in the
hmal ol the chcnusorbed monolayer. Tl1us, although the XPS-rcsults did not re-
veal any of the atnino-gmups with the ITO-surface, such interactions
111d1cated by _the UPS-spectra. Even more dramatic changes of the low-
bmdmg energy clcctromc structure occur for the imino-compound, upon mlcrac-
144 5 Electronic Structure of Surfaces and lnterfuces in Conjugated Polymers
THICI< PC20X-FILM
z
-:-
()
=!
:0

m
)>
(:
z
en
CHEM. + PHYS. PC20X
G>
z
-I
w
1-
r

0
A
z
m
(/)
MONOlAYER ON ITO
C/l
--405 --400 -395
BINDING ENERGY ret. to fF (eV)
lligure 5-21. N(ls) wrc level spectra of the iminu llllxlel mmtxuolll 1'<:20X alhurhcu out ITO. The
upper curve to a thick lilm, lhc ..:entral curve tu an imcnncuiatc thick lilm, and th..: luwer
curve to an ultr.s thin lilm, csscnJi:tlly a mono-layer in thidncss. The bold solid lines art.: the liued
curves and the thin solid and lines al\: the Gaussian peak L-omponcnlS for physisorbcd and che-
misorbcd PC20X, rcspeclively.
tion with ITO. As seen on the right in Figure 5-22, three resolved peaks appear in
the low binding energy region at about -7.8, and -8.6 eY (labeled A, Band
C) for the thick PC20X-Ii lm. As the film thickness decreases towards the limit of
the chemisorbed monolayer, the three peaks coalesce into a broad peak :.tl -8.2
eV, with a shoulder tailing towards low binding energy. Together with the split-
ting of the N Is-emission observed in XPS, these results clearly indicate a strong
interaction of the imino-groups with the ITO-surface.
In summary, the results for the case of the polymer indicate that only the arnino-
nitrogens interacts with the ITO surface while the model studies demonstr.Jlcs that
both amino- and imino-groups reacts with ITO. Thus, ful1her investigations arc ne-
cessary in order to obtain a complete picture. Studies using model systems that con-
tain the whole cmemldinc base SCC.Jucnce have been ini tiated [ 114[.
5.6 Summary
Some del:.tils of the electronic structure of :.t specific metal-on-polymer interface
h:.tve been presented to illustnuc the importance of sut.:h interfaces in dctennining
5.6 Summary 145
C/)
--
C/)
:;;
UJ
z
--
.!!!.
:;;

0
.!!!.
r
>-
Ci) 1-
1-
z CJ Ci)
UJ
z
z
1-
Ci)

UJ
<( 1-
UJ

lr
0

-15 -10 -5 -15 -10 -5
BINDING ENERGY REL. VACUUM LEVEL (eV)
F1gure 5-22. UPS ' l"-'t."Jr r lh
, a n C <lllllllll molt)d Clllll'" >UIId J'C2 (I I\) I .
I C20X <rHII). ;>liM>oi><:d nn ITO l l . . ,.. " <10< 1111111u mtlllcl cnmpuunu
.. "" tIJCmnM curves arc the I tell pl.'\: f 1 k "I
an: I he dtllen:nce SIIC<:tm (Bell) hctwcen in.-rco.sin I
1
. . _ s o tue lo mhcr curves
Tile lower t:urv.:s CUITCSjllllld to tlllr.s-thin y ,,IIIIICI lolms llll I ro uno a clean ITO Stufac.:.
s. cs.-.cnu.o Y a mono-layer 111 lhickncss.
device performance in polymer LEOs ln evet . .
some chemistry that occurs at the inteliace Th:' there always
a1
1
ere IS no such thmg :.ts an Ideal
l -po without interfaci:.tl chemistry of one SOI1 o . h Th me-
conclusiOn :.tpphes
10
the
1
.,., . 1 anot cr. e same
l
. f
11
po ymer-on-( , 0 IIUeface, a.c; demonstmted by the 11
ac 10n o 1e emerald, b d h .
11
er-
und . . I a'>e an . c two oligomeric polyanilinc model com-
po s With ITO. In this context, ll IS clear that the ult' . I .
face will be one of the m . . . . . . llll:.tle contro of the mtcr-
po
lymer-b .. electro . d aJ_Or dctemunmg steps m the exploitation of reliable
... -..ou niC eVICCS.
Ac:knowlcdgcmellfs
.. th_e and t.:oopcr.Jtion of :.til of their collea-
R be ... .. Y_ pet alive ICscut-ch projects, but I.!Speci:.tlly Jean-Luc B .

Eymard Reboun,
a TMR Network

Hoc I t A B ,, .
1
S well .ts by a contr;u.:t Wtlh
t.: ls . . ,escaL-ch on conJU":.tlcd polymen; in L" k.. . . .
end by grant f. h S . . o .
111
opmg Is suppo11ed m gen-
. . . s tOm l e . Natural Scaenccs Resc:.trch Council (NFR lh,
Counc1l lor Engineering Scient;es (TFR) and
1
, S . . ), . e
llonal Bo:.trd tor and Technicul Development (NuTt:K). l lc wcdtsh N:.t-
146
5 Elearouic Structure of Surfaces w1d lmerfuces iu Conjugated Polymers
References
1. W. R. Salaneck. s. Stafstrom. J.L Dredas, s. Anden;son, P. BodO, J. RilSko, J. Vue. Sci. Tecll. A
1988, 6, 3134.
2. Polymr Surfaces (Ed.: D. T. Clark, W. J. Feast), John Wiley & Sons. 01ichcster 1978.
3. J. M. Andre, J. Oelhallc, J. L Bredas, Quwuum Chemislry Aided Desig11 of Orga11ic Polymen;,
World Sing;spore 1991.
4. W. R. Salaneck, S. Stafstr6m, J. L Brooas. ConjugaJed Polymer Surfaces und luJerfuces, Cam-
bridge University Press, C:lmbridgc 1996.
5. K. Siegbahn. C. Nordling. G. Johans.o;on, J. Hedman, P. F. Heden, V. Hamrin, U. Gclius, T. Besg-
mark, L 0 . Wennc, R. Manne, Y. Baer, ESCA Applied to Free Molecules, Nonh-Holl.and, tun-
stcrdam 1971.
6. D. W. Turner, C. Baker. A. D. Baker. C. R. Brundle, Molecular PhlltoelccJron Spec1mscopy, Inter-
SCience, London 1970.
7. S)mcllro1rm1 Nudiatio11 Heseurc:lt (Ed.: H. Winit:k, S. Doniach), Plenum Pre.o;.o;, New York 191l0.
8. Sylldlmlro HudiUIIcm Reseurc:ll: Advunces in Surfuce und llllerfucc &ielce, W1/. I (Ed.: R.Z
Bachrach), Plenum, New York 1992.
9. Pruc:Jkul Surfuc:e Anulysi.f (Ed.: D. Brig&-' M.P. Seah), John Wiley & Sons, 01ichester 1983.
10. W. R. Salaneck, CRC Cril. Hev. Solid Stiltt! Muter. Sd. 1985. 12. 267.
II. H. J. Freund, E. W. Plummer, R. W. S:1lancck, R. W. Bigelow, J. Cllem. Pllys. 1981, 75, 4275.
12. G. Wemlin, Structure und Bomling 45: /Jreukdow11 tif Jl1e PiLJurcs ill PIWIUf!leartm
Spectru, Springer, Berlin 1981.
13. 1-U. Freund. R. W. Bigelow, Plly.ricu Scriptu 1987, /7, 50.
14. C.S. Fadley in ElecJrotl Spt<Ciroscopy: Theory, Ji:dlllitJUCs u11d Applications (&Is.: C.R. Brundle,
A D. Baker), Academic Press, London 1978, p. I.
15. N. S:llo, K. Seki, H. lnokuchi, J. Cltem. S()(:. Furuduy TrUII.t . 2 1981, 77. 1621.
16. G. K. Wertheim, P.M. T. M. van Anekum, S. Basu, Solid Stuu: Cv11u11wt. 1980, 33, 1127.
17. W. R. Sulaneck, R. ErhmdS.'Il)l1, J. Prcjat, I. Lundstrom, 0 . lngauas, Symh. Mel. 1983, 5. 125.
18. C. B. Duke, W. R. Salancck, T. J. Fabish, J. J. Hitsko, H.R. Thomas, A. P..tlon, Pltys. Hl!v. 11178,
1118. 5717.
Ill. W. R. Salaneck, C. B. Duke. W. Ebcrhartlt, E. W. Plummer, H. J. Freund. Phys. Ht:t( 1..<!11. 1980.
45,280.
20. R Lazzatoni, M. Logdlund. S. SiafSirom, W. R. Salancck. J. L Bredas, J. Chcm. Pflys. 1990, 93,
4433.
21. E. W. Plummer, W. Ebertlanlt in in Chemiml Physics (Eds.: I. Prigogine, S. A. Rice),
John Wiley & Sons, New York 1982, p. 533.
22. T. R. Olmo. Y. Olen, S. E. Harvey, G. H. Kroll, J. H. Weaver, R. E. Hauller, R. E. Smalley, Phys.
Rev. 8 1991, 44, 13747.
23. G. Gens!erblum, K. Hevesi, B. Y. Han, LM. Yu, J. J. Pircaux. P.A. Thiry, D. Bcmaerts, S. Arne
linch, G. van Tcndcloo, G. Bendele. T. Buslaps, R. L Johnson. M. Fos."- R. Feidenhans'l, G. Lc
Lay, Phys. Rev. 8 J\194, 50, 11981.
24. A. J. Maxwell, P.A. Brilhwilcr, A. N. Manensson, Pllys. Hev. JJ 1994,49, 10717.
25. P. Rudolf, G. Genstcrblum, Pllys. Rev. JJ 1994, 50, 12215.
26. D. Jones, M. Guerr.t, L. Favarcuo, A. Modelli, M. Fabrizio. G. Dis!efano. J. Phy.r. Clwm. 191)(),
94. 5761.
27. H. Fujimolo, lJ. Nagashirna, H. lnokuchi , K. Seki, Y. Cao, H. Nakahara, J. Nakayama, M. Ho-
shino, K. Fukuda, J. Chem. l'hy.t. l9')Q. 92, 4077.
28. M. LOgdlund, W. R. Salancck, F. Meyers, J. L. BrCdas, G. A. Arbuckle, R. Friend, A. B. I Iohnes,
G. Froyer, MCicromuil:cules 1993, 26, 311 15.
29. W. R. Salaneck, J. L Dr6das in 0fl1UIIk Mu1eriu/s for Elecmmin (&Is.: J.L W.R. Sala-
neck, an<.! G. Wegner), North-Holland, Amstcrd:un 1\194, p. 15.
30. W.R. Salancck, Pllys. Nev. L.cll. 1978, 40, 60.
31. M.J.S. Dewar, W. Thiel. J. Am. Clltm. Sue. 1977, 99, 4M9<J.
32. M. J. S. Dewar, W. Th1cl, J. Am. Clwm. Soc. 1977, Y9. 4'J07.
Referellc:es
147
33.
34.
35.
36.
37.
38.
M.J. S. E.G. Zoebisch, E. F. Healy, J. J. P. Stewart, J. Am. Cltem. Soc. 1985 107 3902
t :redas, R. H. OJanL-e, R. Silbcy, G. Nicolas, P. Durand, J. CheJIL Plrys. 1981, 75, iss
rOOas, Salancck, J. Cltem. Pltys. 1986, 85, 2219.
E. J. L Bredas, J. Chcm. Pltys. 1988, 89. 100).
E. Ort1, J. L Brcdas, J. Am. Cltem. Sue. 11192. 1/4, 8669.
i l.Ogdlund. S. StafslrOm, W. Salancck, R.l 1. Friend, P. L Bum. A. B. Holmes.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
Sunoda, 0 . Utost, F. Meyers, J. L Bn!das, Macromolu ules 1995 28 1959
C.S. T.C. Clarke. Pllys. Ret. Lt:ll. 1983, 5 /, 1191. ' '
M.J. RIL-e, Phys. u'/1. 19711. 7/ , 152.
WP. Su, J. R. A. J. Heegcr, Plly:r. Rt<v. Lm. 1979, 42, 1698.
K. Fc..-.ser. A. R. B1shop, D. K. C:lmpbcll, Pltys. Rev. JJ J9l!J, 27, 4804.
A J. S. Kivel_son, J. R. Sehriclfcr. W.-P. Su, RC't: Mod. Pllys. 1988, 60, 781.
M. Schou m Orgmuc Conduclurs: Ftmdumemals aud Applications (Ed.: J P. Farges) Marccl
Dekker, New York 11194. p. 539. '
J. L. H. R. Chance. R. Silbcy, Phy.r. Hl't( JJ l \182, 26, 51!43.
J. S. M. l..iigdlunll. W. R. lJ. Kartsson D B SwaJl'iOn A G
MacD1anmd, G. A. Arbuckle. SyntiJ. Met. 1\191, -11-43, 1365. ' . .
WD. K H. R. C. U. Duke, A. Pmon, E. W. Plummer, A. J. HL-egcr A. G Mac-
I:U1nt . t1em. Pltys. 1979, 71, 2044. ' .
Salam:t:k, H. R. Thomas. C. B. Duke, E. W. Plummer A. J. Hcc.,er
S_1111l1. Mn 19711/11180. 1.
133
_ o A. G. Mat:Diannid,

Salan.:.:k. C. B. Duke. E. W. Plununer, A. J. 11e.:gcr, A. G. MacDiarmid, Po/r-

M. T:u1aka. H. Fujimoto. M. Shnniw, N. I I. lnukm:hi, J. dt Pllp;,
1
,,. 191!3. CJ,
51. H. lnokuchi . M. Oku. S. Hasegawa, C. Tanaka, J. T:utaka, K. Seki, Symll. Mn 1\191
52
JH__ C. Tanaka.! !"liyamac, K. Kamiya. M. Shimi.w, M. Oku, K. Scki. J. Tsukamoh> S
a.'egawa. H. lnukudu. SyntiJ. MtJ. 111113.55-57, 121.
53. S.A. Br.tw\'skii. N. Kimva. JI:TI' L.u. 11181, .lJ. 4.
54. I? llacriswyl in Ehnmnic <if Conjusmed Pulymer:r 111 (Ed"-; H. Kuzman M M ,I _
55.
56.
57.
58.
.".ng. S. Roth). Spnngcr. Ocdm. 1\1811. p. :'14. y. c
1
I. P. Nguy.,n, V. Ma.s.,..nli.,r. V. H. Tr.tn. A. Guyot, Srntll . Mtt. 19113 55 235
P. Dannclun, M. I..Ogdlwtd_. W. R Salancck. C. frl!driksson, S. A. B. Holmes.
:r';;n, S. Fnehl.l, 0. UtoSl, Mol. Cry.rt. Uq. Cry:n. 1993,228. 43. A.
ledgUI: H. Hazalnnmo, K. T. Park, Y. Gao. ll . R. H.' ich, J. ApJI. Plr>:s 11194 75 7526
E. EuedgUI. H Ruar.tr K T p- k . ' J
111115
,
23

119
_
1 11110
' ar Y. Gao, B. R. Smfuce wtd lnterfuce A11ul_v.us
59. F. M. G:.lvin. R. L Opila, J. of Applied Pllysic.r 1995.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
T. P. P. Lc Rcndu. Ca1lh:r, V. ll. Tra.n, Syllllt. Met. I IIY5, 72, 35.
T. P. J. L Manso!., 111111 Solul fll11u: 19116, 2HJ, 135.
B. R. Hs1eh, E. EltL'tlgui, Y. Gao. S.wuh. Mn 1\196, 269.
Y. Gao, K. T. Part. B. R. J. Clu:m. Phys. I 1192, 97. 69'J 1.
T. ll. R. Hsieh. J. tif Applitcl Plly.\ics I 11113, 7 J, 711'J4.
R_ Hs1.eh, E. K. T. Pa!"' Y. Gao, M<1l. Cryn Uc1. Cryst. 11194, 256, 7 1.
P. Dannciun. M. Fahlman, C. Fautjucr. K. Kacrijama, Y. Sonuda, R. I..:Jaaruni J L BnXJa.,,
W. R. Salant:c:k, Symh. Ml'l. 111\14, 67, 113. '
E. Euedgui, 11. H=lilrimo, Y. Gao. ll. R. 1-bich, M. w. Snull. Met. 19116 7lJ .,
4
7
T. P. Nguyen P Jonn:.nl F. Ver a. d 1> c b J 11 ' ' -
Mn 1\1!1
5
,
7
5, j
15
_ ' g
1
r . ->I<IU unun. M. L1plwwski, V. H. Tr.tn. S_wull.
T. 1-' . Nguyen. S. de Vos, Wtnmm 11196. -17, 1153.
M. Fahlman. D. ll"ljunn.,_ M. Liigdlund. H. H. A. ll . J L
m:c:k. C/um. Plly.. L.ll.
1993
.
2
1-1.
327
. Un:das. W. R. S:.la-
M. Fahhn:m. P. H.-<im_s. D. A. <klS Sanrus. S. C. Mor:llli. N.

K.
A u ' I 1 1 L ., _, R Xing, K H. Friend.
. u . '
11
llk.'lo, u n:u:.s. W .. Salam:cl., J. C/um. l'lly.r. 19')5, :?0.1!167.
148
5 Electro
11
ic Structure of Suifuces wad ltaterfuces ill Co11juguted Polymers
K x M L""dlund M Fahlman W. R. Snlaneck. Cltem. Plays. /..ell. 1995.244. 139.
72 G Iucca. . ang. '
. . R S:ll k J L BrM:ls Bull Mut. Res. !We. 1997. 22. 46.
73. W. anec ' . J L B Cdas. P. Dannetun M l...Ogdlund w. R. Salaneck. Syratlr.
74. C. Frctlriksson, R. Lazzarona, .
Mea. 1993. 55-57, 4632.
75. M. Uigdlund, J. L. Bredas, J. Clrenya. K Mullen Appl. Pltys.
76. Y. Park, E. Eucdgui, V. Choong, . oo, sa 1,
LA:II. 1996, _6Y, P: k E Eucdgui y Goo B R Hsieh PulyuL llltemmimwl 1!>195, 36, 147.
77. H. Razafitnmo,K. 's. .A J . S'ci . 'Polym. U:/1. Ed. 1980. /lJ, 9.
78 T Yamamoto ana..ol --" ' 1!6 1346
K y Yen G G. Miller R. L Elsenbaumer, J. Clrem. Soc. Clrem. Cumm. Ill
79. M. Salo, S. Tanaka, K.' Kaeriyama. J. Chen. !We. Cirelli. CotrUIL 873. . , Wen-
M. Berggren, D. G. Gusaafsson. J. Rasmus.wn, M.R. Amlcrsson, T. Hjettbcrg. D.
Nuture 19\14, 372,
444
.. 1 M l 191111 22 395
g 0 . W. R. Salamx:k, J.-E. OSI.cmolm. J. S),ata .... e. J E. r..' . J L Hre-
2. o Th . J 0 N lsson B Sjogren - vstcmo m, .
83. W. R. Salaneek. 0. lnganlis, B. cmans, a
S. Svcns.wn, J. Claem. Plays. 89, k R L:uzaroni, C. J.L. Bn!-
!14. P. Dannetun, M. S. Stafslrom. W. R. Sa ancc
R. Zamboni, C. Taliani, J. Claem. Plays. 1993. 99, 664.
85. J J Pi reaul\ C(}IIIIIIWlicmiun.
86. M. Boman, 's. S,tafstrtim. J. L. Clae'c ", Plays
1
.
H man H A ren, S. Stafstrom, J. rlays. IC'm. 77.,, "" "
A. s!lmani, E. ..
.. ). <If
"9 J GhaJ "'11 R. Laa.aronl, V. a rente. . . .,,.,.... . .
0
- ' . """ 71i '55
I::le(tmll
wtl Neluted 1'/aelllllllt'IIU I""" '

A Lachkar A Selmani, E. S:ICh.:r, Symh. Met. 1995, n. 73.
90. F.. Elrenin...". C. Frcdriksson, E. A. Scl_mani, J. Claem. Plays. 2187.
9
I. R ........ _,n
1
J R"aa J J Vcrblsl D. Gonbcau. J. Claem. ,. nv,
92 P. Snauwacrt, o ' 4 738
. G c D. Bloor, J. Phys. D: Awl. 1991, 2 . . . . .
93. A.P. MKonkrnan.K G .N."-L K L Tan X-ruv Phuwelecmm Spedrusco[Jic Studtes of Eleclroa<ltVe
94. E. T. ang. . . Lvo, . .
Polymers, Springer, Berlin, 1993. K L T; C H A Huan A.T.S. Wee, Sylllll. Mt't. 1993.53.
95. E.T. Kang, K.G. Ncoh, Y. L. Woo, .. an,
333. J R' J J Verbisl Sytu/a Met 1993 55-57, 1051.
96. X. Deman. G. Crislallo, P. . lg;.l, L"h R . Laz; . ni .J L BrMas. Symla.
97. Barta, T. KugiCJ, W. R. Salancck, A. P. Monkman, J. a crt, z.aro
M. Chtaib. p_ P. Dannetun, M. Ulgdluntl, K. , Uvdal.
98. R. R al:ux:d i.n Metullhed Pltwics 2 (Ed.: K.L. Minai), New York _J991: P: . ')9. ._
W. S C G_s. M Chlaib J J Pircaux in Pol)>llcr-Solid hllcrft"es (Etk. J.J. Pa
99. R. Laxt.aron. '"goarc, ' 13
reaull P. Bcrtr.md J. L lOP. Bnstol 1992, p. 2 .
7
. .
T K ' P. w. R. Salancck, Pmaeduag.r of ICPSI-2, Namur, 1!>19 .: an press.
100. T. f... Johansson, I. Dalscgg, U. Gel ius, W. R. Salancck. Symh. Met. an press.
IOI. M Fahlanan, s. Jasly, A.J. Epstein, Symla. Met. 19\11,lJ5, 1323; .
10;. p_j_ Kinlcn, D.C. Silvcnnun, C. R. Jeffreys, Mea. 1991. 135,
10 . A Talo P. P..ISsiniemi, 0 . Forstn, S. Ylasaan, S.VII tla. Met. _1997,85, I .
104. T. Osada, Onishi. T. Kugler, W. R. Salancck, 1\1\18, unpublashed.
Y. Yang, A.J. Hceger. Mol. Cryst. Uq. Cryst. 1!>194. 256, 357.
I07 y Yang, Q. Pei. J. A
1
1pl. Plays. 1995, 77. 41!07.
H 1 0 P..Jtker y Yang Symla. Met. 1994, 67. 23.
3 108. A.J. ecgcr, . . D: . "d y'z "'ang D D Gebler A.J. Epstein. Sym/1. Met. 1\196, 7X, 3 .
09 H L We A G Mac aanna . "' ' 1 ""k G
I . . . ang, . . 0 Wil . FlOC! A Hilbcrcr F Garten P. J. M. T. M. K apwaJ ' .
110. A. R. Schlalmann, . I '
Hatlliioannou, At'l'' Plays. 6:, J Salem J. A. Goilia, J. Appl. Phys. 1\1\16,
Ill. J. c. Scou. J. H. Kaufman, r
1
c '

c. Scou J. R. Salem, M. Angclopoulos, SymiL Met. 1996, IJ(), Ill .

: :i: T. Ku:kc: M. UigdluOO. W. R. S:llan.x:k. 11:.', 1\1\111, 32, 225
114. T. Kugler, unpublished.
6 Electronic Structure and Energy Transfer
in Solid a-Sexithienyl
Carlo Taliani, Fabio Biscarini, and Michele Muccini
6.1 Introduction
Semiconducting conjugated polymer.; have been widely studied over the last
twenty years for their unique electronic and optical which fundamen-
tally reside on the delocalized n-clectron structure. In the early stages of the siudy
of conjugated polymers it was thought that the n-':=onjugated backbone would pro-
vide Ihc pathway for coherent elcctmnic tr.msport within the macmmolccular unit.
Fut1hcr studies showed, however, that real polymers have a finile distribulion of
conjugated chain lenglhs and it became clear that electron transp011 would ulli-
mately be limited by inten:hain hopping. Oiher !rapping centers for electron trans-
port arc chemical defects of the macromolecular ensemble as well as morphologi-
cal disorder of the material. II was at lhis stage that the use of oligomers had the
fin;t impulse and was widely considered a valuable rouie to the underslmlding of
the inirinsic properties of conjug<lled polymers. In the early nineiies the develop-
ment of organic field ellect transistors (FET), based on u-sexilhienyl (T
11
) by Gar-
nier eta/. fl , 2] and conlirmcd soon afler by Osloja eta/. (3] and Dodabalapur
et a/. f41. clearly indicated lhat lhe availabili ty of chemically pure <llld ordcrcJ
solid-. was the requisite 10 achieve reasonable working conditions for the FET op-
eration. This finding opened the avenue for the developmeni of lhe so-called plas-
tic: elec:t mnics. Disorder moreover is dettime111al not only to electric 1r.mspo11 but
also, to a lesser extent, energy transport. Both charge and energy transp011 are
among the basic steps in the oper ..llion of the organic light emiuing diodes
(OLEO) 15. 6]. Recombination is followed by energy lransfcr within the manifold
of lhe excited electronic slales leading ullimatcly to an exciton. The notion of ex-
citons as lowest in conjugated solids is now univen;ally accepted since
the emission of OLEO is molecular in char.lCter as opposed to band-to-band mdia-
Iive electron-hole recombination. Exciions in molecular crystals were extensively
studied over the Ja.-.t decades (7, 8J. Anisotropic intennolecular intemctions in the
ordered molecular solids were shown to allow the fonna1ion of collective Bloch
electronic excil<llions (Frenkel excitons) in which the excitation is strongly bound
to the mol ecular enli ty and therefore is called tight bound excilon as opposed to
the weakly bound exciton (Wannier exciion) in inorganic semiconductor.;. Never-
theless, the exci tonic band sl11Jcturc of conjugated oligomers is not known and the
rclaiive energy of the lowest singlet Frenkel exciiPn with respect to lhe conduc-
150
6 Electronic Structure and Energy Transfer in Solid u-Sexithicmyl
tion band (the exciton binding energy) is still a matter of controversy. In this con-
text oligomers of polythiophene, and in particular u-sexithienyl (Tt.).
vidcd the basis for a deeper understanding of the nature of the electromc e.xclta-
tions in conjugated systems. Although solid T
6
is the focus of the work
in this article, many considerations drawn here arc of more general apphcat1on to
the conjugated organic materials. . . .
The oligomer approach to the investigation of. properties of matcn-
ab offers several advantages: the starting matenal has a well-del mcd molecular
composition, it can be purified by high vacuum (HV) and/or. rec?s-
tallization, and processed as a thin film by clean techmques such as
in ultra high-vacuum (UHV) in the absence of both an.d cc:>ntammants. It
allows the comparison of film and single crystal properties, wh1ch IS useful wh.en
the con-elation between molecular ordering and intrinsic response of the conJU-
gated material is sought. In Section 6.2 we describe the experimental
for the growth of Tt. thin films in HV and UHV, and the1r by
means of optical techniques and sc.:anning force microscopy. The
ture and the optical properties of T, thin lilms have discussed 111
two recent reviews [9, 10]. We first discuss the electromc structure ol ISOlated T<,
in Section 6.3, then in Section 6.4 we explain how the molecular levels form
Frenkel exciton bands. The spectroscopic investigation of Th single crystal shows
indeed that the lowest crystalli ne level (Davydov component) is accidentally for-
bidden as a consequence of molecular packing and that the splitting. of
levels (Davydov splitting) is as much as 2600 em- . Since the relat1ve
of molecules is the cause of the forbidden of the lowest cxc1ted sohd
level from which radiative emission (fluorescence) eventually occurs, it is clear
that molecular packing is a very impo1tant aspect that controls the photophysics
of molecular solids. The weak fluorescence quantum yield in solid T6. as opposed
to the free molecule, is due precisely to this solid state effect and not, as original-
ly thought, to the crossing of molecular gerade and .ungerude states [II). Sec-
tion 6.5 we will cover the fundamental aspects of thm film growth mechamsm as
a preliminary step towards the control in the way in grow
fonn complex morphological structures. We will show that 1t 1s to delib-
erately achieve various morphologies depending on the For
first time it is pointed out that the film morphology has a selj-qffine t.e.
the film arises from a recurrent building unit on a broad range of spaual scales
which establish a spatial correlation. This result is paJticularly relevant since
charge and energy transpo1t are both affected by disorder, although
the spati al scale at which these processes occur may d1tlerent. In f:U:t charge
transport is a process which explores the few neouest
while energy transport is a dipole-dipole (F6rstcr)med1ated lntcJ-actJon wh1ch ex-
plores a wider spatial range. Regardless of the scale of both charge and
energy transport may be govcmed by the same morphologcal In
Section 6.6 we will present our results on the clfcct of molecular d1sorder on the
electronic properties and on the photophysics ofT 6 both in single crystal and
in thin films and how this affects the polarization charactenst1cs of lluorescence
and dcctrolu,minescencc. In Section 6.7 we summarize our main lindings.
6.2 EA71erimental 151
6.2 Experimental
films grown high vacuum (HV) (base pressure 10-
7
mbar) by sublima-
tiOn of punficd matenal from a Knudsen cell in a moditicd commercial
Auto306). The configuration of the system is constant for all samples,
With the substmte placed 10 em above the quilrt: crucible containing T and nor-
mal . . T (>
. to Jls ax1s. he is heated on its back side by contacting with a resis-
ti ve plate and the effechvc tcmpcmture is calibrated by means of a thennistor
the_ mica surface wi th silver paste. A qumtz microbalance placed in the
proxumty . ol t.he moni tors the amount of the deposited mate1ial. The
qu.artz 1s earned ou.t using AFM by measuring the thickness of pat-
temed Til IJims .. an:_ obtamcd by growth onto a 3 mm diameter copper gid
(2000 mesh pcnodJclty) IJxed to mica and then -cmoved. The deposition mte is
lvs: and the llow of material and heat is when the desired nominal
th1ckness 1s
A second M:t of .was grown in UHV from a Knudsen cell in an organic
depos1110n (OMBD) appamtus (Rial Vacuum, Panna, Italy),
wh1ch was specifically devoted to the growth of molecular materials. The nrowth
chamber . base is 3xl0-
10
mbar. The lilm thickness is monitored by a
quartz momt.or, near the sample holder, which had a sensitivity
of 0.1 Als. The mte ot dcposu1on of Til was 0.2 Als. During growth the tempcm-
ture the sample was detected with a thenuocouple touchinn the back side of
the. nuca which is rcsisti vely heated on the s<Jmc side. The s:.ne procedure de-
scnbed for HV growth was applied to the calibmtion of both the thickness moni-
and the effective temperature. AFM topographical images have been obtained
m contact mode_ 1- 10 Hz scan J<ltes. In order to work with low setpoint
forces and to mmumze the contact area, soli cantilevers (sp1ing constant 0.03-
0:06 were used aJld 1-clativc humidity was kept below 20% by flushing dry
mtrogcn m the measurement chamber.
of matc1ial deposited aJld the I!ITcctivc of the substr.tte
dunng we1-c systematically varied, while deposition mte was held con-
s.taJll. A set ol about 50 samples has been gcnera1cd. T
6
tihns arc stable over
tune, due to the barriers for surface relaxation and
1
-corganization,
and the topographical features remain unaltered over a time span of sevcr.tl
months.
Til sin1e e1ystals were grown l>y under an argon atmosphere wi th
an expc111.11ental appar.ttus described in details elsewhere (12]. Single crystals
were obcamed after. days of growth as self-sustaining plates a few mi lli-
meters long aJld w1U1 thicknesses of the order of 10 J.l . X-ray analysis indicates
[ 121 that surface o_r the single CJystals currcsponds to the be plane. All the
san.lples (thm hlms aJI? smgle were mounted in the sample holder of a
hehum . bath cyoslat lor spectrosCOpiC measuJ-cments. The single crystals were
first a microscope, anJ the mea.'iUI"CillCnls were pcr-
fomled WJt h the hght prupagatmg along the crystal axis. For the Jluorcsccncc
nk!asurcmcnts of single crystals aJld thin films, was provided altcma-
152 6 Electronic Structure a/ICJ Energy Transfer in Solid u-Sexithienyl
lively by the 488 nm line of an Argon ion laser, and by a Nd-YAG-pumped dye
la.scr. The optical emission was collected either by an optical multichannel analyz-
er fitted with a ceo army, or by a photomultiplier coupled to a monochromator.
In the latter case, the signal was processed by a lock-in and the output was fed di-
rectly into a personal computer. Fluorescence excitation measurements were per-
formed by scanning the excitation energy of the dye laser and monitoring selected
fluorescence bands.
6.3 Excited Electronic States in Isolated T6
The molecular structure of T
6
is given in Figure 6- l. The structure is calculated
to be slightly non-planar [13) in the free molecule while it is planar in the solid
[ 12J. Since we mostly dl.al with propenies of the solid. we will consider T
6
a.-;
planar in the following .ton. The electronic states arc classilied according to
the symmetry of the irTl.u .. representations of the molecular point group C
21
,
which are illustrated in Table 6- 1. It can be seen that only two ditrcrcnt excited
state symmetaies are optically allowed, namely A, and B., . The fonner transforms
like a tr.tnslation perpendicular to the molecular plane while the Iauer transfom1s
as translations in the long and in the shon molecular in-plane axes, respecti vely.
In planar aromatic molecules, B., states are expected to be responsible for the opti-
cal tmnsitions at low energies involving 1C electrons while the A,. states, which
have hydrogenoid chameter (Rydberg states). are accessible by high-energy excita-
tions. Long and shor1 axes polarized transitions have different energies but might
have the same symmetry. In order to distinguish between them, we will label
them B,.(L) and B,(M) respectively. In addition to the 'aJiowcd' u11gerade states,
there are A
11
and 8
11
gerade states which will not be accessible by ordinary optical
spectroscopy since they arc optically 'forbidden' according to the pa1ity selection
rule. Nevea1heless, these levels may be optically reached by two-photon spectros-
copy, i.e. the simultaneous absorption of two photons.
s
C
H

xl
n 0 ()
e - . e e .. e e - - -)-- B,ll.l
() I. f J I)

A
1
jN)
l<lgure 6-1. Molecular stnk:turc of u-sexill1icnyl lllC in-plane king()'). short (x) and normal (:)
mok:t:ular axes arc in<lk:.uoo a.s well a:. tbc nf the A. and lJ. slaiClt. s .. -e rcxt for
<li!>(;USJ>ion (Section 6.3 ).
6.3 Excited Electronic States in lso/uted T
6 153
Table _6-1. Cv. molecular poinl group. The ck:clrOnic slates of lhc flat T
6
molecule arc classified
lo ll.lC lwo. foltl axis (C2). invcr..ioo (i). antl gli<lc pl:u1e reflection (a,,) symmetry
111.: A, antl II, cxc1tt:tl slalC.'> lmnslonn hkc ("/) a long lhe molecular axes an<l
are opl_cally alk1wc.J. 1h.! A., slalcs arc wi1h rhe polariwbility ICJL\Ur coenponcnL'
(u). bcmg lbcu:furc onc-phutun lorb1<ltkn an<ltwo-phutun allow.:d.
c21o E

A.o: I I
I H,
u.(,l't <ly_.,. au uxy
Bg
- I I - I
R.,R,
Au
I -I
u,.,. Cl:
- I
T,
Bu
- I - I
I T,, T,.
The nature of lo":'csl electronic transition in thiophene oligomers T,, has
been a . matter of fo_r some lime in the context of the expected cross-
over of_ states. as functton of the conjugation chain length [Il l. Since electron
allccts more the lowest lJ, than the A.o: state, which in shon oligomers
1s at lugl_ter cner<tiY th<m the 8,, the increase in the number of thiophene unils (i.e.
length) a crossover of making the the lowest.
Calcul<tllons by Kohler tnthcatcd lh;tl the crossover may occur at about II = CJ unit
Ill_ 1. including multiple excitations and
mter.u:uon 114, 151 indicate, however, that the lowest excited state
m Tc, .s 8,. oscillator strength of the tmnsition in solution increases
Wtlh cham-length as shown in Figure 6-2 forT,,. 1!=2 to 5. The di-
rect conhnnation of the assignment of the lowest excited states as B,(L) was first
by Laz:zaroni et at: I from the simultaneous observation of the polari-
of the op11cal absorption 111 the UV-VIS as well as in the IR of a minuscule
s_ngle crystal gro":'n from the melt. Fut1her confirmation of the a.o;signmcnt wa.o;
gtven by the polanzcd spectroscopy of Tc-. in stretch oriented fi lms of polyethy-
lene [ 171: A 8, (M) state has been observed at higher enel"'.;ies ( 16, 171. At
the localton ol the lowest 1\.o: state, the two-photon spectroscopy of thin films
showed a resonance at 18 350 em- 1181. which was originall y eaToneously inter-
preted as the location of the lowest nmlccular 1\.o: state. Later studies on the exci-
band structure in the Tt. single crystal (sec Section 6.4) al lowed us to assign
th1s geraciC! t_o a_ of the exci ton band. The two-photon resonance,
than_ bem? mtnnstcally molecular in is the result of intermolecu-
lar anter.u:llons m that split the lowest B,(L) exciton into four compo-
nents, one of whrch ts aw The location of the second 2A state at about
500(} - I bo . K '
em . a ve the smglct, has been assigned by Nunzi et a/. by means
of Kerr ellipsometry (191. Fmally, the lowest triplet level has been located by Pm1
et a/. at 12 200 em- . from I he dependence of the delayed fluorescence excitation
spectrum ?f solid_ T,,. f(>r In 5 1::!01. n,e din:l.t h:alion of the triph:t iudit:alcs
that the smglcHnplet sphttmg, which in turn is a mca.o;urc of the effect of elec-
tron-electron cotTclations, is as high as 6000 em- .
154
6 Electronic Structure ancl &wrgy Tra11sjer ;, Solid u-Scxithienyl
6
e
Sf
u
l
5
0

.::.
c

;;
lC

0
u
c
.2
a
0
..
SJ
"
300
350 400
500
550.
{nml
figure 6-2. Abs01p1inn uf T n uligudu.:nyh l/1 =:! Ill 5) 111 Jiuxanc
6.4 Single Crystal Electronic Structure
The electronic excitations of the free molecule discussed in the previous sc_ction
stricdy apply to the molecule in the vapor in embc<klcd m an
amorphous matrix. The scenario changes dnunaucally 111 sohd where the
Jecular packing is the result of the balance between opposite the_ attracung
Van der Waals forces and the repulsive ste1ic intcmcuons. The mtcr..1ctron of the
molecular levels causes a spread of the excitations into a band which depends
the intennolecular distance, the relati ve orientation of the molecules, and the oscil-
lator strength of the transition. The resulting collective excitation is
ized onto the molecular entity and is tenned "tight-bound Frenkel exc1ton . Opti-
cal excitations, as a consequence of momentum conservation, probe only
levels of the exciton band which correspond to the null wave vector k. In drfl er-
ent directions of the crystal , the k=O resonance depends on the dispersion of the
exciton band in k-space. The spread of the exciton band is also known a'i the Da-
vydov splitting [1:!, 211. In the weak coupling limit 12_1 l each mo_Jecular level, fl!-
gardless of the electronic or vibronic spreads an e_xc1ton band
width is modulated by the rooistribution ul the ell:ctromc oscrllator strength 11110
Fmnck-Coudon vibronic components. These excitonic bands lonn therefore. a
dense manifold of states, which mpidly become a continuum at higher cnergrcs
within the spread of cncrgic.'i of each individual electronic transition: In t.urn, cad1
independent electronic tmnsition fonns an excilou band w1dth m
depends on the intensity of the molecular transUIOil. Also
might fonn localized Frenkel cxcitons. In the solid, in addition to localized
tions, there arc delocalii'.ed excitations in which an electron is pmmoteJ lrorn a
6.4 Single c,:vswl EleciiVIIiC Structure 155
molecule to a neighboring molecule and eventually into the continuum of the con-
duction band. These new states, which are peculiar of the molecular solid state,
are known as charge-transfer excitons (CTE) and remind of the Wannier excitons
known in inorganic scmiconductoP.> in their hydrogenoid character and their ener-
gies converge ao;ymptotically towards the energy of the conduction band. lbese
excitations, in the tcnninology of conjugated polymers, are otherwise called (in-
terchain) polatvn pairs. The reduced Coulomb interaction of the CTE makes it a
preliminary step _for the separation of the excitons into separate charges . . This pro-
cess has been w1dely discussed in conjugated polymers by Bassler and co-work-
ers r221. Indeed inter-layer CfE have been located in the energy range of 2.7-3. 1
eV by elcctroabsorption spectroscopy (23j. Since the CTE marks the lower limit
of the conduction band, towards which the CfE levels converge, we assume that
the conduction band is around 3.0 eV, consistent with the steady increase of
photoconductivity (24). On the other hand, the photoconductivity at the optical
band edge is due to exciton dissociation.
The crystal structure of the vacuum flux grown single crystals is shown in Fig-
ure 6-3 together wilh the direction cosines between the molecular and crystal
axes. The crystal system is monoclinic and the space group is P2
1
/u with four
molecules in the unit cell. By arbitnuily choosing molecule I, the application of
the symmetry opcmtions of the factor group (C
11
,), which is isomorphic with the
space group, generates the other three molecules in the unit cell: molecule 2 is ob-
by applyin? the inversion symmetry (i); molecule 3 is gener .lled by the
ghdc plane reflecllon (a); and molecule 4 is the resull of the two-fold screw axis
rotation (C2). The crystal wavefunctions (w(o;) arc linear combinations of the mo-
lecular wfs within the unit cell and fonn a basis for the ineducible representations
of the factor group (8). Molecular and crystal electronic states are correlated 1ia
site group which is fo_m1ed by the symmetry of the factor group re-
tamed by the molecules rn the crystal. In the cao;c of T
6
, the molecules sit in a
gcneml position and therefore only the identity symmetry operation () is com-
mon to both the molecular and the factor groups. The site group is C
1
and U1c
corrdation is given in Table 6-2. As a result, each electronic level of the mole-
cule, rcgardlc.-..o; of its parity, spli ts into the four dillerent components of the factor
group.
It has been experimentall y shown I I 6, 17, 25, 261 that the lowest singlet ex-
ci ted electronic state of the isolated mok'(:ule (I
1
8,) is polarized along the L axis.
The crystal fi eJJ splits the L polarized molecular state into four crystal states of
which a, and b, arc accessible by one-photon spectroscopy. We usc capital
letter-s lor lrce-molcl:ulc states anJ lower ca...e symbols for crystal states . 1l1e crys-
tal levels b.: and b, Jepcnc.J on the photon wavl!vcctor k allll the con"l!-
l!nertdics are obtained by linear combination of the intemction cxchangl!
1ntcgmls between thl! molecules. Out.! to the conservation of momcmum. only
k=O levels arc optically accessible I:! I 1. For k = O the energy values arc the fol-
lowing:
156
6 Electrunic Structure aud Energy Transfer ill Sulit! u-Sexithienyl
a' b c
L
0.9163 -0.0008 0.4004
M
-0.3440 0.5200 0.7819
N
-0.2051 -0.8542 0.4778
Fagure 6-J. Top: Structure of !he T
6
single cryst.al unit cell. The a, b. and c axes arc
indicated. Molecule I is arbitr.lrily chosen. whilst the numbering of the other molet.-ules follows the
of the factor group symmetry opetations as in the text_ Bottom: direction cosines
between the mulecular axes L. M. N and the onhugonal crystal coordinate system a' , b, c.
is orthogonal to the b monoclinic axis.
E(a
8
) =Eo+ D -Ht, t + 1t .2 + 1, ,3 + 1t ,4
E(au) =Eo+ D + /1, t - l t ,2 - 1t,3 + h,4
E(b
8
) =
0
+ D + lt , t + lt ;l- lt,J -1,,4
E(b
11
) = Eo+ D + l,, t - lt .2 + 1, ,3 - 1, ,4
(6. la)
(6. lb)
(6. l c)
(6. ld)
is the energy of the free-molecule-excited stale (<P*), and Dis the differ-
ence between the electrostatic energies in the ground and excited stales. /1 .t is the
interaction exchange integral between trunslationally equivalent molecules
(J
1
.t =
where the operator Vt . l is the intennolecular potential

energy), while lt.
2
, lu. and /
1
.4 arc the interaction exchange integrals between
molecules. 1l1e excitonic molecule model
[271 prcdtcted a sphHmg as large as I eY of the I B, molecular level 128, 29, 301.
6.4 Sillgle Ct}'Stal Ele<tmuic Stmclllre 157
Table 6-2. Correlation diagram of !he C
2
point group of the T., molecule (left column) with
clll factor .group for solid T,, (right column) ,.;, the site symmetry c, group (CCllt<.T). L. M. ano.J N
mc.bcatc thc pnnc.:apal molocular tr.msition dipole anon\Cnl,, whilc a. b. and c arc tl\C crystalline axes_
Molecular symmetry
Cv,
A ..
(L.M)B.,
Site .. ymmctry
c,
Factor group symmetry
c211
b,(ac)
A more refined approach uses the t wo-centers potential expansion, which consid-
ers the intemction between point muhipoles located at the centers of the two
charge distributions. Since the exchange integml interactions vary as l/r
1
and the
numbers of interactions increase as 1''. one has to choose spherical shapes for the
convergence or the sum to be guaranteed (Ewald sumo; melho<.l) 1311. This proce-
dure has been successfully used, e.g., the anthracene crystal [32j. The funda-
mental requisites for the point-dipole approximation [8) to be valid are: i) the
pole must be than shortest intem1olecular distance, and ii) high--
er m. the mulllpole expansion can be neglected due to the strength of tbe
transtllon dtpole moment We point out that the fonner conditi on does not hold in
the case of T
6
and therefore the ab::.olute energy values of the four factor group
cannot. be correctly predictccJ. However, we expect that the energy
level ordenng obtained by the calculation still holds. The qualitative scheme for
the crystal enero,;y levels corresponding to the 1
1
8, (//L) molecular level, a.o; de-
rived from the Ewald dipole sums, is reported in Figure 6-4. The calculated val-
ues of the

and

exch:mge interaction integmls arc negligible as a conse-
of the essentially two-dimensional character of crystalline Tc, (see Fig. 6-
3). Thts leads I( sec Eq. (6. 1 a)-(6. 1 d)l to the deucneracy of the a and b crystal 0 If . ,,
components with a); and b):, respectively. We note that the lowest component (a,)
is formally allowed. However it is c:.kulaled, within the oriented gas model
(OGM), to be vanishing :ts " consequence of the relative orientation or the lransi -
158
6 ElcLmmic Stmcwrc and Energy Transfer in Solid u-Sexitllicnyl
tion dipole moments and of their orientation with to the crystallographic
axes. The a, component is therefore a 'dark' leveL Htgher order effects
the oriented gas model (OGM) may allow some intensity in the au component, tn
which case we would expect it to be completely along the b crystal
axis. 1l1e upper b., component is instead a 'bright' level (optically allowed) and is
polarized in the ac crystal plane. Emission is expected to take .place the
est Oavydov component for the efficient non-radiative rclaxauon wtlhtn the exct-
ton band [7]. In order to predict the energies of the Oavydov levels, one to
take into account the total molecular wavefunctions. Correlated quantum-chenucal
calculations have been performed [33) to describe the nature of electronic excita-
tions in crystalline T
6
. Since the interlayer interactions are negligible (vide supra)
we consider clusters of T
6
molecules by taking the relative coordinates from the
crystal structure within the be layer. A single contiguration
al ism has been used in combination with the Hartree-Fock semtemptncal mter-
mediate neglect of differential overl ap (INDO) technique (34}, t? t.he
singlet excited states. The evolution with cluster size of exctlatton energtes
from the ground state to the two Davydov components <.wtth a, and b,
tries) is displayed in Figure 6-5. When the cluster szc. the dtffcrence
between the a., (b-polarized) and b, (ac-polarizcd) transtllons mcreases and satu-
rates for about six molecules (sec Fig. 6-5).
b.(ac); b
1
t
1
B.(L) ----.._
a.. (b); a.
Free Crystal
Molecule
l' igure 6-4. Qualitative energy level diagram of the 1
1
B. exciton b;md stroaure of Tc. _at K=O derived
by lhe Ewald dipole-dipole sums for excilalion light propagatmg along the a cry!.1.al :IAIS.
6.4 Single Crystal Electrcmic St111cture
3.4 .----------- ----- -,
-o- low-energy OavidOII compooent (a)
-o- . high-energy Davickw compooenl (b.)
3.2 -
6 CT excited Slate (b.,)
3.0

2.8
"' <:
w
2.6
-o--- -o
...o---
--
--
o---
2.4

2.2 + --.-- -.---.---.._:;.--.:;_.--1
2 3 4 5 6 7
Scu of the aggregate
159
l' igurc t ... S. Ex..:llUun ..:ncrgie frn111 lhc 1!-ruond state tu the twu [}.IVyduv (aH and h.J ;L'
a function uf the T" du,tcr sit..:. TI1c du,tcr.; arc built with the <.T)'Sial structure considering T
1
, mole-
cub lying within 1hc san..: b.: layer.
6.4.1 Davydov Splitting
The b- and c-polarized absorpti ( spectra of aT
6
single crystal at 4.2 K are reported
in Figure 6-6a and b. The lowest energy resonance is completely b-polarizcd and lies
at 18 360 em- . At 20 945 cm-
1
in the b direction there is a very intense and broad
peak followed by the typi..:al spectml shape of a vibronic progression. At the same
energy the c-polarized spectrum saturates because the light is completely absorbed.
The detailed vibronic assignment in b and c polarization is reported in Table 6-3.
We assign the b-polarizcd transition at 18360 em- to the lowest au Oavydov
level. We recall that the lirst sharp resonance in the two-photon excitation spec-
trum of a polycrystalline lihn wa.'i found at the same energy of the one-photon
resonance of the single crystal I 18 I and was originally interpreted a.-; an intrinsic
molecular gerttdt! level
In view of the exciton structure obtained from the

single crystal we conclude that the two-photon resonance is due to the Davy-
dov component of the 1
1
B, lowest si nglet instead. 1l1is is indeed in agreement
with the expectation of a degenemcy of the and a, Davydov levels. The b,
component is polarized in the ac crystal plane and should not be observed in b di-
rection. For this transition to be obseaved directly we should be able to mea.-.ure
the absorption in the c direction for energies higher than 21 ()()() em- . However.
the c-polarizcd absorption spectrum saturates due to the thickness of the sampl e
under investigation, which is in the mder of 10 J.lm. The b, Davydov levd is ob-
served in the b-polarizcd spccoum a1 20945 cm-
1
a.'i a consequence of opti..:al
160
6 Electronic Structure and Energy Trwufer iu Solid u.-Sexithicnyl

2.3
1.8
..-.
0
0
--; 1.4
0
a
._
0
0.9
<
0.5
0'
0.0
19000 19500 20000 20500
18500
Wavenumbers (em.
1
)
F
. 6-6a b- and c "'>larizcd absorption spcctr.t of T
11
single crystal a1 4.2 K. f?' :md o: arc_ two
tgun: r . . the (c--. 6 4 1) The moM mtcnsc vtbr.lltonal
Hert.berg-Tellef false origins as dtscusscd m text .,..-._tton
ntOlles are indicated.
misalignment of the sample. The energy between two Davydov
components leads to a measured Davydov sphttmg of 2600 em . . .
In the polarized absorption spectra (see 6-6a) the actlvtty of
false origins is ea!;ily recognized . . The false are by the_
of the electronic origin with totally symmetnc (TS) Nevertheless, the
tensity of the polarized vibronic bands is obviously from that tf
h I
.
0
ld be due to the Franck-Condon mcchamsm. A conststent mter-
t e coup mg w u . . ,
pretation of the experimental spcctr..1 involves the Herzberg-Teller vtbromc cou-
pling.
6.4.2 Her.tberg-Teller Vibronic Coupling
The tr.tnsition moment Jl between the llPN(P,)
and (II are the electronic and vibr.ttional wavetuncttons rcspectt vely, ts delincd as.
(6.2)
3.42
.......
ci 2.28
Q.
c
0

0
U4
(/)
.0
<
0.00
18000
6.4 Siugle Cty:;t11 Elertnmic Stroctun: 161
(b.)+ 1275
20000 22000 24000 26000 28000 30000 32000
1
Wavenumbers (em )
Figun: 6-6 b. b- and cpolarw:d absorption spco.:tm or T
6
single crystal at 4.2 K extended to higher en-
ergy. Above 21 UUO o.:m ' the b-polarizcd S[l<.-o.:trum shows bmad which are discussed and as-
signed in the text (Section 6.4. 1), while in o.: the light is <- 'Ontplo.:tely :tbsubcd.
By expanding the electronic transition moment operator p(Q) as a Taylor series in
the nuclear normal coordinates about the equilibrium configuration Q
0
, one obtains:
(6.3)
Substitution of Eq. (6.3) into Eq. (6.2) leads to the following expression for the
vibronic transition moment
J.l = (cJ>N(P,(Q)!Jt(Qu)!4'>c(Pj(Q)} + )QoQdcPc(Pj( Q)) + ...
(6.4)
The tirst tcm1 of Eq. (6.4) represents the Fr..1nck-Condon coupli ng in which the
electronic transition moment JL(Q) is independent of the nuclear coordinates and
the polarization of the transition is that of the electronic origin !lPN}- 1l1e second
term of Eq. (6.4) represents the Her.tberg-Tellcr (H-T) vibronic coupling. 1l1e in-
dex k runs on the normal coordinates of the molecule, hence when the Condon
approximation is relaxed, the electronic transition moment acquires a dependence
on the nuclear coordinates. Within the HerLbcrg-Tellcr mechanism. two electronic
excited states couple via a molecular vibmtion which induces a 'borrowing of os-
cillator strength from the higher electronic excited slate to the vibronic level of
162 6 Electronic Structure w1d Energy Trtmsfer i11 Solid u.-Sexitllienyl
Table 6-3. Vibr:uional assignmem of the b- and c-polarizcd absorption .or T6 single crySlal at
4.2 K The proposed assignment is in ugrcemem lhe lllOSt VJbrdllonal modes found by
Birnbaum et ul. 1641 in Lhe excitmion spcclra of nkllnx ISOlated tctrath1ophene (T4) al low temper.u.urc.
em ' c Polarizal ion b Pol;:uizaJion
l\v (cm-
1
) l\v (cm-
1
)
18360 Uu-0
18486 0'
18657 0 "
18700 0+340 (0)
18832 0'+340 (+6)
19 015 0 +660 (- 5)
19017 0 " +340 (+20)
19318 0 " +660 (+I)
19635 0+1275 (0)
19646 0 " +660+340 (- I I)
19817 0 ' + 1275 (+56)
19945 0+ 1590 (- 5)
19952 0 " + 1275 (+20)
20077 o + t590 <+ 1>
20252 0 "+1590 (+5)
20945 h,
21450 0 +2X 1590 (- 90)
22250 bu+ 1275 (+)0)
23535 1275 (+40)
29190
the lower eleclronic excited state. In fact, the matri x f?r H-T-induced
transitions from the zero-phonon ground state lwc} to the v1bromc state of
t he excited electronic state jQ>N} can be expressed as:
= LMjN8M((MIJli<Pc})/(E((J>M) - E(cJJN) - {6.5)
F s are the unperturbed energies of the electronic and vibr..ttional respec-
t" 1 and 8 is a constant energy factor which depends on the state.
r:.n E
4
. (6.5) that of (/>M is 111 th1s case
and that the correction decrease.'> with the mvcrse energy m1smatch between the
relevant levels. . . . 1 . . . d . 1
In the case of T
6
the lowest excited smglet state 1s I 8,. and 1s pola'2ze a ong
L (vide supru). A second intense electroni c. state. at about 36<}00 em
1

signed to 8, (liM) (1 6, 30]. Therefore, the v1bromc
tween 1
1
8, (IlL) and the higher 2
1
8, (liM) onl y be totall?'
vibmtions (s<.:e Fig. 6-7). The transua? n as rotated
polarization direction of the lendmg. 2 (liM) Wllhlll
the oriented ga.o; model. is c-polanzed w1th, a polar1zaton of .. .
We a.o;sign the peaks at 184g6 em- (0 ) and I H657 em (0 ) ol F1gU1 c 6-6.1
10 vi bronic Ievell., acting as false origi ns which mc generated by Herzberg-Teller
6.4 Single Crystul Elel:lrVItic Structure
163
Figure 6-7. llcrzbcrg.Td l.:r vibmnk coupling scheme in lhe
case of T..,. Tite two lowe:-t singlet excited (lB. :md
211,.) cuualk in 1111ally synunclrio.: (11
11
) inducing oscilla-
- --'-------- Q tur stre ngth honuwi ng from the 28. clectroni.: st.atc 10 tho.:
Ill. "il>mnio.: st:uo.:.
coupling of the 1
1
8 , and 2
1
8, electronic excited states via a modes at 126 em-
and 297 em- , respectively. Yibronic progressions whose description is
reported in Table 6-3 arc built on both false origins. The activity of totally sym-
metric modes at frequencies 340 em- , 660 em- , 1275 em- , and 1590 emis
observed. This assignment is confirmed by the observation Utat the same Herz-
berg- mechanism is acti ve in emission. Figure 6-8 shows the high energy
pan of the fluorescence spectrum and the low energy pan of the absorption in b-
and c-polarizations. We a.o;s ign the emis.-;ion false origin A, 165 em- below the
origin of fluorescence, to H-T coupl ing with the ground state totally symmetJic
phonon mode, which in absorption gives rise to the 0' 11-T false origin (promot-
ing mode 126 emin the excited state). The false origi n C is due to the ground
state totall y symmetric mode at 306 em- associated with the absorption 0 ' H-T
false origin (promoting mode 297 emin the excited state).
1l1e room tempemturc Raman spectrum excited in pre-resonance cdnditions
[35] indeed shows bands at 169 em- ' and 306 em -. which arc in agreement with
the modes observed in the lluoresccncc spectrum and that have been assigned by
ab initio calculations to tmally symmetri c vibrations 11 31.
The b-polarized absorption bands (sec Fig. 6-3b) at 20 945 em- , 22 250 em-
and 23535 em- arc assigned to a vibronic progression built on the b, Oavydov
component with the totally symmetric mode at 1275 em- .
164
6 Elcctrouic Structure and Energy Trwufer iu Solid u-Se.xitllienyl
Q)
0
c:
Q)
0
Ill
Q)
L..
0
:J
u.
' ..
..
..
..
C
t
'
..
..
::
.
:: ;: ::
.....
. . - ..
.. ...
._.,: .::
1/c
-
306
8
.
'
:.)\
18000
165
126
0'
i\
. .
..
: :
297 0"
.
.
--
: ..
; .
..
18250 18500
18750
- 1
..... ...
..
1/c
Jib
2.0
1.8
1.6
1.4
1.2
)>
rr
1.0
U>
0
-.
"0
0.8 g:
:J
0.6
0.4
0.2
0.0
19000
Wavenumber {em l
6-8. b- and c-polariCd absorJ
1
tion and nuon:sccncc spcclr.l in. the
cnc. The nuorcsccn.:c A and C currcspond w the 1"1:-c ungns 0 :IIIli 0 dcnhhcd
in absorplioo.
6.5 Thin Films
6.5.1 Growth in High Vacuum
In molecular Ulin films the structure and hence the
f ons differ substantially from their counterpart m a crystal. a smgle .crystal
1
' . t table thermodynamic phase of tht: molecular matenal, the thm
represen s a s
1
h tl of thm
can be regarded as a metastable or kinetic fom1 of aggregation. n t . e .
films by high-vacuum sublimation a nux of hot gas molec.ules a
colder substrate surface so that condensation takes place betorc the thcnnahzauon
of the molecules is achieved. The resulting morpholog.Y. depends not .only on the
. olecular propcrties and coopemtivc eiTccts ansmg from the
mtnnslc m b 1 1 t , a uons and
I
t r. tons but also on the nature of the su strate-mo ecu c Ill cr. c
ar me ac 1 . d. IT .
e.-;pecially on the kinetics of growth (e.g. impinging mte, nucleatiOn.' 1 us1on, coa-
lescence reorganization desorption). 'fbe latter is controll ed by the mtcrplay among
ex such as deposition rate . t.empemture and
of deposited material, viz. ti me of or
it is important to understand and control the k111ellc.:s ul . growth Ill to

the ba.;ic relations between (ilm structure, molecular ordenng. and the rclcv.mt clcc-
6.5 TIIi11 Films 165
and optical properties, as well as to obtain films of reproducible quality. It was
found by X-ray diffraction (XRD) that T
6
films grown at room deposition tempem-
ture (RT) possess long-r.mge molecular order [3, 36, 37) and therefore there is a
spontaneous tendency towards ordered aggregation. Upon changes of the deposi-
ti on temperature, enhanced anisotropy in the electrical properties was observed, as
correlated to structural (XRD) and morphological (SEM) changes [38). These obser-
vations led to the conviction that T
6
films on silicon consist of stacked layers of T
6
molecules wiUt a more or less enhanced molecular order within each layer. Evidence
that layered growth in oligothicnyls on silicon starts from the early stages was in-
ferred from AFM observations on quinquethicnyl (T
5
) [39), albeit an extensive in-
vestigation at larger thickness was not carried out. It was shown by optical linea
dichroism [301 that the ordered growth ofT(, decrcast:s and eventually fades out
at increa.-;ing thickness. Furthcnnorc, the dominant growth direction, i.e. the molec-
ular orienlation with rt:sped to the substr..tte being either planar or homeotropic, de-
pends on the nature and structure of the substmte [40). Thus, it is important to carry
out growth studies with well-defined and characterized surfaces, which has not been
the case in the majority of spectroscopy and electrical investigations and device aj>
plications. The extensive defects (structural, chemical, morphological) present on
surfaces such as glass, oxidized silicon, 4uartz, and ITO-coated glass oflen hinder
the intrinsic feature of the growing film. such as surface roughness and gmin bound-
aries. In U1is context, metal surfaces are excellent substrates which can be chamcter-
izcd i 11 situ by a wealth of surface science techniques. Extensive work on quartcrthic-
nyl ('f4) and end-cappro oligothicnyls grown OntO noble metal low-index surfaces
[41-451 has demonstrated that the resulting films exhibit planar orientation, and thilt
the structure of the tirst molecular ad layer can be commensurate with the underlying
metal surface mesh. Growth onto noble mt:tal surfaces is a suitable template route for
ordered planar growUl, and ordered lilms several monolayers thick with strong in-
plane anisotropy (46, 47} have been obtained by exploiting the intrinsic anisotropy
of Au( II 0) missing row reconstructions.
Another approach is to start with atomically smooth and clean surface.<> such as
mica, highly oriented pyrolitic graphite, and metal dichakogenides, as substrate.'>
for thin tilm growth. Mica oiTers the advantage that its hydrophilic surface might
be a reasonable model for the growth on the technologically mor.e relevant silicon
wafers, lTO, and glass. n1us, we unde11ook an extensive work study on T
6
fil m
growth on freshly cleaved ruby mica aimed to elucidate the quantitati ve aspects
as well as the ba.o;ic kinet ics of Tt, li lm growth.
6.5.2 Thin Film Morphology
llte morphol ogy of Tt, thin films is very sensi tive to the growth conditions
501. Most of the earl ier optical studies have been canicd out on granular lilms,
whose typical morphology is shown in Figure 6-9. However. a hmad morphologi-
cal diversity, rang,ing from islands (sec Fig. 6- 10) to layers and lamellae (sec Fig.
6- 11) can he ohtaincll varying experimental parameters. Such a complexity <triscs
166 6 /cctrvnic Struc:wre and Em:rgy Trcm.ifer in Solid u-Sexitltienyl
from the dominance or suppression of one or more intervening mechanisms of
growth because the diffusion of molecules on the fonning film is changed by the
deposition temperature, the amount of material, and the time of growth.
The early stages of growU1 involve nucleation and formation of islands (Fig. 6-
10). Density of nuclei, lateml size, height, and molecular order within the islands
depend upon the deposition temperature. At RT the islands (::::::500 nm diameter)
exhibit regular features like sharp comers and multiple peaks in the distribution of
the topogr..tphical height, which are integer multiple of 2.4 nm viz. T
6
length 150).
By comparison, the islands at 150"C are much larger and exhibit mono-
molecular temce steps but their edges are branched rather than regular, as in the
growth of diffusion-limited aggregates [51 ].
At increasing thickness, the film morphology at RT becomes granular. Small
gmins (few tens of nm in diameter) fonn upon completion or the film. then the
gmin size increases with the amount of material. This tmnsition from 20 islands
to a 3D film is similar to a Stranski-Krastanov [51) growth lmnsition. although
owing to the non-equilibrium conditions, this simple scheme should not strictly
apply. It is interesting to comparc the evolution with thickness described above
with that of a film grown at high temperatures (150"C) and depicted in Figure 6-
11. At 150C nucleation of a few tens nanometer-wide protrusions takes place
after an almost complete fi rst monolayer has been formed. This tirst monolayer
exhibi ts a considerable degree of order, which is apparent from the sharp edges
around the voids. 1l1e average step height of this monolayer with respect to the
bottom of the voids is 0.6 nm, which suggests that molecules in this layer lie
tlat mther than homeotropic on mica. The nature of the imemction driving the for-
mation of such a fi rst monolayer. where the molecules lie probably sideways, is
not clear, but might be an electrostatic attraction between a partial positive charge
localized on the S atoms of T
1
, and the negatively charged mica surface. Around
the outgrowths protruding from the tina monolayer (whose hei ght from the mono-
layer is twice T
6
molecular axis) the islands grow layer-by-layer. The terr..tee
height 2.30.4 nm corresponds to T
6
van <ler Waals length, i.e. the molecules in
the film are oriented homeotropically with respect to the surface. At about 50 nm
a prolifemtion of elongated nuclei occurs [50], which at larger thickness evolves
into a network of oriented lamellae. Lamellae are the result of a change in the di-
rection of growth or simply a recrystallization phenomenon. Such type of growth
tr.msitions might be specific to anisotropic materials and cannot be modeled
strictly by canonical growth modes (Frank-van der Merwe, Stmnski-Krastanov,
Volmer-Weber) [5 11 of atomistic growth prot:esses.
The growth mode for 300 nm thick tilms was analyzed hy means or the evolution
of the grain size with the deposition temperature l4gl. The mean grain size (A)
grows according to an Ani1cnius behavior with an activation energy
, =0.360.04 eV. This value is in good agreement with our model calculations
(481 based on independent experimental parameters. which yield 0.27 eY for tnms-
lational and 0.5 cY for the rotational barriers experienced by a single T
6
moh:cul e on
the van der Waals surface potential generated by stacked layers ofTb molecules (sec
Fig. 6-1 2). The corresponding grain size distribution is skewed on the large sizes and
is invariant with the deposition temperature. This suggests that grain growth lakes
6.5 Thiu Films
167
(,..9. Typic;! granular 111orphology or
T,: gmwn at <lcpositiun T=25 C ;md
II = 10() nm. Height r;mgc is 41 um
(lmlll hlm:k tu white).
Flj;Urc 6-10. bland grnwth al: (a)
dcpu!>ilillfl C. fl =5 11111: lhl
1'= 150 c. ft = Jt\1\1
(1- ll. Evnlulinu nf lht: 111<111Jhulu!!Y with
III' J'I!;"JIIg nf (rc-
(}lltlc<l :t' lhc unlllin;al li hu Jhid .ncss) at .tq
11
,,j.
linn 'I'= ISO C.
168 6 Electronic Strucwrc wuJ 1!/wrgy in Solid cz-Sexithienyl
rr rT '.).'
1.11'
Jl
....
EE N
Ftgun: 6-12. Model for the calculation of the van tier Waals potential experienced by a single T
6
mol
ecule on a T6 ordered surfoce. Eoch molecule is modeled as a chain of 6 polariwblc spherical uniL'I.
and the surfaL'C as slab, layer containing molecules (only part of the cluster is
shown). TIIC niO<lel is ba;;cd on X-r.ty di ll'roction and dielectric constant experimental data. TilC two
configur,llions used for evaluating the COrrllgation of the surface potential are shown. Adapted with
pennis:.ion from Ref. )48).
place by coalescence at expenses of the smaller grains, as a consequence of mndom
diffusion in two dimensions. Since the standard deviat ion increases linearly with the
mean size, growth in high-vacuum is not suitable to yield homogeneous grain size.
This might be a limitation when the aim is to tailor properties with gmin size (e.g.
peak in the photoluminescence) or for nanofabricution.
For a given thickness and increasing deposit ion tempemturc, the film morphol-
ogy changes gmdually, mther than abruptly, from gmins to lamellae. This behav-
ior is similar to the order-disorder pha.-.c tmnsitions of the second order, although
here the more ordered 'phase' is obtained ut higher temperatures [49). A conve-
nient way to locate the transition is to observe the evolution of the orientational
order of the domains. Since lamellae (see Fig. 6-16) stretch along prclerential di-
rections (related to crystallogmphic directions of the mica surface), we proposed
an experimental procedure to construct an angular tensorial property from AFM
images simil ar to the measurement of the angular order tensor, which is used to
locate the director in scattering experiments on oriented nematics. The relevant
'order parameter ' here is the mean second Chebyschev polynomial (l:os 2u},
where a is the azimuth of the long axis of a lamella wi th respect to the preferen-
tial al ignment direction. Details of the method are given in Ref. [49J. At the onset
of lamellar growth, the second Chebyschev polynomial undergoes an abrupt in-
crease of slope, which all ows us to locate accurately the temperature of the tmnsi-
tion (Fig. 6- 13). In this fashion we have been able to construct a 'kineti c'
diagram of the different morphologies of T
6
as a function of deposition tempem-
ture and thickness, which is shown in Figure 6- 14. The kinetic nature of the
growth process is evident when the temperature evolution of the mean size versus
I rr is ploucd for diiTcrcnt film thicknesses (sec Fig. 6-15). The curves are parallel
in the semi-log plot, as the mean grain size decreases with thickness at a given
tempemturc while the activation energy is the same, being the process governed
by self-diffusion. Furthermore, the transit ion from gr.tins to lamel lae with tem-
6.5 Tlti11 Films 169
T(OC)
fo'igurc 6 13. Oricntational oruer parameter vs de

ten . , . , . . . .
and lantellac. rcspc.:tivcly. Str.ti .. Ju lines reprcsc I I be . r f 'Jtalurc. Clrdcs and S<ju;trcs arc
gmin <lat:t. respc.:tivdy. Affitptc<l fmm t{cr. H.Jr." Sl tl or t tc lamellae dat;t aud mean value or the
at _d<X:reasing temperature as the film thickness is decreased
. nee . 1> can be obtained also at lower deposition tern
(lew tens C) lor a suttablc decrease of thicknc.-.s TJ
1
1
s v
1
, , ,
1
pc
the I . r . . . . . Ul: ICC IS conststent With
cvo ulton o molecular order momtorcd by optical dichroism [ 26J.
6.5.3
Scaling Behavior of Surface Roughness
of sh<tpc <llld anisotropy in T
1
, films Slii!"Csts thatth re . . . . ..
rncrca.-;c Ill tht.: mok:cular ordt.:rin" ami hictarlly . 1.: 1 ts a plugtcssrvc
d . . "' r "tea structures a th
tempcra_ru_rc This suggests that at higher t;.n eratures and s o e

ttor_l. progressrvely approach the crystal phase. Therefore b
postliOn tcmpct'Uturc at a thickne and a tc l'o . . l t . g de-
. ,, ,, I II S a nee II IS po 'b) t
a contmuous set of metastable hascs between th . . '. . . sst e_ o
him up to the crystal. It is then to ask whyc atsgot.lvrOeJn>t c polyhcrlyslalhne
pears a d h . e. morp o ogy ap
. . ' . n ow II would be possthle to change it to another. This is the very I" " I
unpotant step towards a real .
1
1
1

1
H:s
. . . . . . . con m o llc spatial <trr..mgemcnt of molecules in a
fi_lm. and the unphcattons for controlling the optical <IIIli clcc.: llical pnpc
1
, ..
1 Vtously 1 J tcs arc o )-
170 6 Electronic Struc:ture and Energy Transfer in Solid a-Se.xitllienyl
---
N
a
=i.
..._..,
10
"

vo.l
0 .01
2.2 2.4 2.6
JOOnm
0 IOOnm
.a. 50 nm
2.8 3.0
--
3 .2
Figure 6-14. Avcrdge domain vs. inverse temper.uurc for diiTercnt film lhickncsses. Er-
ror bars represent the mean absolute error and stmight lines the be.st lit for each film Dotted
line is the locus of the lransition from gr.tins to lamellae. Data for 50-nm films arc from the
correlation length of the topogr.tphy lluctuations. Adapted from Ref. (50(.
In order to answer these questions, we analyzed the film morphol ogy quantita-
tively by means of the scaling behavior of the surface roughness q [51 , 52),
which is detined as the root-mean square (r.m.s.) fluctuation of the topogmphy.
The basic ideas of this approach can be ill ustmted by means of some general con-
cepts. In general, the morphology of real surfaces depends on the length scale of
observation r. However, for some surfaces termed self-aftine, the morphology is
scale-invariant after the vertical dimension is anisotropically rescaled relatively to
the length/scale. Self-affinity implies that the surface roughness obeys a power
law o(r) :=:::. r" where u is the roughnc.'>s exponent which identifies the universality
class of growth 153 J. Sclf-aflinity implies that there is a spatial com:lation of the
Jluctuating interface on scales of length r r..tnging from the dimen!'>ion of the smal-
lest structural unit to a correlation length beyond which the value of a satumtes.
Thus, a self-affine interface (which is the analog in nature of a mathematical frac-
tal object) is gencr..tted by propagation on larger scales of some elementary motif.
The ba..o,;ic mechanism which leads to the organization of smaller structures onto
the resulting architecture can be inferred by measuring the exponent a. ThercJ'ore,
this framework yield-; important information on dynamic processes occurring on
50
0
0
lamellae (2D-3D)
I
I
I
I
I
islands
and
terraces (2D)
50 100
grains (3D)
150
200 250
h(nm)
6.5 Tlti11 Films 171
300
Then of high-vacuum-sublimed T6 fil ms as a fu!ll:tion of,._._,;_
ma l>U r.ttc t rc ness h. """fAT."
scale can be extmcted from data obtained on the more easily
access e mesoscoptc scale.
in adopted for measuring the scaling behavior from AFM

The power spectral density (PSO) of the Fast Four-

. . . I : l . c.: . pogmp lY '(x, y) is estimated [54), then averaged over the
azunut 1a angle f1J to yteld the radial PSO (/) as detailed in [55 J:
2tr
PSDU') =
j df1Jil;(f cos fiJ.! sin fiJ) j

2
0
(6.6)
From the Wicner-Kinchine -theorem the inte!!mted PS
ness vs the length/scale': , D yields the r.m.s. rough-
a() [ ]' I'SD(f)/ilj] {
l / r
(6.7)
Here, the mean height (It) - 0 Ec: (6 1)
I h L . . . . . - , . ts calculated on an image with scan
. J ts the spattal lrcqucncy (i.e. the inverse di stance) and f. . 1 , N
qutst lrcqu 1c n
1
"''"' ts t1e y-
. et y. lC ana ysts lor the relevant scalt.tl
( 1
1 u 1 o ''" es vtz. corrc ' Ilion
eng
1
roug lllcss exponent, etc.) tun he catTicd out either on the roul!htwss ;h-7)
172
6 /ectro11iC Stntcture and Energy Truusfer in Solid u-Sexitllicnyl
or on its reciprocal space analogue (6-6). We found th<tt the former is more robust
with respect to fitting procedures. . .
In Figure 6- 16 we compare two images of the same san1ple at d1fferent magm-
fications. lf the image side is taken as a ruler, then the length of lamel_lilC
turns out to be invariant. Furthermore. as more details arc resolved at mcrcasmg
magnification, it is apparent that the fi lm texture is made increasingly
lamellae. The existence of such recursive pattern emerges from the companson of
the corresponding radial PSD, shown in Figure 6- l 6c [56}. appear to be
the continuation of each other, revealing respectively more deta1ls at larger
(see Fig. 6- l6a) or at higher resolution (see Fig. 6- 16b). With these concepts m
mind, we have analyzed the morphological transition in T6 fil ms from grams to
100
,,
..... .. - ...-.. _.
(c)

3 4S6ll9 l 456 119
10
z
10
to
,. Cun) . .
Figure 6-16.. (a) and (b) Morphulllgy url",,lilm (lr= IO(lnm. T= 1_50 'C) at I\YU dill'en:nt
(c) the corrcspornling angularly <IVeragcd fnlln E41. (6.7) (empty and full
tivcly). Line is bc,t-lit accortling to the phcnomcnolugK:al n (r)= a,. .... ll-cxp(- r/c,) l 1561.
6.5 Thill Films 173
lan1ellae [57]. ll1e former exhibit a modest self-affi nity over just one order of
of the spatial length scales. while the latter display a self-afline behav-
IOr more than 2.5 decades. which is unusually large in natuml systems. The
tmns1llon corresponds to a continuous change in the dominant mechanism of
growth from purely diffusional (a= I) (581, in the case of granular films, to mo-
lecular beam epitaxy (MBE)-typc of growth (a=0.66) [59] for lamellae (see Fig.
6- 17 a). In the latter case. molecular diffusion is fast and the growth of the inter-
face takes place. by anchori ng at tetTace edges. We also showed that a strajghtfor-
wanl way to the mean gr.1in is by means of the correlation length of
the surface fluctuations rather than usmg the conventional approach of area mea-
-..
E
::1.
..........
llJ>
1.4 f
1.2
1.0
grai ns
I
t
----I--L _,_ ------__
0 .8
1 ,, I I
___ ____ ____ ____ __ ____ ______ ___ ____ ____ ____ _ ! ___ _
0.6
10
8
7
6
s

3
2
8
7
50
(a)
100 150 200
T(C)
f

2 .0 2.5 3 .0 3.5
IOOOff (K
1
)
l' lgur c 6- 17. (;I) Rnughn.:"-' ' "'I"'IICIII iu.-.,..,.. arc
proolctll>ll.' .f purely dinu,iunill ttlut-da.,hed) 1!1111 anll MUE growth (!191; (b) length vs
mversc tlcjiOSitlon T. Wcghtcu !Jc,t-lit Anhcuius CI(Uatun is plnllctl a.' the line. Adaptctl fmm
Rd. j!\71.
174 6 Electronic Structure cmd Energy Transfer i11 Solid u-Sexitltienyl
suring, which is rather arbitmry in the case of compact grains. TI1c square of the
correlation length seems, in fact, related to approximately the mean gmin size,
and hao; a comparable activation energy (see Fig. 6- 17 b). Furthermore, a mini-
mum saturation roughness can be achieved in T
6
films just below the transition
from grains to lamellae (in the case analyzed for films at 150C), which together
with the large domain size and the increased molecular order {48-50j suggests
that an optimal morphology for seveml investigations and applications can be ob-
tained. Such analysis is also useful to monitor the effectiveness of processes
aimed to control the roughness of thin film interf.tces, such ao; thermal annealing
[601.
Experiments on transport, injection, electroluminescence, and fluorescence
probe the spatial correlation within the film, therefore we expect that their re-
sponse will be sensitive to the self-affinity of the film. This approach. which we
proved useful in the analysis or AFM data of conjugated molecular thin lilms
grown in high vacuum, has never been applied to optical and electrical
on these systems and might be an interesting route to explore. We have started to
assess the influence of differe m spatial correlations in thin films on the optical
and the electro-optical properties, as it will be described in the next set: tion.
6.6 Disorder Effect on Energy Transfer
6.6.1 Single Crystal Fluorescence
The fluorescence spectm of il T
6
single crystal at 4.2 K polarized along the b and
c crystal axes arc shown in Figure 6- 18. In both polarizations there is a sharp
component superimposed on a broad background. It has been shown that the
sharp emission occurs in less than <l ps after excitation, while the broad emission
takes place at longer delay times as a consequence of energy tmnsfer into Imp-
ping species below the exciton band {61]. Previous experiments showed that the
relative intensity of the unstructured emission increases when the structural order
of the sample decreases, as is the case of more defected crystals [61 J. Absorption
of up to 1000 em- below the bulk electronic origin has been by fluo-
rescence excitation spectroscopy [611. It is clear that the structuml quality of the
sample is reflected by the concentration and depth of the defect states. Defect
slates may arise from T
6
molecules which experience a local molecular environ-
ment different from the bulk. A crystal defect (vacancy, dislocation, etc.) or a
chemical impurity may modify the molecular environment leading to a lowering
of the energy of the excited electronic state which, at low temperatures. causes an
efficient exciton energy tmpping. These slates, which act as cflicicnt emiHing cen-
ters, are quite common in crystals [7J.
The origin of fluorescence is at I H 332 cm-
1
and is b-polarizcd. Comparing the
origin of Ouorescence and absorption (sec Fig. 6-H) we notice that, although both
6.6 Di.wrtler Ejfe<t 1111 Ellet:r:y Tm11.y(er
175
80
c polarization
60
b polarization
40
20
0
15000 16000
17000
18000
Wavenumber [em']
Figure 6-IH. T., .:rystalpularit.cd lluorcS<.'CIICC , 'CI 2 .
on the origin and on the A. 13. a lid C tal . , . .t . .'t. K. ll1e matn v?ro111c lxin<ls built
6.6. 1 ). ""' :lfc llldK.Ih:d. Sec text fur d1scuss10n (St-ctiun
arc b-polarized as expected ro D d
_ , . . . . .
1
"" . ov component, there is a shift of 28
?ledl .dTfilus mdtcates tlJat the optical emtsslon originates from a molecularly local
tz e eet state {X-trap) w f -
band
. d b .s a consequence
0
energy tm.nsfcr from the exciton
an su sequent trappmg We th
k at I H 332 - . . . . asstgn . htghest energy emission
: bo - . em to. a shallow X-trap whtch mamtams lhc same polarization of
orig, n in
Th . . . . . . ' ms rumcnta resolutton
e mtnnstc absorphon ongm hnewidth, detcnnined with by the . ,
sct-up used to tncas
11
. .
1
expenmcnta
. ure Je emtsSton, ts 12 em- (full width of h If .
f:Vhm) _to_ the 8 em- (fwhm) of lhc tluorescencc ori in a2
;he X-tr.tp is a well dclined localized

L S u . bthe crystal is alfcctcd by a residual inhomogeneous
evcra -po an zed sharp bands are assigned as ro d . .
vibmtions at 699, 738, 10
56 1169 1460
. d g totally symmetnc
, (' ' - an l504 em but It on the fluorescence
fl sec F:g. These modes are in excellent agreement with those ob-
crystal Raman spectra thai we measured exciting at 1064
Except for the strong C==C stretching mode at 1460 c - 1 .
11
h .
show a sho
1
1 p . . 1 - Ill a t esc modes
. rogesston lllltled to the hrst vibronic conlJ>Onetlt . d. . I
tivcl w ,. k d. Ill tcatmo a re a-
y ca . ts1?111on along these normal coon.Jinates in the excit d . TI
complete a.o;signmcnl or b- and c-polarizcd spcctr<t is
blc 6-4. Uy gomg to htghcr energtes the vibronic h<tnds huih nn lhl'g nri .. in " .;,.,
176
6 Electronic Suucture a/Ul Ellergy Trallsfer in Solie/ a-Sexitlrienyl
. . . f lhe b ant! c-polarizcd fluorescence spectra of T" at 4.2 K.
Table 6-4. Vibr.!IJOnal assgnment o
b Polarize()
l:iv (em-
1
)
0-0w
699 broad
731! sh
1383 2 vw
1460 s
1504 w
1793. 1 s
2148.3 w
2 195.0 w
2502.9 broad
2828.9 broad
2924 w
2961.9 vw
3252.8 w
e Polarized
t::.v (em-
1
)
165.4 vw
247.6 w
265.6 vw
306.3 m
355 vw
416.3 Ill
521 .7 vw
861!.8 vw
903.8 vw
952.3 w
1009.6 m
1047 m
1217.2 w
1301.8 w
1358.2 m
1537.9 w
1570.3 w
1614.7 sh
1633.2 m
1670.5 w
1686.1 m
1723.5 s
1754.7 l>h
1774.3 vs
1809.9 s
11!79.2 w
2474.3 broatl
3234.8 w
3278.9 w
Assignment
Origin. 11!332 em
1
Fulsc origin A. a"
False origin B. al<
A - 107 (+6.8), ""
False origin C. ""
B - 107 Hl.4), (IJ(
c - 107 {- 3.0), "
c - 2xl07 (- 1.4). a,.
(0..(}}-699 (0.0), UN
(0-0}-731! (0.0), a"
A - 699 (-4.4). ""
A - 738 a"
B - W9 (- 5.7), u"
c - (-4.3). ""
c - 731! (- 2.7). til<
(0-0}-1 056 { +9), :Ia!
A - 1056 (+4.2), a
13 - 1056 (+1.1!), a,.
c - 1056 (+4.1 ). til<
(().()) - 1369 {- 14.2), l ll<
(0-0) - 14()() (0.0), (I"
(0-0) - 1504 (0.0). (II<
A - 13W (- 3.5). a"
A- 2Xf!J9 (-6.9), a
B - 1369 {+1.9), u"
A - 1460 (- 7.8), ""
c - 1369 {+4.8). (IJ(
A - 1504 {- 16.7). al<
B - 1460 {- 15.9). u,.
B - 1504 (- 3.1), ""
C - 1460 a,.
(0..0) - 1056- 738 (+0.9), tl"
C- 1504 (+0.4). a,.
c - 1460- 107 (-5.9), " "
(0..0) - 1460- 699 (+10.7). ""
(().0) - 1460- 738 (+3.0), (II<
c - 1460- 699 (- 9.0). ll"
(0-0)- 14W- 1056 (+13. 1), " "
(0-0) - 1460- 1369 (+0.1), al<
(0-0) - 2x 1460 (-4.0 ). ""
(0-0) _ 1460- 1504 (+2.1). a"
C - 2xl 460 (-8.5), a.
(0-0) - 1460- 105<> - 731! (+1.2), til<
C - 1504- 1460 (-8.6), (II<
6.6 Disorder Effect 011 E11ergy Tm11sjer 177
1llblc 6-5. CompariS(>n of the a" vibr.1tioual nnb in the ground and excited states. 1lle totally sym-
metric vibro1tions nf tbc gmund state in the R:unan sp<..-ctrum excited in prc-n:sonancc coldi-
(351 and in the ll uun:sccncc )62( arc compatctl with the of t1b i11ilio calculations
(131. The cnm:spmk.ling vihmtnns in the xcik'<.l late arc IIJCOIMII'I:d in tlJC absurptiun spectrum.
Ground late
Raman Auorescence
{em-
1
) (em '>
169 165
306 306
383
699 699
1460 1460
1504 1504
C:llculation
(cm"
1
)
147
305.5
31!5.7
702
1459.1>
1511
Ex<.itc<.l state
Absorption
(em-
1
)
126
297
340
660
1275
1590

sec bcocling
(39), esc beocling
a. (38), esc bending
a .. (33). esc bending
a
11
(II), CaCa, CfJCP stretching
a.(IO). OJ.CfJ stretchi ng
totally symmetric (TS) moues acquire substantial c polariwtion intensity. 1bis ef-
fect is due to a tmnsition moment 'rotation' as a consequence of Herzberg-Teller
mixing of the lowest 1
1
8., (IlL) to the higher i B, (liM} via totally symmetric
modes. This effect is particularly evident for the 1460 and 1504 em- modes. The
increasing intensity of these modes could be due to the vibronic coupling becom-
ing more elficient the lower the energy difference is between the vibronic band
and the lending slate. We notice thai the vibronic band at 16872 em- , which is
assigned as the C=C stretching vibmtion built on the origin, gives rise to stimulat-
ed emission when pumped with energy as high as 35

[63].
While the origin is almost completely polarized along b, the c-polarized spec-
trum is twice as illlcnse at lower energies starting at about 18000 emin corre-
spondence with sharp c-polarized bands at (A) 18 167, (B) 18084, anti (C) 18026
em- . At the same energies the spa:trum starts 10 show a broad background.
The A, B, and C bands, are origins of vibronic progressions with totally sym-
metric vibrations at 107. 699, 738, 1056, 1369, 1460, and 1504 em- as shown in
Figure 6- 18.
The comparison of the vibr,llional modes energies, determined by i) Raman
scattering, ii ) 11uoresceJK'C, iii) ttb initio calculation, and iv) absorption, is reported
in Table 6-5. We note that, as in the case of T
4
[64). the C=C stretching mode of
1460 emin the ground stale tlecreases its frequency significantly (1275 em- ) in
lhe first excited electronic
6.6.2 Thin Films Fluorescence
It has been shown in Section 6.4 that thin films grown by sublimation on insulat-
ing substmles possess a high degree of order, which is rellected in the dichroic
behavior of the optical absorption [ 17, 40. 65, 66). Since the long molecular axis
forms an angle of 32" with respect to the film normal, the molecular arnmgement
is similar to that of the single: ctystal on a he fucc. Til..: low temperature ah-.urtl-
178 6 Eleclrrmic Slruclure ami Energy Transfer in Solid a-Sexilhienyl
tion (L6 K) of the thin film is compared with the polarized absorption of the be
single crystal at 4.2 K in Figure 6- 19. The low energy spectrum of the tilm shows
sharp bands, which have a linewidth that is of the same order of the low tempera-
ture absorption of the single crystal, indicating that the film indeed possesses a
high degree of ordering. Remarkably the a,. origin is also observed in the film as
a shoulder together with the 0' and 0" Henberg-Teller false origins. At contr.LSt
wi th the sharp absorption, the tluorest:ence is quite broad and, moreover, totally
different from the fluorescence of the single crystal. The additional and more in-
triguing observation is that the fluorescence spectrum varies from film to film de-
pending on the preparation conditi ons. This difference may be quire large a.-. in
the case shown in Figure 6-20.
In retrospect, by inspecting the lirer.llure, we find a confirmation of this vari-
ance (see for instance Ref. [67]). Peak intensities of bands originally assigned to
Franck-Condon components of the excitonic emission have r.tndom relative inten-
sities. This would not be possible if the bands were intrinsically vibronic.
we know that the excitonic emission, as ir is observed in single crystals, is r..tther
sharp at low temperatures, we were forced 10 reconsider the assignment of the flu-
orescence of thin films. From the temperature dependence of the fl uorescence effi-
Sil1gJe Crystal
16000
1/c
I
:'""
..........
..
20000
Wavenumber (em')
4.2 K
1.6K
24000
F1gure 6-IY. Ollnparison of the b- anc.l c-polari/.cd s ingle crystal absorption sp<.'Ctra al 4.2 K with the
absorption of a polycryslallinc thin lilm al 1.6 K. Note thai the a,. origin is also
ob:.crvcd in the lihn.

c:
Q)
0
C/)

0
:J
u:
12000
6.6 Disvnler Effec:l 011 Energy li-tmsfer
179
14000
16000
18000
20000
wavenumbers [em"' ]
. lcmpcr.uun: (4 K) lluorc.-.ccncc l>pcclm of lwn uiiTcrcnt films of 1: prepore' u----

1 en:nl COuuiiiOOS. " - "

ciency we have shown that rudiative emission is consistent with an Arrhenius- ct"-
vated process and the exislence of two indepcJldent decay channels [68j TI a
1
_
solved n . . me, re
. . . uorescence m the_ ps rime scale reveals tha1, at short times after
the spectrum 1s predommantly cxcitonic. AI delay times longer than 50
lhe spec.trum becomes broader and broader acquiring the spectral characteris-
tics of the cw and ar longer times it is totally dominated by the bro d
features l?l , 68j. _Th1s 1s a clear indication that excitation relaxes quickly into
of band diffuses in space, during the lifetime of the excita-
tion, explon ng an area defined by the diffusion length If dun
11
g th' . . d
walk th . IS 1an om
e VISlls a s1te whose characteri stic electronic energy 1
than th, ex t b d d . . . IS ower
. c c1 _on an an 111 add1t1on rhe tempcrmurc is lower rhan rhat required
to exit from 1t, then rhe excitation is eventually t11pped 1'he b
0
d
th fi ... , . . . ' r a emiSSIOn IS
ass1gncd etlcct. Smcc rhc emission is broad rhc trap is not
on a spcctfJc sue wil h characreristk energy, otherwise rhe emis-
s_tOn_ he shaq_> :1s m lhc of X-uaps (1itlt: .\'llflra). The broad
tJCS are mstcad of an mhomogcncous cner"y d'tstrlbur
1
o
11
of
bl , f 1 , 1 . co an enscm-
e o mo ccu es thai have a packmg which diflcrs from the predominantly or-
180 6 Electrouic: Structure ami Euergy Tnmsfer in Solid u.-Sexithienyl
dered packing of the bulk. We call this ensemble an aggregate. Even a small num-
ber of aggregates is sufficient to act as an efficient trapping agent. The trapping
efficiency is determined by the relative weight of the exciton diffusion length and
the density of aggregates. An independent confirmation of the aggregate nature of
the emission is given by the comparison of the spectrc1 obtained by exciting at dif-
ferent energies, above and below the bottom of the exciton band. The site-selec-
tive fluorescence experiment is shown in Figure 6-2 1. The spectrum is indepen-
dent on the excitation energy until it reaches about 17 700 em- . At excitation en-
ergies lower than about 17 260 em- , in the last two curves at the bouom of the
figure, the fi rst peak of the emission at 17 300 em- disappears and the rest of the
spectrum becomes broad. This indicates that the first peak is due to a different
species from those which arc responsible for the rest of the spectrum. This obser-
vation suggests that there arc at least two different sets of aggregate states in the
film. 1l1e relative density of these states may be different from sample to sample.
There arc aggregates which arc stable in the grounll stales and aggregates which
are only stable in the excited stale. The Jailers are also called excimcrs 171. We
may distinguish between these two possibilities by looking at the fluorescence ex-
citation spectrum. This is reported in Figure 6-22. A clear peak is observed at
17 700 em - I. At thi s energy the absorption spectrum shows only a smooth tail.
The peak at 17 700 em - I locates therefore the energy of the aggregate and shows
that the aggregate is stable in the ground stare [68j.
Wavelength (nm)
600 700 800 900
20000 18000 16000 14000 12000
Wavenumber (cm'
1
)
Figure 6-21. Sile-selcctive fluorescence me.JsurcnlCnls of a T., lhin 111m. Starting from Jhc lop spec-
trum the exciJalion energies were al 17tl60. 17700, 17390, 17240. 17095, an<.l 16950 cm'
1
, rcspcc
lively. Tile reminiscence of the exciJing laser lines is shown by lhc sharp peak on Jhe lcf1.
6.6 Disorder Effect Ull Euergy Trcmsfer
181
Wavelength (nm)
400
450
500
550 600
1.2 650
1.0
'
::j
l
.!!!.
0.6
c
1
.2
!
i
u
I
X
0.6
y
w q
Q)
D
0
c
Q)
0
.
'
(I)
0.4
fl! 0
0
t
::::J
u::

0.2
t
b
i

0.0
24000
22000
20000 18000
16000
Wavenumber (em' ')
Jo'igurc 6-22. Auorcsccncc cxciJaJ
1
o
11
f .
15 380 to 17 3()() em- . In lhis energy fi:m dcrccted al energies spanning from
m s unc Jangcc.l.
6.6.2.1
Morphology-Dependent Polarization of Fluorcsct!
and Electroluminesccnce nee
As we discussed in Section 6.5 the mo holo f . - .
to the growth co
11
d
1
11
0
. If gy
0
T6 lhJn h lms s very sensitive
ns. we now restnct the t d fl
lure we have shown that dur, ng de o .:t. h s u. y ' ms wuh granular srruc-
. . P s1 1on t e gr.un SJ'"' and d , h.
gr.uns mcreascs rapidly h . . . . . . "" Ol' enng WJt 1n the
cases, the height f lh _mcrea:; mg substrate temperature [29, 37, 69]. In all
o c steps of the films morphology measured b AFM
that, whatever the dimensions of rh . . T . Y show
mutely upright on the We 6 ap_Proxi-
to aggregates Aggregar. .
0 1
at emJssJon 111 thm lllms 1s due
cs may or may nor have
1
prefe . t'. 1 .
granular structure. If they do ' t h ld . . . ren a onenrauon m the
to check this effect we havd result m a pol<tnzcd tluoresccncc. In order
thin films. Moreover, we lluorcsccnce on
phology allecrs the degree of lluorcse p I t>: of _chcckmg If and how the mor-
. cncc po anzaron. For this p h
stud1cd the fluorescence polarization . . . . we ave
age gmin diameters, in the range <.hiTerent aver-
text we have rc a d . . . . . an . nm, and 111 the same con-
p r II: a scncs of one l.tyer Tb-bascd hght cmiuing diodes (ITO/
182 6 Electronic Structure and Energy Tra11sjer in Sulitl Cl-Sexitllienyl
T&'Al) having the same range of avemge gmin sizes (200-1500 nm). On these
LED devices we have also measured the polarization degree of electrolumines-
cence. Measurements were made in a plane perpendicular to the substmte with the
viewing angle changing from 0, along the normal to the substrate, to (90),
perpendicular to the normal, as shown in the Figure 6-23. Within an amorphous
film, emission of light is isotropic. but the measured angular dependence of emis-
sion varies approximately with the cosine of the viewing angle because of refmc-
ti on and reflection at the fi lm surface [70]. The angular dependence of externally
detected light is determined by a competition between the emission distribution
within the film and the effects of refmction and refl<.'Ction described above. In our
experimental contigumtion, the relative intensities and angular dependence of ver-
tically (V) and horizontally (H) polarized light arc detennined by the components
of the transiti on dipole moment of the aggregate with respect to the direction of
observation. If the transition dipole moment is oriented parallel to the long molec-
ular axis we expect the vertically polaril.Cd intensity to vary approxi mately as the
cosi ne of the viewing angle, and the horizontally polarized intensity to peak at
some angle to the normal. However. the intensity of both polariations is equal at
the ov viewing angle since there is rotational :.ymmctry about the normal to the
film. We note that interference and microeavity ell"ccts can also make U1e emis-
sion peak at non-zero viewing angles. These effects. however, arc easily tlistin-
guishable from those of molecular orientation because the intensity of the vertical
anti horizontal polariwtion:. is approximately U1c same for the fonner but quite
tliffcrent for the Iauer. Simi larl y, if any of the light that is waveguidcd in the film
is scattered into the forward direction we expect it to be isotropically distributed,
and therefore not to contribute to the polarized emission.
Figure 6-24 a shows the angular dependence of the fluorescence anisotropy (H-V)
in fi lms made at temperatures of 22 "C (ca. 200 nm gmin diameter - case A), I 04 oc
aluminium
T6 (-ve contract)
molecules
lllll///1///1/l/11/11/
111//1//11/lll/11/1111
v
detector
H
normal to
the film
Figure 6-23. Sketch 11f the expcrimcnt:tl armngcmcnt for mc;t,unng the angular llcpcndcncc of Ouorcs-
cenc.: and clc.:trulumincsccm:c. The viewing angle U is van!.lll between - 90 " <lllcJ +90v.
6.6 Disvrtler Effect un Energy Trcm:.fer
183
0
>
2.5
'
2
Q)
u
1.5 c
Cl.l
u
Cf>

0
:;,
u::: 0.5
a)
0
-90
>
'
0
4
Q)
3.5
v
c
Q)
3 v
Cf>
2.5
Q)
c

2
e
1 5
v 1
Q)
jjj
05
b) 0
-90
....
6-24. a) Pular l'l:Jln.""<:ntatrun ( from - 90 . '" +'XI I t II . .
arusutrullY (I I-V l in T,, fi lm,. walh rai n ,,z . ( I c(l() ur l< .angular dcpcru.kn<.-.: uf lluun.""<:cncc
200 . o ' .1.-,; 0 ' IIIII (un.n MjU'U"C ' ) '"'" (1"11 .
nm (open can:lc') b) n1c .
111
,. ul r . .. f .-- vvv nm a ctl ''rclcs) ant.l
I
. o il uCJ)CI!uCilCe 0 clc.:trul 1 . , '
rom th.: LEO cuntactcd part
11
1 th , .
1
11
anc,.,cncc anasutropy (H-V)
c 1oa111e 1oamp cs.
(ca. 600 nm diameter - CCJSe B) and 155 oc . I .
from the film grown .:t rootn re (ca. nm dtameter - case C). Flu-
h
mperature s completely u I . ed
t _ ough X-ray measuremenrs show that . h til . npo anz even
. sue t ms are well ordered Ani ot . b
S<..'en, however, Ill the fluorescence of the film "th . .. , . . : . s can e
and the degree of polariwtion h_lgheL r
Ill I e polar plot are in fact clearl . . . . gmms. OU<;S
First of all we notice that the are more in case C.
the long molecular axis. Secondly the de rec of t_ Is mdeed parallel to
the average grain size. Fluorescence as . r h . b. IS dependent on
the result of energy rmnsiCr which i;l d ely discussed m this section, is
spati al scale of morphology. which are
The
the exciton diflusion len nth of the most pct"f-.... r y I ,liS higher than
d . d o ...... mo ecu ar smgle cry ral . ("
ecu es nm). Tile grai n size dependence dl.>t:s not rcllect th. f h s s J.e .. _ew
of the diffusion len nth und poltr
1
., .,
11
-
011 1
. ere ore t e compctliJon
o .... nemoy loss at the r 1 b
observed by AFM. The self-similar ro rt rh . . . . , .. . :' c ua oundaries
in_ undcn;tanding this apparent In help
Wi ll be a series of hieran:hil:al structures th . orp ?_ogy IS there
space. Groin bo d . . .
1
. . at arc smular at d11lerent scales of
by AFM arc ower. from those directly observed
y to be responsible ol the polariwtion memorv loss.
184 6 Electronic Structure and Energy Tmnsfer ill Solid u-sexithienyl
We assume that at the grain boundaries aggregates, that are responsible of the radiative
emission, are randomly oriented and therefore giving rise to isotropic emission.
Figure 6-24 b shows the angular dependence of elcctroluminescence anisotropy
(H-V) measured on the same samples as were used for the fl uorescence experi-
ments, making proper contacts. The electroluminescence is isotropic in the film
with average grain diameter of 200 nm and is more and more anisotropic at high-
er avemge grain diameters. Moreover, the anisotropy is larger in the case of elcc-
troluminescence than in fluorescence. This indicates that, in addition to the energy
tmnsfer govem<.'d polariu ui on memory, there is another effect which is affected by
morphology and is contributing constructively to the polarization memory. We ar-
gue that this effect is charge recombi nation. Charges have a better chance to re-
combine and form excitons within the ordered bulk than at the grain boundaries
in the case of larger gmins than in the smaller ones. Once the exciton is formed,
it dilfuses wit hin the ordered bulk and eventually emits from the ordered bulk
rather than bclllg trapped at boundaries.
6.'6.2.2 Morphology-Dependent Energy Transfer
In the previous subsection we showed how the morphology of vacuum-sublimed
polycrystalline films affects the polarization properties of lluorcscencc and electro-
luminescence. Here we show that, by controlling the film morphology, the energy
lntnsfer within the film can also be controlled, thus allowing l11e modification of
the spectral properties of the emission. We consider four representati ve film
morphologies (sub-monolayer, islands, layers, and grains) which have already been
discussed in Section 6.5. The variation of the low temperature fluorescence spectra
and its relati on to film morphology is shown in Figure 6-25. For sub-monolayer ar-
chitectures the fluorescence spectrum shows the sharp excitonic features observed in
the single crystal, and the residual contribution from molecular aggregates results in
a broad background. The cxcitonic electronic origin and the 1460 em- vibronic
Franck-Condon progression built on it, are clearly identified. In U1e fihn morphol-
ogy characterized by non-inter.tcting islands, the molecular aggregation is still unfa-
vorable and the mdiati ve emission retains a strong excitonic chamcter. The layered
morphology leads to an increased relative weight of aggregates emission which
smears out most or the excitonic sharp components. The gmin-likc morphology
gives rise to the typical broad bands fluorescence spectrum that we discussed
above. II is entirely due to emission from molecular aggregate states !61] and none
of the excitonic features persist. The energy level of the first aggregate (A in Fig. 6-
25) is located at about 700 em- below the boHom of the exciton band. A progres-
sion of the intense C=C stretching mode ( 1460 cm-
1
) genemtes the low energy fea-
tures of the aggregate spectrum. Since this aggregate acts like an cfTi cicntlr..tp for the
excitation, any excitonic (sharp) feat ure is smeared out from the fluorescence spec-
trum. From the optical behavior of the different molecular architectures it ".tppears
that molecular aggregates arc funned due to Lhe coalescence of different gr.tins of
material. At the gmin boundaries, ensembles of molecules ean indeed be tom1ed
with intem1olccular intemc.:ti ons diiTerent from the bulk, lt;ading lo low cnergy-local-
il..cd electronic states.
6. 7 Cullclusions
185
sub-monolayer
12000
14000
16000
18000
Wavenumber 1 em 1
Figure 6-25. '11<:\:lr.t m 4.2 K of T I . . . .
grams; b) island.,; d) sub-nwnolaycr wuh. morphology by: a)
layer architecture O.Xrc;L'i(:s the cncnov tr.
1
. lli . wcr nslly of aggregate stales in the sub-mono-
. . . cv uiL\ Cr C ICICII<:y IO low cncr, t 1. . tJ
qwrcs donunant cxcitonic (sec Sc ( ,_
6
.,
2
gy ' a c' an the lluon:!>CCJI<:C ac-
" lOll n .. . ) .
. possibility of controlling the morphological and strucrur I d . h
td ts a fundamental requirement for the . d a t. sol-
emrOsston properties of a lumincscem material within an ,. uhcttbth!Y. of

t e ( LED) device. tg emtttmg
6.7 Conclusions
In article we have reviewed the results of a oint " . . . .
logtcal invc.'>tigottion of a-scxithicn I T J and morpho-
whil'h is assi .. netl to I 8 s,)l.t . . yl ( The sml::lct ckx:trunic lcvd,
o ,. . t s 111 lle smglc crystal tnt f 1
1l1e SltlJClurc of the exciton hand is by the ltne. lcvclsd.
u a sorptwn an
186 6 Electronic Sttucture ami Energy Transfer in Solid a-Sexitllienyl
fluorescence-polarized low temperature spectra. The Davydov splitting between
the lower opticall y allowed a., crystalline level and the higher bu level is mea-
sured to be 2600 cm-
1
giving the first piece of clear evidence of the extent of the
intermolecular interactions in a model-conjugated oligomer. The large energy im-
plied in the splitting could be an important factor in determining the sequence of
the excited states and the photophysics in real conjugated polymers in general. In
this case the lowest Davydov component is acc:idemally forbidden as a conse-
quence of the peculiar molecular arrangement within the unit cell. This fi nding
explains the dramatic reduction of the fluorescence quantum yield in the solid as
compared to solution. Most of the vibronic intensity is via the Herzberg-
Teller coupling. We show that the energy transfer in the solid state is highly sensi-
tive to the morphological structure and to the molecular ordering. Fluorescence is
mostly excitonic in the single crystal while it is dominantly due to aggregates in
the case of ordinary thin films. Thin film growth in high-vacuum has been exten-
sively investigated by atomic force microscopy. The effect of two relevant growth
pammetcrs (deposition temperature and film thickness) on the morphology has
been quantitatively analyzed to obtain growth relations. The large variety of mor-
phology in T
6
fil ms, grown by high-vacuum sublimation, ari ses from the kinetic
control of the growth process. Films of reproducible quality and features can be
obtained by controlling the growth conditions. The growth relations of T
6
films
were inferred by measuring the evolution of morphological properties from AFM
images using statistical methods. In particular, we showed, using topogmphy scal-
ing arguments, how morphological tmnsitions can be monitored by meru1s of the
roughness scaling exponent and the correlation length of the topogmphical fluc-
tuations and interpreted in terms of changes in the controlling mechanism of
growth. The fact that in T
6
films a self-affinity in the topographical features eK-
ists, should also imply that those phenomena (such as charge injection, transport,
recombination, and eKci ton diffusion) related to the spatial conelation of molecu-
lar sites, to the extent of short-range intermolecular interactions, and to the local
ordering, are sensitive to the morphology ru1d could be used as probes for the
morphological changes. We reconcile in this way the different optical behavior of
the single crystals as well as of the polycrystalline films grown under dilferent
conditions. Excitonic emission is indeed shown also by thin films with a high de-
gree of ordering. Fluorescence <md elcctroluminescence of different thin film
LEOs with different morphologies are strongly inlluenced by the grai n sizes and
we show that films with average grain size of more than 600 nm manifest a polar-
ized LED emission. Finally, by controll ing the early srage of the growth. we show
that energy tmnsfer is strongly aiTected by the development of aggregates at the
gmin boundaries where individual coalesce into one another.
Ac:ktrowledgements
R. Danieli, W. Gebuuer, 0 . Greco, E. Lunedei, R. Mahrt, R.N. Marks, R. Michel,
P. Morelli, M. Murgia, P. Ostoja, G. Ruani, P. Samorf, T. Virgi li, R. Zamboni, D.
Bcljonne, J. Cornil , P. Vivi lle, R. Lazzaroni, J.-L. Bredas. H. Bas.-;lcr, F. Gamier,
G. Horowitz, and A. 13rcc have participated to the work which is reviewed here.
Rt!ferem:es 187
thank Beatrice Stefanelli for help in the prepamtion of this manuscript. We ac-
knowledge support from the EU-TMR Prognrnunc SELOA FMRX-Cf960083
and CNR-PF-MSTA II Progeui Coordinati DEMO and FREMO. '
References
I. F.Z. .Pcng. G . D. MtiiN: 199tl. 2, 592.
2. F. R A. 1'. Scicun 1994, 265, 16ll4.
3. P. Osi<IJ' G. Gucrn. S. Rv,suu, M. Servidori. C. Taliani. R. Zmnboni Symlr Mel 1993 54 447
4. A. Dodal:xllapur. L. lors1, H. E. Kal7., Sdt11ce 1995, 26H. 270. ' ' '
5. C. W. Tang. S. A. van Slykc. Al'fll. Plty.v. Lm. 1987. 51, 913.
6. J. H. D . D.C. '\ R llrown. Nmure 1990, J47, 539.
1
C. E. Swc.:tlhcl};. l; ltTtmmc Pmn:r.w.f in Crystuls, Clan:ndon Pres:.. Oxfvnl
8. g . S. II. ley. .11"iftltLr in Molecular Cry.11uls, Benjamin, New York 1%1!
9. _ cg r m. HandiHHJk. of Cmuluctin Molc-mle.r 1vul PtJI)met:r \-lol 1 (II. S N l .
Ecl.). John W1lcy & Sons Lid 1997. '
1
wa
10. C. laliani W Gebauer i 1 H Jl .r (Jr
. . I ""' ""'" t!J 1,'!11 m1<l Polythwplll!l/1!.\ (0. Fiehuu &I ) Wile -VCH
Wemheun 1999, 361. ' y '
I I. B. E. Kohler, J. Ctum. Phy.1. 1990. <;J, 51l31!.
12. G. Horuwill.. U. Bacher A Ya.'-'klr P. L.an F. o.;, . J L "
1995, 7. 1337. ' g. l lalll.C. ave. F. Gam1cr. Clwm. Mtll<r.
13. A. Dcgli 0. More, C. Taliani, J. T. R Zamboni F. Zcrbeuo J Cl PI
1996, UJ.I, 9704. 11!111. 1ys.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
R. D. M. Helbig, S. Rcllls..-h, Chem. Phy.. 1995. 201, 309.
D. BeiJOIIIIC: J. Com1l. J. L Brcd01s, R. H. Fric11d , Srmh. Mtl . 1996 76 6 1
R. l .al.J.arom. A. J. J>al S Ro 1 G I' R z.. : C ' :
.. :.s
1
" ,u,uu. . mbon1, .. rahmu, Smtll. Mtt. 19111 42 23'i9
H.-J. P. K. V. HolTmann. D. Odkrug. J. Mol." 1993, 2YJ. i49
N. .. Dante!! G. Kua111. R. Zamboni. C. Taliani. Phys. &
11
1992. 68, 919 . .
N. P. Rillmond, F. Chan-... J .-M Nunz.i. 01<'111 Phy.f. Lrll. 1993, 201. 351.
P. Lllklw.:hr, H. Port. B. C. Wulf. Clttm. l'hys. Lt-tt. 199<. 260. 1::!5.
A.S. I>Jvyduv. nwory of .. l'kuum l'n.''" New Ynrk 197 1
U. II: O. D.C. M. 1-1<-'llllct.l..:, /'hy.>. He 1J 1990. 42. 91!30.
L. M. Uhnuv. S. l . P..lllu, G. Rua111 , C. H1li:mi. A. A. Tcvusuv. s. G. Yudin R Zan ho C''
Phy.r. Lru. 1995. 2.l2. 401. ' Ill, tlt!lll.
24. 0 . Dippel. L. Brandl, H. Ba.\,lcr. R. Danicli R Zambu11i C ""a1"
1
an
1
Cl PI L
2/6. 411!. ' . ' .
1
' ll!lll. I)'S. i'll. 1993,
25. Y. K:ull:mir,u. K. Suzuki. N. Y. M Kuroda. Jim J A
1 1
1 p
U097. n . ly.r. 1996. J5,
26. H.-J. .P. Bauerle:. K. V. D. Ocll.rug. M<'t. 1993. 61. IU.
27. M. K.t,h.l. Spc 1 lntlctt!'Y tif tlu .1nl<'c/ .\ttllr, Plenum Pn:s ... New Yurk 1976
28. PAl. P. Valal. V. Winlgcns. 1: OcluiTn:. J>. Sriva,rava P. Lul' F Garlllc J
l_l".f. IC'III. 77 W, 9155. o '
19. H. J1m. J. t\fll>l. 1'/ty.r. 1994 . l.l. 1031.
30. II. J. l::gdh.1.11. 0 . Odkntg. SP/l: 1995. 2.1112, 3'./ll.
31. P.l'. Ewald, Ann. Pltys. 1921, M, :!5.l.
32. M. R. Philpou. J. Ctum. Pl1y.r. 1971 . 54. Ill.
33. E. Lu11Ctlci. D. Bcljonn.:. J. ClHltil. J. L. UrccJa.,. c. Tahani. J. Clwm. l'fly.. lm.
34. J. kidlcy. M. Zcmer. J1u-orr1. Chuu. An<1 1973. 32, Ill.
188 6 Electronic Structure a/UI Energy Transfer in Solid u-Sexithienyl
35. G. Ruani ellu., J. Cil.etiL Phys. (submiucd). 1991:1.
36. a. Servet, S. Ries, M. Trotel. P. Alnot, G. Horowitz., F. Gamier, Adv. Muter. 1993, 5, 461.
37. A. J. Lovinger, D. D. Davis, R. Rucl, L. ToJ>i. A. Do<I:Jbalapur, H. E. Katz. J. Mat. Res. 1995, 10,
2958. De P. S R
38. R. Scrvcl, G. Horowitz, S. Ries, 0 . Lagorse. P. Alnot, A. F. lol re, . nvastava,
Hajlaoui. P. L<Ulg, F. Gamier, Cltem. Muter. 1994, 6, 1089.
39. o. Bohmc. C. Ziegler, W. Gopcl, Sy11th. Met. 1994, 67, 1!7.
40. D. Octcr, H.-J. Egclhaaf, Ch. Ziegler, D. Odkrug, W. Gopel, J. Chem. Plrys. 1994. 101, 6344.
41. E Umlrdch. M. R. Fink, AppL Phys. A. 19116, 61, 565.
42. E Umbach. W. Gebauer, A. Soukopp, M. Bassler, M. Sokolowski, J. Lumi.1L. 1998, 76-77. 641.
43. w. Gcb;mer, M. Bassler, A. Soukopp, C. Vaterlcin. R. Fink. M. Sokolowski. E. Umbach, Chan.
Pllys. Le11. 11197, 266, 177.
44. W. Gebauer, M. Sokolowski, E. Umbac;h, ChenL Phys. 1998, 227, 33.
45. A. Soukopp. K. Gtucklcr, P. Btiucrle, M. Sokolowski, :. Umbach, Adv. Mmer. 1997, 8, 902. .
46. M. Buongiorno Nan.Jelli, D. Cvctko, v. De Renzi, L R. Goner, A. Morgante. M. Pelot,
F. R. Danicli, S. Rossini, C. Taliani, R. Zambom, Phys. Rev. IJ 1996. 5J . 1095. . .
47. s. L. Floreano, D. Cvctko, A. Morgante, S. Moc.lcsti. F. Bisc;arini, H. Zambom, C. Tahan1,
Ad. Muter. submiucd (1998).
41!. F. Bisc:arini, R. Zunboni, P. Samori. P. Ostuja. C. Taliani. l'hy:r. lJ 52, 14 !l(>l!.
49. F. His.:arini, 0 . Gn:co, A. U.uria, R. Zamhoni, C. Taliam, M11l. Cryst. Liq. Cryst. 1996: 2r,l(), 203:
50. F. Bisc:arini in Scwmi11n Pm/H. Micm.rmpJ' of l'o/.l'llll'l:r (11. Ratner, V. V. E<k). ACS
Uuok. Wa,hington D.C., 19911. . . .
51. A.-L. H. E. Stanley, Fmtwl Ctmn'JIIS i11 Swjilt'c Gmwt/1, Cambru.lgc Cum-
blidge UK 1995. .
52. Y . .C. Yang. T.M. Lu, G.-C. Wang. Diffmctimr fmm Rough Srufur:es tmd Dyllmnrr: Grmvth
Frmus, World Sc:icntilic Publil>hing Co . Singapore 1991.
53. J. Krim, G. J. Mud. Phys. 1995, lJ 9. 599.
54. J. F. Jorgensen, Scan11i11g Pmbe Image Pmces:ror (SI'W), 3rd cdn., ,
55. P. B. BouiTakhrcdc.linc, C. Amrn, 0 . Vatt.:l, E. Andre, R. Gclmdo, F. Salvan, Eumplys.
Lcll. 1993, 22. 717.
56. S. K. Sinha. E. B. Sirota, S. Garorr. Plrys. Rev. IJ 198S. JH. 2297.
51. f. Biscarini, P. Sumorl, 0 . Greco, R. Zamboni, Plrys. Rev. Lc11. 1997. 78, 231!9.
58. D. E. Wolf, J. Villain, umJIIty.v. Lcll. 1990. IJ.
59. Z.-W. Lui, S. das Sanna, Pltys. Rtv. Le11. 1991. 66, 2341!. . .
60. P. Vi ville, R. Lazwroni, J. L. Bn!das, P. Moretti. P. Samori, F. Bis.:ann1, Mmcr: 19')1!, 10, 51.
61. R. N. Marks. M. Muccini. E. Luna.lci, R. Miche l. M. Murgia. R. Zambom. C. Tahan1, G. Horo-
wilt.. F. Garnier, M. Hopmcier, M. Oestreich, R. F. Mahn, PI!Yf: 227, 49.
62. M. Muccini. E. Luncdei. A. Brce, G. Horowitt.. F. C. raJao, J. Cllem. Pflys. 1998,
108, 7327. . !i 4(-
63. G. Jlorowitz, P. Valat, F. Garnier, F. Kouki, V. Witgcns, Opuc. Mtlll'l". 1998, '
64. D. Birnbaum. D. Fichou. R. E. Kohler, J. Clrem. l'hy.t. 1992, 96, 165.
65. 11.-J. l::gelhaaf, PIID Univcrsilat Tiibingen, 1996.
66. D. Frchou, G. Horowitz, B. Xu, F. Gumier, Symll. Met. 1992, 48, 167. . .
67. w. Gebauer, c. Vaterlcin, A. Soukopp. M. H. Pun, P. Uaucrlc, E. Umh:J<:h, S}7JIIJ.
Met. 1991. 87, 127. . . . M I . J
61!. R. N. Marks. R. H. Mic:hel, W. Gebauer, R. Zambom, C. ratram, R. f. Mahn, lc opnlCJcr,
Plry.f. Cflem. B 199H, 102, 39. . . . . . .
R.N. Marks, F. Biscarini, T. Virgili, M. Muc:cini , R. Zmnbom, C. Tal1a111, J'/u/. Tra11s. R. Soc.
umd. A 1997, 355, 763.
70. N. C. Gn.!cnham, R. H. Friend, D. D. C. Br.tdley, Adv. Muter. 1994, 6, 491.
7 Spectroscopy of Photoexcitations
in Conjugated Polymers
Paul A. Lane, Sergey Y. Frolov, and Zev Y. Vardeny
7.1 Introduction
The combination of cllicienl phololuminescencc (PL) and ease of processing ha-;
gener..tted much interest in conjugated polyml!rs with respcl:l to their usc in light
emitting diodes (LEOs) and other optoclcctronil: devices [1-5]. 11tis interest h:l!;,
in lum, led lll ex1ensivc investigations imo the nature and dynamics of photoex-
ciled states. Phmoexcilalion dynamics in conjugated polymers span a wide r.mgc
of timescales. Singlet excitons self-lrap and migrate on a subpicosecond timescale
and decay within approximately one nanosecond. Long-lived photocxcilations
such a-; polarons. bipolarons, and triplet excitons arc formed by the non-radialive
decay of singlet excitons and have lifetimes exceeding a millisecond at low tem-
peratures. As a consequence, multiple spectroscopic techniques are required to un-
dersrand the photophysics of these novel materials.
We have investigated the photophysic.-; of conjugated polymers using a varie1y
of linear and non-linear spectroscopies. Photomodulation spectroscopy (PM) uses
two light sources whereby absorption of a pump beam modulates lhe transmission
or reflcclance of a probe beam incident on lhe sample. PM spectroscopy can de-
tect a variety of phenomena, depending upon the ti mescale of the me:l!;uremenL
Transient PM sLUdies with nanosecond or better resolution have detected slimulat-
cd emission (SE) and phmoinduced absorpti on (PA). also known as excited state
absorption. Continuous wave (CW) PM spectra include contributions from PA.
photoluminescence (PL) from spontaneous emission, and electroabsorption. The
Iauer signal is caused by electric fields <arising from photogenerJted charged exci-
lations. As photocxcitatilm Jynamics in conj ugated polymers span a wide range
of timc.-;calcs, we have employed both tmnsienl anJ CW PM spcctrosl:opies lo Jc-
tect photoexcitations and measure their relaxation dynamics. Optically detected
magnelic resonance (ODMR) has also been employed lo delennine the spin of
long-li ved photoexcitations.
Conjuguted polymers ure centrosymmeuic systems where excited states have
definite purity of even (A
1
:) or odd (B,) and electric dipole lr.msitions are allowed
only between slates of opposi te pmity. The grounJ stale of conjugated polymers
is an even parity singlet slale, wri llcn <L" the PM speclroscopy is a linear
technique probing dipole allowed onc-t>holon trJnsitions. Non-linear spcclrosco-
pics complement these ml!asuremcnts as they can couple to dipole-forbidden Iran-
190 7 Speclro.Kopy vf Plwtocxcitatio11s in Conjugated Pvlymers
sitions and reveal the existence of even parity states not detectable by li near spec-
troscopy. We report studies on the two-photon absorption (fPA) and clectroab-
sorption (EA) spectra of conjugated polymers. By measuring the two-photon ab-
sorption spectra, it is possible to clarify and enhance our understanding of U1e
physical states of these polymers. Employing ilie Z-scan technique enables accu-
rate identification of TPA bands, since it measures real as well as imaginary x
0
'.
EA probes change in ilie absorption spectrum due to an applied electric field and
are sensitive to both even- and odd-parity states.
7.2 Experimental Techniques
7.2.1 CW Photomodulation Spectroscopy
In the continuous wave (CW) experimental setup a sample is constantly ill umi -
nated by a probe beam and the steady state change in the transmission is detected
(see Fig. 7- 1). An argon ion laser has been used to genemte the pump beam and
the probe beam was from an incandescent lamp (tungsten or others), pr<XIucing a
broad spectrum (0.5 to "'5 J.lm) l6 ]. Both pump and probe beams arc directed
onto the sample film and the tmnsmiued probe light is collected, filtered Uuough
a monochromator, and detected by a photodctcctor. Both the pump and the probe
Arlaser --- 7\
/
/
/
prObe ,
c /)

( .----h
monochromator
7-1. diagmm of the
CW PA spectrometer.
7.2 EJ.pelimental Tedmiques
191
'"':'ere di spersed across the sample; the probe is assumed to have a uniform inten-
sity and the pump a Gaussian di stribution.
the 6.T in .the sample T is very small (6. TIT
-:= I 0 a phase-scnstttve (lock-Ill) detection technique has been used. TI1c pump
ltght ts a. a rclcrcncc frequency (usually in the audible frequency
mngc), therefore !:. T ts modulated at thi s frequency too. The modulated t:. Tis de-
tected a lock-in amplifier referenced at the same frequency. By simul taneously
mea-;un ng !:. T_ and ! and the wavelength of the probe light, ilic spectrum
of 6. TfT stgnal ts obtamcd. Tile tmnsmitted probe light f(tl) through the sam-
ple ts represented by:
I (cl) = 1(0) e-"'
1
( I - R)
(7. 1)
!(0) is the probe light incident on the film, a is the absorption
c?cfltctent, cl the film ilitckncss, R the rctlectivity, and reflections from the back-
the film neglected. 1l1e absorption coefficient is equal to the density of
excuattons multtphed by the absorption cross-section (a= na). The pump beam in-
duces changes in both u. and R:
t:.I(d) = I(il)( I - R)(e- llwt - I ) - t:.R . /(O)e- <nllul' (7.2)
6. / is in '.ransmission with the pump on and the pump off.
Alter normalwng the equatton by l (cl) and assuming t:,.(.({/ 1 it follows that:
6.T t:.R
- = - 6.u.d - -- .
T 1- R
(7.3)
In all our conjugated polymer samples R is less than 0. 1 and 6. R!R < 10-6 [7 j . Be-
cause!:. TIT typica!ly in the range of 10-
3
- 10-
5
, the second tenn in (3) c-.tn be
neglected. Thts rclatton holds onl y in the small signal li mit (!:.ad 1) for iliin
films, where the pump light is absorbed uniformly, creating an equal di stribution
of t:.a across the film.
For. lock-in amplification ilie pump is modulated m a reference frequency w
(sec Ftg. 7_- I), whtch means that t:.T is not constam over time. Rather, its magni-
tude (and tls phase) depends on the modulation frequency [81. In order to find the
t:.T_(w), u.s assume that the recombination dynamics Hre
monomolecular wtth a smgle hletunc T. Then we can write for the number den-
sity of excitations N at time t :
c/N(t) = G(t) _ N(1)
dt T
(7.4)
where G(t) is genemtion mte and N(I)/T describes the monomolecular decay
rate. The rate G(t)= yP(f)/luv, where P(l) is the pump power, ftcu the
energy of a smgle pump photon, and )' the quantum clli cicncy of the photl>cX(' ita-
192 7 Spec/lvscupy uf Plw10excitaticms in umjugatecl Polymers
tion. We take into account only the fundament411 Fourier component, neglecting
the higher orders:
G(t) = G(w)e- ;"". (7.5)
Assuming N(t) has the same form and substituting into (4), we find:
G(w)r
N(w) - -t
- I + (w-rl l + (wti
(7.6)
Relating N(t) to the absorption cross-section a(lla=Na)
/1T [ I WT ]
--= - i G(w)rad.
T I + (wr)
2
I + (wrf
(7.7)
The first term in Eq. (7.7) is the in-phase signal, which has the same pha_se as
that of the pump, and the second term is a quadmture or out-of-phase s1gnal,
which has a 90 phase relative to that of the pump. Their resr<:ctive de-
pendencies are shown in Figure 7-2. The normalized change_ m trans_m1ss1on can
be related to the excitation cross-section and quantum y1cld of genemllon:
11T S liw
a(.'.)= - ---
T yrPabs
(7.8)
where a(.'.) is the photoinduced absorption (PA) cross-section at the probe wave-
length .'., and Sis the illuminat(:d area of the sample [9]. .
The decay of photogenerawd charged exciwtions _as p<>larons and btpolar-
ons should be bimolecular. In this case, the rate equauon IS wntten:
dN(t) = G(t)- R(N(t) )
2
.
dt
(7.9)
The dependence of the in-phase and quadrature lock-in detected signals on the
modulation frequency is considerably more complicated than for the case of
monomolecular recombination. The steady swte solution to this equation is
straightforward, dN fdt = 0 => Ns.'i = JG/i?. but there is not a geneml
N(t) to the inhomogeneous differential equation. Furthermore, the
will vary throughout the sample due to the Gaussian distribution ot the pump Ill-
tensity and absorption by the sample
(7.10)
where r is the distance from the center of the pump beam. z is the penetration
into the sampl e, a is related to the beam width, and u. is the
cient. If one fUJ1her int:orpor.ues diffusion, the rc:-.ulting problem ts non-tnvml.
7.2 EJ.]Jerimentul Techniques
193
0. 1
0.01
10
--In phase
- - Quadrature
/
/
/
/
/
/
/
/
/
/
/
100 1000
Frequency (Hz)
Figure 7-2. Frcqucnc:y dependence of lhc in-pha:,c anti ljU<Illr.uun: PA sit:nals.
1 o
Whi le it is possible: to simulate the modulation frequency dependence, this must
be dune on a case by case basis.
7.2.2 Optically Detected Magnetic Resonance
Optically detected magnetic resonance (00MR) has yielded val uable information
a?<>ut of long-li ved photocxcitations of conjugated polymers. The tech-
mq_ue rehes upon the intemction of exci tations with an applied mag-
For a patt1clc wuh non-zero spin, placed in a magnetic field, the Ha-
miltOnian 1s:
(7.11 )
is the spin of 'if a tensor defining the intemction of the par-
!lcle the field, and f! 1s the apphed magnetic ticld. The g-tensor is diagonal
m_ a ?asls set Ill the symmetry of the molecule and possesses three
A-; there 1s only a very slight in the g-valuc for conju-
polymers [IOJ. the tensor can be replaced wtth a constant and the Hamilto-
man reduces to
(7. 12)
For spin resonance <ESR) measurements, the sample is placed in a rcso-
between the pieces of an electromagnet. The mag-
netiC lldd 1s mcrcascd. wh1ch Jndutcs a Zeeman splill ing of the exdta-
194 7 Spectroscopy of Plzotoexcitwions in Conjugatetl Polymers
tion energy levels. Resonant absorption or emission of microwaves occurs when
the splitting of the energy levels matches the energy of the microwave photons
(hv;::=yJ
8
H). Magnetic resonance also has an effect on photoexcitation dynamics
as the absorption of microwaves will equalize the populations of the two coupled
spin sublevels. Consider two triplet sublevels X and Y with sublevel populations
11;. generation rates G;, and recombination rates R;;::= 1/r;. Under steady state condi-
tions dll;ldt=O and from Eq. (7.4) we can write
n; = G;/R;. (7. 13)
At the resonant field, the two sublevels are coupled and have generation and
recor!lbiJlation rates G = (Gx + Gr)/2 and R = (Rx +Rr)/2, and populations
iz = G/R. The difference in the total triplet population at resonance and under
satur.Jtion by microwaves is:
- Rx- R\.
Jn = nx + lly - 211 = (111' - llx)
Rx+Rr
(7. 14)
Population redistribution among magnetic sublevels produces a change in either
the absorbed or emitted light associated with the excitation. 1l1Us, magnetic reso-
nance can be optically detected, replacing direct observation of microwave absorp-
tion by the pammagnetic species. This scali ng up from the microwave to infrared
or visible frequencies makes ODMR extremely sensiti ve: up to I 0
5
times more
sensitive than conventional ESR.
For spin- 1/2 excitations such as electrons and holes in nomml semiconductors or
polarons in conjugated polymers. a single resonance is found centered at the field
Ho = lzvfgp (7. 15)
where p is the Bohr magneton. Magnetic dipole intemctions between the unpaired
spins composing triplet excitons add additional tem1s to the spin Hamiltonian:
- - 2 tn2 2 n2
J/ s- s= gJluH S + D(Sz- 3.)-) + E(S .. - .)_):) . (7.16)
The zero field splitting (ZFS) pammeters D and of the triplet exciton are:
(7. 17)
E =--IJ ---
3iJi (l -x
2
)
4 ,.s
(7. 18)
(a)
AI I (b)
! ! j
Magnetic Field
..
7.2 Experimemal Techniques
195
Zeeman 'Piiuing nf triplet exciton sublevels
Ol thc_a[lphcd magnetic field. (b) Change in PL in-
tensity at magnc!K: resonance.
;;;ere_ X, y, T _r are co-ordinates of the spins in the triplet state
e ues o_t ttu: spm Hamrhonian depend upon both the ma nitude . . .
leld and tls dtrcction relative to the principal axes of the I ot ..;::e
onentatron of the molecule relative to ii determines the ener ies of th e. e
levels hence, the reson. fields Figure 7 3 show . fe tnplel su.b-
. r fi - s a ragram o energy e
app :d lor the applied tield aligned along the z princi al a:i
to the_ applied is unaffected by
downwards. . e s are mtxcd, wrth one spltt upwards and the other split
A single triplet has three resonant fields, two due to 11m -1 t . . . .
one due to Ill =+'> . . . s- ransll tons and
. "s -- tmnsrtt ons. For amorphous or polycrystalline sam les
are formed due to conrri butions from <til ossibl: : two
ol wrth to applied field. The full-field
o ns=l transrltons ts centered about H, and has th , 1 II ,
cal potnts: u c o owmg cntt-
singularities at 11 = H
11
(D _ 3E)/
2
gfJ
shoulders at 11 = Ho (D + 3E)/
2
g{J
and steps at H = Ho Dfg{J
The lwlf:field triplet powder pauem due to A.,, -2 tra .
0
h
= s- nst ons as a
singularity at
and a shoul der at
II = V(llo/2l- ([)2 + 3&)jg2p2
H = {Ho/2){ I - H<D - )/Ho]
2
} .
(7.19)
(7.20)
(7.2 1)
(7.22)
(7.23)
. The ODMR spectrometer resembles the PA spectrometer h F
Wtth the sample placed in a microwave cavity between the 11.1. .7-1,
The sample _is constantly ill uminated by the
mrcrowaves arc coupled into Lhe .. t
1
h ns.
gurde Changes J/ PL cavt Y 11roug a wave-
. tn or r, m probe tr.msmission arc
1
tectcd b 1 k
y oc - 111 am-
196 7 Spectroscopy of Photoexcilalicms in Conjugated Polymers
plification of the photodiode signal, with the lock-in refe.rcnced to the microwave
modulation frequency. We describe the two different kinds of measurements as
PL- and PA-detected magnetic resonance (PLDMR and PADMR, respectively).
Two kinds of PADMR spectra can be measured: H-PADMR spectra in which {JT
is measured at a fixed probe wavelength A while sweeping the magnetic field /1,
and A-PADMR where fJT is measured at fixed // on resonance, while A is varied.
PADMR spectroscopy is especially valuable in deconstructing PA spectra with
contributions from multiple photoexci tations with differing spin signatures.
7.2.3 Transient Photomodulation Spectroscopy
In many respects the time-resolved pump-probe technique is similar to the CW
counterpart. The use of pulsed laser light permits direct probing of both the mag-
nitude of the PA and its dynamics. n1e experimental arrangement is practically
the same as for the CW version, i.e., both pump and probe beams are focused
and overlapped onto same spot on a sample. In addition, the pump and probe
pulses are synchronized so that the time interval 1 between them is constant and
confined to a certain time r.mge (in our case up to 3 ns).
A critical difference between the tmnsient and CW measurements is that while
the CW probe source unifomdy illuminates the sample, both the tr.msient pump
and probe beams have Gaussian distributions. Equation (7.7) can be rewritten for
the transient case as:
IJ.T y Eabs
- -T = -, (r'! 2) a(A)f(t)
IV
1
+ r
2
{7.24)
where Eab is the absorbed pump energy per pulse,f(t) is the rc.o;ponse function of
the material, and r
1
and r
2
are the diameters of the two light beams. Two impor-
tant functions, a (A) and f(t), determine the magnitude and dynamics of f).Tff.
However, the above fommlas are good only when the time delay t is sufficiently
greater than the pulse duration of the pump and the probe light pulses. In order to
find a more gener.sl expression we have to use a slightly different approach. We
take into account that the pulses are not infinitesimally short. Their time depen-
dencies are given by the intensity functions l prubc(t) and lpump(l) and shown in
Figure 7-4, where the time dependence is considered on very short time scales in
the order of femtoseconds. The material response function j(t) is assumed to be
instantaneous with some relaxation time r.
Seveml laser systems have been used in our time-resolved PM measurements.
For the measurements, a colliding pulse mode-locked (CPM) dye laser
was employed lll ]. Its characteristic pulsewidth is about 70 fs, however, its wave-
length is fixed at 625 nm (or 2.0 eY). For ps measurements at various wave-
lengths two synchronously pumped dye lasers were used ( 12). Although their
time resolution was not better than 5 ps, they allowed us to probe in the probe
photon energy mnge from 1.25 eY to 2.2 eV. In addition, a color center lao;er
7.2 Experimentul Techniques
197
...
0 tot t
Fagure_ 74. Excilalion anti probe alon ' with nit< . . . .
trdllSmtsston ill> fun\:tions uf lh.: punln..p be _,_
1
. S tlcnsny anti ..:hanc in
,. ro "" ay tunc. c
(CCL) can be easily incorpor t d h' - .
I
a e mto t s configuration It gives us the . d"' t' I
Spectf'd range of 0 17 1 0 86 y . . il ul IOna
CCL is 20 ps.' be .the mode-locked
A gennaniUm detector has been used lor tl1 , d t . y ufsmg a saturable absorber.
Th
. c c ect1on o the CCL . n
e ex pen mental setup for th 1 . ,-. . lA,;
1

CPM laser is shown . F 1 u ;;.a ast (lemtosecond) measurements using the
One of the is

coming out .or the. CPM.
autocorrelation analysis. The other bea pulse duratiOn usmg an
pump and probe beamo; Af , . . m a common source for both
pump portion is directed.. t ths beam spht mto two ponions (30nO) the
10 o an acousto-opllc rnodul
1
(AOM . . '
modulate the pump intensity with SUPers . fi a ), whch able to
ponent of the AOM . . . . . o uc re_quences 1131. In the mam com-
MHz) . t Pczo-ele_ctnc crystal, a la.o;t oscillating electric field (I 00
'' es a San Ill" aCOUStiC w h' J d' 'fi
magnitude of ta d.<> . . ave, w c 1 Jt mcts the incident li<>lll The
c s n mn wave Js modul t <.1 1 11 c
MHz the result being th; modula;ion of genemtor .at 4
the zeroth or the first order in the diffraction at , . . cam. We use ether
surements we have chosen the ;wroth d . p . as a pump, and 10 our mea-
tude of the modulated pum wer Our. cr, so. the magni-
crystal, the femtosecond d1sperson
feet a set of four prisms hao; been used . . . . .' _o compens?tc cl-
sion, which nullilics the posi ivc a hnc<rr negat ive dspcr-
198
7 Spectroscopy of Photoexcilalicms in Conjugated Polymers
Ar"taser
ao modulator
delay stage
"0 "0
0 c
CT 3
Cl> "0

sample
7-5. Schcmalic diagr.1m of lhe
PM spcclmmctcr.
The probe ponion of beam, on the other

deter:bclines
3

th and Probe P
ulses The t1me delay can van
tween e pump
with. the resolution of less than I fs. . d . . 11 1 . nd focused with a single lens
1
11 d probe beams are ma e p.lra e a .
e pump an . th .' le is placed with its substmte in front of Jt (t?-
onto a sample. Usually: . e. sa';;:' !Teet of hotooxidation. Visually, with the md
wards the beams) to mmnnze e e . . an overla d. The magnitude of
of a _the (Eq. (23)). A_fter the
the sgnal f!.T cntccdally detpehe loc'-,n final adjustments optimizmg the
n 1 has on "" ' 1 h tod
sg a . . . . .t 1' he probe light is detected by a SJ con p o e-
erlap are made to maxumze ' . 4 MH I
with a build-in filtering that inn
der to avoid the scattered pump h gh_L. whctcdh 'b with a JJ2 plate_ Then the
th polari;wtion of the pump IS rota y I he
setup: . . ti t f the detector is set in such a way that on y t
polanzallon analyzer m ron . . . rture is used to block
probe light passes through ln addton, a small sze ape .
off the remaining hght. . . . l'ficd and sent to a fast lock-in
The electrical signal from the detector IS preamp ' I data
. computer which can take one or severa
amplifier. Jt dgoesl tTho ae delay is by the computer through a
nts for a gven urne e ay. d the
po . II UNIDEX ll (Aerotech). The translation stage movements an
stage . er . . th ne or seveml points are recorded for
data acqustJon arc synchromzed, so at o . I . . t' o (S/N) sev-
. . d I ) 11 . rove the -to-nOJse m '
each stage posillon (tunc cay .d d With this PM system, normalized
eml time scans can be run an average .
changes as small as 5x I o-o can be measured.
7. 2 E.l:perimental Teclmiques
199
7.2.4 Non-Linear Optical Spt.'Ctroscopy
We employed two non-linear spectroscopies to probe even parity A
11
states in lu-
minescent conjugated polymers, Z-scan for two photon absorption (TPA), and
electroabsorption (EA). Various experiments that probe the two-photon-allowed A
11
states have shown that, for luminescent conjugated polymers, a single, strong
two-photon-allowed transition is observed above the 18,. state. By measuring the
TPA spectra over a wide spectml mnge, it is possible to clarify and enhance the
understanding of the physical mechanisms involved in the observed properties of
conjugated polymers. Employing the Z-scan technique to measure TPA spectr.l en-
ables accurate identification of actual absorption peaks, since it measures real as
well as imaginary i
31
This allows the of dispersion in the real pan of
i
3
'. which must accompany TPA bands. Furthermore. since the Z-scan can direct-
ly detect signs of the complex l l components, it avoids the misidentification
of one-photon satumtion as two-photon spectral 1151.
The index of refraction in a non-linear optil:al material can be written:
(7.25)
where E is the electric field of the incident photons. Self-focusing occurs as a
combination of a positive n2 and a spatial variation of the laser intensity in which
the beam is more intense at the center than at the edges. The result is that the re-
fmctive index of the non-linear medium in the center of the beam is larger than
that at the edges and the medium acts as a positive lens focusing the beam. Self-
defocusing occurs if u2 is negative. The experimental apparatus used to measure a
reduced-aperture Z-scan is shown in Figure 7-6 inset. A Gaussian beam is tightly
focused by a lens and passed through the non-linear medium, where z is the dis-
tance between the sample and the focal plane. Consider the case of a sample wi th
negative 112 As the sample is moved towards the locus, the im:rcased power den-
sity results in a negative lensing etTcct with a net result of collimating the beam
and consequently increasing the detector signal. As the sample moves to the +z
side of the focus, the negative lensing eflcct diverges the beam and reduces the
detector signal. For an open apenure Z-scan, the aperture is removed and two-
photon absorption will decrease the ligh transmitted through the sample. Exam-
ples of open and reduced-aperture Z-scans perfonncd on a cumulene containing
oonjugated polymer are shown in Figure 7-6 1161.
Open and reduccd-apenure Z-scans were conducted on polymer solutions to
eliminate anomalous etlccL-; associated with optical damage and surface inhomo-
geneities. cs2 was used a-; a reference material to dctennine the peak on-axis in-
tensities at each wavelength, since it has good optic;.JI quality. a large, fust. dispcr-
sionless n2, and has been previously wcll-dmracteri zed by absolute Z-scan mea-
surements. To obtain the high peak powers required for Z-scan experiments, a re-
generatively-pumped dye amplifier system wa-; employed. A Qu:.mtronix fre-
quency-doubled Nd : YAG lser provides excitation for a synchronously pumped
dye la.-;cr. A dye amplifier was built to amplify the 76 Mllz dye la..,er
200
1.8
c
1.6
0
Ui
.,
1.4
e
en
c
1.2
e
.....

G>
.!:!
"iii
0.8
E
0
z
0.6
1.00
c .98
0
Ui
.96
"' c
.,
t=

G>

"iii
e
0
z
7 Spectroscopy of Plrotoexcitatiuns in Ctmju8ated Plllymers

0
-5
0
Z (mm)
0
Z (mm)
- 10
-5
. d. . (b) Open a" ... '"rc Z-sc01n.
__ _. r\ , z.scan Inset z -sc01n schematiC aJ;rJJn. 1!'""-
F"igure 7-6. (a) Redu""" ape urc
. h" h peak powers at the desired wave-
pulses at a reduced mte_, _thereby were thus amplified up to 50000
lengths. The_ rcpelltlo25n mOtHe ie pulses at up to 300 GW/cm2 peak in-
times, resultmg m lO ps, z
0

tensity. . z . rocedure whcrl!in we pcrfonn a reduced-
We employed a comparatlvc ed by reduced and open-aperture Z-
aperture Z-scan Oil cs2 y ?. . elcngth The pcak on-axis inten-
h I mer solution at a part leU ar wav . . . . . '
scans t e po y . . h CS peak to valley transmiSSIOn change usmg
sity, _Jo. IS then axis of refmction. Based on the
previously measur va u . . . by ll7}
work of Sheik-Bahae et al., the equation tor /o IS given
_

W jcm2 (7.26)
10
- 5.6 x 10
5
7.2 Experimemal Techniques 201
where is the maximum transmission change observed in the reduced-aperture
CS
2
scan and OD is the optical density of the neutral density filter. This equation
takes into consideration losses as a result of reflection from the glass cuvette.
Z-scan measurements were conducted over the spectral mnge of 576 to 846 nm
using various laser dyes in the three-stage dye amplifier system. TPA measure-
ments at 770 to 790 nm were obtained by employing a regeneratively amplified
titani um: sapphire laser system. A pulse repetition rate of I kHz and lock-in detec-
tion was employed to reduce noise. Z-scan data were saved and analyzed gtaphi-
cally to acquire the tmnsmission changes. The non-linear index of refraction, 11
2
,
was then directly calculated from the tmnsmission change [ 17). The non-linear ab-
sorption, a
2
, was calculated at the z=O position (the point of highest intensity) by
itemtively solving the e4uation
dl (r)
2
= - ttuf -
(7.27)
where I (r) is the Gaussian-distributed intensity and Clo is the linear absorption.
Electroabsorption (EA) spectroscopy, measured using an electric field to modu-
late the absorption, enhances the ji11e structure in a material's optical absorption
spectrum. An electric field perturbation applied to the material under investigation
creates small changes in the electron wave functions accompanied by small
changes in the electronic e nergy levels that can consequently be measured as
changes in the <tbsmvtion. In principle, EA spcct1-:1 be analyzed by compari -
son with Lhe lirst deri v<tli vc of the linear absorption since the lB., Stark-shift leads
to a derivative-like feature. Disorder in most polymer films, however, leads to a
distribution of polarizabi lities and energies of the I Bu exciton, so that a first deri-
vati ve analysis of the EA spectrum is not possible. Although the EA spectrum
can be modeled by a series expansion of the absorption spectrum
= 'cnd"(ad)/dE"). such a phenomenological approach often lead<; to un-
realistic interpretations. In this paper, we will show a model for calculating the
EA spectrum, which also accounts for the TPA and transient PA features.
The experimental setup for the EA measurements is shown in Figure 7-7. A
small sine-wave source was connected to a custom-built step-up transformer, the
output of which was connected to the electrodes. Electrodes for the application of
an electric field were deposited on a sapphire disk in an interlocking finger geom-
etry, as shown in Figure 7-7 inset. The gap between electrodes was 20 J.un, which
pem1itted a lield of the orde r 10
5
V/cm. The films then cast on these electrodes
were from polymer solutions. TI1e samples were contained inside a cryosl<1t for
measureme nt-; at low tcmpcmturcs. A mcchanically-dmppcd light source (typic<tl-
ly a xenon lamp) was focused on the ent rance slit of a computer-controlled mono-
chromator. The light was tihered to eliminate second-order scattering ctfects and
prevent detector suturation. The light was refocused on Lhe sample with a mi rror,
and detected by a UV-cnhanccd silicon photo<.liodc operated in the photovoltaic
mode. This configumtion mini mized any and heating of lhc
polymer films. TI1e photodiode clect1ical output was directed to a com-
puter-controlled lock-i n amplilicr. 202 7 Spectroscopy of Photoexcitations in Conjugated Polymers
l'igurc 7-7. Schcma1ic of the EA
spectrometer. Inset: Silmple geometry with
interlocked metall ic stnps.
For each EA spectrum, the transmission T was measured with the mechanical
chopper in place and the electric field off. Tite differential tmnsmission /H' was
subsequently measured without the chopper, with the electric field on, and with
the lock-in amplifier set to detect signals at twice the electric-field modulation fre-
quency. The 2/ dependency of the EA signal is due to the quadratic nature of EA
in materials with definite parity. I:J.T was then nonnalized to I:J.Tff, which was free
of the spectral response function. 1o a good approximation {1 8], the EA signal is
relmed to the imaginary part of the optical third-order suscepti bility:
4nw 2
- I:J.T j T = I:J.a.d =-1m (x(
3
l( -w; (.u, 0, 0)) x F d
ru:
(7.28)
where d is the film thickness and n is the refmctive index. The zero-frequency
components in Eq. (7 .27) are from the low modulation tield frequency electrodes,
which are negligible compared to the frequency of the optical field.
7.3 Poly(para-phenylene vinylene)
7 .3.1 Absorption and Photoluminescence
The absorption spec1rum of poly(2-methoxy-5-(2'-ethyl-hexyloxy)-para-phenylene
vinylene) (MEH-PPV) is shown in Figure 7-8a. Phenylcne-based conducting poly-
mers such as MEI I-PPV exhibit multiple absorpt ion features extending well into
.c
u;
c
Q)
0
(U
(.)
:;::;
a. 0.5
0
0
Q)
(.)
0.8
c
Q)
(.)
(/)
0.6
Q)
c
.E
:J 0.4
0
0
.c
0.2
a..
0
2
1.4
7
3
Po/y(para-phenylene viny/ene)
2.5
3
3.5
4
4.5
5
Energy (eV)
( b)
1.8 2
Energy (eV)
1.6
2.2
2.4
Figure 7-8. (a) Abso t ' d
unit. rp IOn an (b) photolunuuc.'il:cocc spectrum of 000-PPV l . .
nsct. polylfk:r rcpc:ll
the ultraviolet. The absorption spect.rum . . . .
band !hat peaks at 2 4 eV (I) t . dd' IS composed of four bands: a low-eneroy
4 7
wo tltonal weak b d . h o
. cV (II and Ill) and a broa-' b d an s wu peaks at 3.7 and
o u an centered l 5 9 V (
works by mult iple groups 119
201
h
1
. a e peak IV). Recent
entire absorption spectrum or' PPV
the of lilting the

tmnsition and is most probably tite IS the mam dclocali zcd n-n*
tmnsition followed by seve I h ol an_ mhomogcneously broadened
bands are no! well resolved due th ra onon The phonon side-
distri bulion in this fi lm. In _u n:lattvcly broad conjugation
vbrallonal satellites were well rcsotv I : . ( dtson.lcrcd MEH-PPV lilms,
. C( Ill a w) II. The origin of hatul I I
203
204 7 Spectroscopy of Plwtoexcitativns iJ1 Conjugated Polymers
been a matter of controversy, assigned either to charge conjugation symmetry
breaking caused by the substitution, or to the existence of short PPY chains in the
film [20, 22]. No such controversy exists for the remaining bands. Bands HI and
IV are due to transitions between localized and dclocalized states.
1be PL spectrum and onset of the absorption spectrum of poly(2,5-dioctyloxy-
para-phenylene vinylene) (000-PPY) are shown in Figure 7-8b. The PL spec-
trum exhibits several phonon replica at - 1.8. I. 98. and 2. 15 e Y. The PL spec-
trum is not corrected for the system spectral response or selt:.absorption. These
corrections would affect the relative intensities of the peaks, but not their posi-
tions. The hi ghest energy peak is taken as the zero-phonon (0-0) transition and
the two lower peaks correspond to one- and two-phonon transitions (1-0 and 2-0,
respectively). 1be 2-0 tmnsition is significantly broader than the 0-0 tr.msition.
This could be explained by the existence of several unresolved phonon modes
which couple to dcctronic transitions. In this section we concentmte on films and
di lute solutions of 000-PPV, though si milar measurement!'. have been carried out
on MEH-PPV 123}. Fresh 000-PPV thin lilms were cast from chloroform solu-
tions of -5% molar concentration onto quartz substrate:.; the fi lms were kept un-
der constant vacuum.
7 .3.2 Transient Photomodulation
The tr.msient PM spectr..a of 000-PPV films at 300 K, measured from 0.75 to
2.2 eV, are shown in Figure 7-9 for time delays t =O ps and 1.2 ns. The PM spec-
trum at t=O ps can be divided into two spectral regions. Above liw= 1.7 eV we mea-
sured llT>O. 1be close resemblance of the llT>O band to the CW PL spectrum leads
us to assign this band to stimulated emission (SE) [24, 25]. The contribution of the
steady state PL to the delay time-dependent SE signal was small (<5%) and could be
easily subtracted since it did not depend on the tmnslation stage position. Below
nw= 1.7 eY we observed two PA bands peaking at 0.9 eV (PA
1
) 1101 and 1.5 eV
(PAz). The decay dynamics of theSE, PA., and PA
2
bands arc compared to those
of the PL band in the inset of Figure 7-9. Except for PA
2
, all show a single exponen-
tial decay dynamics with lifetime r..,.:::::240 ps. which is equivalent to the decay of the
photogencr..atcd excitons <.lcnsity. PA
2
initially follows the 1-.ame exponential decay
dynamics up to -300 ps, then it <.leviates and becomes much slower dominati ng
the PM spectrum at longer times. As seen in Figure 7-9, the PM spectrum at
t = 1.2 ns contains only a single asymmetric PA band, which is slightly blue-shifted
from PA2o whi le PAt an<.l SE are barely detectable at 1.2 ns.
We observed similar PM spectra in 000-PPV dilute solutions, shown in Fig-
ure 7-10. PAt. PAz and SE can be again identifie<.l at the same probe photon ener-
gies as those in films. r., in solutions, however, longer ( - 440 ps, see Fig. 7- 10 in-
set), and PA
2
deviates from a single exponential dynamics at times longer than
I ns. The primary excitations in 000-PPV dilute solutions must be singlet exci-
tons, since the polymer chains are isolated and hence, the possibility of exciton
dissociation into polaron pairs is greatly reduced. Then from the similarity of the

0.5
0
<J
....!..
'6-0.5
T-
-1
0.6
7.J Po/y(paru-pheny/ene vinylene)

t(ps)
0.8 1
1.2 1.4 1.6 1.8
Photon Energy( eV)
SE
\0 ff
\ 2
. d Q)
0
2 2.2
205
Figure 7-9. PM of 000-PPV Iii . .
dcc<!y dynami.:s of I' A and SE. ' Ill at pump-probe delay limes of 0 and I ns. Inset:
' ' I
1
2 2.2
1.2 1.4 1.6 1.8
Photon Energy(eV)
rrgurc 7-10. PM S(X:Cirum of 000-PPV . I .
Inset: decay dynamil-li of J>A barTds and Sii. so utron at pump.pmbe dchly times of 0 and I us.
206 7 Spectroscopy of Pho10excitalio11s in Conjugated Polymers
PM spectra and their decays in 000-PPV films and dilute solutions, we conclude
that the primary excitations in 000-PPV films are also singlet excitons [26]. The
long excitonic lifetime and a corresponding high PL quantum efficiency [27] indi-
cates that 000-PPV is a high quality polymer material, which is very suitable for
electrooptics and laser action applications [28].
The two transient PA bands discovered by ps PM can be directly associated
with singlet excitons via a measurement utilizing three pulsed laser beams, as
shown in Figure 7-11 inset. In essence, the singlet excitons are used as an optical
switch. The switch is turned on by photogeneration of singlet excitons by a pump
beam at t=O ps and turned off by stimulated emission induced by a dump beam
at t=t
1
The dump beam fluence was in the order of 10
13
cm-
2
llle pump beam
is tuned within the absorption spectrum and the dump beam is tuned where there
is stimulated emission, but no absorption or PA. The effects of this switching are
measured by a probe beam at 1=1
2
, which is tuned within PAa (0.8 eV) or PA
2
(1.5 eV) spectral r.mges. Any changes in the PA dynamics due to SE require that
the PA band is related to singlet excitons.
figure 7-lla compares the respective transient decays of PA
1
with and without
the dump pulse at 1
1
= 150 ps; the difference in the PA decays is also shown. It is
seen that the PA magnitude is reduced (or switched off) at t
1
by about 20%. llle
magnitude of PA reduction is linear with the dump beam intensity up to a 30% re-
duction in llT. This switching eflect is caused by the decrease in the singlet exci-
ton population, 6N, due to SE induced by the dump pulse at 1
1
The reduced PA
at t>t
1
continues to follow the same exponential decay as for t<t
1
, since the re-
combination process is monomolecular in origin with no correlation among the
photogenerated excitons and thus N(t) is not affected by 6N at Ia. As seen in fig-
ure 7- ll a this also leads to an exponential dynamics for c5T(t). We also tried vary-
ing the delay time Ia between the pump and dump beams [29] and found that
c5T(t) decays follow the same exponential fom1 with lifetime Ts, independent of t
1

This simple decay form can be readily explained by a SE process at t-ta. Since
6N(t
1
) is proportional to N(l
1
), where 6N(1
1
) is the number density of dumped ex-
citons, the decay dynamics of c5T will follow those of llT.
In Figure 7-11 b we also demonstr.tte the excitonic switch for PA
2
. In this case
we kept the pump at 2.3 eV, the dump at 2.0 eV, and tuned the probe to 1.5 eV.
Again we show PA
2
decays with and without the dump pulse at Ia = 200 ps. It is
seen that c5T is formed at t=t
1
, providing di rect evidence that both PAa and PA
2
are due to singlet excitons. In contmst to the switch at PA
1
, 6T decay in the PA
2
spectml range depends on t
1
At ta =0 ps 6T(t) decays exactly as llT(t). However,
lo r 1
1
>0, ()T(t) deviates from llT(I) and the deviation increases with the switch-off
time, Ia. as seen in Figure 7- ll b for oT at ta = O and 200 ps. The rea.-;on for this
more complex behavior of PA
2
is the mixed contributions to PA
2
at t>O ps
from both singlet excitons and longer-lived species. We shall now show that the
long-lived species arc triplet excitons, to rmed by intersystem crossing of excitons
from the singlet to triplet manifolds. ()Tis caused by singlet exciton alone, since
triplet excitons do not mdiate and therefore cannot be influenced by the dump
pulse via SE at 2.0 cV. Then. since the contribution of triplet excitons
with ta. the deviation of 5T( I) from !J.T(t) becomes more apparent at longer 1
1

7.3 Poly([>ara-phenylene vinylene)
201
1000
.
to -
I
I
' ""
I s:: " -
uTff ...
I -w ....
I " :. .
.,,, ... .._. - .:,. .. -
1 ()-5 - """";:
0 400
800 1200

1600
2000
Figure 7-11 (a) D.:cay
0
. r ., .
ynamtcs o r'At wnh without the 1 J
1
. .
pump. dump, and prob.: pulses. (b) <lyn;unics r P. . l ump pu sc. nsct: tune profiles of the
for ' = 0 and ' = 200 ps. . o 'A2 wnh and Wtlhoua the dump pulse. Shown
of singlet consisting of two PA bands and an SE
urn, amed. esse.ntaal states diagram shown in Figure 7-12. The
P. eam tnduces transttaons from the ground state (lA ) t lh fi . II
caton
1
c t te (IB ) c
11
o e rrst a owed ex-
a 11 r O owmg a relat ively samail relaxation ( - 0 1 V) ..
occurs hum the relaxed I B to the lA I . du . S . . c emassron
I
. . . 11 .c n ;a llaon to E. PA from IB 1 1 .,,
energy cvcls as anduccd lor the even-pari ty mA and kA . . . II o u.,. lCr
cent elegant theoretical calculations h;ave assign;d the nAo: We note .. that
tons and the kA . b. .
1
g o c arge tr.tnster exca-
th . to a aexcuon, a bound sto.atc of two cxcitons [30] Ho
err exact character cannot be inferred fr.,..,tn our PM . wever,
v measurements.
208
$'1.4
.,
>::
E'
.,
ill 0.6
7 Spectroscopy of Phowexcitatio11s ;, Co11jugated Polymers
a
F.gure 712. Configur.!lion coordinate diagram o(
the foor essential states s.howing the photophysical
processes. Also shown is the calculated PA spec-
trum based on level energies from EA spectroscopy.
7.3.3 Non-linear Spectroscopy (TPA and EA)
The existence of even parity states lying above the IBu have been identified by
two-photon absorption (TPA), two-photon tluoresccnce excitation [311. and clec-
troabsorption (EA) spectroscopy. We measured the TPA spectrum of 000-PPV
by Z-scan [32] showing both the rea] and imaginary components of X(3) Figure 7-
13 compares the linear absorption spectrum of 000-PPV to the spectra of the
real and imaginary molecular second hyperpolarizability. The imaginary compo-
nent, y", is proportional to the TPA coefficient a
2
, while the real component, y',
corresponds to the non-linear dispersion, 11
2
The y" spectrum shows a clear peak
at eV, 0.5 eV above the peak of the IB, absorption band, and a shoulder at
eV, which may cotTespond to a second TPA band. They' spectrum clearly
indicates dispersion near the two y" peaks, as expected from Kramers-Kronig
analysis, and permits us to identify two distinct TPA bands.
Figure 7-14 shows the EA spectrum of 000-PPV up to 5.0 eV, measured at 80
K with an ac electric field F= 1.4xl0
5
V/cm. The intensity of the EA signal
11T!TocF
2
, showing the dominance of the quadratic field term in EA of conju-
gated polymers. The EA spectrum is composed of strong features in the spectral
range of band 1 in a(w}, followed by weak features in the region of bands 11 and
Ill. Since it is known that localized states have a weak contribution to the EA
spectra due to their low polarizability [33), the EA result indicates that localized
states are indeed involved in bands II and lll. This, however, cannot resolve the
controversy of the origin of band 11, since band II in the leading models is par-
tially due to localized states.
1nere are three main EA spectral features in the energy range of band 1: a deri-
vative-like feature with 7-Cro-crossing at 2.29 eY, followed by vibrational features,
and an inducctl absorption band between 2.9 and 3.2 cV. 111e features below
2.5 eY are the results of a redshifted IB, exciton energy, and its phonon side-
bands (Stark shift). These features are more easily observed in EA than in absorp-
.......
>.en
.... -
.iii c:
c :J
Q)
Cl

-a

0.'-
o.e
-
0)
<;J 4
0
X 3
::J
z
-
- ;.- I
cf) 2
(\J

0
,....
X
::J 0
Cll
<1)
-->- - 1
14
1.2
Q8
Q.6
(14
112
0
2
2.8
2.5
3 :13
Erergy (eV)
(b)
eV(Zhv)
(c)
3 J.Z 3.4
eV(Zhv)
3.6
7.3 Poly(p(lra-pflellylene vi11ylelle)
209
3.8
Jo' igun: 7-13. (a) Linear absol]>lion
of 000-PPV, (b) part
of )' In two-photon
aoo (c) real p;m of )'
(propoo1ooruol lo lhe nonlinc:or in-
dex of rcfrm:oion. 11!>
lion because of the dependence of the exciton polarizability on th . . .
length. These samples arc disordered and show '1 )I )0 . , e
galion lengths (211 s .. . b . . . I 'CI. ndcr.mcc ol shorlcr COIIJII-
f h h . sorpllon probes all conjugation lengths, the domi-
nance o t e s orter chams leads to a mostly featureless abs .
Elcctroabsorption, on the olhcr hand, is a x(3) prn.ess 'lttd.therc. o, . rphon
'"" ore pre crcnlt<sll y
210 7 Spearoscopy of PhutoexcitaJions in Conjugated Polymers
4
3

2
mA
9
T
<]
...!.-
...
0
.... 0
-1
-2
1.5 2 2.5 3 3.5 4 4.5 5
Energy (eV)
Ji'igurc 7-14. Measured (bold line) and cakulaletl (lhin line) EA spcc1r.1 of [)()()..PPV.
probes the remaining longer conjugation lengths. This gives rise to the sharper
spectral features and also explains the emergence of the phonon side bands.
The induced absorption band at 3 eV does not have any corresponding spectral
feature in u(w), indicating. that it is most probably due to an even parity state.
Such a state would not show up in u(w) since the optical transition IA
11
-> ntA
11
is
dipole forbidden. We relate the induced absorption bands to tmnsfer of oscillator
strength from the allowed lAg ..... lB., (absorption band I) to the forbidden
I A
11
-> mA
11
tmnsition, caused by the symmetry-breaking external electric field. A
similar, smaller band is seen in EA at 3.5 eV, which is attributed to the kA
11
state.
The kA
8
state has a weaker polari:zability than the ntA
11
, related to a weaker cou-
pling to the lower l Bu state.
We successfully simulated the EA spectrum by calculating the imaginary part
of the third order optical non-linear susceptibility [35]. The sum over stales (SOS)
model developed b6 Orr and Ward [34 J was used to calculate the third-order opti-
cal susceptibility X
and simulate the transient PM and EA spec-

tra reported here [35]. This particular model is useful because its formulation is
not affected by singularities as are some other common fom1Uiations [36]. This
model includes the four essential states, shown in Figure 7- 12, namely the IA.o:
(the ground state), lB.., the mAg. and the kA
11
, four phonon replicas and a chain
length distribution function. Calculations were carried out using summation over
the stales shown in Figure 7-12, and their strongly coupled vibrations using ap-
propriate Frank-Condon overlap integrals (see above). The fitting parameters were
energies of the IBu, mA
8
, and kA
8
states, their dipole couplings and relative con-
figumtion coordinate displacements, &]; whereas the frequency of the strongest
coupled C;::C stretching mode (1600 cm-
1
) was directly detennined by Raman
scattering.
7.3 Pu(\tJXJrttphellylene 11inylene)
211
, The EA shown as a dashed line in Figure 7- 14, is in good
agreement wtth the measured EA spectrum. Using the fitting pammeters of the
EA spectrum, we were also able to calculate the PA from the relaxed l B exc
10
to the utA and kA 1 1 . h "
1
n
PA .r( .o: usmg t e Huang-Rhys approximation. The calculated
. shown
Ftgure 7- 12, agrees very well with the experimental PA

_at 1-0 ps (see Ftg. 7-9 and 7-10) and thus validates our nodel The
Lion ot th . post-
- e even state ts also tn good agreement with the TPA ba 1d t
-3.5 eV shown m F1gure 7- 13.
1
a
7.3.4 CW Photomodulation
As noted above,_ the decay dynamics of PA
2
deviate from the respecti ve SE d
PAt Whtle the two latter features are due to singlet excitons PA co
contnbuttons from longer-lived species. We probed these spe cies by. 'cw2P'At . ams
Lroscopy. The 300 K PA . . spec-
lh . spectrum of a 000-PPV film ts shown in Figure 7-15
e pump beam was modulated at 700 HL. and the PA spectrum is dom t d b '
peak e the r.llio of the in-phase and quadrature si na:;,a :c
ma!e excttatton hl etune of about r:::::O. J ms. Above 2.0 eV th . . .
denvattve linesh h. h . e spectrum has a
. . . ape, w c resembles the EA spectrum shown in Fi ure 7- 14
ThtS StgnaJ IS due 10 a COmbination Of bleaching of the ground state
and EA due to photogener...tcd charged excitations. An additional PA band
surcd at 80 K _shown below, has a peak at :::::: 0.4 e v. The bands at 0 4 d
eV dtlfercnt modulation fre4uency dependency and are d
1
.
dtslmct excttauons. t; uc o
In-phase
10
f5
<I
I
-
CS
T""
-5
Quadrature
1.5 2
Probe Energy (eV)
2.5
Figure 7-15. In-phase :1110 tju:tdr.uun: I'A of 000-PPV.
212
7 Spet:lroscopy uf Plwluexcilllliuns i11 Cunjuguled Polymers
The spin signature related to the CW PA spectrum can be readily at
low temperatures by PADMR [37]. The PADMR n:easurements were earned out
at 10 K on a 000-PPY film utilizing S-band microwaves at 3 GHz. The H-
PADMR spectrum of a 000-PPY film, measured with the probe wav_elength set
to 800 nm, is shown in Figure 7- 16. The H-PADMR consisted
asymmetric band with a peak at 390 and symmetnc band _at
1065 Gauss. Both bands are negati ve wh1ch means that magnetiC Ieso-
nance increases the recombination rJte of excitations and thus reduces the as-
sociated with the.-re excitations. The low-field signal is due to flm. = 2 transitions
of triplet excitons, i.e., it is a half-field triplet powder pattern. We were unable to
detect the full-tield triplet powder pauem. It has, however, been measured at X-
2
-en
0 .....
c
:J
-2
.0
....
-4
ro
E-<
tO
-6

-8
300
350 400 450 500
Magnetic Field (Gauss)
0
-en
.....
c
-2
:J
.0
....
ro -4
-
E-<
tO

-6
(b)
-8
1020
1120
1040 1060 1080 1100
Magnetic Field (Gauss)
l' il,!un: 7-16. (a) Half-fi clll and (b) H-PADMR spcclm uf DO().PPV.
7.3 Poly(para-phenylene vinylene) 2 13
band (9.35 GHz) and to be 1000 Gauss wide centered about [3H].
1be band at I 065 Gauss IS due to spin- 112 excitations, i.e., polarons.
F1gurc 7-17 compares the ).-PADMR spectra at 390 and 1065 Gauss to the PA
spectrum measured at HO K. The triplet A.-PADMR spectrum tits very well both
the PAz band measured by tmnsiem PM spectroscopy (see Figs. 7.9 and 7. 10> and
the CW PA spectrum (sec f-ig. 7- 15). We therefore condudc U1at the slower PA.,
arc due to inten;ystem crossing (ISC) from singlet to triplet
havmg a much longer lifetime than singlet cxcitons. The lSC rate in n-conj ugated
polymen; has been generally assumed to be low. However, it can be enhanced in
fi lms due the presence of paramagnetic (spin I) 0
2
molecules (39j.
Assummg that PA2 1s composed of contributions from both singlet and triplet ex-
citons, we calculate for flT(t) atluv= 1.45 eV:
(7.29)
where a and constants. In Eq. (7.32), a is given by a,-r./asr
1
sc. where as and
a, are optical cross-sections of PA at 1.45 eV for singlet and triplet excitons,
and L-.c is the intersystem cros!>ing time. From the PA
2
dynamics
(see Ftgurc 7-12.b) we found a==0.06. Then from <_..=240 ps we calculate
sc-4 ns, _assummg as and nl" are comparable at 1.45 cY. The same analysis for
PA2 decay m DOO-PPV solutions gives
20 ns. The slower ISC mte in solu-

tions is consistent with the lower dissolved 0
2
density.
Analysis of the spin- 1/2 A-PADMR spcctnnn is more complicated as it contains
two .rcat_ures with. increased and decreased transmission. As the photoexcitation
density IS propOI1IOnal to - fiT, we describe these as PA-qucnching (!5n<0) and
_(ou >0) bands. We defer detailed discussion of the spcctnnn to the
tollowmg section, where we compare the dopi ng, PA, and PADMR studies of u.-
sexithiophene (cL-61) and polyU1iophcne. Magnetic resonance is found to enhance
2
-1
0.4
\.........-
/
I
/ x4
0.8 1.2 1.6
Probe Energy (eV)
/
.... ,.,.,.
2. 0
.l'igure 7-t7. Spin- 112 (MJiilllinc) lripk:l (d;o,.hc"\.1 hnc) ..1-PADMR "fll.."\:lr:l nf DOO-I'I'V.
214 7 Spectroscopy of Photoe.xcitations in Conjugated Polymers
the recombination rate of spin-1/2 polarons. As like-charged polarons can com-
bine to form bipolarons, magnetic resonance can increase bipolaron populations
and yield a PA-enhancing signal. Our results thus indicate that polarons in 000-
PPV have two absorption bands, P
1
at 0.4 eV and P
2
at 1.4 eV, and bipolarons
have one absorption band, BP
1
at 1.1 eV. Comparison of the spin-1 /2 ).-PAOMR
spectrum to the 80 K PA spectrum leads us to assign the low energy PA band to
photogenerated polarons. The existence of charged photoexcitations explains the
photoinduced EA signal above 2.2 eV.
In summary, we found that photogenerated singlet excitons in 000-PPV films
arJd dilute solutions have a strong SE in the visible, and two associated PA bands
in the NIR spectral ranges. These bands can be used to fom1 an ultrafast excitonic
switch with variable switching times, providing direct evidence of the primary ex-
citations in 000-PPV. In addition, we detem1ined the ISC time into the triplet
manifold to be of the order of 5 ns and solved the puzzle regarding PA2 at 1.5 eV;
we found that both singlet and triplet excitons strongly contribute to PA at 1.5 eV.
7.4 Polythiophcnc
7.4.1 Linear and Non-Linear Absorption
Figure 7-18a displays the linear absorption of a P3BT film and the polymer re-
peat unit. The absorption spectrum is broadened by a combined effect of phonon
side bands and inhomogeneous broadening caused by the conjugation length di s-
tribution and impurities in the films (40, 41 ]. The onset of linear absorption char-
acterizes the energy of the lowest lying exciton, which corresponds to the pump
photon energy of 2.2 eV used in the ps measurements. The TPA spectrum is
shown coincidentally with the absorption spectrum and has a clear peak at 3.2 eV,
about 0.5 eV above the 18" peak (32]. There is a shoulder about 0.3 eV above the
first TPA band, though the dispersion data in this case is not as clear as for 000-
PPV.
The EA spectrum in Figure 7- 18b shows that the Stark shift or the lowest lying
exciton produces a characteristic derivative-like feature (uajDw) around 2.5 eV
[40]. 1his energy corresponds to the vertical 0-1 transition in the conligur.1tion co-
ordinate diagr.un (see Fig. 7- 12). The lowest exciton energy level is Stokes-shifted
with respect to the absorption maximum and is located at approximately 2.2 eV.
However, there is considerable residual absorption below 2.2 eV extending into
the near IR region. 1his is extrinsic to the polymer film and may be associated
with the presence of defects and impurities. As with 000-PPV, even parity states
couple to the ground state via the intermediate level of 18" exciton. They are not
observed in the linear absorption spectrum, but can be detected by TPA and EA
spectroscopies (291. As discussed above, the electric ticld mixes states of different
parities, which can allow one-photon transitions between I A
8
(ground stme) and
7.4 Polythiopheue 215
1.6
1.2
c
0
....
a.
0.8
.._
0
(/)
.0
<(
0.4
0
2 2.5
3 3.5 4 4.5
Energy (eV)
6
(b)
c
4
0
...
a.
.._
0
2
(/)
.0
co
0
.....
...
0
0
Ql
w
-2
t.5 2 2.5
3 3.5
Energy (eV)
(
Fib)guEnA 7-11!. (a) One- an<l two-photon an<! absorption of PJBT
spt!Clrum uf PJBT
(401. Indeed, the EA in Figure 7-18b shows two posi-
tiVe b.mus at -3.3 eV and -4.2 eV, wh1ch have been associated with the mA
and kA
11
states L40J. 11
7.4.2 Transient Photomodulation
Figure 7- 19 the ps transient PM spcctm for time 1=0 and t= 1 ns
where - 11T/T IS ploued versus the pruhe photon energy. The PM spectrum .. ;
216
1.0
0.5
t::
.....
.1 0
..,.
0
t='
t::
1
loO
0
0.6
7 Spectroscopy of Phoroexcitations in Conjugated Polymers
{a)
f;;;-
t=Ops
{b)
cP
Cl
0
0
0
t=1ns
0
0
6iln
0

Cl
0
B PA3
'6

0.8 1.2 1.4 1.6 1.8 2 2.2
Photon Energy(eV)
Figure 7-19. Transient PM spectra of P3BT films at (a) ps and (b) 1 ns.
t=O ps (see Fig. 7.19a) consists of increased transmission (f.T>_O) above 1.7 eV
and PA (f.T <0) below J .7 eV. The PA consists of two bands, whtch label PA,
and PA
2
The similarities between Figure 7-12 and 7-22 lead us to asstgn the PA
to tmnsitions from the I 8" state to the mAK and k.AK states. The f.T>O spectrum
is quite similar to the CW PL spectrum (see Fig. 7-19 inset) and we therefore
sign this signal to SE from IBu to JAK induced by the probe beam. The SE_ ts
shorter-lived than the PA as is seen in Figure 7-19b. At t= I ns there rcmams
only a bmad, long-lived PA band (PA
3
) with a shoulder extending into
hw> 1.7 cV region; no SE is observed and we also note that PA
1
has almost dts-
appeared from the PM spectrum. These results bear a striking to
those shown above on DOO-PPV, although the shape of the longcr-hvcd PA spec-
trum is quite diflerent. We return to this result in the following section. _
Because of the similarity between the ps spectra of DOO-PPV and P3BT hlms,
it is reasonable to assume that the PM at r=O ps in the latter films is also mostly
due to the photogencrated intrachain excitons. In order to confirm this assump-
7.4 Polyilziophene
217
tion, we have compared the photoresponse dynamics of the SE, PL. and the two
PA bands in P3BT. The region of long-lived PA overlaps with the short-lived SE
region and this makes it difficult to measure the co&:recl SE decay. Nevertheless,
the PA contribution to the SE signal is minimized when the SE decay dynamics is
measured at probe energies near 2.2 eV. Figure 7-20a compares the SE decay at
580 nm (2. 14 eV) and the PL dynamics in P3BT; it is seen that the two transients
follow each other. As can be seen from Figure 7-20b, there is also a correspon-
dence between the SE and PA1 decays, showing that PA
1
is also due to the emis-
intntchain Since both SE and PA
1
decays are due in part to non-ra-
dmttve recombinatton (or exciton dissociation), which may differently affect the
SE and PA
1
optical tnmsitions, some discrepancy is observed in their respective
decay time const<mts (see Fig. 7-20b).
100
:::i
eli
10
(a)
0 100
10-4
(b)
--SE(580nm)
- - Pl{700nm)

}/ 1\vv
200 300 400 500 600
t(ps)
"-. PAt= 94 cxp( 11162ps) + 2J cKp ( -lilns)
"-.
"'-
...._ .._.. PA
1
(0.853eV)
,_._
""'""""'A""""'
1600
2000
FiJ!urc 7-20. Comparison bcawccn lr.msicnt decays of (il) Pl. and SE and (b) PA
1
and SE in lihns of
PJBT
218
7 Spet.:truscopy uf Plwtoexc:iWtion.v in Coujugated Polymers
We note that for all transients (SE, PL, and PA
1
) the photoresponse decay is
non-exponential, which is an indication of a broad distribution of typi-
cal of slrongly disordered materials [9]. However, the PA2 decay dynam1cs
in figure 7-2l a is markedly different those of _SE . PL, or PAa .. fast m-
tial decay of PA
2
can still be associated wuh the excllomc decay: wh1ch demon-
strated by fitting both PA
1
and PA
2
decays with biexponenllal (see
fig. 7-19 and 7-20). In both cases there is a fast decay component w1th about a
150 ps time constant which conesponds well to the SE The much
lived PA component (PA
3
) must therefore be due to other than regular
singlet excitons. Figure 7-21 b illustrates this fact, showang the at
the isosbestic point (J..=770 nm, see Fig. 7-19), theSE 1s ex-
actly compensated by the excitonic PA
2
. The rcmaanmg response. charactenzes th_e
secondary photoexcited species associated with PA
3
. These spec1es are non-lum1-
500 1000 1500 2000
t(ps)
500 1000 1500 2000
l(ps)
Jolgure 7-21. Photorcspon.'IC a1 (a) 1.5 eV (PAz? and (b) lhe is_o:,bcstic poinl in t>3BT lilms
ahc crossover from s&imululoo .:mbsion 10 phutomduccll .Wwrpuun.
7.4 Polytliiopliene 219
nescem and have very little observable PA companion in the IR region (the PA
1
region). We also note that PA
1
is photogenemted within the time resolution of our
apparatus ( -5 ps) [25, 42). We show below that both polarons and triplet exci-
tons have PA in this spectral region, giving two possible origins of the long-lived
PA.
SE is present only in sufficiently thick films of P3BT. If the sample is too thin,
i.e., its OD at 625 nm is less than 0.6, then SE is not observed and only PA is
present in_ this case. Figure 7-22 illustrates this situation, depicting two normal-
Ized tmns1ent PM decays measured at exactly the same experimental conditions,
except for the samples thickness. Gain can be observed in the thicker film (sec
Fig. 7-22a), but no gain is present in the thinner film (see Fig. 7-22b).
Oased on this experiment, we come to the conclusion that the photoexcited
states in the bulk of the sample and those dose to its surface are different The
pr-obe beam may ei ther reexcite photocxcitations. detecting PA, or induce transi-
tions back to the ground state, resulting in photon emission or SE. For surface
states in P3BT lilms, the probability of the first process (PA) could be greater
than that for the second (SE). Such states may not contribute to PL either, which
has been conlinned by a lower PL quantum yield of thinner !ilms [43]. These sur-
face photoexcitations may be associated with defects created as a result of poly-
mer oxidation. Their concentrmion in the is higher than ahat in the bulk
of the film. The PA from these excitations can inacrfcrc with the otherwise observ-
able SE and cancel it out. Even when a P30T film exhibits absolute gain at
t=O ps, the photoresponse consists of the excitonic SE combined with the PA
which can be due to the same excitons, or a Y other excitations present at
same time (see Fig. 7-22). This observation is similar to the previous reports
of PPV-based polymer fi lms [25. 42), where intrachain excitons have been fom1ed
with low quantum yield, probably due to poor films quality.
40
20
6"
0 .,

(ij
E
-20
0
1\
I \
\
'
--PA(Ihinner film)
- - SE+PA(1h1cker film)
c
E
I- 40
<
-60
80
0.5 0 0.5 15 2
t(os)
1
1
igun: 7-22. Oplical gain in PJBT lilms: nonnulizcd 011 Ul .:V in a &bin film (l>Oiid
line) and a lluc.:k rilm (brukcn line).
220 7 Spectroscopy of Pltotocxcitatiuns in Cuujugated Polymers
7 .4.3 CW PhotomoduJation
There has been much controversy regarding the nature of excitations in
conjugated polymers. This controversy bears on the of elec-
tron correlation effects. Adding a charge to a cham causes a
neous distortion of the chain. Thus, the proper descnpuon of the excita-
tions in polymers with non-degenerate ground states arc polarons w1th .spm S= 1/2
and bipolarons with spin S=O. Figure. 7.-23 sho":'s an energy level
conjugated molecule in its neutral, ox1d1zed (cali on), and .
lion) states. Upon removal of charge from cham by .chem1cal
or photoexcitation, a structural relaxation the h1ghest
bital (HOMO) and the now singly-occup1ed (SOMO) mtrudcs the gap.
For luminescent oligomers, the parity of the molecular orb1tals
even and odd. Thus. a positive will .hav_e two
and p as the third possible trJns1t1on (P
3
) 1s d1pole forbidden. a
live wi ll have two similar transitions, though P1 may be slightly_
due to differences between positive and negative charges (charge conJugatiOn
synunetry violation). Upon removal of a second charge the same
is a further structural relaxation, resulting in the energy dmgrum on the nght s1de
of Figure 7-23 for a positive bipolaron. . . _ .
The point at issue is whether or not the molecular p1cture w1th
acting n-electrons is applicable to conjugated po!ymers. The alternaove
tion is one with weak Coulomb intemctions. In th1s case, the molecular orbtta_l de-
scription is inappropriate and none of the above are_
forbidden. we explore this issue by companng the spccm1 _of_ excitations
of polythiophene and a-conj ugated sexithiophene (a-6T). Slmllanlles the
PA of polarons in a-6T and polythiophcne lead to adopt the p1cture
for charged excitations and, hence, the electromc of conJugru_ed poly-
mers. We show below that PADMR spectroscopy d1stmgU1sh the absorption spec-
tra of polarons and bipolarons.
The absorption and photoluminescence (PL) _spectra a-6T at 80 K
are shown in Figure 7-24. There is an onset of absorptJOn at. 2.1 eV,
sharp peaks and a maximum a.t eV. A band .'s seen at
4.5 eV and is due to direct exc1tallon of the nng . We take the first
peak as the 0-0 transition and calculate an opt1cal gap Eg=2.4 eV. The PL spec-
Jt-Jt
. l
lt-n+

l'igurc 7-23. Schematic tliagmm of en-
1
ergy and optical mmsicnts of
tl
II sp2+
ncutr.tl molecule, polaron W'") and bi
p+
polan
upl).
7.4 Polytltioplrene 221
1.0 1.0
$' 0.8 0.8
0
"!a
c
0.6 0.6
0
:J

.a
0
...
0.4
.!!
0.4
(D
:s
._J

II)
ll. 0.2 0.2
<
0.0 0.0
1 1.5 2 2.5 3 3.5 4 4.5 5
Energy (eV)
Figure 7-24. PL anti abM>rption
of u-6T film.
llllm has a well-defined vibronic structure and is a mi1ror image of the abso1-ption
spectrum close to the absorpti on onset.
The doping-induced absorption (DIA) spectrum of a-6T doped by FeCI] in
CH
2
CI
2
solution is shown at light and heavy dopant concentrations in Figure
7-25. for light doping. the spcct1ll m consists of two absorption bands (P
1
and P
2
),
which arc the signature of polarons. At higher doping concentrations. another
band (BP
1
) appears at the midgap and the two polaron bands diminish. ESR stud-
ies have reported a sharp increase in spi n density for light doping followed by a
decline at higher <.loping. These results indicate the formation of spin- 1/2, singly-
chmged polarons at low doping. TI1is is followed by a second oxidation step.
which results in the formation or spinlcss. bipolarons al high dop-
ing. We note the formation or an absorption band at 2.4 eV in the most heavily
doped sample. This can he explained by Lmnsitions from the HOMO to the
LUM0+2 or the HOM0-2 to LUMO (441.
The in-phase and quadrature PA spectra of a-6T measured at 80 K with a mod-
ulation frequency of 200 Hz arc shown in Figure 7-26 l44J. TI1c spectrum exhi-
bits three bands at 0.80, 1. 1, and 1.54 eV, respecti vely; each of which is accompa-
nied by a high-energy phonon replica. TI1e bleaching of Lhe in-phase PA above
1.7 eV is due to thermal modulation of the PL due to heating of the sample by
the probe. The rcl;tti ve positions of the PA bands com:spond to the DIA bands
shown in Figure 7-25. The red-shift of the PA bands relative to the DIA bands is
due to differences between solution and fi lm properties. Hence, the bands at 0.80
and 1.54 eV are tentatively assigned to polarons and labeled P
1
and P
2
; the band
at 1.10 eV is assigned to bipolarons and labeled 13P
1
. As can be seen in Figure
7-31, BP
1
almost completely disappears in the quadrature specll-um, proving that
trapped bipolarons are shorter lived than tmpped polarons .
Figure 7-27 shows the frequency dependency of the in-phase PA bands in a-
6T, measured at the maxima of the various PA bands. As expected, the two polar-
on bands are correlated with one another, having vi rtually the same dynamics. In
contrJSt, the bipolaron PA hand al 1.1 eV is Vil1Ually nat from 10 to 1000Hz, in-
dicating that trapped pol. 1s arc longer li ved than tr..tppcd bipolarons in u-6T
The excitation lifetime), moJcled by comparing the data in Figure 7-27 to
222
0.8
>-
- "iii
: 0.6
Cl)
0
iii 0.4
u
;::
c.
0 0.2
7 Spet.:lroscopy of PlwtoexciltJtions in Conjugated Polymers
0.4 0.8
( 1 BP
1
!\
! 0
! I
I i
! '
l \
I \
I '
\.....
! \
; \
i \
;
!
1.2 1.6
hv (eV)
2.0 2.4
Figure 7-25. Doping induced absorption uf u-6T at low (solid lin.:) and bigh (dolled line) doping con-
centrations.
5
4
3
1
0 2
1
1.2 1.6 2.0
hv (eV)
Figure 7-26. In-phase and quadr.uure PA spectra of u-6T film.
2.4
the prediction of Eq. (7.7). In order to model the frequency dependence of the P
2
band, lifeti mes of between 20 !lS and I ms were required. In there is re-
latively little variation in bipolaron lifetimes. The fit to the BP
1
band required
only lifetimes of 10 and 50 llS. Polarons and bipolarons have been shown to be
tmppcd by defects [45]. Hence, these results suggest an extremely broad distribu-
tion of polaron trap energies and a relatively narrow distribution of bipolaron trap
energies. We should note that tl1e intensity of the BP, slightly decre;:tses as vc is
varied from 10 to 1000 Hz. This may indicate that a smart fulClion (Jf bipob:roos
are relatively long-lived to I ms) or due to a slight of a vjbro-
nic sideband of Pt to the PA at 1.1 eV.

7.4 Po/ytlriopltene 223

........... .........
hr 1()3 104 10S
Modulation Frequency (Hz)
d.:pcndcn..:c uf lhc PA of u-6T li lm, <II the p.:al..s uf the
0
(a)
v.
(
-5
g
C.0-10
..!..
"'

Triplet
-20
Spin-1/2
300 400 500 1000 1150
Field (Gauss)
(b)
--.
c:
:J
v
.e

l::
'?
P,
p2
7-21t (u)
11-I'ADMR and !b) )..
0.4 0.8 1.2 1.6 2.0 2 .4
I'AOMH spectra of 11 -6T film. The
Probe Energy (eV)
Hf pularuns, und lriplct cxd-
tuns arc labeled.
224 7 Spectroscopy of Photoexcituticms in Conj11guted Polymers
The H-PADMR spectrum, shown in Figure 7-28a, includes both a narrow reso-
nance at g:::::2 due to spin- 1/2 polarons and a half-field powder pattern due to
spin-1 triplet excitons. The .A.-PADMR of t riplet excitons, shown in Figure 7-28b,
consists of a single, broad band centered at 1.5 eV with a peaks at 1.4 and
1.55 eV. As observed for 000-PPV, the spin- 1/2 .A.-PADMR contains both nega-
tive (On<O) and positi ve (On>O) bands. The energy of the two negative PADMR
bands coincides with the two polaron PA bands P
1
and P
2
This is consistent with
the concept that these two bands are due to spin-1/2 polarons and further indi-
cates that magnetic resonance reduces the steady-state population of polarons. The
presence of a broad, PA-cnhancing PADMR between 1.0 and 1.45 eV suggests
that magnetic resonance results in higher populations of bipolarons. In order to
explain this result, we consider bipolaron generation and recombination processes:
Generation : p J: + pi - np2
(7.30)
Recombination : np2.t. + pT- -+ p.l. (7.3 1)
(7.32)
where So is the ground state. As bipolarons arc spinless, they can be formed only
from like-charged polarons with antipamllel spins. Hence, this is a spin-dependent
process which may be enhanced by magnetic resonance. While the recombination
process in Eq. (7.30) is not spin-dependent, magnetic resonance reduces polaron
populations, which may in tum reduce the recombination r.ue of bipolarons. We
conclude that microwave absorption, due to magnetic resonance, leads to in-
creased steady-state bipolaron populations by either increasing their generation
rate or reducing their recombination mte.
With the above results from a -6T in mind, we consider the CW PA and u-
PADMR spectra of P313T. The PA spectrum of P3BT at 80 K, measured with a
modulation frequency of 20 Hz, is shown in Figure 7-29a. Both of these spectra
have peaks at 0.55 and ::::: 1.5 eV, though the relative peak intensities arc not the
same in the in-phase and quadmture spectra. The in-phase and PA sig-
nals are equal at 1.5 eV, whereas the in-phase signal at 0.55 eV is much weaker
(L1T
1
N 0.6 L1TouT). Thus, even though the li neshapes appear to be the same,
one of the peaks must contain contributions from two different excitations. The
apparent discrepancy was resolved by measuring the in-phase PA spectrum wi th a
modulation frequency of 20 kHz, as shown in Figure 7-29b. The spcctllJm is
dominated by a PA band at 1.56 cV. We thus conclude that there are two di stinct
types of long-li ved photoexcitations; the first has a single PA band at 1.56 cV and
the other has PA bands at 0.55 and 1.5 cV. Comparison of the in-phase and quad-
mture signals at 0.55 cV results in a rough lifetime of r::::: 13 ns. As for the Iauer,
both excitations contribute to the PA at 1.5 eV, and from this we can deduce that
the first excita tion must be much shorter-lived than the second excitation.
A deeper insight into the nature of the CW PA is provided by PADMR spectros-
copy. The .A.-PADMR OJcasurcmcnts were perfonned at 10 K with the magnetic
Ci)
.E
::J
..0

<0
I

In-phase
10
Quadrature
0 .4 0.8 1.2 1.6
Probe Energy (eV)
In-phase
8
2
0
0.4 0.6 0.8 I 1.2 1.4 1.6
Energy(eV)
0.2
0
.().2
.0.4
.0.6
.0.8
1
0.4 0.6 0.8 1.2 1.4 1.6
Probe Energy (eV)
20 Hz
(a)
20
20kHz
(b)
1.8 2
1.8 2
7.4 Polythiophene 225
.. igurc 7-29. PA spcclra or P3BT tilm,
mc.Jsurcd with a modulaJion fn.-quen<:y
of (a) 20 Hz and (b) 20 kHz.
7-30. A-PADMR SJ><.'dra or
P]BT liims, a1 lhc rcSlmanl
fields fur spin-II:! species (solid line)
und lriJ!lcl cxcilons (dashed line).
fie_ld set ,to th:, of the powder or the peak of the spin- 1/2
resonance (st:c Ftg. 7-30). The tnpleti,-PADMR spectrum contains a single ne"ative
at 1.5 eV we therefore conclude that triplet excitons arc the
The spm-112 J.-PADMR contains both negative and posi tive bands, as ob-
served for both 000-PPV and c.t-6T. Based on the PA and J.-PADMR spectra of
226 7 Spectroscopy of PlzotoeJ:citatiolls i11 Co11jugatcd Polymers
a-6T, we attribute the two negative bands (On<O) to polarons and the positive band
(On>O) to bipolarons. We thus conclude that dipole selection hold for both conju-
gated oligomers and polymers. This result is of fundamental importance to conju-
gated polymer photophysics. These are molecular materials, where the charged
photoexcitations reside in molecular orbitals rather than free cruTiers in bands.
Photon absorption in P3BT films primarily leads to the fonnation of intrachai n
singlet excitons, which can be identified by their characteristic tr.lOsient PM spec-
trum consisting of a SE band and two PA bands. These excitons are short-lived
(150 ps) due to both radiative and non-radiative decay channels. The latter in-
cludes the fonnation of triplet excitons and dissociation into polaron pairs. We
have also detennined that P3BT films are very susceptible to photooxidation; the
defects created on the film surface during the film deposition actually prevent SE.
Thus, the photophysics of fi lm surfaces differs significantly from that of the bulk
P3BT films. Multiple CW spectroscopies have been applied to study long-lived
photoexcitations in u-6T and P3BT. We have detennined that polarons have two
subgap PA bands and bipolarons have one. These result-; indicate thm dipole se-
lection rules hold for charged photoexcitations and that these charged photoexcita-
tions reside in molecular orbitals.
7.5 Fullerene-Doped DOO-PPV
Photoinduced metastable charge transfer from a n-conjugated polymer onto C60
has stirred widespread interest due to implications for the photochemistry of var-
ious organic and biological systems [46-48). Persistent photoconductivity in ful-
lerene-doperl polymers has drawn particular attention due to possible applications
as low-cost photovoltaic devices L49, 50]. Fullerene/polymer blends have been
studied by CW PL and PA spectroscopy [5 1, 52], photoconductivity [53], and
light-induced ESR (LESR). Doping both quenches the PL and decreases the emis-
sive lifetime, depending on the dopant concentr.uion. This behavior is consistent
with ultrafast charge Lr.tnsfer tO C60 and attributed to non-mdiative quenching of
singlet 1
1
B., excitons by positive polarons injected onto the polymer chain. It is
similar to the effects of photoinduced oxidation, which also quenches the PL. In
the case of carbonyl (C=O) formation by photoinduced oxidation of PPVs, the
lifetime of the remnant emission is also sharply reduced [54).
7.5.1 Transient Photomodulation
Both the spectrum and dynamics of the transient PM change m<lrkedly upon Coo
doping. The doping concentration is given in mol%, where I mol% doping is
CtJUal to one c60 molecule per hundred polymer repeat units. The PM spectrum of
pristine 000-PPV film, measured at t=O, 100, and 1200 ns, arc shown in Fig-
5
0
-5
,......_ -10

(a) pristine
<l
I
-
6
....
0 4
2
0
-2
-4
6
1.2 1.4 1.6 1.8 2.0
Photon Energy (eV)
7.5 Fullereuc-Doped DOO-PPV
227
Figure 7-31. Transienl PM spcclm of
(a) pristine 000-PPV anc.l (b)
10 mol% Coo: 000-PPV. measured
2.2 wiah c.lclay limes of 0 ps (circles).
:!00 ps (SI.juarcs). anc.l 1.2 ns (dia-
monds).
ure a. The SE spectrum (!J.T/T>O) is the same as the PL spectrum, which is
by phonon Fig. 7- 11 b), whereas the photoinduced absorp-
tion (PA; !J..T/1 <0) comams a sangle PA band peaking at 1.5 eV. This band was
shown above to be due to photoexcitcd singlet excitons [25]. The PA not
change up to 1.2 ns, when the SE signal has diminished, showing that there is no
PA above 1.8 eV at t=O ps. 1l1c PA at t = 1.2 ns has been attaibutcd above to a
combination of and t.riplct cxcitons. The PA onset and peak arc similar at
l.Oanol%. <;l.cl dopang (see Fag. 7-3 1 b), but the PA spectrum above 1.5 eV is en-
urdy daflcrcnt, extending to above 2.0 cV. Whereas the SE of 10 mol%
Coo: 000-PPV is quite shoat-lived ps), the PA decay at 1.5 eV is much
Hence, PA _in Cc-111-doped 000-PPV appears to be due to a photo-
fonncd wathm ...... 5 ps and with a lifetime r >I ns. We note that the tran-
saent SE and CW PL spcctr... arc essentially unchan<>ed 0 and 10 mol%
doping, which indicates that the l""<tdiativc species is :he same in both pristine and
doped films.
The transient SE dynamics of C611 : 000-PPV fi lms at doping concentmtions bc-
t:ovcen 0 and I 0 mol% arc shown .in Figure 7-32a. 1l1e SE decay is roughly exponen-
tial and can be lit to ot an exponential and a long tail f=/u cxp (-t/
(53). The SE hktamc 'sE gradually decreases as the c(J() concentrat ion in-
228
160
OiJ120
5
w
"'
80
...
40
00
7 Spectroscopy of Plrotoexcitaticm.1 in Conjugated Polymers
100 200 300400500
1 (ps)
600 700
(b)
2
:i

"'

c

0..
.l'l
80 '
.ri
so..
Z;-
40
(I)
c
______ ___ _120
4 6
f
60
(mol%)
8
0
10
7-32. PL dc.:ay ur 1)()().
PJ>V lluping cuoh:cnlr.sliuns.
(b) Chungc in PL inlcnsuy. curl\!lalcll
lu lhc llcli:cl Spi!Cing. ht'iel: PL spcclra
vs doping conccnlrJlinn.
creases, from 200 ps in undoped, pristine 000-PPV to 30 ps at 10 mol % doping.
This change is correlated with changes in the integmted PL intensity (see
Fig. 7.32b), which is proportional to the quantum yield 'I These results are strik-
ingly remi niscent of the effects of photooxidation on PL observed by Yan et ul.
[25}, who demonstrated that as the density of carbonyl bonds increases, both rsE
and the PL intensity decrease. Our results therefore suggest that the observed elfects
of C
60
doping are due to exciton diffusion and subsequent dissociation at photoin-
duced defects injected onto the PPV backbone. The PL spectrum (see Fig. 7-32 b
inset) is unchanged by doping, indicating that the same singlet excitons are respon-
sible for SE in both the pristine and heavily doped samples.
For a 30 diffusion process of excitons towards defect centers with spacing r, the
relation ?trvL=cD.,,.c should hold, where Dcxc is the diiTusion coelf ident and
10, depending upon the distribution of defects [56]. Tite spacing betwel!n de-
fects r
0
is given by = n
0
1
and the total defect density n
0
=n
11
+11
60
, where 11
11
is
the density of native defecLo; in the pristine 000-PPVand llc>U is the dl!nsity of phmo-
gencmted defects. For a native defect density equivalent to 0.5 mol% doping, we
found that at various Coo doping concentr.ltions ?otrvL=const. From the 30 rela-
tion, we estimate that, for excitons in 000-PPV, 10-4 cm
2
/s, fairly
close to 2xl0 -
4
cm
2
/s, which was previously obtained for excitons in MEH-PPV
fi lms from photooxidation PL quenching dynamics [531.
In order to determi ne the nature of these novel photocxcitations, we compared
the PLOMR of both C
1111
-doped and pristine 000-PPV, shown in Figure 7-33.
The PLOMR of I 0 mol% C(.cJ: 000-PPV is roughly 10 times as intense as that of
7.5 1-'ullln m-Dot)('<IDOO-PPV
1.4,------ --- .-------
1.2
-
...J 1.0
ll.
::Jo.a
a..
!e 0.6
..,
0 0.4
T"
229
the undopcd sample and also contains a doublet resonance at 1072 G. The most
striking difference between the two spl!ctra, however, is the appearance of a
"'200 G wide resonance about g 2 with clearly resolved shoulders at 1045 and
_1095 G. In addition, a weak half-field accompanying signal appears at G
m doped 000-PPV, shown in Figure 7-33 inset. The half-field triplet resonances
that are seen at 390 and 400 G in pristine and doped PPV, respectively, are due to
PPV triplet cxcitons.
We can refute several explanations for the observed broad resonant spectrum
(BRS) around g::::: 2 and its accompanying half-field resonance in C
60
: 000-PPV.
It cannot _be due to PPV triplet excitons as the spectrum is too narrow L57].
Although ats width is similar to that of C
60
triplets eCoo) [58}, there is no evi-
dence of fu!lerene PL in any of our samples. Moreover, magnetic resonant en-
hancement of
3
Cfl<J decay would lead to the creation of more ppy+/Cffl defect
cente.rs, yielding a PL-quenching resonance, not an enhancing one. We therefore
suggest that spin intemct ions between charged polarons may explai n the BRS fea-
an? its half-field companion in Cc.o: 000-PPV. The two possibilities are
antcractmg polarons on the polymer chains or Ci.c,JPPV+ complexes. We refer to
both as polaron pairs, taking into account that the negative polaron
be_ cathcr on the polymer chain or the fullercnc molecule. Tite spin Hamilto-
man ( // s.s) of such pairs consislo; of Zeeman terms and an exchange tenn:
// s-s= tfil :if,. + fJH If,, s,, + s, .. 1' . s,, (7.33)
h
...
V: ere li"!' and 1 are the exchange-coupling tensors, respcc-
ttvely, H ts the magnetic field, und S,. and S
1
, arc the spin-1/2 electron and hole
respectively, the pair. If we assume the g-tensors are isotrop-
IC, d1fl enng only 111 thetr pnnctpal value, and have the same principal axis as the
! -tcnso_r, then th_e first _term reduces to g.fJHm..,,.+g
1
,/JHms
11
We may separate the
tsotropac and amsotroptc poations of the exchange tensor in Eq. (7. 1) by defining
l o = (1_, + 1,. + J:) and J , = J: + 111 etc. For the cusc Ct:2 - g
1
,)fJ/1 J, s s is
C4uivalcnt tO that Of a of idcntkal ions 159j and Cilll OC wri tten as:
230 7 Spectroscopy of PlwtoexciUJtions i11 Conjugated Polymers
(7.34)
where S =S,. + S
11
and s; = S
1
xS2.r etc. Eq. (7.37) is equivalent in form to that of
a spin-spin Hamiltonian with an even (singlet) solution at Es = - l o and three
odd (triplet) sublevels centered at Er = lo.
As 1; + 1; + = 0, Jl s-S can be rewritten in terms of two independent param-
eters:
(7.35)
where [)' and E are the ZFS parameters of the exchange triplet. The triplet form
of 11 s-s for the odd solutions now reads:
(7.36)
Comparing the BRS in figure 1-.:n to the predictions of &js. (7.19) lo (7.2 1).' we
determined D' = 115 G and E = 22 G. These exchange ZFS parameters predact a
lw/f-jicld resonance at 530.5 G I Eq. (7 .22) 1. in good agreement with the weak
half-field signal seen in Figure 7-:n.
The full-lield 1-1-PAOMR of the 10% c, .. ,: 000-PPV sample taken at 1.3 eV (sec
Fig. 7-34 inset), has roughly the same lineshape as the PLDMR (see Fig. 7-33) en-
abling us to sepamtely measure the absorption spc.ctr.1 of isolated polarons. at
H= 1072 G and the pair species at H= 1050 G. The polaron il-PAOMR consists
of two bands with maxima at 0.45 and 1.4 eV, in good agreement with the previous
results on pristine 000-PPV. We note that no signal attributed to bipolarons could
be detected. This suggests that photoexcitations resulting from dissociation of singlet
excitons remain paired, in agreement with the BRS. We further note that this is a
confimtation that the bn>O band detected in 000-PPV, a-6T, and P3BT is not
due to a defect species or unintentional doping. Otherwise, this signal, if any-
thing, should be stronger in the fullerene-doped sample. The pair A.-PAOMR al.so
contains two bands, but the high energy band is blue-shifted by about 0.4 eV wath
respect to P
2
of isolated polarons. We label these bands PP
1
and PP2. The similarity
between the PP
2
band and the broad ps transient PA spectrum of 10% 000-
PPV film (see Fig. 7-3 1 b) enables us to identify the latter spectrum as mainly due
to polaron pairs gcner.1ted in less than 5 ps. . .
Our results also shed light on the long-lived PA_
1
band detected an trJnsaem PM
measurements of P3BT (sec fig. 7- 19) and can explain changes in the PA spectra
observed in scveml ps transient measurements of films of PPV derivatives at ener-
gies around 1.8 eV (9, 25, 60). In good PPV films tr.1nsicnt PA spectrum
shows a PA band of excitons at 1.5 eV whose dynamacs match those ol the PL
and stimulated emission (SE) (9]. However, in measurements of oxidized [251 or
C
60
-doped fi lms 1601, there appeat'S a new PA band at about 1.8 eV whose dy-
namics are not cotTelated with those of the PL and SE. Based on our il-PADMR
results here, we aurihute the new PA band at 1.8 eV to polaron pair excitations.
These may be created tia exciton dissociation at extrinsic defects such as carbo-
7.5 Fullerene-Doped DOO-PPV
231

0.4 0.8 1.2 1.6 2.0
Probe Energy (eV)
Figure .i-PADMR Ill mol% C,., : DOO PPV, llle<lsurcd :lllhc peak uf Jhc spin-1/2 sig-
nal (pohtmns) or the broad spectrum (polaron pairs). The 11-PADMR spectrum is inset.
p+
Pair
p-
7-35. uf the energy levels and optical
lr.msallnn of oppu,.atcly-chargcd pulurons and polaron
pair...
nyls or complexes. TI1is solves a puzzle in the field of
photophysacs Ill PPV whach has recently been extensively debated.
Our a:esults on polaron pairs are summarized in Figure 7-35, a schematic dia-
gram of the energy levels and_ optical tmnsitions of polarons and polaron pairs.
polarons and polaron_ paars have two optical transi tions; the polaron pair
PP2 at a hagher energy than the P
2
tmnsition and the pair tmnsi-
tJon as rclatavely weak. The shift of the energy levels is due to the Coulomb
allractwn between the oppositely-charged polarons composing the pair. Mizes and
shown that a Coulomb interaction between polarons compos-
mg the paar, shafts the energy level positions. Due to their mutual attraction the
energy of the negati_ve polaron shift upwards and those of the po-
laron down.wards. and Conwell predict three transitions; the highest
(PP2>. 1s with res1x.>ct to the high energy P
2
tmn-
suaon. II the transumn, whtch translcrs :111 electron between the purtially occupied
232 7 Spectroscopy of Pholoexdlations in Conjugated Polymers
levels of the two polarons, is weak or forbidden, lheir calculations are in agree-
ment with our experimental results.
Using a variety of transient and CW spectroscopies spanning lhe time domains
from ps to ms, we have identified the dominant intrachain photoexcitaLions in
Coo-doped PPV films. These are spin-correlated polaron pairs, which are formed
within picoseconds following exciton diffusion and subsequent dissociation at
photoinduced PPV .. /Ct;
0
defect centers. We found that the higher-energy PA band
of polaron pairs is blue-shifted by about 0.4 eV compared to that of isolated po-
larons in PPV.
7.6 Summary
We have demonstrated the power of combining a variety of spectroscopies in
studying the photophysics of conjugated polymers. Photoexcitation generates
singlet excitons with lifetimes of approximately I ns. Singlet excitons are chamc-
terized by one stimulated emission band and two photoi nduced absorption bands.
The PAis due to absorption from the lowest odd-panty I Bu state to the even par-
ity mA
11
and kA
11
states, which have also been detected by two-photon absorption
and electroabsorption spectroscopy. These results are summarized in Figure 7-12.
Triplet excitons arc formed by intersystem crossing of singlet excitons and have a
single PA band. The dominant charged species arc singly-charged polarons having
two PA bands and doubly-charged bipolarons having one. These results arc sum-
marized in Figure 7-23. In fullercne-dopcd 000-PPV, we have detected the polar-
on pair species, consisting of two oppositely-charged polarons bound by Coulomb
attraction. The absorption spectm of polarons and polaron pairs are compared in
Figure 7-35. Fullercne doping of 000-PPV quenches lhc PL efticicncy by injec-
tion of positive polarons on the polymer chain, leading to the fom1ation of long-
lived polaron pairs.
References
I. Proceedings of the 1996 International Conference on Synthetic Metals, Syntll. Met
2. J. H. Burroughcs, D.D.C. Bradley, A. R. Brown, R.N. Marks, K. Mackay, R. H. Friend. P.L
Bums, A. B. Ho lmes, Nuwre 347, 539.
3. D. Braun, A. J. Hccger. Appl. Pllys. Leu. 58, 1982.
4. G. Y. Cao. G. M. Treacy. F. Klavcller. N. Colarncri, A. J. Ht.q;cr, Ncrum: 1992, 357,
477.
5. N. C. Gn:cnham. S. C. Mor.llti. D.D. C. Bradley. R.H. Friend, A. B. Natwl! 1993, 365,
62/l.
6. X. Wei. Ph. D. University of Utal1, 19'J2.
References 233
7. Z. V. Vanlcny in Orgu
1
;. M, l fi
1
,,.,
3

1
c utenu s ur Pltutunics (Ed G Zemi) El S
77 . SCVICI" Clence, Amsterdam
8. C. Botta. S. Lunati: R. Tubinu, D. D. C. Br.J<Jicy, R.H. Friend PI/ t.
9. Froluv. PltV tlte.m. Univcn.ity nf Utah l 9%. l Rev. 1993, 8 .J8. 14809.
10. T. Nugu.:hi . Plly.l". Rta: L<'ll. ll. 21!6.
II. . M: Mas!>:J<:hus.:u, ln,tituh: uf Tcchnulu. 19114
12. G. K.mncr, Ph. D. 17u.w:r. Umvcrsity uf 199t gy .
13. (&1. : r: Talllir), Sprinl,!cr. N.:w Yurk 19711
14. 0 . E. J . P. Gurtlun. R. L. t"ual... in Ultllljll.l"/ 1'/t,.,,;,c'll V " ..
s.:nthal), Spnngcr. New York
11
I (&Is. 0 .11. Auston, K.IJ. Ei-
15. V.A. Sh:lkin, S. Abe. Phy.>. Ret. 1994. IJ 50, 4306.
16. R. K. PILD. Tltc.,i.>, University of Utah and in )I I
17. M. Shctk- Uahac A A Stid T W I .
18. M. s. z. v varJ:n et %i' IE."EE_J. uf Quulltlllll ElectrolliCS 1990, 26, 760.
1997, 56, 15712. ' y. OL.ala, K. Yoshmo, Y. Ding, T. Barton, Pltys. Re'\ B
19. M. J. Y. N. Ganstcin. Pltys. Re't Leu. 1994, 73 2504
20. Y. S. Abc, S,lmlt. Met. 1\196, 711, 2 19. .
21. K. Ptchlcr, D. A. llalliday, D. D.C. Bmdlcy P. L Bum .
demcd Mau.-r 1993, 5, 7155. R. H. Fncnd, A. B. Huhncs, J. Pllys . c
011

22. M. Oaandro!l.'.. S. Mazumdar M Lic . P. A Ll
Plty.r. Rr1\ IJ 55. 141!6.' l>S. nc, z. V. Vardcny, M. Hamuguchi, K. Yoshino.
23. J. M. Lcng. S. Jcgli nski, X. Wei. R.E. Uenner z V V: d . .
Leu. 1994. 72, 1.'\6. .u cny, f. Guo, S. Mazumdar. Plty.
1
Ret\
24. M. Yan C'/ al . Pity.>. Rttc l.tn. 72. IICH.
25. M. Y;.m, L. J. Rolhhcrg. E. W. Kwot:k T M M"ll . I" .
I "b"d
1
"n Nn Lu 1995 75 1992 w G
et II . , I ' 76. K47: J. W. BlatdJiilld <'I a/ t ;j .19% . -: . mupncr
Plty.r. un. l71.
111
76, 1513; T ,., a/., CJwm.
26. N. T. Harrison rtal .. Phys. RC' a: uu. ll. l l!lll.
27. I.D._W. SumuciN ul . PII)"S. Re. IJ 52. RII.S73.
28. S. l rulov. W. Gcllcnnann. M. Shkunuv z. V V: de .. .
1997, 729. ar
11
Y M. 0.akl, K. Yo.Juno, Plty.r. RC'I: u u.
29. S. M. P. A Lane W G lie . -
Leu. 711, 421!5. . c nnann, z. V. Vankny. M. O.taki. K. Yu,hino. Plty.r. Rrt:
30. M y <'h" < M
" mto. -' azumdo.ar. Swu/1. M<'t. 1 X5
1001
31. C. J. Bakel 0 M Geisen D D C B "'I . . . .
32 R K M r.,... ey. C/
1
"
111
Plrv.r. Lt.u. 19'J3 201 127
cycr. M. Lacss, R E Bcnn r w G II
Ding T J Btn . : . c . . c crmann, z. V. Vardcny. M. OL.aki K y
deny). si>IE Pr .. :" Op3/l("td Pm/Jt.r of Coujugatttl Poi)WIC'rs "' (Eds: L.J. z v ;, . .
. occeumgs 145 (Ill pres.\). .,. . . var-
33. L. G. WciM:r, Plrys. Ntv. Lt.u. 46. 1156.
34. B. J. Orr, J. F. Ward, Mol. Phys. 1Y71. 20, 53.
35. S. V. Frolov, M. J> A. Lane., W. Gcllcnnann . .
Rev. Leu. 19Y'7, 78, 4285. z. V. VlJllcny, M. Owka, K. Pllys.
36. A Willetts, J. E. Rit.-c D M B La
37 X '" . I . ur nu, D. P. Shcltuo, Cltem. P/t)s. 97 7590
nea l!t II . Pllys. Ntv. &u. 1992 68
38 P. A La! . . ' "'"'
. . . 1C, .J. Shmar, K. YosJuno. P!tys. Rrl: 1W6 8 54 9301!
39. et u/., Pllys. Rev. 19%, IJ
53
,
449
1!:
40. S. Jcghnskr. PltD thtt.ris, Univcn.ity of

41. R. Ker.amg. U. Lemmer R Mahn K L
19!.13, 70, 3!!20. . . . . co. II . Kun. H. Bassler. E. O. Giibcl, Pltys. Rev. &II.
42
M. Yan. L. Rothbcrg U R Hsi h R R All"
43 S F 1 X ' c ano, l'lns. Nt: IJ .J9 9419
Ill nv, Wea, W. G.:llcrmann z. V \( 1. E. El
44. P. A l;uac X '"ca Z. V "-- . J 1'. .an . . m:nfrcuud, J. Cltrm. Ph, .. , .. (in press)
. . ""' . v.uucny lll>hw k E "I . ...
Plt.s. 210. 229. . . s ' . ..:JrcnlrcumJ, M,. lhmhim, A. J. Frank. Cllrm.
4
5. J. E. Ehrcnfrcu11d J Comil J L
0
.
Mrt. 69. 401. ' acda.,, R. Pugh. M. lbr.>him. AJ. Fr;ank, Srm/r.
46. Y. Wang. Nanttt' 1992 . .f56. 51!.'\. .
234 7 Spectroscopy of Plwtoexcirations in Colljugated Polymers
N S
S . nc L Smilowitz. A.J. Hcegcr. F. Wudl, Sdence 1992,258, 1474.
47. anc&
1
' &;/ St 1 Comm 1992 82 249
48. s. Morita. A. A. K. Yosh&no. . e A J a: Stucky. F. Wudl. Appl. Pllys.
49. N.S. Sariciftci, D. C. Zhang. V. Sr ov, . .
Lett. 1993, 62, . K . H A k' K Yoshino Jpn. J. Appl. Phys. 1992. 31, L890.
50. S. Morita, A. A. Z:lkh&dov, T. .&wa&, K Yoshino, K.Kikuchi, Y. Ac.:hib.l, }f>n. J.
51. S. Morita. S. Kiyomatsu, M. Fukuda, A. . ov, .
Appl. Pflys. 1993. 32, . y Snlauov F. Wudl, A.J. He.:gcc, Sflllll.
N
. S. Sariciflci, L. Snulowllz, D. Omun, G. Srdanov. .
52.
Met. 1993,55-57.3125. . . k I ME Galvin T M Millcc Pfl}'.f . urt. 1993,
53
_ M. Van, L.J. Rothberg. f. Pap;1dun1tr.1 upou OS,
Hess. z. V. Vardcny, F. Wudl, Phys. Rev. Leu. 1992.68,666.
a: Kmabel et al . Pllys. Rev. 1994p. h8 501, 1975 968.
56 B Ya Balagurov. V. G. ys.- "'' r ' . t'R 1991 8 44 10617
p A La J Shinar F Wudl Pllysrca evww , _
57. L S. nc, : J Sh' .' J P. Engel T.J. Barton, L Junes. Pllys. u-11.
58. P. A. l.:.lne, L.S. Swanson, Q. X. N&, . mar, . : 199S 8 51 10028
1992 68. 81!7 ; P.A. Lane, J. Plly.mul ' ' .r T . '(on Ions
A A
br. B Bleancy in Elec.:tiVII ParwnaKIIellc Resmltll&ce o, rwur '
59. . agam, .
Press, Oxfunl 1970, p. 502. .
2
37
60 N S Sariciftci, A. J. Hccgcr. bu. J. Mod. 1994. 8 .
. H. A. MiLes. E. M. Conwell. Phys. Rev. 1994, n 50. Rll - 43.
61.
8 Photophysics of Methyl-Substituted
Poly(para-Phenylene)-'I)'pe Ladder Polymers
Guglielmo Lanzani, Sandro De Silvestri, Giulio Cerullo,
Salvatore Stagira, Mauro Nisoli, Willi Graupner,
Gunther Leising, Ulrich Scherf, and Klaus Mullen
8.1 Introduction
Conj ugated polymers arc essentially chains of carbon atoms having in common n-
clectrons dclocali zed along the backbone. The nature of the primary photocxcita-
lions in conj ugated polymers is a long-standing question, which has been
addressed both and expc!rimentally. The tightly-bound exciton pic-
lure, assuming strong electron correlation, seems now the most appropriate de-
scription of the electronic structure, in contrast to the initially proposed band-like
theory. However, this model cannot fully account for the charge photogeneration
mechanism in such systems given the relatively small energy required to ionize
the initial exciton state. In this contribution we discuss the photophysics of a pro-
totypical n-conjugated polymeric semiconductor, namely a methyl-substituted
poly(para-phcnylenc)-type ladder polymer (m-LPPP) II), as investigated by sub-
picosecond time-resolved spccuoscopy. m-LPPP is a good model system for in-
vestigati ng fundamental physics of conjugated polymers due to the narrow inho-
mogeneous broadening that allows a clear resolve of its features and distinction
between intr.1-chain and inter-chain properties. Our investigation provides a rather
complete picture of the photocxcitations scenario in m-LPPP, which has general
validity in the class of polymeric semiconductors. In addition the results contrib-
ute to the basic understanding of the phenomena involved in the applications of
m-LPPP, which is used as the active layer in blue light-emitting electrolumines-
cent devices l2J and lasers [3, 4}.
The chapter is organized as follows: in Section 8.2 a brief overview or ultrafast
optical dynamics in polymers is given; in Section 8.3 we present m-LPPP and
give a summary of optical prope11ics; in Section K4 the laser source and the mea-
suring techniques are described; in Section 8.5 we discuss the fundamental photo-
excitations of m-LPPP; Section 8.6 is dedicated to r..tdiative recombination under
several excitation conditions and describes in some detail amplified spontaneous
emission (ASE); Section 8.7 discusses the charge generation process and the
photoexcitation dynamics in the presence of an extemal dcctric field; conclusions
are reported in the last section. 236 8 of Methyi-Substilllted PPP-Type Ladder Polymers
8.2 An Overview of Previous Results
Pioneering work on ullr.tfast optical dynamics in conjugated polymer:; (CP) was
carried out by C. V. Shank and Z. V. Vardeny on polyacetylene (CHx) (5, 6]. CHx
is the first synthesized CP and probably even now it remains the most extensively
investigated, both theoretically and experimentally. These early works showed that
CPs have ultntfast optical response with non-exponential recovery dynamics.
Most of the population decays in the mnge of l ps, with a tail in the ground state
recovery that extends to the ns time domain and longec. Quasi steady state photo-
modulation spectroscopy has shown that a fraction of photoexcitations is trapped
at defects, and survives up to the ms time range. The non-exponential decay of
the transient tmnsmission change (described by a power law -r'") was ascribed
lO geminate recombination of the photoexcitations, assigned to charged topologi-
cal kinks (Solitons) of the dimerization pattern (7}, after mndom walk along the
one-dimensional chain. Deviation from the inverse square root depcmlence ex-
pected for ideal infinite chains was explained by chai n Lenninations, i.e. the very
same defects that cause conj ugation length distri bution. The photoiU<.Im:ed trans-
mission spectrum, containing two intmgap absorption bands, was r..tlionalized
within the one-dimensional band-like picture for Peicrls semiconductors (7). The
early imerprelation was entirely based on intr.t-chain properties, even if inter-
chain energy mi gmtion was known to occur. For instance tr.msient Raman experi-
ments with ps resolution showed that this process is quite eflicienl in mixtures of
high and low gap conjugated segments (8].
The trans isomer of CHx is non-luminescent, while the cis isomer emits light
TI1is observation drew the auention to emitting polymers with cis-like carbon
structures, opening the route towards appl ications. Among luminescent and elec-
troluminescent materials poly(p-phenylenevinylene) (PPV) is by and large the
most studied. The ps transient transmission di tTerence spectrum of PPV contains
stimulated emission (SE) and a broad unstructured photoinduced absorpt ion (PA).
TI1e two compete because of substantial spectral overlap and PA kills SE in a
few ps. This finding was initially discouraging for lasing applications of PPV {9).
A consequence of PA and SE having different dynamics is that at least two differ-
ent photoexcitations should be considered. The emiuing state, responsible for SE,
with general agreement is assigned to singlet exci tons, whereas the assignment of
the dark state is under debate. L. J. Rothberg and co-worker:; have proposed this
PA to be due to polaron-pair, i.e. a pair of coulombically bound charged states lo-
cated on adj acent chains ll 0 J. The key point of this model is that n overlap be-
tween adjacent chains may reduce the energy gap between neutral and charged
states, thus allowing for spontaneous genemtion of interchain p<tirs or correlated
charges. This assignment has been, however, t-'Ontrastcd by seveml groups whose
results were explained by only considering imrachain tightly bound exci tations
[ 11, 12] or extrinsic effects related to oxygen { 13). Nevertheless polaron-pairs re-
main an important concept which can be used to mtionalize a number of experi-
mental results, such as optical detected magnetic reslmance and ullmfasl photo-
conductivity [ 14].
8.3 Optical Properties 237
The role of disorder in the photo h . , . f .
tensively described by lhe wo k p o. conJugated polymer:; has been ex-
worker:;. Based on ultrafast cam l . out In Marburg by H. Bassler and co-
o ummescence (PL) (15 1 ti ld d ed
cence quenching ll6J and site-selective PL . . . . Je -m uc lumines-
Siale thermalization was proposed h' h I 17], a model for excited
w' tJ . h . . w c consden; mtcrcha . . .
. ' 1111 t e mhomogcnousty broadened de . . . . . . m_ excllon mgmtJOn
mterpretation of our results in m-LPPP ol states. 'Vt!e base part of the
some in Secti ons 8.4 and 8.6. on t s model, which WJIJ be discussed in
While the importance of inter-chai f . , . . . . .
photo-excited state is now generally n k e Ill dctennuung the late of the
(CPG) mechanism is still a lll<tller of l_he_ charge phorogenemlion
slates (polarons) are formed b . the molecular picture
dsorder I 18j in this case the fl . y _mtelc am excton breaking assisted by
fer charJcter, (pol:tron-pair) . ?m1aktodn of an intermediate slate with charge tmns-
. . s nvo e A second 1 d I h. h .
mer-ltke description of the int -a h . . .: n o e, w Jc mducles a Wan-
be . ' c am excllon propose . h . d. .
responsible for charae generatio 119! . . . s on-e aan ssoc.ation to
This mechanism docs tl:< uire f l , . has :1 secondary role.
based un phohx:onducti.VIty 1111'' . . < llll.ltlun ul an Hllcrmcdiiile state. Fin:.lly
l:U.'iUICillenls ('>Of d ' '
and hole exdtation Was sun nested El t . . ill .I band-to-band electron
ments on m-LPPP l EDs r . d : cl,; Je s assisted pump-probe ex peri-
. p cscnte m Secti on 8.6, are ai med to clarify CPG.
8.3 Optical Properties
In 8- 1 we show the chemical structure f . .
gallon and the reduction of dcf . _o .. !he in conju-
porate a poly(p-phenylene)(PPP) b kbo wa..., the mam moll vatJOn to incor-
D I h . ac nc mto a ladder poly ,
ue o I e sJde groups auached to th PPP . . mer slllJclure [21!
polar solvents is Th' . . . the . ch_am excellent solubilit y in
h
. . IS IS e prereqUISite f od
1gh Opi icaJ quality. A detailed present t' f I or pr polymer films of
a JOn o 11e synthesis, sample preparation,
R
R:.C,.,H, R'=C6H,, Y=CH
1
l' igure H- 1. Chcllli.:al
238 8 Pltotophysics uf Metltyi-Substitwed PPP-Type Ladder Polymers
and cw optical properties of m-LPPP films is reported in Ref. [22]. Here basic
properties arc mentioned, such as absorption and photoluminescence, which are
strictly connected with the following discussion.
Time-integrated photoluminescence spectrum of m-LPPP film, for low excita-
tion fluence (0.3 m.J/cm
2
) at 3. 18 eV with a circular pump area is reponed in Fig-
ure 8-2a as a solid line. It displays a well-resolved vibronic structure wilh 0-0
transition at 2.67 eV (465 nm). In a previous study on m-LPPP [23], a strong PL
band in the yellow region was observed and attributed to aggregate emission. The
absence of this component in the sample under study indicates that no such aggre-
gation is taking place. The 0-0 transition is partially re-absorbed due to the small
Stokes shirt between emission and absorption. Ground state absorption is reponed
in the inset of Figure 8-2a and shows clear mirror symmetry with the emission
spectrum. Absorption in the sub-gap region is very low (< 12 cm-
1
) with a steep
onset leading to a maximum value c.Lm:u. 1.1 x I OS cm-
1
and the fluorescence
quantum yield is about 30% (24].
At high excitation lluence (2.4 mJ/cm
2
) the emission spectrum collapses into a
narrow line located at 2.53 eV (see Fig. 8-2a. dashed line), slightly blue-shifted
with respect to the low intensit y emission. TI1e process strongly dcpenus on the
shape of the excitation area. For a rectangular spot, li ne narrowing occurs at
55
i.e. 45 times a lower lluence than for a small circular spot, whi le the
,.....
::i
.;
'-'
1:::
0
u;
.,
e
u
..J
j:l.,
2. 1
. .., 2
2.4 mJ/cm
(a)
" II
I I

I I

.
-,
0-2 0-1
'
(b)
I
I
I
I
0.055 mJ/cm
2
40 Jll1l
Jmm
2.2 2.3 VI 2.5 2.6 2.7 2.8
Energy (eV)
Figure 1!-2. (a) Normalil.co PL spec-
tra of m-LPI'P films ;II 1'= 77 K for
cxcitalioo at 3.2.:V (39() om) wilh a
circular al 1w.1 cJiOi:rcm Ou-
eoces: 0.3 mJ/cm
2
(solid line) and
2.4 mJ/cm
2
line). The insel
shows lhc room lcmpcritlurc absorp-
tion spect rum of m-LPPP. (b) Nor-
malized PL spectrum for cxcilalioo
wilh a rectangular spol at a nucnce
of O.OSS mJ/cm
2
(from Ref. 1251
with pcnnbsion).
8.4 Experimemal 239
spectral position of the nanow pe k .
prctation of such peculiar (see Fig. 8-2b). The inter-
tO eCtlOn 8.6.
8.4 Experimental
8.4.1 Conventional Pump-probe
of the experimental set-up is shown in Fi u -
Tt. sapphire lru;cr system with chi ed . . . re_ 8 3. Th_e laser source was a
pulses at 7HO nm and 700 Jl] cnc7 .. Which provided 140 fs
pulses at 390 nm were generated b ot I kHz. The excitation
in a 1-nuu-thick LiBlO crystal Thy c harmonic of the fundamental beam
and the exci tation dfoc
1
u
2
scd to a.,spot size of 80 J.im
c n an m.J/cm- per pulse. Pump-
Continuum
gencr.uion
Conllnuum
probe beam
OMA
roO
390nm
Pump beam

Interference
filler
l
140 fs
Figure M-3. of lhc cxpcrimcnlal M!l-
up for pump-probe experi-
ment,. SJ IG: MX(lno gcncrJiion
PO: pholudiocJ.:; OMA: opli<:ill noul-
;onalw.cr.
240 8 Photophysics of Methyl-Substituted PPP-Type Luddrr Polymer:.
probe experiments were carried out in the visible and near infrared spectral range
using the white light supercontinuum genemted in a thin sapphire plate. Mirrors
were used to collect the supercontinuum pulse and to focus it onto the sample in
order to minimize frequency chirp effects. The following measurements were car-
ried out: i) the whole white light pulse was spectrally analyzed after passing through
the sample using a spectrometer and a silicon diode array. Transmission dill'erence
spectra are plotted as f!.Tfl', where f!.T is the pump-induced transmission change, ob-
tained by subtracting pump-on and pump-off data, and Tis the sample transmission.
In the small signal limit where !!.a is the absorbance change associated
to the excited state population N (f!.u. =uN, where u is the transition cross section)
and d is the sample thickness (for very thick samples dis replaced by the pump pen-
etration depth). f!.T>O is associated to photobleaching (PB) or SE, f!.T<O to PA.
Averaging over about 10
2
data acquisitions allows a sensitivity of about 10-
3
in
6.Tn; due to a small chirp of the pulse the overall time resolution in this experiment
is 500 fs; ii) the evolution in time of the is measured in a narrow spectral
window of I 0 nm using interference filters in front of the Jctector. In this case
we use a pre-amplified photodiode and the standard lo<:k-in technique. This allows a
higher sensiti vity of about 10-1 in a beucr time-resolution, which is limited
by the experimental cross-com:lation to about 200 fs . In both experiments the pump
beam was linearly polarized at the magic angle with the probe; iii) photoinduced
anisotropy decay was measured by setting the pump beam at 45 o with respect to
the probe and collecting two sets of data with an analyzer placed in front of the de-
tector pamllel or perpendicular to the pump polari7-Lttion; iv) cw photoluminescence
spectra, collecting the light emitted in a direction perpendicular to the film, were
recorded using an optical multichannel analyzer and aver..tging over 100 to 1000
laser pulses.
8.4.2 Field-Assisted Pump-Probe
In these experiments we used single layer LEOs prepared by spincoating m-LPPP
from a toluene solution onto indium tin oxide (ITO)-coated glass substrates. After
annealing approximately 100-nm-thick m-LPPP layers for 24 h at 70''C, alumi-
num electrodes were applied by vacuum evaporation. l11e layout of the experi-
mental set-up is shown in Figure 8-4. The pump and probe beams pass the glass.
ITO, and polymer to be reflected by the aluminum. With no voltage applied lo
the LED, we measured conventional tr.msient pump/probe spectr..t, as previously
described. With the device biased we measured the total dynamic.:s in the presence
of the electric field (6.TI7)F In order to detect small field-induced changes of llT.
we applied a modulated voltage to the device and referenced our detection at the
field modulation (MF) frequency. In this way we detected only field-induced
changes in the spectra. which we call Following our nomenclature
In this spcctm a fie!ld-induced increase has the same
sign as that of the photoinduced transmission signal, whilst field-induced reduc-
tion has the opposite l>ign.
8.5 Tht Prillltll)' Plwto(.tdtutions in m-LPPP
241

390nm
Pump beam
OMA [?J--;,
'
'
1'0
Interference
filkr
.Figur,c 8-J. Layout of the cxpcrimenJal :.CI-up for ficld-
asststcd SfJL"Ciroscopy. PO: pholooiodc
OMA: oplrcal mullrchanncl analycr.
. We estimated that the characteristic lime f, . . . .. .
With a mobility of 10-J em:! v- s- d OJ tJaveltng to the electrodes,
em, is 10 ns for a 100-nm-thick _maxunum field of I MV/
movement of lhe charge caniers are _cttccts caused by the
surements and can be neglected o fti h er than the tunescale of our mea-
the time-behavior. In be identified looking at
elcctnc fieiJ etlects on the transition --u Mf . flu includes
molecular levels, and is expected to . strength, u, and Stark shifts of the
they not depend on pump-probe state trans!tions
they tncrcase with time l(lllowi" the ly. hcrcas fm excucd state tr.msJtions
A.,.. . ., pu sc cross-<:orrclat' N
ul Mf' sgnals arc ascribed to field
1
11
d d h . on. on-mstantaneous
d
. - uce c anges m the po I .
ynanucs of the photogencrated species. pu allon densty and
8.5
The Primary Photocxcitations in m-LPPP
In this experimental result-; are described w . .
pump-probe technique to m-LPPP by applying the
_of hqUtd nitrogen 1251. These results all !n at the tempera-
Citations of m-LPPP and the tna,n rei . ohw the JdentJlJcatJOn of the primary ex-
. . axat1on c annels h . .
1
excJtatJon density re<>imes rc invest'g t d . d . 1 part Jcu ar, the low and high
. "' ' a e 111 or cr to get n . 1 .
processes associated with the emission r . . . a JllsJg II mto the physcal
mc-narruwmg phenomenon.
242 8 Plwtophysics of Methyl-Substituted PPP-Type uulder Polymers
8.5.1 Overview of the Experimental Results
6.Tff spectra for excitation intensity of 0.3 mJ/cm
2
and different pump-probe de-
lays (r
0
) are shown in Figure 8-5. Positive 6.T for probe energies higher than
2.3 eV were measured, and negative 6.T for lower energies. Since there is no
ground stale absorption in the positive 6.T region, we assigned it to stimulated
emission of the 0-1 and 0-2 lines. In the PA region a sharp band at 1.4H eV can
be seen, which decays on the same timescale of SE and a weak PA band at
1.9 eV. Following the time evolution of the 6.Tff spectrum up to r
0
=400 ps the
decay of the main features can be seen and finally two PA bands are left in the
spectrum, at 1.9 and 1.3 eV (see inset of Fig. 8-5). Upon increasing
the excitation densities, up to 12 mJ/cm , the shape of the 6.Tff spectrum changes
dramatically in the positive signal region. This is shown in the upper panel of Fig-
ure 8-6: a dip in the SE spectrum develops around 2.64 eV (470 nm) and at very
high excitation density SE changes sign turning into PA. The lower panel of Fig-
ure 8-6 shows that this intensity-dependent PA has disappeared within about 4 ps.
The dynamics of the SE peak at 2.53 eV is strongly affected by the excitation
density, as shown in Figure 8-7, where SE decay for three different excitation
-rd=400 ps
-rd=40 ps
-rd=4 ps
2%
1:::
.....
<l
-rd= o ps
1.4 1.6 1.8 2.0 2.2 2.4 2.6
Energy (cV)
Figure 1!-5. Transmission difference spcclm of m-LPPP a1 7=77 K excited al 3.2 cV for various
pump-probe delays. The inscl worns oul the low encrsy region for 0 ps (solid line) and 400 ps
(dashed line) delay. Doping induced :1bwrp1ion (DIA) data an: also fur comparison (from Ref.
(251 wilh pcnuission).
8
5
Tlte Prinwry Plwtoe.xcitations in m-LPPP
243
-0.025
-0.050
2.4 2.5 2.6
Energy ( e V)
2.7

<l
SE of m-LPPP films
ill K: (aJ al 0.6 ps pump-probe de-
lay for mcn:asins pump (b) for
7.2 nt.J/cm
2
Cltl"italion at two
delays (from Ref. 1251 witlJ
pcrn"'-"on).
conditions is reported Th
. . e decay timescale be . h . . . . .
denstltes, reaching about 2 ps for the highest comes s ortet fot htgher exctlatJOn
8.5.2
A Model for m-LPPP Electronic Structure
We assume that standard Coulomb-correla d
[I J] properly described the intrachain etc .le . models for luminescent polymers
immchain photocxcitation generate sin of In this case
(Bu). which are responsible for the s;ont .odd _panty
the pump energy in our cxpcrilllcnL-; is Since
e latgcr lhan the Onlt<"al ll ;on
244
8 Photophysics of Methyl-Substituted PPP-Type Ladda Polymers
2.53 eV
0. 12
-2
0
2 4
time delay (ps)
obc delay at three differ-
" 7 SE '- ty at 2.53 cV in m-LPPP at T=77 K vcr.;us pomp-pr
Figure o ""'-'
1
)
. t' on fluences (from Ref 125) with pcnmsston .
cnl CXCil<l I
. d t be hot states. lntrachain thermalization may,
the initial excttons are expecte
0
.
o the pump pulse dumt1on.
however, occur WI _un 0 I .b . transition is initially centered at2.5 I eV,
The SE band asstgned to the -h romcl .... ated PL spectrum at low energy den-
. d m tto t e lime tn cg.. .
t.e. blue-shtlte wt respcc V F I err a red-shift of the decaytng SE spcc-
sity, which is located_ at 2.48: . h or

in time-integr..tted PL
trum can be seen. which rcac t 8-8 Spectral relaxation of SE can be ac-
within about 10 ps: as tn energy sites. such as longer l:Onju-
counted fo_r by . 26 This is a collective thermalization pro-
galion chams wtth a smallet gap [ ]. redistribution and it is typical of

11
the intmchatn excess energy .
cess that may o ow . . .
1
LPPP films containing aggregates, the rot-
disorder molecular nin' of the phntoexcitations. In this case
gration process to a qutck. lr..typ,. g PA band which is assigned to intcrchatn
spectrum contatns a broad . . . ked [261 and the PA of
6
A . . It the tntnnstc dynamtcs ts mas . .
species l23_. 2 }. s a resu_ T d I order to exclude intrachain
singlet excttons cannot be tdenll .. n hown that oligomers with no conJuga-
as [ IS]. Transient photoinduced
tion length do
wfth ump polariz.ation parallel and

anisotropy. obtatncd by cfdt'onal more direct information supp01tmg
dicular to the probe, provt es a t t
1.2 I 494
-
c: 8.496
:J Ul
..ci 0,8 en
498
.........
f-<
<! 0,4
0
2,3
8.5 The Primary Phowexcitatious ill m-LPPP
2,4
Energy (eV)
2,5 2,6
245
Figur e 8-H. SE spectra of m-LJ>J>P lilnt.'< at T: 77 K for pump-proi)C delay:> 0 lsulid line) und 12 ps
(dal.hcd line). rditx<ttion: the inset shows the position of the SE peak a function of
delay.
the interchain thennaliz.ation. In general, photoexcitation with linearly polarized
pulses induce optical anisotropy in the film. Titc initial dichroism is lost because
exciton diffuse to chains with different orientation. This process is extremely fast
in amorphous regions where a single hop to the adjacent chain is enough to change
ll1e initial geometry of Ute excitations. The experimental evidence of polarization
memory loss in m-LPPP lilms [2SJ, to be discussed later in more detai l, demon-
strates that energy diffusion is actually taking place within the photoexcited vol-
ume. We understand polarization memory loss and spectral relaxation as experimen-
tal signatures of the same phenomenon, namely the thennalization of the excited
state through interchain migration.
SE dynamics versus excitation intensity, shown in rigure 8-7, points out the
presence of a fast exciton depopulation process. For low excitation densities the
SE decay is nearly exponential with a time constant of 25 ps, while for higher ex-
citation densities it becomes increasingly non-exponential and the fast component
of the decay is complete in less than 2 ps. We conjecture that the observed deple-
tion of exciton population at high densities is due to ASE along the 111m plane.
ASE, which is a process which has no threshold, acts as an intensity depeudeut
mechanism of population depletion. Note that the probe interacts with the exciton
populatio11 stimulating emission perpendicularly to the lilm For this rca-
son, upon increasing the cxcilatiun power. we tine of the spcmtct-
''emts emission but not of .\tiuwlated emission.
PA at 1.48 eV instantaneously, shows spectral relaxation to the red, and
decays on the same timescale of SE, a.-. shown in Figure 8-9. We assign the ob-
served PA to singlet Bu exdton transitions towards higher lying even parity (A..:)
states. We can speculate on the nature of this state within the proposed model. A
pos.-;ihle candiuatc for the final stale is the illtrac:lwill biexcitun. However, its en-
ergy level is located below the two-exciton state by an amount equal to the hind-
246
8 Photopllysics of Methyl-Substituted PPP-Type wdder Polymers
1.2
1.0
0.8
"""":'
::1
..,j
0.6
........
E-
<l
0.0 1---.-Uo
- 10 0 10 20 30 40
time delay (ps)
Figure 89. Modulus of 6T versus pump-probe delay at 1.41S cV and 2.53 cV (from Ref. (25) with per-
mission).
ing energy. Since this cannot be larger than the exciton binding energy, estimated
to be about 0.5 eV [27], the biexciton level is expected to be 5 .ey._
exciton to biexciton transition would then appear at 2.3 eV and thts ts
thus ruled out. A second candidate is the continuum state, but electromodulatton
spectroscopy shows that this is located at 3.3 eV [27), implying a _transiti?n en-
ergy of 0.5 eV. The remaining possibility is the so called mA
11
state, t. e. a htgh ly-
ing even parity state with a large dipole coupling. with I Bu state [II], and that
is expected to play an important role in the rcspo?se.
shoulder seen at higher energy (around 1.55 eV) ts asstgned to a vtbromc repltca
of the singlet exciton transition. The shift of 0.07 eV corresponds to energy of
a vibr.ttional mode which is observed in absorption and electro-absorptton [27].
The PA bands 1.3 eV (950 nm) and 1.9 eV (650 nm) present ditrerent dy-
namics and a longer lifetime with respect to the singlet They should
therefore be assigned to different photoexcitations. Let us first dtscuss the. PA at
1.3 eV. The same PA band has been detected by steady state 6.TIT
(cwPA) on m-LPPP films 128). In these measurements bean:'
chanically modulated cw laser and the observed_ have ltfetunes tn
the ms time domain. Based on temperature, exctlatton mtenstty, an_d frcquenc7 de-
pendence, it has been assigned to triplet-triplet tr.tnsitions. We that as-
signment is also true for our time domain. Due to spcdr.tl wtth the
PA band we cannot di stinguish between slow gcneratton vw
and ul trafast generation via non-geminate electron-hol e or
fission. However, the latter is unlikely because the energy lor gencraun!? a tnplet
pair is expected to be larger than the pump photon enei'6Y The lowest smglet
cited state in m-LPPP is located at 2.7 eV. Exciton fission from 3.2 cV would nn-
8.5 The Primary Phoroexcitutious in m-LPPP
247
ply a huge singlet-triplet energy separation > l.l eV, a value that seems to be
rather unlikely.
The PA at 1.9 eV and its vibronic replica at 2. 14 eV have been observed in m-
f!PP films . by various cw techniques: doping induced absorption, charge injec-
spectroscopy, and (29]. these reasons they can be unambiguously
asstgned to charged spectes. the mset of Fig. 8-5 we show for comparison the
match of the data obtamed by chemical doping of m-LPPP films with our
transient results. that the_ occurrence of the same absorption spectrum for dif-
ferent and u:-clnstent tcchmques strongly suggest the assignment to isolated or
weakly mteractmg polarons, in contrast to polaron pairs. We conclude that
stales are phmogeneratcd within 500 fs, since the PA at 1.9 eV is already
tn the 6.TIT spectrum at rv=O. and does not decay within our experimen-
tal _time range, . up to 400 ps. The process can be either intrinsic or extrinsic, i.e.
asststed_ by an tmpurity such as oxygen. A conclusive statement on the generation
can not be a! this Additional infonuation on the CPG pro-
1s extmcted by electnc ltcld-asststed experiments that are presented in Sec-
lion 8.6.
8.5.3 High Excitation Density Scenario
The spectral of SE upon increasi ng excitation intensity is shown in
Fig: 8-_6. V.:e tt as superposition of SE and a new PA band with diiTercnt
Transient photoinduced anisotropy provides use-
mformatt on lor the of the transi tion moment of the species respon-
for The m-LPPP him ts a uniform distribution of randomly oriented
chams wluch docs not display macroscopic dichroic properties. If the transition
of the excited and the ground slate are parallel, the initial polarization
ralto p*=PAu/PA.t. is [30]. lf _lhe transitions moments are tilted with respect
to one ;not her the p* ts given by p* = (I +0.8 a)/( 1-0.4 a), where
a =(3 cos. C/J-! )12 and q, .' s the angle
2
between the transition moments. The resull'i
tn Ftgurc 8-10 lor 6 m.Jicm excitation intensity show that there is com-
and PA an.J that PA is proportionally stronger in the perpen-
The maxt.mum reduction of SE occurs at ro= 1 ps, indicat-
mg a_ ume constant lor PA of 200- 300 Is. In order to evaluate the PA
ratto we should know how the SE behaves. We assume that the ini-
llaJ. SE ratio is 3 becau:o;e no substantial exciton migration is going to
dunng overlap tunc. At rn= I ps. p* for SE is reum:cd by the
same observed lor PA at 6!)0 nm. bcc;Iusc the faller describes the ell ect of
the singl_et exci ton polarization free of ;my uther competing ellccts.
Based thts 1.1ave been able Ill that p*( 1 ps) lor PA at
470 nm ts .. 1. 1. 8. Tlus 111 ytdcls an of the tilt ing angle ur appruxi-
50 unccr1at nty by the inuin:ct evaluation of p. Thi s result
s: however, stgntltcant because tt tndtcato::s that the PA tmnsition moment is tilteu
With respect to the chain axis. l11e cllect can not be assigned to ultrafast exciton
248 8 Photophysics of Methyl-Substiwted PPP-Type Ladder Polymers
0.08
0.04
0.00
I-<
-I-<
<l
0.00
-0.04
0 I 2 3
time delay (ps)
Fi uri! ti-10. 6Tal 1.112 eV (a) and 2.64 eV (b) in m-LPPP lilmsal 7"=77 !< for polariza-
parJIIcl (solid line) and j)i:rpendicular (clashed line) (from Ref. 125) w11h penmss10n).
diffusion because this process can at most lead to p* = 1 . and it
th . f AT '"e propose assignment of the PA to mtercham exclUJIIOits
change e Sign 0 L.l YY' r
whose skewed transition dipole moment reflects the local
uy The anisotropy decay data indicate that the state ts fonned w1thm I ps
in about 3 ps. Note that the of a high PA on
a very short timescale is common to other conJugated polymers, as for_ mstanc_e
ppy 1 13] but it has never been discussed._ Due the spectral w1th SE, tt
is not easy to infer information on the 1ntens1ty dependence can only
s ulate on the nature of this species: One poss1bl11ty IS
reactions take place at high den_s1ty, _to.
of excitonic molecules or other by-products ot exc1ton fus1on, such as polamn
pairs (i.e. pair of Coulomb-oorrclatc<.l charges).
8.6 The Emission Process in m-LPPP
In the revious section we have shown that for an excitation above the
PL lin:-narrowing threshold, the shape SE_ spc:ctrum
This demonstrates that the spontaneous em1ss1on sp1ke IS not due to a nov_ twns;
lion existing in the photoexdted material, as would be the case for exc1tomc mo -
8.6 Tire l:./uissio11 Process i11 m-LPPP
249
ecules. The conclusion is further substantiated by the observation that exciton
condensation depends only on the density of the excited species and not on the
shape of the spot, in contrast to the results in m-LPPP. Collective or co-
opemtive emission processes are instead to be considered. An experiment of exci-
lation cross-correlation PL in m-LPPP films above threshold have shown that the
characteristic time associated with the emission phenomena is about 2 ps [31j, i.e.
much longer than the expected de phasing time (I 00 fs) . This argues against super-
fluorescence, leaving ASE as the most favored mechanism to account for PL line
narrowing iri m-LPPP. G.J. Denton et aL have reached the same conclusions for
PPV [32].
It has been demonslr.tted that the whole photoexcitation dynamics in m-LPPP
can be described considering the role of ASE in the population depletion process
(33). Due to the collective stimulated emission associated with the propagation of
spontaneous PL through the excited material, the exciton population decays faster
than the natuml lifetime, while the electronic structure of the photoexcited materi-
al remains unchanged. Based on the observation that time-integrated PL indicates
the presence of ASE while SE decay corresponds to population dynamics, a nu-
merical simulation was used to obtain a COITClation of SE and PL at different exci-
tation densities and to support the ASE model !33). The excited state population
N(R,t) at position R and time t within the photoexcited material is worked out
based on the following equation:
1.0
0.8
--:- 0.6
::>

1-
<l 0.4
0.2 -
0 2 4
6 8
Time delay (ps)
Figure 11-11. Sui ill line: l!J.T ill . .'i3 .:V lir llilfcn:nt CM:ilallun Oucncc,, o.,,hc<l lines: lining oil-
lamed frum lhc rhcurcrical 11111dcl in rho: l.:xt (frmu Rd. f.l:ll with pcnnb,lun).
250
8 Plwtophysics of Methyl-Substiltlled PPP-Type Ladder Polymers
where Wp is the genemtion rate due to the pump pulse, T the
cay, y the bi-molecular recombination constant (related to exci_l<?n-exciton
lation), J
1
ot is the photon rate crossing the volume dV at pos1t10n R and ume t,
and G is the spectrally integrated local gain for photons the dV.
Note that the model contains two intensity-dependent recombmat1on mcchamsms:
ASE and exciton annihilation. Both are active in the photocxcitcd volume and
should be simultaneously taken into account. From comparison of the
simulated results with the experiments (see Fig. 8- 11) we extract the peak gam
cross-section Up. relevant for lasing application, up-::::::5.15x 10-
17
cm
2
and the bi-
. . 5 104 3 - 1
molecular recombmauon constant y-:::::: x em s .
8.7 Charge Photogeneration in m-LPPP
In systems. sudt as quantum-conlincd and conju-
gated polymers, the first step of optical absorpt ion is the creati?n of bound elec-
tron-hole pairs, known as excitons 1341. Charge photogenerauon occurs
when excitons break into positive and negative This process 1s of essen-
tial importance both for the understanding of the fundamental physics of
materials and for applicati ons in photovoltaic devices and . S1nce
exciton di ssociation can be affected by an external clectru.: held, hcld-mduced
spectroscopy is a powerful tool for studying CPG. . .
In inorganic low-dimensional systems, weakly bound exc1tons show. Stark sh1ft
of the optical absorption and fully dissociate in the presence relatively. small
tields (10
4
V/cm) parallel to the confining barriers [35). The t1me evolut1on of
these phenomena has been measured by transient experiments t!'c of
an electric field which determined a strong dependence of the Iomzatlon t1me on
the tield [36). In conjugated polymers, there is an extensi_vc of litera-
ture on electric field-induced CPG in the stationary regime [16), wh1lc only few
experiments have been carried out in the time The evolution of
CPG was investigated either via transient quenchmg of photolummescencc [16.
37] or photobleaching [3S 1. or via photocurrent measurements [39]. The. photolu-
minescence and photobleaching quenching are indirect probes of CPG, smce they
cannot monitor the product of exciton dissociation, and in photocurrent measure-
ments only mobile chargl!S can be detected with a limited time resolution of a few
tens of ps 139}. . .
We have studied Lhe temporal dynamics of CPG in m-LPPP _by
field-assisted pump-probe experiments on LED structures, as m_Sccuon
S.3.2. The narrow line-width PA assigned to polarons (see Section S.5.2) 1s a fin-
gerprint of charge generation in m-LPPP. Monitoring the dynamics PA
band enables us, for the first time, to directly observe the CPG dynamics m a con-
jugated polymer with sub-picosecond time resoluti<?n. [401: . .
In Figure 8-12 we !>how the field-induced transm1ss1on spectra
(11T!T),.,.. for negatively biased LED at 13 V and at d1flcrent pump-probe delays.
8. 7 Chaf1:e PlwtfJgent.'rtllicm in m-LPPP 251
I .H 2.0 2.2 2.4 2.6
Probe Energy (eV)
1-!gur c 8-12. Ficld-imluccd diffcrcnliat spoclm (6TmAII' fur a positive bias of 13 V ami
drflcn:m pump-probe delays (from Ref. (40( with permission).
We. a 11T,.,F signal for energies hi gher than 1.8 eV, and a weak
pos1t1ve s1gnal lor lower energies. By applying an electric fi eld to the polymer,
we_ expect to sec quenching of the singlet exciton population due to dissociation.
sh?uld lead to the observation of a decrease in singlet exciton features, re-
sultmg m negauve 11T MF in the SE region and positive 11TM,.. in the PA region. If
polarons arc generated, !1T11w should also contain a corresponding increase in the
polaron PA. (l:l.Tfl)MF signal at Tv=5 ps displays all these features; we ob-
serve t":'o negat1ve bands, at 2.5? and 2.35 cV, which correspond to a quenching
of the smglet and negat1ve bands, at 1.91 and 2.1 e V respectively, which
are due lo mcrease m the polaron PA spectrum (and its vibronic replica). For
probe lowc_r than 1.8 eV, we observe positive 6.T
11
u:. corresponding to a
quenchmg of smglet exciton PA. Note that for probe energies larger than
2.65 there 1s a strong negative (11TIT)M,.. signal; this feature is present also at
ncgat1ve_ pump-probe delays and is due to static clectromodulation, caused by
Stark sh1ft of the slate op_tical Lmnsition. At longer pump-probe delays, be-
cause of the dec-.ty of smglct cxc1ton population, both field-induced changes in SE
and PA arc very small. At T0 =400 ps the remaining PA is due to the long-li ved
polarons !!Cncmtcd by the electric li dd at earlier times. We can thus conclude that
252
8 Plwtoplaysics of Methyl-Substituted PPP-Type Ladder Polymu.\
0
2 3 4
4
':'
0
2

g
0

10 20 30
0
4
Figure 8-13. Field-induced diiTeren-
lial trans mission (- 6Tfl),.,r at 1.91
(solid line) and 2.53 eV (dots} as a
function of pump-probe delay. In
the upper panel we also show. as a
dashed
line. the pump-pulse aulo-
0 t OO 200 300 400
correlation (from Ref. [40) with per-
Time Delay (ps) mission).
the (l:lTrnMF spectra provide direct evidence of field-induced exciton dissociation
into charged slates.
More detailed infonnation on the kinetics of field-induced phenomena can be
obtained by studying the (l:lTrnM,.. signal at selected probe as a
of pump-probe delay. We monitored field-induced exciton at the sm-
glet SE (2.53 eV) and at il<> PA ( 1.5 I eV), and that of CPG at the
polaron PA (1.9 1 eV). At rv=Ops (see r-ig. _(llTrn,.w arc zero;
this means that there is no sig11ijicant exciton dtssuc:wtum on rite twu:sc:ale of the
pulse duratiun. Thus, we can rule ou_t a licld-induc_ed reduction of
strength as the main quenching mechanasm. The PA at 1._9 1 eV has
an initial fast rise, growing to of its ti na! value wttlun 2 ps (Ftg. 8- 13a).
followed by a slower increase on the 40 ps timescale (sec Fig. 8- 13b) pla-
teau on the 400 ps timescale (see Fig. 8- 13 c). The field-induced SE quenchmg at
2.53 eV also shows an initial fast rise, reaching its maximum value by ro=2
foll owed by a slow decay; for ionger time delays. the signal vanishes, due to_ cxca-
ton recombi nation. The field-induced signal at 1.5 I eV has the same behavaor as
that at 2.53 eV, but with opposite sign, being a PA quenching.
-1 0 0
8. 7 Clwrge Phntogeneratima in m-LPPP

Neg. bias

' ..
10 20 30
Time Delay (ps)
40
253
Figure 8-14. (a) versus pump-probe dch1y at 1.91 eV for V,...=- 16 V and pump excitation
intensi ties 1.2 m.l/cm
2
lin.:) and 0.24 m.l /em! (da..;IK.-..1 line). l11e inset shows (- 6Tfl)m a1
1.91 eV ;md 20 ps versus cxcit:uinn inlcnsity. (h) same as (a) pu1H(l excitation intensity 1.2 nt.l/cm
1
With V.,...,. =-16 V (solid line) a nd V.,,,=-8 V (dashed line). 11lC inet shows (- 6T//)Mf" at 1.91 cV
and 20 vcr.;us field: open squan:s=positivc bia."; filled circles= negative bias (adaplcd from Ref. [40J).
We investi gated the dependence of CPG on both exci tation density and applied
voltage. Figure 8-14a shows that the kinetics of polaron fonnation docs not
change upon lowering the pump fl uence by a faclor of 5. This is in contrast to
the possibility of CPG through bi-molecular exciton fusion and subsequent auto-
ionization (411. A plot of the fidd-induccd polaron population at 20 ps versus ex-
citation density (see inset of Fig. shows a strong saturation, which sets in at
the threshold value for ASE. We explain this as bei ng due to depletion of the
singlet slate caused by ASE and by bi-molecular excitt>n-exciton annihilat ion.
Both proCl..--sscs occur on a timescale that hccomcs faster than charge separ .ui on at
moderate excitation inlensilies, thus competing wi th CPG.
Polaron ki netics is also unaffected by variations in the applied voltage, as
shown in Figure 8- 14 b. 1l1c inset of Figure H- 14 b shows CI'G eflicicncy as a
function of the applied dectric licld. Symmeli)' wi th respect to the LED bias volt-
age rules t)Ut space cnccls and cxciloll-C<!Il"ier interactions. In addition. we
note that (/lT/fhw has a 'lu;adratic tkpcndencc on thc electric field, similarly to
254
8 Plwtophysics of Methyl-Substituted PPP-Type Ladder Polymers
E=2.53 ev
0
s 10 15
20
Time Delay (ps)
lo"igure 8-15. Fichl-induccd exciton breaking r:ue y(t). calculated from Eq. (8.2). inset shows the
experimental field-induced S 4ucn..:hing aJ 2.53 eV the cx..:rton 4ucochmg M st-11' (I) cal-
culated using Eq. (8.2) (solid line) (from Ref. 1401 wrth pcnmssson).
PL quenching data f 16, 37}. The characteristic energt supplied by the F
be esti mated as cF (eV), where F is ;:bout 10 and
exciton delocalization length, is about 10 A [27). obtam _eY_. whtc:h
provides the order of magnitude of the exciton energy 1f gen-
emtes non-correlated polarons. It will become clear m the followmg sect1ons that
this estimate refers to interclwin-lwt cxcitons.
The interpretation of our CPG data is compl icated by the o_f compa_ra-
tively fast mdiati ve and nonradiative decay channels for the wh1ch
compete with the field-induced dissociation. ln order to a ptcture of
the observed mechanism and disentangle it from the smglet exc1ton dcl.'ay dy-
namics, we define the following phenomenological time-dependent parameter:
I dNPMF us I dPAMF
y(r) = ---= - - - -
NsF dt Up SEF dt
(8.2)
where NsF=SE
1
.1us is the singlet exciton population in presence an electric
field, N
1
,M...-=PAMJJCTp is the field-induced populallon, CTs(CTp) IS the cross-
section for stimulated emission (polaron absorptiOn). SEF=(ll.Tf'Dr measured
2.53 eV and PAMp= (ll.Tfl)
11
1
F measured at 1.91 eV. In this calculation th_e contn-
bution of singlet PA at l.9 1 eV was correctly subtracted. A plot of 1s
in Figure 8- 15. If singlet exciton breaking in the an electnc field IS a
first-order process that directly results into polaron !onnallon, y represents the
8.7 Charge Plwwgeueration in m-LPPP 255
field-induced exciton-breaking r.1te. To check the validity of this hypothes is, we
to demonstrate that we can reproduce the measufC?d singlet exciton popula-
tion quenching using the following equation:
I
SEMF(t) = SE(t) ( exp [- J y(t')dt'] -I)
0
(8.3)
in which the only free parameter is the ratio uiu,.. The result of this calculation,
using y(t) as obtained from Eq. (8.2) and u!/a
1
.=2, is shown in the inset of Fig-
ure 8-15. 1l1e good agreement between the experimental and the calculated field-
induced SE quenching signal strongly supports our conjecture of exciton dissocia-
tion into polarons, without intenncdiatc charge-transfer states. Thi s is further
strengthened by the ohserved quadmtic field of the polaron genera-
Lion (sec inset rig. tS- I 4 h), which, as recently proposed, indkates a neutral precur-
sor stme for ch;u-ge generati on t42).
The plot of )'(/) suggests that CPG occurs on two separate time regimes. One
is highly dispersive and Lakes place within the fi rst 2- 3 ps. The other is only
weakly time-dependent and persists for longer delays. The initial rate can be as-
signed to CPG driven by exciton migration towmds lower energy sites within the
disorder-induced density of state COOS) 125). During such thermaliwtion, hot ex-
citons reach dis.wciatiou sites, whereby charge generation takes place either by an
on-chain LI9J or inter-chain process I 16]. Note, however, that only the fanner
model predict-. exciton separati on into uncorrelated carriers. In section 8.5 we ob-
served that thennalization to the bottom of the DOS occurs in a few ps, in agree-
ment with the measured timescale for dispersive y(r). The lack of electric-field de-
pendence of the CPG kinetics can be considered as further evidence for the diJTu-
sion-limited nature of the proposed dissociation process. Wi thin this model CPG
becomes negligible once the exci tons have reached the bollum of the DOS. where
their mobility is dmstically reduced 143].
The small and weakly time-dependent CPG that persist<> at longer delays can
be explained by the slower diffusion of excitons approaching the localization edge
fl 5]. An alternative and intriguing explanation is, however, field-induced on-chain
dissociation, a process that docs not depend on the local environment but on the
nature of the intrachain state. The one-dimensional Wannier exciton model de-
scribes the excited state [44). Dissociation occurs because the electric field re-
Coulomb barrier, thus enhancing the escape probability. 1l1is picture is
mterestmg, but so far we do not have any clear proof of its validity.
256 8 Plrotoplrysics of Metlryl-Substiluted PPP-Typc Ladder Polymers
8.8 Conclusions
Based on sub-picosecond time-resolved spectroscopy we obtained a picture,
sketched in Figure 8-16, of the photoexcitation scenario in m-LPPP films. Absorp-
tion of photons with energies larger than the optical gap_ an
excited state (l), which loses excess energy by intra-cham vtbr.llJOnal redtstnbu-
tion (2) and by interchain energy migration {3). The timescale for the former
mechanism is not known, but it is reasonable to assume it is short. of the order of
100 fs. Interchain cooling, which is identified by spectral relaxation of the SE
band and by memory loss, occurs on the I 0 ps timescale. Note that
the two mechanisms are strictly correlated because accepting chains acquire an en-
ergy larger than their own gap. This excess energy is however fairly small, mak-
ing a cold-exciton mignuion picture plausible. As long as the excited slate can
propagate there is a finite prubabilily of dissociation (5). Elcctrit: field
this process, and this is uctually how it was possible to d_irectly_ detc:ct. 11, deter-
mining the timcscule und the dynumics. We find thut dtssocauo_n
becomes dominant, even for fields exceeding I MY/em. Th1s unphes a fimte exci-
ton binding energy of the order of w- eV. The absorption spectrum of the disso-
ciution product indicates that non-correlated polarons ure formeJ. This finding is
better explained by the on-chain dissociation model, while the sample geometry,
in whi ch the electric field is perpendicular to the substrate, is more natumlly asso-
ciated to an interchain hopping. A conclusive statement on this complex subj ect
could not be reached. Thennalized singlet excitons are associated to a PA transi-
tion at about 1.5 eV (6), which displays a vibronic replica at 1.57 eV, and a SEat
2.5 eV {4). The characteristic PA band at 1.3 eY, assigned to triplet excited states,
is observed in the PA spectrum for 400 ps pump-probe delay, pointing out the
presence of radiationless decays, which selection rules (7). .
In the case of a high excitation density, amphficauon of the spontaneously
photons can take place, the emitted light being guided _through film. ASE
depletes the exci ted state and results into a peculiar hne narrowmg of the emtss1on
spectrum, which Fks at the gain At very high excitation ex-
ceeding 10
20
em- , a new species appears mthe PA spectrum. We propose 1Lo;
rnent to interchain excitations, either neutrdl (bi-exciton) or charged (polaron-pair).
l<' igurc 8-16. A picture uf lhe photocxcitalion !iCC
nario in m-LPPP. see lcxt for a discussion. p+ is a
pos lltvcly charged chain (polaron), whih: x- can
be either a ncgalivcly charged chain or an electron
su..:h as oxygen.
References
257
This PA is in a direction with respect to the main optical
transttton, and partmlly overlaps wuh SE, causing optical losses .
. The proposed scenario is mainly based on the molecular approach, which con-
stders polymer as an ensemble of short (molecular) segments.
mam_ pomt m the IS that the nature of the electronic slate is molecular,
I.e. _locahzcd_ and discrete energy levels. In spi re of
of model, _m wh1ch plays a fundamental role, Lhe descrip-
tion ot the ba'iiC 1ntracham properttcs remains unsutisfactory. The nature of th
I ed e
owesr exc1L sl4.!te 111 m-LPPP is still elusive. Exlrinsit: dissociation mechanisms
charge transfer al accepting impurities) are not clearly distinguished from
mtnns1c ones, and Lhe question of intrachain vcP.>us intcrchain charge sepamtion is
nOl yet answered.
. Our show qui te unambiguously that the fate of the exci ted state is deter-
Wllhm t1_1e first 10 ps. This calls for new expcrimcms in the ultmfast time
to raised hen.:. 1l1e uvailabi lity of high quality materials,
m of punty, and processabili ty, is un essential re4uirement for suc-
In_ a complete optical and electrical characterization with cw
IS Ill h1gh demanJ in order to provi<.k a st:tble background onto which
_can be built. _For this_ reason we feel that an inter-disciplinary
approach. whtch mvolvcs chcnusts, cngmcers, anJ physicists, wi ll be the success-
ful stmtegy.
References
I. U. _Sdlerf. A. Uuhncn. K. Mullen, Muknmwl. Ch<'m. 1992, IY.l . 1127.
2. S. A Niko. G. Leising. U. Scherf. Af1111. Phy.f. Lm. 19%, 6X. ( ()I.JO.
3. S. _S_'agu-.t, M. Zavclaui-Ros.i. M. Nisoli, S. De Silvc..,lti, G. LanlOIIli, C. Zcnz. P. Malalooi G
lcismg. Appl. Phys. Leu. 1998, 73, 2860.
4. U. _Lcmnler, Quw_uum Electmnicx Cmifacnn. Vol. 7, 1998 OSA Technical Oige..l
sencs (Opttcal Soctcly ol Anlenca. Wa.\hington, DC. 199!1) p. IJ.'i.
S. C. V. Shank. R. Yen. _R J. On:nslein. G. L. Baker. Plrys. Lm. 1982, 411. 1660.
6. Z. V. Vanlcny. J. 0 . T.-C. Chung. A.J. Hllcgcr. PltyJI. Leu. 1982, 411, 1657.
7. A. J. S. K1velson. J. R. Schnclli:r, W.-P. Su, Mod. Phy.
1
._ 198!1, 60, 7R 1.
8. G. L. X. Zln:ng. G. Fig:ui. R. E. l3cnncr. z. V. Val\lcny, / '/ty.<. u lf. 1992, 68, 3104.
9. M. Yan, L. J. Rothberg, E. W. Kwock, T. Miller. Phy.f. l<co. Lm. 1995, 75. l<m.
10. J. W. P. Hsu. M. Yat.. T.M . Jcdju. L. J. Rothberg, B. R. INch. Phys. l<to: 1J 1994.-111,712.
II. J. M. Lcng, S. Jeghnskt, X. We1, R. E. Benner. Z. V. Vardcny F. Guo S. Ma:t.Ulndar Plou J(ev.
Leu. 1994, 72, 156. ' ' '
12. J. W. S. W. Jessen, L. B. Lin, J. J. Lih. Gusl:tfsun, A. J. Epslcin, 0 . K. M. J
Marsella, 1. M. Swager. A.G. M<tcOianni<.l, S. Yumagucht 11 Hamagudti f'/ors f<eo l.cll 1996.
76. 1513. . . . . . . .
13. G. J. Demon. N. N.T. Harrison, IU{ Friend, Phn. ull. 1997 7X 733
14. V. Oyaknnuv, E. Frankcvich, Cltcm. Ploys. 199!1. 227. 2t)J. . .
15. R Kersting. U. Lemmer, R. E Mahn. K. U.-.1. li. Kur.r. 1-J. ll it""lcr E GlillCI f'hr 1(,.
1
,_..
11 I \111:1. 711, 3R2U. . . . . . .
258 8 Pllotopltysics of Metllyf.Substitutecl PPPType Lndder Polymers
u Le M Deussen H J Bakker R.F. Mahn, H. Kurz, V. I. Arkhipov, H. Bass-
16. R. KersUng, . mmer, .
ler E.O Qibel Phys. Rev. Lell. 1994, 73, t440. 42 9830
H'. D.D. C. Bradley, M. Henneckc, Phys. Rev. 8 1990,
M Gailberger, H. Bassler, Pii)'S. Rev. 8 1991, 44, 8643.
M. c J M Vissenberg. M. l M. de Jon g. Ph.vs. Rev. Leu. 1996. 77. 4820.
19. D. J. Wang, G. Yu, A. J. Hecger, Rev. Lett. 1998, lJO, 2685.
U. Scherf. K. MUllen, Makromol. ClleiiL Rapid Ctmunwl. 1991. 4S9kothcim J R. Reynolds}.
U Scherf in Hwul/xJok of Conductig Polymers, 2nd edn, (&Is:. T. S ) . 363
22. M I od.ker New York 1997, Chapter 14 (Coljugated Struclllr:s' p. . I"""
arce . . . M N" r S De Sitvcsm U. Scherf, Pll)s. Rev. Lell. 77",
23. W. G. Leismg, G. Lanz.an1, ISO I,
24. s. G. U.

w. Graupncr, G.
25. G. Cerullo, S. Stagtra, M. NISOil, S. De Sahesln, na,
Lc
"sing Pllys Rev. 8 1998, 57, 12806. . H B .. lc E 0 G""'""AI
; . U s ncr M HopniCicr R. Hcnmg, ass r, "'""
26. R. F. Mal.n, r. P..lll.:k, U. Lemmer, K. egU S I :rf K. Mlilien Phys. Rev. 8 1996, 54, 1759.
P. Haring Bolivar, G. Wegmann, H. un, : . e lC
1
;".,.. 0 ,
669
h G
" 'esea G Lc1stng Syult. Met. ,.,, CY#,
27 G Meinhardt A. Horvat " '
1
' .
1
m M 501
' 'S &I K Pci.Jit,.;h G Leising u. ScllCrt, 5)11111. Met. of
28. W. GGr.supucr, T. J er; K J>ctriL.:Ch S Tasch' G. Leising. M. Gr.supner, A. Hcnncucr. Su<.
29. W. raupncr, . os
Plast Eng Thch P..1pcrs 1997, XUII. 1449.
30. P. A . . Lyle:w.s . Struve, Plwwchem. 3G5'\. anL.ani U Scherf, K. Mullen, W.
G. Kr:uw:lbint.ICJ", M. S. Stat;lra, .
1
'
31. Graupner G Leising Appl. P/ry.<. Lm. l <Hl. 71,2725. '""' 547
' . 1i '1c M A Stevens H H friend Alv. M<1wr. 1.,,, V,
32. G. J. Denton, N. css r, M Za
1
: . R . :i S De Silvcstai G. Lanwni, W. Graupner,
33. S. Stagira, M. Nisoli, G. Cerullo. . . vc am uss ' . . '
G. Leising. Cllem. Plys. Lett. F S Blumstengd. R. H. H. H.
34. E. L Frankevich, A. A. Lymarev, . o I
HortK>ld Pllys. Uel\ 8 1992, 46, 9320. Wi . T H Wood C A Bur
D A B
M.Ilcr D.S. Qlcmla. T. C. Damcn, A. C. Gossard, W. ICgnmnn, . . ' ..
35. . . I
1'\ls, Pllys. U!tt. 191!4. 53.
2173
Fcld p

s w Koch E. o. Gobel . K. W.
. T M . M Koch J. mann, . ..- . . .
36. G. von Plcs.o;<.'ll, erer, .
1
' R JJ
1996 5
3 t 3688 A. Alcxandrou, J. A. Kush, E. E.
Goosen J M Kuo. R. F. Kopl, P ays. ev. ' ' - ' 1990 42 9225
. . ; . . u J M Hoo ' T. Fukutawa, Y. Hase, Plr>s. Rt:v. JJ '
Mendez, M. Zacha g . E. O GObel R Kcrsting, H. Kurz, U. Lemmer, R.F.
37. V. I. Arkhipov, H. Bti.o;slcr, M. Deussen.
Mahrt, Pltys. Rev. 8 1995, 52, 4932. I G J De ton R H Friend, H. L. Anderson, ClleiiL
38. G. E. 0' Keefe. J. J. M. Halls, C. A. Wash, . . n , . .
Phys. _1997, 276, 78.' hcn D Schafer.Siebcrt. G. Leising, Plys. Rev. 8 1988,
39. tl. Btc,er, S. Roth, Y. Q. S . M N r E.J W List G. Leising, S. De S1lvcstn, Pltys.
40. w. Gr.1upner, G. Cerullo, G. L.ant.ana, . aso I,
Rev. Leu. 1991!. 81, 3259. C . 1 Oxford University t>rcss.
4
1. M. Pope. c. E. Swcnbcrg, in /ec:tmnic Pmc:ess.:s 111 Orgumc Y-1111 s,
New York 1982. P. 158. A M Hor J L Gootlman J. Plays. Cl1t:111. 1998. 102,
42. z. D. Popovic, M. l. Khan, S. J. Atherton, .
Ylsseatbcrg. M. J.M. de Joog, Plrys. Ut:v. 8 57,2667.
43. 62
44. S. Abe, J. Pl1ys. Soc. Jpn. 1989, 58.
9 Solid-state Aspects
of Conjugated Semiconductors
Wilhelm Graupner, Stefan Tasch, and Gunther Leising
9.1 Introduction
Conjugated semiconductor.; can exhibit energy bandgaps of 1 eV up to several
eVs depending on the choice of Lhe ( I) building blocks, (2) the number of such
building blocks, and (3) Lheir precise atTangemenl wiU1 respect to each olher.
Therefore, they cover the region of natTOW bandgap materials which absorb and
emit light in the infrared region (a) and show reasonable charge transpo11 proper-
ties. However, via the visible region (h). they evl!n extend to the ullraviolet spec-
Inti mnge (c), performing like inorganic wide bandgap materials. This versatility
and seveml other advantages such as mechanical llexibility, very high photolumi-
nescence quantum yields (PL QY), easy production of large an:as outweigh the
intrinsic instability of conjugated molecules to photl)-Oxidation. ExL-cpt for appli-
cations where long-term stability is not required 111. a proper encapsulation h;L-; to
be used to introduce conjugated semiconductors for technical applications; such
an encapsulaJion is for example intrinsic to applications such as capacitors and
batteries [2 ] .
This chapter is organized as follows: after a brief introduction into the class of
conjugated semiconductors we will discuss the solid state properties needed in or-
der to achieve the fuuctionalities required for efficient device operation, based on
this class of materials. Very different degrees of short aiUI long rctnge order can
be obtained in conjugated semiconducton;; we will describe U1em and discuss
their consequences on macroscopic properties of films of Lhese materials. Since
the properties of the excitt!d swtes in conjugated semiconductors are bolh a highly
relevant question of fundamental research and essential for applicat ions we will
treat the field of excited states spectroscopy in a scpamte section. This section
will be followed by a treatise of device cJlJJec:ts of light emiuing devices made
from conjugated molecules. Before concluding we will brielly discuss the photo.
physics of e.xciwtiou eucrgy trwufer and the propct1ies of hi ghly emissive conju-
gated systems under higlz excitation densities.
260 9 Solid-state Aspects of Colljugated Semiconductors
9.2 Materials
. th lOSt imponant conjugated semiconductors and
In Figure 9-1 we . e n 2 h s the chemical structures of the family
. their solid state propentes.
9
- s_ o:sed to describe the different synthetic
of para-phenylenes (PP). Thts IS b . na desirable properties from
str.ttegies are apphed in Refs. [3, 4]. Figure 9-
conjugated semaconductors, ted matetials are not processible in this
2 a shows the pure . be both evapomted or solution pro-
side-groups (R1 and R2d inAFig.
cesse . . . h I mers out of a solution to be processe . re-
9-2b), whtch enable t e po Y . nies of conjugated materials is pos-
markable improvement m the electromc prope
.. o -e
1
E - ? oev
1
'>9
cis (CH).
1
o=10 10 n em r
.. s .. I " t
trans (CH).' o=10. -10 U em '-11= ""'
t481SO 3 l I
!-doped Shirakawa (CH). . o=10 U em
H
f)O(N"QN}
H H
ISO 3 1 I
doped polyaniline o=10 n em
101
tot
148150 2 I I
doped polypyrrole o=10 n em
PLOY= 35

EHO-PPP: PLOY = 40%
1
s
1
{film)
CN-PPP: PLOY = 46 %1s'{hlm)
para-hexaptlenyl: PLOY = 30 .4
1
!>2
mLPPP: PLOY = 30% lr-2 {likn)
.
1
. . - lheir properties have been
. w a few selected .:OnJugalcd po ymcrs arru 0-
l'igurc 9-1. Matcnab overvtc .. - 00-PPI' J>uly(2..<.JecyiOJty- 1.4 phcnytcnc). EH
r-J ,.Lbrcvtauons arc """" t '-I 4-
compilcd and the '"' owmg "" . ppp p
1
(2-(6' -cyano-6'-mcthyl-hcply oxy,
PPt> ... CN p
1
(
1
2rt enylcne). and J>LQY= photolumincs
phcnylene), m-LPPP ... mcthyl-substnutcd ladder-type o Y
1
.:cm:c l.jllantunt yield.
9.2 Matentlts 261
-f<o>t
(a)
R1
-fQt
(b)
R2
M
(c)
(d)

Figure 9-2. Based on the conjugated backbone of a pam-phcnylenc the most common principle
tures of .:unjugatcd mukcuks arc (al the pure b.1cl..bone: (bJ a backbone with attached side-
groups R
1
and (c) a latklcr type-conjugated backbone: (d) and (c) represent diiTcrcnt types t l f
polymcrs. where (dl a side .:h.ain-1!-raft .:upulymo:r .JULI a single chain-block copulymcr.
sible by using a ladder-type approach to stabilize the conjugated backbone; gener-
ally speaking this strategy has advantages inherent to its chemistry but from the
solid slate physics point of view it also allows the suppression of torsional de-
grees of freedom. In Figure 9-2d and Figure 9-2e we have shown diflcrent types
of copolymers, whereby Figure 9-2d represents a side-chain graft-copolymer and
Figure 9-2 e a single-chain For completeness we would li ke to
mention that the methods of Jin:ct polymerization onto a substmte, e.g. electro-
chemically, and the subsequent conversion of a processible precursor-polymer are
also valuable approaches to obtaining films, consisting of the pure conjugated
backbones.
In general, Figure 9-2 b to e show stmtegies to make conjugated polymers
more processiblc but it must be noted that the ditrerent synthetic approaches do
not only result in different degrees of (a) c:lzemica/ purity but also alter (b) the
physical propcnies due to intrinsic differences. Compared to a pure conju!!atcd
262 9 Solid-state Aspects of Conjugated Semiconductors
backbone the planarization of the backbone in the ladder-type or the in:
creased torsion of neighboring conjugated units due to solubtlwng
are such intrinsic differences which have direct consequences on the eleclromc
properties (see Section 9-5).
9.3 Functionalities in Devices
Solid state light emitt ing devices require several their
Figure 9-3 describes a conventional multilayer hght emtsston devtce (LED),
which consists of an hole injecting indium tin oxide (ITO) electrode, usually on a
substrate, and organic layers sandwiched between the ITO electrode . and a m_etal
electrode, which inj ecL-; electrons into the active luye_r. The three_ acttve, possibly
organi c layers (A, B, C) have to pcrfonn the tasks ol (I) enhancmg or (2) block-
ing charge transport, and (3) emission of light: these also (4)
enhance charge injecti on from the electrodes ellher v_w a better band alignment
good adaptation to the electrode surface. Another leature of A can be .ts
ability to (5) prevent diffusion of oxygen from the IT?. electrode the a.cu,ve
layers. Tasks ( 1) and (2) result from the fact pos1t1ve and negat1ve charges
can have very diflerent mobi lities in some the charge trans-
port properties in the respective layers should be op11m1zed. . , .
Figure 9-4 shows two more advanced on an
improvement or change in the light emiSSIOn ol layer B
In both cases the goal is to achieve a color conversiOn. In the process_ of
color conversion (ECC) (51 a highly photoluminescent color convers1on layer ts
brought close to the electroluminescem layer. This has the of
possessing just one electroluminescent blue or !Jitrav_Jolet (UV) and as
emission colors as color conversion layers are applied on top_ of 11. !herefore, a
red- reen-blue (RGB) pixel can consist of three blue or UV p1xels the color
r..-.m:fom1a1ion carried out by three different photoluminescent layers.
This technique can increase the of a convertmg r_he blue oc
UV light to other colors since our eye JS most sens111ve 111 the green at 555 nm.

ITO
A
B
c
ligure 9-3. CutJvemicmaf muhilayer light de
vice (LED): indium tin oxide (ITO) clectnl<le 01_1 a sub-
active layers A (hole WtllSJXll1). B (enuller): C
(clcclron and a melal ciCl:lrodc. A possable
layer has bt.-cn omiued. which would pre-
vcnl the cunjugat<-t.l nKIcculcs from phutn<>llidOJtion.
Y.J Fmu:timwlilies i11 Devices
263
a)
b)
9-4. Cutor (a) shows the llCl'tkd for cxtcntal color conversion. (b) for
tntemat l-otor converston - lop nght: cnlargco.J view of the layer whkh cunsisls of a matrix
Oll1d culur-cunvcnm:; dup;mo.J., (hlack duls).
However, the will nor_ enhance the external quantum yield of the LED,
moreover, proper opt1cal coupling between the layers has to be achieved in order
to the QY too much [61. One of the obvious problems is the princi-
pal requirement of havmg the ITO-covered glass substrate between the color con-
verter the layer. This can also lead to color bleeding, an etTect where
the enuuer _layer .excttes not only the conversion layer, it is supposed to
but also netghbonng ones.
:n1e process of inlemal color conversion (ICC) l'ill an eflicicm tmnsler of exci-
energy l7J can, however, not only change the emission color but it can also
mcrease the external quantum yield of the LED (see Section 9-7). The most sim-
ple approach to understand this is the fact that most emiuers show the effect of
concentration quenchi ng, i.e. cmiuers of the same kind brought close to each
other a very PLQY. Incorporating the same emiuer in a liquid or solid
state soluuon 111 a strong increase in the PLQY, often up to 100%. There-
fore, the sepamt1on of the tasks of charge tmnsport. CaJTied out by the major com-
ponent of an LED, the matrix, and li ght emission, perfom1Cd by an emiuer, which
up than I% of the active layer, can signilicamly increase the external
y1eld_ of an LED. One application of this lechniliUC is the producti on of
hgh_t _ LEDs based on only one active layer 181. Figure 9-5 summarizes the
functonaltlies to be expected from materials used in eiTicicnt light emitting de-
vices.
264 9 Solid-state Aspects of Conjugated Semi'01/ductors
Possibility to
introduce
preferential ordering
(texture)
Charge
InJection
Ada plablc
Interlace
I
I
High rnobtfity for charge
carriers of both polanties
Htgh PL
quantum
yteld
Figure 9-5. Funccionalities to be from materi:tls to be uset.l in cl'ficicnt light-cmining devices.
9.4 Order in Conjugated Semiconductors
While there is much to discuss about order in fi lms of different conjugated mole-
cules, a comprehensive survey of the structural properties of various conjugated
polymers can be found in Ref. (9}. This section focuses on the relati on between
microscopic order and macroscopic properties, and on structure-property relations.
An example of a highly ordered conjugated material is the conjugated para-hex-
aphenyl its crystal structure is shown in Figure 9-6. PHP adopts a monoclinic
crystal structure (a;;: 8.091 A, b=5.568 A, c=26241 A. P=98. 17") [1 0]. PHP fonns
hi ghly emi ssive polycrystalline films upon evaporation of the molecules onto a sub-
strate. Its morphology can be influenced by controlling the evapomtion conditions
[II]. It is possible to rub a NaCl subslr.tte with a teflon stick at cicvalcd tempera-
lures ( 138] in order 10 obtain a preferential orientation of the PHP molecules depos-
ited onto the substr,Jie during evapor..1tion. In the elastic electron diiTmcLion pauerns
of the textured hexaphenyl films in Figure 9-7 it is clearly visible that the material
represents a typicul polycrystullinc behavior wi th well developed diffml:lion peuks.
Moreover, the intensi ties of the (00 I) peuks in relation to, l<>r cxumpk, the (20-1 ),
(21- 1 ), (020), und ( 120) arc much too low for an isotropic polycrystalline material
with a random distribution of crystallite orientations. Therefore, the electron-diffrac-
tion pattern in Figure 9-7 provides evidence for the expected texturing due 10 the
teflon rubbing of the substr.Jte; a macroscopic slate of order was induced. Further-
more, in the inset of Figure 9-7 we show the intensily of the (020) electron diffrac-
tion peak as a function of the angle between the rubbing direction, which corre-
9.4 Order ;,, Coujugated Semiconductors
265
8 & &
(11-2) & & &

.................
(20-3)
t' igure 9-6. Crystal structure of hexa-
phcnyl, whereby the solid gray bar rc-
che substr.ttc pl:mc. n
1
c muno-
unit c.:cll is sketched in thin solid
ltncs.
>.
- 'iij
c
Q)
-
c
0.5
1.0
(11-1)
(11-2)
(110)
0
"' 180
8.
1.5 2.0 2.5
3.0
35
4.0
momentum transfer (A-1)
F'.gurc 'J-7. clcch'Oit-diiTr.JCtion . altern of . .
dtCCS arc using the intn,Janar . akh:ghlt.ly hcxaphcnyl lilm. The Miller in-
....,,. . ( - - .,. u..,tc 10 Ret I I 37( 1 1
.....-.. as a Ulk:tiOn u( th.: lllc lllcnSJty of the \020)
teAt) - t.skcn fi\1111 Ref. II lltt.: ntum tmnsfcr aut! the Tcnun rubbing t.lirt!t.' tion (,.,c
. . th N Cl cr stals and the measured momentum
sponds to the [001] dre:cton of e a fi Y
0
o
45
' o l80 225 and 315. This
ti
y, harp maxtma are observed or ' ' ' ' 001
trans er. ery s . d' . th t the PHP b axis is aligned par.tllcl to the [I
d ery good 1n tcatt on a - . . 'd b
provt cs a . f tJ N Cl substmtes This assumption Is also confirmt: y
und lll 0) dnecttons o 1e a .
polarized. diffraction, one can also study the momen-
In addtlt on to e e asltc e e . . . in contrast to those photons that only
tum-transfer-dependent energy loss results of this electron energy loss
transfer energy to the sample ;_8 In the two figures (top and bot-
spectroscopy (EELS) are shown PHP films are shown, which are
tom) the electron energy loss spectra d r )endicular to the molecu-
dependent on momentum trdnsfer both pe_ b til o' the sample
k' d 1 ge of the mtrmstc amsotropy o 'J
ltJr axis, therefore, ta mg a van a transfer amllel to the PHP axis (see
and of the experiment. For the . . pf 0 07 or 0.1 A - the tmnsi -
Figure 9-8. top) ut low transfer to the si tuation ob-
tions are nearly vertica_l m the th . . k cuused by the plasmons
served for optical expenments. For thts sttuallon_ e pea I rb' t I (HOMO) 10
. . h h' h t occupted molccu .tr o a
related to an lrom ' . e .:. is the dominant peuk (peak I, in
the lowest unoccupted molt.:cular o ua
2 4 5 6 1 8 9
energy (eV)
c
0
'fi
c
.2 4
:1: q=0.1 A
.2
"C
Ql
.tl
Q"0.2A''
0
c
2 3 4 5 6 1 8 9
energy (cV)
. . . . ' ccxturoo hcxaphcnyl lilms for diiTen:nt value:, of
f<iuurc 9..g . TCJfJ: loss funcllon Ol lughJy . . pl . . n'"loo lo the same CXCIIallon. f3o<
<> 1 . 1. . . . The wnn<X:t . . .
tmnsfcr ro the mo ccu m axis. I rr . r, r <.liiTcrcnl value..' of momentum lr.JIL\Icr pcrpcodic
tom: Los:. function of texrurcd ms u I :-d lo equal ai'Cil.\ under the
Icc l . . . In both PnpltS the speclm were llllnna JLC ular to the mo u ar axis. .,..- .
between 6 and I! cV - taken from Rt:l . II JIS).
9.4 Order in Co11jugared Semico11ductors
267
Figure 9-8, top). For higher values of momentum transfer (0.2 A-1) a new peak
(II, in Figure 9-8, top) appeetrs which is related to lhe excitations from HOMO to
LUMO+ I. In u quasi band structure dt:scription this peak is equivalent to the tran-
sition from HOMO-I to LUMO [1 38). COJTespondingly, increasing the momen-
tum lranstcr leads to the transi tions HOMO- I to LUMO+ I as well as IIOMO to
LUM0+2, which are depicted as peaks III and IV in Figure 9-8, lop. The strong
momentum-transfer-independent peak at 7 eV corresponds to excitations where
the ini tial and the final state belong to bands derived from the benzene orl>ital,
with a high electron densi ty at the C-atoms which arc not invol ved in the C-C
bridging between tl1e rings. In Figure 9-8 (bottom) the corresponding transitions
for momentum transfer perpendicular to the PHP chains are shown. The peaks be-
tween 3 and 4.5 eV result from the fact that there is a slight contribution from
chains which arc oriented in such a way to give a momentum transfer parallel to
the chains. The excitation at 4.2 eV is also observed in optical experiments l i39J
(see Fig. 9-9) and was predicted by band structure calculations I12J;- it is u con-
sequence of the three-dimensional nature of the PHP electron system in the solid
crystalline slate. The higher lying transitions are due to tmnsitions from the
HOMO 10 a non-bonding state and are polarized in the direction perpendicular to
the molecular axis I 13j.
From the optical absorption of two different hexaphenyl films, one with its
chains predominantly stanJing upright on the subsu-ate, lhe other with the chains
randomly di stributed in all orientations, similar structure property relations can be
concluded [139j. By compari ng the calculated absorption coefficient [1391 per-
perulicular to the chains with the observed optical absorption spectm of bolh
films we see thut the optical absorption, plotted in Figure 9-9, in the visible and

Optical density (abSOfbance)
2
..
u
c

.c

.c
ct:
1
0
200
,--
1 a \
\ I \
!: I \
1: \
? \
\ , _____ _
c ----- -
300 400 500
Wavelength (nm)
600
100
Figure 9-9. G!kula!-.-d ab,orption L'(lCilidcn! pc.-p.:ndicular 10 fl<lllt hcxaphcnyl (c) comp.ncd 111
!he experimentally dctcnnin-.-d absvrptiun J>e.-p.:tk.lkular (b) and parullcl (il) lo rhc - tal.cn I rom
Rcr. 1 13<JJ.
268 9 Solid-state of Conjugated Semicmrductm:s
ultrnviolet range is mainly determined by the dielectric function parallel to the
polymer chain. Again the peak around 4.2 eV is predicted and found for absorp-
tion with the electric field perpendicular to the chains.
l n on:Ier to summari ze thi s section it must be nmed that the possibility to eva-
porate conjugated oligomers in such a way that their chain axes point predomi-
nantly in one direction allows us to determine the anisotropic electronic properties
of conjugated molecules. From these studies i t becomes evident that in order to
obtain polarized absorption or emission of light as required in polarization filters
or LCD-backlights, the application of conjugated molecules is one of the most at-
tractive areas of application for these materials.
9.5 Excited-state Spectroscopy
The term excited slate spectroscopy can have two ditfcrent meanings, both of
which will be treated in thi s chapter: (I) probi11g the dijfertnt excited states of a
material, the pathways to reach them, and the properties of these states and (2) a
significant population of one or more of the (xc:ited states and the subsequent
probing of the contribution of these stales to the material's properties. Before
going into details, a selected set of principal experiments in the area of excited
states spectroscopy wi ll be oullined. In order to detect the excitation process with-
in a bulk material one can use:
I . The most ubiquitous method of tra11smission spectroscopy, in which the
amount of light passi ng through a sample is determined. Very often the influ-
ence of reflection and scattering is neglected and the rntio of incident and trans-
milled intensity (/Eo) is linked to the absorption coefficient (a) and the sample
thickness (d) by Lambert-Beer's law (see Eq. (9. 11 )).
E = Eo exp( - ad) (9.1)
2. One way of measuring true absorption is to employ photothermal deflection
spectroscopy (sec Fig. 9-1 ). ln this case the absorbed light, leading to a slight
heating up of the sample, is detected by the tempcr.Iture-depcndent deflection
of a laser beam passing dose by the sample. The obvious advantage of this
method is that it really measures the absorption coefficient (a).
3. Photoluminescence (PL) and photocurrent (PC) excitation spectroscopy provide
insight into the contribution of the excitation to the population of emissive and
conduct ive states. However, in both cases the shape of the spectra is highly de-
pendent on sample geometry; in PL excitation spectm the samples have to be
opticall y thin and in PC excitati on spectra the location of the charge-genernting
region influences the magni tude and shape of the spectra.
4. The technique of trJnsiem or quasi steady state photoinduced absorption (PIA)
allows the papulation of excited states and also probing the optical
!i.5 Excited-state Spectroscopy
269
of these states or of the states into which the excited states dec .
g. 9- I_Q). The advantage or this technique is that it probes both .. (seed
absorpuve states. emss1ve an
9.5.1 Excited States
_9- 1 0 the principal scheme of excited states involved i .
cesses n a conJugated molecule. After the abso lion of li n optical
ferenl CJUantum eneruies (A A A ) . .
1
'"!' ght (hv) of several df-
involvement f o . '!' " 2 '. smg el excnons (SE) are formed due to the
o phonons. Smglet excJtons can create t j 1 . ,..
tersystem crossin<> (ISC) Tt . b . . . . . r pet excJtons (TE) vw m-
o 1c a sorption Wlthm the triplet ch
posed of lrunsitions of sever. 1 -rr . s eme s agam com-
. a uJ ' enng quantum energies (T. T T ) d
mvolvement or phonons. Tile emission pruc .. b d" 0 lh . . 2 . ue 10 the
singlet excitons to the ground tia of the
solved photoluminescence s x:. H . ., _I A./}. nse to a well re-
into charged states .called swgl,et can also dissociate
optical tmnsitions p p p Th,
1
. e ploucd pos111ve polaron with its
served i . h . . ,d, . ! l c_ po aromc and the lnplet tr .lllsitions can be ob-
n an p otom uced absoq)lJon (PIA) experiment.
y;r;(
- - - - - -r-..--
L l t l.
p,
hv
0
,_

0
PIA
I urn inescence
--_..;L.....- ---L-.l......J._ 0 - - - - -
absorption PIA
Frgure 9-10. &heme or excited of a conu tcc.l mukcul .
sever.JI tliiTen:m ,
1
uamum (II
11 1
. c. Ancr Lhe absorpuou of (Ill) uf
(pi "" . I
1
1l. "lllglcl exciluus (Sc) an: li>OI cd d h
meru o Singlet cxc.:itons can cre:uc in
11
1
. . . TE . . ' uc lo I c lnvolvc-
within the triplet is ag:uu ( . ! IWI crossing (ISC). llu:
ergtcs (r, . T1. 7-,) due lu the involvement ,,. e u !>l:vcr..tl dtffcn:nt quantum en-
lion of the exciton' lo the g\und sllatcphunun,. CIIII,Siun pmce"s by mdiativc rccomhina
I . I'ICI lr.Jnstlluus L L L ivc . . II
.., .. >l.o ununcsccnuc 'JlCClrum However si
1 1 1
. I 1 ' .; s nsc lo a we 1\:solved
polarons. We have llolt' . . ... .. ,: ' g c can aiMl di:..,ociate into charged M<llcs
. "" a pusr "c pu .nun wuh ns opt1 1 . r p
lllplet can be ol>!.crvr..'ll in a phot . ttl ccd . b c.l
1011
' P,. l llc polai\Kli.: and
(1401.
011
u a '"!Jlltun (PIA) cxpcnmcur - l<1l.en from lkf.
270 9 Solid-state Aspects of Coujugated Semicouductors
It was shown that the wide gap semiconductor poly(para-phenylene) (PPP)
1 h d v es [14) The electrontc
be used as lhe active layer m blue- tg t-emtumg e tc . . .
ro erties of conjugated polymers depend strongly on lhetr structural
Th p p for the synthesis of poly(para-phenylenc-ladder
e mottvatton h' cd b a plananzauon
(LPPPs) was the increased overlap of lhe rr-e_lectrons, ac . . Y _. _
1 mer backbone [15). AL the same ttme lhe synthests vw a polymer
closure reaction of a substituted polymer _[16) results tn _a
s!:ucture with a very narrow conjugation length dtstnbutton. For all
::ons some results from this material are used to illustrate lhe field
state spectroscopy in conjugated materials. In 9-11 have:. . e
transmission difference speclr'J, which were obtamed by a transtent PI tee
for methyl-substituted ladder-type
K excited at 3.2 eV (for details see Ref. [17)). tgure s ows, . . . m-
sarnplc transmission aL differem times after the laser pulse_ .the S:.
1, Since the tempoml extent of the laser pulse ts below 200 fs, l e pro.
c. . f 4 40 and 400 ps represent the Li me-resolved PIA spcclrJ after the am-
tunes o ' r. , 9 10 an be seen
al of the excitation. Most of the shown 111 .- . c . :
2.3 and 2.5 cV stimulat..:d emission from singkL exctlon ..:mtsston (L,, L2) ts
,.' 400ps(X 10)
--,
1.4 1.6 1.8 2.0 2.2
Energy (eV)
\
\
.. .. n cncc s ctr.t of m-LPPP at T=77 K excited at 3.2 _cV li>r var-
l'gurc 9-11. Twnsamsst011 cia crfi /rr 1141) l11C inset :rooms nut the low energy rcgton for 0 ps
ious pu_mp-probc c.lcluys absorption (DIA) arc also shown for
(solid hllC) and 400 p:; (uas ICu IIIC "'
c.:omparisnn (accnrdiug Ill )142)1.
271
detected. Around 1.9 eV we can observe the polaronic transition P
2
with its vibro-
nic replica P
3
at 2. 1 eV. The polaronic nature of this tmnsition is establi shed by
comparison of the spectral signature at 400 ps with that of a sample after redox
reaction. producing singly charged slates. At 1.5 cV a transition from the exciLL-d
singlet exciton stale into higher lying levels was detected. The triplet transition 7j
1
at 1.35 cV is only ohscrvCll al longer tim..:s, because of its slow formation
due to intersystem crossing. In lhe following sections these states and transitions
will be discussed in greater detail.
9.5.2 Neutral Photocxcitations
Singlet excitons with binding energies of a few tenths of eV arc lhe primary
photocxcitations in conjugated molecules. The mosl basic spectroscopic experi-
ments concerning their propetties are optical Lmnsmission measurements. Figure
9- 12 compares the absorption calculated from a transmission experiment with the
PL excitation spectrum of a thin m-LPPP lilm. It is evident that the spectra are
identical and lhal lhcy show Lhe tmnsitions A
0
, A
1
, A
2
and higher, depicted in
Figure 9- 10. We have also included both the elcctrolumincscence (EL) and PL
emission spectra of m-LPPP, showing the transitions f...z, and higher, as de-
picted in Figure 9-10. As pointed out before, one of the best methods to measure
absorption is photothennal deflection spccuoscopy. This was also applied to m-
LPPP and the result is shown in Figure 9- 13. The result of this experiment is
highly encourJging in tem1s of the very low absorption below the onset of ab-
sorption due to the rr-rr* tmnsition, which is found at 465 nm in Figure 9- 12.
From the photothermal deflection experimem, it can be concluded that the absorp-
tion changes between 465 and 500 nm by about four orders of magnitude. In inor-
ganic semiconductors such a low subgap absorption is indicative of a very small
defect content. Regardless of lhe origin of the subgap absorption in conjugated
molecules, the result shows that m-LPPP is suitable as a laser medium in that re-
gion as far as loss due to absorption is com.:erncd. In addition, the photothermal
deflect ion method does not probe scauering, therefore this loss mechanism must
be treated separately. In conjugated polymers with a well delined effective conju-
gation length a steep onset of the density of staLes at the band edges is expected.
The fuctthat this is confirmed by the results in Figure 9-13 further establishes the
high chemical Jefinition of m-LPPP.
A further clear establishment of the absorption due to singlet excitons and the
phonons coupled to them is lhe elcctroabsorption experimem reported in Re[
[18] . The main results are shown in Figure 9- 14: the top panel shows Lhe absorp-
tion spccuum of m-LPPP at 20 K. It becomes clear that the peaks at 2.7, 2.9, and
3. 1 eV, representing A0, A., and A2 (see Fig. 9- 10) are not the only vibronic repli-
cas. There arc additional peaks between these dominant ones if the experiment is
conducted at low temperature. The bottom panel in Figure 9- 14 shows a so-called
clectroabsorplion spectrum which is obtained as the modulation (or change) of Lhe
absorption under the application of au electric field. Below 3.2 eV the electroah-
272 Y Solid-stule Aspects uf Ccmjuguted Semicouductors
-
:l
.e
c
0

13
X

0.
oCS
...._
-u
,....
Qo
m
,....
0
0
...,
...,
(1)
n
(1)
Abs
a.
c
<U
.0
0
(/) _____ /
.0
<( 300 350
300

10
c

=

..8 0,1
"" E
[ O,Ol
I E-3
c
IE-4
e.
__ .. , ,
0 300

.
/
400 450 500
Wavelength (nm)
550
D)
c
-
600
Figure 9-12. Absorption photolumi-
nt!SCencc excitation spectrum (PL.,.). photo
lummcsccnce (PL). aud electrulumincscmce
(EL) of mLPPP.
400 500 600 700 800
... _, '.
k-
_........satUJ" tion of P ps
.... ..
J. r

..

--a sorption
1
ir cnsity o
- U lv-VIS at sorption
'
. .A. I t
ifiV" r
., v'
""'"
400 500 600 700 800
wavelength (nm]
10
0. 1
0.01
I E-3
IE-4
Figure 9-13 .. Absorption spectrum
of mLPPP. <.lc:ll:m1ined using
pholothermal dc:tlcclion spectros-
copy (PDS)- from Rd. [143[.
sorprion (EA) specrrum of m-LPPP can be described by the rigid red-shift of an
excitonic state located at 2 ..711 eV, which is caused by coupling this state to even-
parity states staning at 3 .. 2 eV (so called nAK) (1 8] .. 1l1is is also expressed by the
good agreement of the first derivative of the absorbance spectrum and the EA
spectrum; all the significant features of the EA spectrum ure well by
the fi rst derivative of the ubsorbance. Therefore, the binding energy of the exciton
in m-LPPP cun be esti mated to be about 0.5 eV .. Moreover, there is no significant
contribution to the EA spectrum from the second derivutive of the ubsorbance,
which is very often present in the EA of disordered polymer films. This
fuel points to large conjugation lengths in m-LPPP. Above 3.2 cV a different
mechanism, namely the electric inlluence on the continuum stutes, is responsible
for the EA spectrum.
Fimtlly, we would like to point that one of the easiest to intluence
electronic protx:rties of conjugated oligomers and polymers IS to vary the cham
-
"i
'
["
r
t..
..
, .
r-
r
9.5 Exdted-stale Spectmscopy
273
2
--opCJcal deflslty
-g
1
0
2.9 3.0 3.1 32 3.3 J ...C 3 ..5 3.6
Energy[eV]
- - d(ad)/dE
--6ad. 53 kV/cm, 20 K
.a
20

-20
-40
2.5 2.6
3.1 32 3.3 3.-e 3.5 3.6
Energy[eV]
9- 14 .. Absorption (lop) and clt.."o.:rruabsorptiun uf a mLVPP lilm at 2() K. Nuh: the resolution of
at least two phonon (sec text).
Jn 9-15 the chain length-depenllence of a sample of the tr.Jnsitions
an Fagure 9- J 0 !s the tmnsitions include the singlet exciton ab-
A2. the tnplet excuon absorption T
0
, T., T
2
, and finully the emis-
Sive lmnsllJOns ith Lit L2 of the singlet excitons. The position of these transi tions
on the chain length and also on the stale of the conjugated backbone. It
IS obvaou_s that the spectrum of the planar-backbone m-LPPP is com-
pletely that of the non-planar oligophenyls. Consequently, a very
Stokes shtft 1s observed between absorption spectra anll photoluminescence
emtssaon spectra of the m-LPPP .. This is the rcsul! of the suppression of geometri -
cal reluxatt on of the upon electronic excitation. In orllinary PPP, how-
the coplunar (qumOJd) suucturc exists only in the excited state due to rotu-
uonal degrees of frecllmn between neighboring rings.
274 9 Solid-state Aspects of Coujuguted Scmricouductors
2 3 4 5
Energy [eV]
l'igurc 9-15. Triplet absorpliun. singlcl cmb>iun. and ah>nrpliuu (from left lu righl) uf (frum lnp lo
bouom) m-LPPP [1441 and hcxaphcnyl tilm.\ [145) :tl 90 K. and pura-<1ua1cr- and lcrvhcnyl m 77 K
in lclrclhydro-2-mclhylfuran [ 146[.
In summary, all the transitions expected for the neutral states of a model sys-
tem for conjugated polymers, the m-LPPP. were observed and described and all of
these transitions aJso show clearly resolved vibronic replicas due to coupling to
vibronic modes of the backbone.
9.5.3 Charged Photoexcitations
One of the charged species encountered in conjugated systems is the singly
charged positive or negative polaronic state. Polarons are characterized by their
charge, by the lauice distortion around them, and their electron paramagnetic ac-
tivity due to the unpaired spins. Furthermore, they can be detected in PIA experi-
ments by the transitions P., P
2
, P
3
, sketched in Figure 9-10 and by the infrared
active vibmti onal (IRAV) modes due to a charge redistribution along the back-
bone.
In Figure 9- 16 we show the PIA spectra of m-LPPP, which exhibit the P
1
-tran-
si tion and lhe IRAV-modes for different qualities of the LPPP. In conventional
routes to PPPs. defects such as bmnchcd chains and !urge torsion anglc.o; of neigh-
boring rings are known to appear. These defects act as electron and/or hole, shal-
low or deep Imps [19, 20], which limit the mobility of charge carriers [21). The
synthetic route towaros the LPPPs prcvems the described defects. One of the man-
ifestations of this behavior is the well resolved vibronic structure seen, e.g., even
in the EA spectm in Figure 9-14. However, even within the class of LPPPs there
are different qualities; we have selected three diOcrent materials:
1000
00'
I
C>
600
s
....
0
4000
'- 2000
f-
....
0
.l
-.;
..!!..
_,
...
.6 g
-
0
.:g

0
2000 3000 4000
Wa v e number (.l/cm]
2. 6 2.6 3 3.2 3.4 3.6
Eneray [eV]
9.5 Exerted-state Specl1vscopy
275
9-.16. absorption of (a) s-LPPP. (b) 1-LPPP, and (c) Ccnrcr: photornduced ab-
of (a) :\LPPP. (b) m-LPPP. Top: pholoinduccd abS<lrplion spectrn of
(a) s LPPI. (b) 1-LPPP .md m-LPPP allcr login/oxygen trcalmcm (sec lcxl).
- the . s-LPPP, which consists of a ladder-type PPP bockbone wi th an
cham lengLh of 20 phenyl rings, average
- the . 1-LPPP, which consists of a ladder-type PPP b kb h
ac one wu an averdge
chatn lenglh of 40 phenyl rings, and finally
- m-LPPP, which _consists of_ a melhyl-subslillllcd ladder-type ppp backbone
Wllh an average cham length of 50 phenyl rings.
absorption speclra of these ma1erials arc shown in the bouom panel of
9-.1 ? spectra II becomes clear lhat I he m-LPPP shows the lon-
gest length 1_231 lhe best resolution of vibronic progression.
and the ons:t of 1231. Thcn:forc, one would ussume the m-
LPPP to be a malcnal of the htghcst chemical definition. This is indeed con-
276
9 Solid-stute Aspects of Conjugated Semicvnducwrs
firmed by the PIA spectra. The top panel of Figure 9- 16 shows the PLA spectra of
these materials. As expected the high definition of the m-LPPP and consequentl.Y
its low defect content lead to a very low polaron signal in the pure san1ple. Th1s
can be understood by recalling that a quasi steady state PIA spectrum
the absorption of photogenemted stales such as polarons. Polarons are stabllzcd
or tr.1pped by defects within a conjugated polymer, consequently. a low ddect
content is connected to a low polaronic PIA signal. This statement 1S for example
in excellent agreement with the work of Pichler el al. on
poly(para-phenylenc vinylene) (PPV), where basically no polaromc PIA IS found
in comp<rison to a strong signal in standard PPV. . . .
Furthermore, the shape of the polaronic PIA in the three IS
also quite revealing, especially the relative strength of the electron1c
as compared to the IRAV-modes. As described in L23J and Refs. thercm, the larg-
er the r.ltio of the intensity of the P
1
-transi tion with respect to the IRAV modes,
the larger the effective mass of the associated charged defcc.t polaron).
The PIA spectm confinn our assumpt ions concerning the sample quahty deduced
from the absorption spectra and: (a) the polaronic signal weakest (or de-
tectable) in the high-quality m-LPPP. and (b) the e1Tect1ve 1s. al so
highest in the lowest quality s-LPPP. In order to clabomte on the
ent LPPPs can be photo-oxidized, in order to introduce chem1cal wh1ch
wi ll stabilize the polarons. The effect of this procedure on PIA spec-
tm is shown in the center panel of Figure 9- 16. The most stnkmg d1fferences are:
0.001
90
:'
-; : -!-----
:.. !
...... .!
150 2 10 270
Temperature [K]
Figure 9-17. Pholoinduccd absorpt.ion in s-LPPP at 0.26eV _versus (filled Full
lines reprc.o;cnt the model results (lower curve for two acllvallon encrg.cs, haghcr. curve for one). 1bc:
dolled lines reprc.scnt the decay nates for the -0. 12 eV (a) ami - 0.37 cV (b) actavatcd processes; the
dash-dolled horizontal line ro:prc:.ents the tcmper.!turc-indcpendcnt part .
9.5 Excited-state Spec:Iroscopy 277
- even the photo-oxidized m-LPPP shows a clear polaronic PIA spectrum due to
the introduction of chemical defects which were barely present in the pure m-
LPPP but present in the s- and 1-LPPP;
- as expected from the defect-mass-to-PIA relationshi p: as the lowest quality ma-
terial s-LPPP shows the strongest P
1
-tr.1nsition relative to the IRAV-modes;
- furthermore, there is dear correlati on between the shape of the P
1
-transition
and the materials: s-LPPP always shows the peak at the highest photon quan-
tum energy, followed by 1-LPPP.
In order to study the charged photoexcitutions in conjugated materials in detail
their contribution to charge transport can be measured. One possible experiment is
to measure thennally stimulated currents (TSC). Next, we will compare the results
of the TSC-expcriments, whi ch are sensitive to mobile thermally released charges
tmppro after photoexcitation, to the temperature dependence of the PIA signal
(sec Fig. 9-17) which is also due lo char6ed states as discussed previously.
First, we would like to address the question how sample quality inll uem:es the
obsecved results. Synthesis and sample treutmcm inlluence Jhe electronic proper-
ties of conjugated materials in a deli ned way 123). We have already shown 131 J
that the shape and intensity of photoinduced absorption spectra in ditlcrent repre-
sentatives of the LPPPs may vary Fig. (}-16), indicating at least differclll tmp
densities but also different electronic properties of these traps. depending on the
synthesis and subsequent treatment of the polymers. However, the electronic prop-
erties for this class of polymers can be understood in terms of eflccti ve conjuga-
tion length 123- 251 charge tmnslcr by photocxcitation or redox reactions L31 J and
also upon intense visible inadiation under the influence of oxy-
gen [23]. Therefore, by optical spectroscopy (absorption, photoluminescence, or
photoinduced absorption) we can assess the quality of a sample.
f'Or the chamctcrization of the trap levels we appl ied the thennally stimulated
cunent technique following the initial rise method [26J which was successfully
applied to other conjugated polymers [27]. The device consisted of a sapphire
substrate with an interdigital gold electrode structure on top of which a 200 nm
thick polymer fil m was drop-cast. The gold electrodes had an overall length of
87.5 em and a gap of 20 11111. The substrate was mounted in a cryostat and cooled
to 90 K. After illumination of the active area of the device at 454 nm for 2 min a
voltage was turned on yielding an electrical field of 4x 10
4
V/cm across the elec-
trodes. Any increase in the dur.1tion of ill umination above 2 min does result in no
greater TSC, therefore 2 min of illumination under the chosen condit ions result in
satur.ttion (filling of all avai lable traps). As the temperature, T, of the device was
increased we observed the stimulated current depicted in Figure 9-18 a. Trapped
charge carriers arc thermally released and an electric current is gcner.ttcd. As the
linear heating rates were varied between 0.06 K/s and 0.25 K/s, the maximum
current al ways appeared at 167 K. This can be attributed to monomolecular ki-
netics with non-retrappi1tg traps L26]. Without prior ill umination, no significant
current change is detectable during the heating cycle (b).
It must be noted that the prerequisite to sec distinct in a TSC experi ment
is a steep onset of the dcn)oity of states at the band edges. This is fully fulfilled
278 9 Solid-state Aspects of Conjugated Semicouductors
3 4 5 6 7 8 9
1000/T (K
1
)
10 11
Figure 9-18. Themmlly stimulated current of s-
LPPP with (a) and without (b) p rior to illumina-
tion.
for LPPP as discussed in the previous paragraphs, especially by the results plotted
in Figure 9-13.
The electrical cum:nt of a coplanar imerdigital gold/LPPP/gold device is space
charge limited due to p-type charge canier traps localized in the bandgap [28].
This can be inferred from the field dependence of the dark current at room tem-
perature. The thermally stimulated cutTent exhibits two peaks, corre-
sponding to two distinct trap levels E: and ;, which can be calculated from the
rise in cunent, /, below the peak temperature:
,
In(/) =-+ consl.
kaT
(9.2)
By the integrating the current over the time for each peak we determine the num-
ber of charge carriers which equals the number of tmps N, (under the condition
that all traps were occupied at the starting tempemture):
J ldt = eN,
peak
(9.3)
where e denotes the elementary charge. In Table 9-1 the results for the trJ.p depth and
the trap concentration n, are summarized. The schematic band diagram in Figure 9-
19 illustmtes the trap distribution in the bandgap. The assumption of a trJ.p-distribu-
tion mainly centered around two energetic levels is backed by the results obtained
upon varying the heating mte. We found only a corresponding change in the current
intensity but no changes in the peak shape and the position of the maximum of the
TSC (curve A) (see Fig. 9- 18); no additional teatures appear in the peak.
The PIA-investigations were carried out under dynamic vacuum (p< w-
5
mbar)
and at 77 K with films cast from toluene solution onto KBr substrates. For the
dispersive method f29, 30] the globar, the KBr-prism premonochromator, and the
gmting monochromator of a Perkin Elmer were used in the
spectral range of 0.25 to 1.24 e V. The pump beam was chopped mechanically
t
279
f. Table I. Trnp depth and dens it in LPPP T .
1: levels obtained from the TSC PIA temper-.uure at peak current, and EftA are the tmp
c.; .; lh expcnments N . d th
e trap coucentrmion, res!X-"Ctivcly " 'an 11, are c number of tmps and
1;,. (K)
t;sc (cV)
(eV)
N,
,, (<.:111-.1)
167
0.11
0. 12
235
0.4
3.6xl0
11
t.oxto
17
0.37
5.6xl0
111
1.6xi0
16
X
Au
l PPP
Au
Figure 9-19. Band diagram of LPPP with hnle tr.r sand ' . . ' . .
hand.
1
,
11
valence txuu.l 1:: ..: .r .
1
P
1
. gnlt.l o.:k"Ctmdcs With EvA< vacuum level. Ec
11
d
. . ro.: 1111 eve f. lnudw
11
, n r c r .o L
trap ISlrrbution, X affiruty and </> ; ,.. " "gy. anu trap tlcptll,, 11,tt.)
Au wor" oun.:trun of the gold clct:tnxk"'.
using the chopper frequency the reteren f . EG .
Research lock-in amplifier 124. ll1e probe ;: . . or \&? Pnncet?!1 Applied
quency, which W<Lo; used <Lo; the . , . ..

at a different frc-
Princcton Appl" .I R I tclcrence l o .t SC(ond lock-m ampli fier (EG\&G
teu esearc 1 model 521 0).
1be PIA spectm obtained show ,
1
1 . .
Fig 9-17) . . . . : . at e ectromc lransuton peaking at 0.26 eV (see

which
on perature is depicted in Figure 9- 7. ]. c dependence of the PIA mtcnstty
1o mterpret the magnitude of the PIA si , . . .
generation of states will be discussed It :, equatton for the photo-
(
.
1
. uescn s l e change of the n be f
s a es, n, wtlh respect
10
time
1
d d. . urn r o
p=excitation density) and the'

rate kp (k==const.,
nctics) and can be wriuen as follows: c " -mversc Cltme, (Jl=Order of ki-
dn
- = kJJ - ,,,,
dt .
(9.4)
The number of photoexcitcd states in dynamic equilibriut . . . . .
cay rate =creation rate (dn!dt=O): n "q s obt,uned lor de-
280
9 Solid-state Aspects of Conjugated Semiconductors
1
ncq = l ex !Pl"
(9.5)
In a steady state experiment the PIA signal Y is proportiona! to 11eq. the
PIA with a lock-in amplifier means exciting the sample w1th a penochc
pendent pump photon flux. The latter can be by a ':ave
switches between a constant flux and zero photons w1th a l-1( As
shown in Refs. [321 and [33] the PIA signal, measured with a lock-m an1phfier Y.
shows the same functional dependence on pas ne._. in Eq. (9.5). For the monomo-
lecular (jt = I) and bimolecular (jt =2) case the influence of r depends on r., the
lifetime of the observed states, as follows:
consl. for r 1 r
y = ex r for > r
(9.6)
Upon varying the l:hopper period between 6 and 9-+ we a increase
in the signal with increasing chopper period

S_mce Y 1:. not hnear tn r '?D

ms r has to be in the order of 100 ms. I 1:-. the only tcmpcmture-dc.:pcn-
factor, which represents a decay rate varying with 1; changes Eq. (9.5) to:
[
kp ] ; [ I
nC<! = l(T) ex l(T)
(9.7)
A satisfactory description for our experimental results is obtained for a nOXJ <n of
the following form:
) ]
_ 1
[ (
-w.) (-w2 . ,.
nC<!(T) = A exp kuT + Bexp kuT + E
(9.8)
Here ku is the Boltzmann's constant, A represents a W1
w are the activation energies for a thermally enhanced decay of the photom-
slates, E is the temperature-independent part of the deC<.Jy factor . and B re-
presents the relative weight of the W:!-activated . .
The exponent 1/p in Eq. (9.2) was found to be 0.65_ for_our sampl es [31 ]. W1th thts
value we attempted to model the experimental curve 111 F1gure by Eq. (9.8). We
obtained 0. 12 and 0.37 eV for the energies W1 and W2. respectively. numbers
mean that the 0. 12 eY process reaches the magnitude of the
decay rate, , al 170 K, while the 0.37 eY process re<iche:> th1s level at 200 K .md
becomes the dominant decay channel above 220 K (see F1g. 9-17). .
The photoinduced absorption and the e_lcctrical c.:haracteristics of the
LPPP show that the optoelectrical propert1es are strongly on car
rier traps in the bandgap. From aromatic ll 1s known that
rities and structural imperfections fonn Jocahzed states L34). LPPP f'lnns
neous and dense films with a interehain distance of about 20 A and ncghgt-
9.5 Excited-swte Spectroscopy 281
ble long range order. We propose that the --.. 0. 1 eV tr:.tp level is a result of local
variations in the electronic band structure due to the influence of neinhborino
b 0
molecules (aggregates or small crystallites). The -0.4 eV level occurs in a much
lower concentration and results from chemical defects in the polymer backbone or
impurities which break the conj ugation of the polymer.
An alternative interpretation for the activated behavior of the photocurrem and
the PIA-decrease with temperature was proposed by Townsend et a/. [35]. They
assigned their experimental to a thern1ally activated interclwin-hopping
mechanism for bipolaron-like charged soliton pairs, the experiments of which
were carried out on Durham trans-polyacctylene.
In electroluminescencc devices (LEDs) ionized tr.tps form space charges, which
govern the charge carrier injection from metal electrodes into the active material
1211. The same states that trap charge carriers may also act as a recombination
center for the non-radiati ve decay of excitons. 1bcrefore, the luminescence effi-
cienc.:y as well ao; charge carrier tr:.msport in LEDs are influenced by traps. Both
factors delenninc the quantum efficiency of LEOs.
The excellent agreement between the TSC and PIA results has two implica-
tions. First, since the TSC method probes the product of mobility and carrier den-
sity, whi le the PIA probes only the c.:arrier density, there seems to be no dominant
influence of temperature on the c.:arrier mobility. This was also found in other con-
jugated polymers like trans-polyacetylene 119. 36). Second, photoconductivity
(observed via the thcnnal release of photocxcited and trapped caniers) and photo-
induced absorption probe the s;une charged enti ty 136, 37j.
2
....-;"

::I

<(
......
u
<i.
L
......
0
A
<i.
0.::
c
0
---+-- '
I 1.5 2 2.5 3 3.5
Energy [eV]
Figure 9-20. Polarunic absurplKHl in m-LPPP :t1 1.9 and 2. 1 cV. as by photoinduced absorp-
lion \:t), charge-im.lu<X.'ll absorption in dcviL-cs (b), and rcdox-rcac-
lion (c). 011/y undcr phlliOCxcilalion which both IIL' IItrtll wul <"IWI"!(l!d 'P<'ci<w is llr!! triplt'l .vig-
11<11 <II I .J ,,y ul.w o/t.w:nttl.
282 9 Solid-state Aspects of Conjugated Scmiconcluc:turs
Concerning the nature of electronic traps for this class of ladder polymers, we
would like to recall the experimental facts. On comparing the results of LPPP to
those of poly(para-phcnylenc vinylcne) (PPV) [38] it must be noted that the ap-
pearance of the maximum cun-cnt at 167 K, for heating rates between 0.06 K/s
and 0.25 K/s, can be attributed to monomolecular kinetics with non-retrapping
traps [26]. In PPV the density of trap states is evaluated on the basis of a multiple
trapping model [38), leading to a trap density which is comparable to the density
of monomer units and very low mobilities of IO....s cm
2
\1
1
s-
1
. These values for
PPV have to be compared to trap densities of 0.0002 and 0.00003 traps per
monomer unit in the LPPP. As a consequence of the low trap densities, high mo-
bility values of 0.1 cm
2
v-
1
s- ' for the LPPPs are obtained [39].
The final remark of thi s section concerns the polaronic transition of m-LPPP
around 1.9 eV, where we can observe P
2
with its vibronic replica P
3
at 2. 1 eV. In
Figure 9-20 we show this polaronic absorption in m-LPPP as detected by photoin-
duced absorption (a), charge-induced absorption in conventional light-emitting de-
vices (b), and chemical redox-reaction (c). Only under photoexcitation, which cre-
ates both neutml and charged species, the triplet signal at 1.3 cY is also observed.
9.6 Electrolumincscence Devices and Models
The basic processes in EL devices are as follows:
(i) charge carriers of opposite sign arc introduced into the active layer;
(ii) positive and negative charge carriers move in the active layer under the ap-
plied voltage i.e. electric field;
(iii) charge carriers of different sign intemct with each other in order to form excited
species. One decay channel of these excited species into the ground states is
dipole allowed, so that a radiative tmns ition under emission of light occurs.
Depending on the free charge carrier concentration (intrinsic or extrinsic) of the
conjugated polymer, this arrangement can be better described as a metal/semicon-
ductor/melal (MSM) or a metaUinsulator/metal (MIM) device [40, 41 ). For ar-
rangements of polymers with a high charge carrier concentr.1tion (n> 10
11
cm-
3
),
which can be due to the chemical synthesis, the prepar.1tion technique, or doping,
band bending can occur, which is chamcteristie for MSM structures [40, 42]. Due
to a recent improvement in their synthetic routes l43j, many c.:unjugated polymers
are nowadays avai lable having a lower defect concentration and hence lower
charge carrier concentr.ltion. On using these polymers in LEOs, rigid band condi-
tions are usually observed, which arc typical for MIM structures 141, 44-461. Ri-
gid band conditions mean that the bands arc not bent at the interface due to space
charge regions (sec below) and the electric field drops continuously across the
polymer layer thickness (sec Fig. 9-2 1 ).
The other way to produce EL devices is based on a pin junction 1471. A pin
j unction with conjugated polymers wa.-; realized by electrochemical doping of the
9.6 Elec:lroluminescem:e Devices and Models
283
-,
L8
fl)t I
t-
Eg

M2
U+
Erl (+) -
..
....
.ff
o--
M1
z.
Po:jvm er
Figure 9-21. EL in PLEDs. VB ... valence band LB cond - .
M,.M2 ... Metal cii!Ctro<.les U ... hias z z I rfi ucung band, V ... polcllltal;
p- . . 2 lilt' ace layer:v 1:: b ndga p+ -
... posnave and neg:uive polarons; .. . Fenni energy. and <f> wori, II ... a p, <uou
polymer in an cell 148J. The working principle and the rfor-
of such a ltght-emmmg-electrochemical cell (LEC) rr be d . bedpe
section 9.6.3. WI cscn m
9.6.1 EL Devices from Conjugate.'<! Polymers
with a High Defect Concentration
A conjugated polymer of a high charge carrier concentration (n > 1 on c - 3) .
two metal electrodes, can be understood as a MSM struct;e 4C;r-
A SCilliCOnductor can he desclibcd ts a mucrial Wl.tll . , . . . r . I.
t 11 . 1 .1 ernu energy, wh1ch
yp.lc.t IS Wlthm energy gap region at any tempcmlure. If a semicon-
?uctor Is brought mto electncal contact with a metal either an oh
1
nc
0
. .
1

mg S honk 1 r a rect1 y-
1 . c y. Is t?nned at the The nat ure of the contact is dcter-
_mned by. t.hc c/J cncrgc1ic tliflcrcncc between the Fermi level
a
1
.nd vacuum level). ol the semiconductor relative to the mclitl (if cf.
ccts me neglected- see below) l47j. c
In a first approximation. coniu"atcd "'llyn
1
1
" w
1
tll
1
1
11
II I
. .. . ' o ' " g c large earner con-
dcscn.bcd as p-typ.c semiconductors whereby holes seem to be
lhc maJonty ch.trge camcrs. Dcpcndmg on the workfunction of the polymer rcla-
284
9 Solid-state Aspects of ConjugtJted
tive to that of the electrode, either a rectifying contact (if cPscmiconducloc><P,nclal) or
a non-rectifying contact (if is formed. .
The rectifying nature is due to a negative space charge zone 10 the
which is created as soon as the polymer and the metal elect rode are electn_catly
connected, because electrons flow from the metal into the sc:mi_conduclO_r until
Fermi level of the two materials is equalized. Hen(."C, a bu1lt-10 Vh;. IS
generated, where V
1
,;= cPscmicon<luctor cP,ncat On an external _ b1as voltage,
the voltage mainly drops over this high resistance regton across the mterface,
not over the bulk of the polymer, so that the corresponding charge depleuon
width at the interface and also the potenti al banier at the interface can be con-
trolled with the applied voltage (rectifying metal-semiconductor contact).
In a tight-emilling MSM structure the two metal electrodes selected such that
the work functions of the electrodes are ncar the edge of the valence band (VB)
and the conducting band (CB) of the semiconductor, respectively. so th?t oppo-
sitely charge catTiers are injected from the opposite electrodes. ohm1c and a
rectifying contact is therefore fom1cd in the MSM (sec Fig. .
The charge canicr depletion width, W, at the rcctllymg contact. wh1ch torms a
Schollky barrier. can be calculated using the following Eq. (99) 1471:
W=
21;11 ( <P - cp"' _ V _ kT)
qNo q lJ
(9.9)
where is the dielectric constant , cP
5
and cP,. the workfunction of the semiconduc-
tor and the metal, No is the charge density in the depletion T i_s the abso-
lute temperature, the elementary charge and V potential at the JUnction.
For a j unction of a conjugated polymer, whtch has an energr gap of
3 eY (around the value of the polyphenylenes) and a free catTter concentratiOn
n> 10' 7 cm-3, with a low workfunction metal (e.g. when cP,.=2.7 eV, the value
melal1
CB
VB
setriconductor I
polymer
vacuum level
Hgurc 9-22. Energy diagmm of a
scmicooduelor/mctal Schouk y barrier
(!J> ... workfunction. Xs ... cleclron affinity,
/
1
, . ionizalion potential, Er.b:lndgup,
melal2 w ... dcplclion width).
9.6 /.ectrolumiuescenc:e Devices tJild Models 285
for Ca) a depletion width below 30 nm is obtained. By applying Eq. (9.9) to cal-
culate the depletion width for simi lar junctions for conjugated polymers with a
low canier concentration, such as pure soluble conjugated polymers, values for W
are obtained which arc far above I 00 nm under opemting conditions. However,
the of the active polymer layer is usually of the same magnitude, so
that W ts extended over the whole active polymer layer. For that reason the MSM
model is not applicable for contacts of a metal wi th a conj ugated polymer with a
low_ intrinsic canier l n the polymers with a low s;harge
earner conccnlr.llton sandw1chcd bet ween t wo metal electrodes behave more like
MIM stmctures (sec foll owing section).
As above, the free charge canier concenlr.ttion, lien. in conjugated
polymers ts mainly dctcnnined by defect-. introduced by the chemical synthesis. It
IS well known 1491 that 11,.
1
r can also he intentionally increased by means of chem-
doping (with transfer atoms, molecules, or salts) resulting in a drastic
tncrcasc in the conductivit y. Unfortunatel y, wi th respect to the application of
doped polymers in LEOs. ul the same time radiative recombination processes arc
strongly quenched due to the prcsem:e of dopants. ln spite of this there have been
several developed based on s lightly doped cnnjugatcd polymers, which are
charactenzcd by low onset voltages but also by low efficiencies 150-53].
9.6.2 EL Devices from Conjugated Polymers
with a Low Defect Concentration
A polymer with a low defect- and tr.1p concentration (n< 10
17
em-\
wh1ch ts arranged between lwo electrodes, can be described as a MIM structure
[45, 47]. In_this anangement rigid band conditions exist within the conj ugated
polymer (F1g. 9-21) m contrast to MSM structures, where the bands arc bent at the
polymer/metal interface (Fig. 9-22). To obtain an optimum device performance the
met:tl electrodes arc selected so that the energetic diflcrencc between the band edges
of the polymer and the work functions of the electrodes are minimal, which in fact is
diflicull to realize, especially for high bandgap polymers t54j. .
Jn a simplified picture, the EL emission process in the MIM structures can be
described in as follows (Fig. 9-2 1):
. When an _field is applied in the forward direction (i.e. high workfunc-
llon contact ts postll ve) positive charge canicrs arc injected into the layer from
the high workfunction contact and electrons arc injected from the tow workfunc-
tion contact. The charge carriers need not be injected into band levels of the con-
jugated polymer but can be directly injected into the polaronic levels, as recent
experimental result s (muinly obtained from light -emitting elcctrochemicul cells}
and theoretical studies conli nn HX. 55, 561. These carriers move as polarons un-
the of the field and meet each other within the active layer.
Patrs of pos111ve and negauve charge carriers can fonn weakly or strongly bound
states depending on the nature of the electronic structure or the active layer.
These bound neutral excited can either be singlet (spin=O) or triplet states
286 9 Solid-stale Aspects of ConjuJ:llted Semicom/ucwr.v
(spin=l) which detennines if the decay of these states into the ground state is
dipole allowed (radiative decay==? emission of light) or dipole forbidden (nom-a-
diative decay==? dissipation as heat). The dipole-allowed radiative recombi-
nation of these excited states finally causes EL emission.
As depicted in Figure 9-21, in an ideal case the applied electric field,, drops
linearly through the polymer layer. This internal electric field can be calculated
from the applied bias voltage, U, by
gale = _u __
ml d
polymer
where dpolymcr is the thickness of the active polymer layer.
(9.10)
However, the effective internal electric field in the device deviates from the
field calculated using Eq. (9. 10) due to the internally built-in field (see above) be-
cause of defect charging in the active layer f55) and interface etfects [57].
1bus it has been shown that thin insulating layers (in the nanometer range) at
the interface mctaVpolymer in a PLED can significantly reduce the onset electric
field necessary for EL [58-63]. This is still not fully understood and has been as-
cribed to band bending at the intertace l64J.
Furthermore, molecules, which are adsorbed on surfaces (especially oxygen
and water) can strongly interact with the polymer, so that chemical reactions al
the interface can occur [57]. Surface states are formed, which can also cause a
band bending at this interface region and therefore affect the internal electric field
[65]. This interface layer appears to hinder the diffusion of gases and metal atoms
further into the polymer and the subsequent chemical reaction of the electrode ma-
terial with the polymer and can therefore be quite important for the operation of
EL devices [66]. TI1e diffusion of oxygen from the electrode into the polymer,
which was observed for ITO devices [67], can also be decreased by introducing a
thin layer of polyaniline [68]. For real systems, the metaVpolymer junction there-
fore can be understood as a MxPolymer structure, where x represents an interta-
cial layer of currently undefined nature.
9.6.3 Electroluminescence from an Electrochemical Cell
One idea to realize a pin junction with conjugated polymers is to create it in situ
by electrochemical doping. By using the conjugated polymer in a solid state elec-
trochemical cell, the production of bipolar light-emilling pin junction devices can
be realized [69, 70).
The working principle of the polymer light-emitting electrochemical cell is
shown in Figure 9-23:
The active layer consists of a polymer having electronic conductive, ionic con-
ductive, and luminescent properties, is blended with an ionic salt [48]. The poly-
mer with the required properties can be realized by a blend of a conjugated and
an ionic conductive polymer [481 or by specially designed polymers [71- 73].
.

51.6 Elec:tmlwnim:sceuce Dvic:es und Models
287
f-
ionic salt. ionic and
electronic conduclive
polymer

F"agure 9-13. diagram of the EL
(4!!I (a) CcJI be' . I . m an cleclrocbemical celt, reproduced from Rei
oorc "PP ymg a voltage (h) d
gr.llion and radiative decay where M Site as ". 11-type, and (c) charge mi-
d h 2 e <!<:troUt::;, Q ... Oxtdu_ed (p-lype doped) . ,.
... re u""" (n-lypc doped) species; * ... clcc:tron-hole pair. species,
This JJ:<>Iymer blend is then arranged between two electrodes eithe I .
sandwich struct (F 9 ')
3
.
8
. r m a P anar 01
, d . . ure g. -- a). Y <tpplymg a voltage, ions in the blend dissoci-
an are transported_ to the electrodes f74J. The vollage therefore docs not lin-
early dr?p over the acllve layer as for MIM structures but drops ac . . .
cuiliulat
1
on h ross an 10n ac-
zone at t e mterlace and not in th b lk f 1
f, tli . . . . . . e u o t te polymer [74). There-
c ect,_ve_charge _camer lflJectiOn occurs at compambly low voltages 175 761
te a h1gh voltage is applied, electrochemical doping. due, to tl;e
. o _t e charge canier on the polymer chain and the ions occurs
m e VIcmuy of the electrodes. An 11- and a [Hype layer arc cr ated .
the electrodes on the opposite sides of the cell (Fig. 9-23b) At cth . at
tween these t I . . - . . . . e m er .tee -
. . _ wo a JUnct ion 1s lormcd. Under the .'tpplied field the
0
_
Sitely charged c_amers_ dnlt to the respective electrodes and meet in the rc
the .electrochemically mduced pin Junction (Fig 9 23c) By the t t. gf
f 1 d - m emc Ion o pos-
'.'ve negatively carriers, excited neutral states are formed
can su sequently decay radiatively. '
The arrangement of the LEC rr
. s o er some advantages compared to the PLED .
'?an MSM or MIM arrangement f4l:!]: s
(1) the_ onset voltage of the LEC is quite low (2-3 eV) in the range of EJe of th
.. active polymer layer; x e
(11) the electrodes torm ohmic contacts to the polymer and hence a h"gh
flo d h. J b h I CUITent
w an a 1g l ng tness can be obtained at low openlling voltages.
9.6.4
Carrier Injection and Charge Transport
_foll_owing section an overview, of scver.1l models describing the ch , .
ner lllJCC{IOll and tr. . I1 r LED . . . argc C.tr-
. cd 1 . . anspo o s b.tsed on polymers and oruanic materials is
on
. .
1
po ynu:r wit a low dclect concentration will be discussed. A de-
senpt1on ol LEOs. based on Jlillymers with a ddcd , .. ,n ,.,..
288
9 Solid-sltJie Aspecis of Conjugaied Semiconducwrs
found in e.g. Ref. (77]. Depending on the nature of the polymer/metal
and on the magnitude of the barrier height at the interface, several mechamsms
arc responsible for the charge injection into the polymer.
9.6.4.1 Thermal Emission
The kinetic energy of charge carriers in a solid increases with
ture and therefore the probability that a charge carrier passes a g1ven bar-
rier also increases. The thermally induced current flow of the charge earners from
a metal contact into a polymer film can be derived from the equation,
which describes the temperature-induced emission of hot charge earners from a
metal surface
. A'T' _'l!:
}til = e u
(9. 11)
where cJ> is the potent ial batTier. q is the charge of the carrier. T the tcm-
per.rture, and A* the material-tlt:pcndcnt effective constant.
It considers that the emitted carriers arc pulled away lmm the surface by an
electric field. On desctibing a metaUpolymer tmnsition thi s the
back flow of the injected charge catTiers into the contact has to be taken mto ac-
count L47]. In MPM structures a temperature of
rent versus voltage (IN) curves, which is characteristic for thcm_uomc
often occurs for very low appl ied fields an&or for MP contacts wllh a bamcr
height. l n MIP structures the potential barrier heights fr?m. the to msulator
are usually very high and the contribution of the thermtontc emtsston process to
the current flow in the device is negligible.
For exan1ple, the /IV chamcteristics of devices based on the aluminum
complex Alq3, where Ag-Mg or ln-Mg are used the can be
by thermionic emission of electrons over the bamer hetght at the electron tnJCC-
tion contact/Alq3 [78].
9.6.4.2 Field-Induced Injection
Under high applied electric fields, electrons c;m surmount a potential ba_rrier even
at very low temper..1tures. This process is based on field-induced tunn_elmg of the
charge canicrs across potential .. The f?r the tunnehng depends
strongly on the height and the w1dth of the . .
The field-induced tunneling across a potenttal bamcr can be descnbcd usmg
the Fowler-Nordhei m equation 1791:
. N T 2 ( qE ) 2 b.tflo
}FN =-- -- e
cJJ
8
akT
(9. 12)
9.6 E/ectmlumitwsccflce Deices ami Moclds
289
where is !he electric field and '' is a par..1meter which depends on the shape of
the burner, T the absolute tempcmturc, A* is a material parameter, and cl>u the po-
tential barlicr height.
When the lidd-induced tunneling currents arc analyred in a log (//
2
)
versus liE plot, a straight line should be obtained. lhe height of the potential bar-
rier can be derived from the slope of this stmight line using Eq. (9. 12).
In MIP structures large barTier hei ghts exist at the interface of mctaUinsulator.
!herefore, the charge carrier injection can be described by field-induced tunnel-
mg. The current versus electric field characteristics of MP structures can 1i fitted
to a straight line at high appli ed fiel ds in a Fowler-Nordheim plot, when the bar-
rier heights at the interfaces are large compared to kT as it has been first de-
scribed by Parker 180] which is characteristic for field-induced tunneling.
However, the values for the current, which are obtained using the Fowler-Nord-
heim with the actual device par..1metcrs, are several orders of magnitude
181, 821 h1ghcr than the values for the measured cutTen! in real devices.
Besides injection mechani sms, in order to describe the IN characteristics of
LEOs, the charge transport mechanisms in the bulk have to be taken into account.
electrical in the solid slate is determined by the product of the
camer C01Kentmt1on and the carrier mobility. In conjugated polymers both enti ties
are material dependent and, i. e., arc different for electrons and holes. Electrons or
on a conjugated polymer lead to a relaxation of the sunounding lat-
tice, lormmg so-called polarons which can be positive or negative. Therefore, the
conducti vity, a. is the sum of both the conductivity or posi ti ve and negative
polarons (P ):
(1 = l'llp ''I' + l'lll" ''I" (9. 13)
where 11 and Jl arc the concentmtion and mobilit y of the respective species p+ and
p- and e denote the elementary charge. In contr..1st to C<uTicr injection, which de-

IIXAJ

IUU
g
10
c
v;
c
.,
"C
c
Ul

:::>
u
UUI
IIJW<I"""'I""'w
t::! t ur)h:abn..:-c.J tuuh!IIC)'
(.1) unhafOMh.:aJ Nn111..n
(41 htth !arias
(5) hw;.kt Nuu.ll<tiU
Ill
Vuhagc (V)
IUU
Yagun: 9-24. tunneling: /IV cb:rldcristics uf urg;nlk LEOs for \lllriuus c;uTicr
and b;uricr hciht' (l.. lt
1
.=1t. = IO"" 1/> = =02 2 11 - JO ''
11
- )()" " - '> - 02
(I 0 ... I' N .. p - .. ,., - ..
J ... IU . 1/>P=O.:!. <1., = 0.-l; 4 .. . p
1
,=1t. = 10-<>.
fowler Nordheim Iii <1., =0.2

(donc<l curve). Rcprullucctl rrum Ref. IHJI.
2YO 9 Solid-state Aspects of Conjugated Semiconductors
pends on the properties of the polymer/electrode interfaces, carrier transport is a
bulk property of the polymer layer.
Peyghambarian et al. modeled the dependence of the current flow and the effi-
ciency of devices on various device par.tmeters as the (balance of the) charge car-
rier mobility and the barrier height at the interfaces for devices, where the current
tlow is detem1ined by Fowler-Nordheim tunneling (see Fig. 9-24) [83]. In this
case. the current flow through the LEOs is injection limited and dominated by
Fowler-Nordheim tunneling and the following characteristics are observed f831:
ngurc Y-24 shows that the onset of the current is fairly imlcpcm.lelll of the mobil-
ity of the charge carriers but strongly depends on the barrier height at the interface
(see Eq. (9. 12)); in particular the potential barrier at the charge injection contact of
the charge carriers with the higher mobility determines the current flow through the
device. The increase in the current flow above the onset is much steeper for highly
mobile charge carriers than for caniers of low mobility. In the case that the mobilities
of electrons and holes arc strongly diflerent, the type of carrier with the higher mo-
bility determines the steepness of the cun-cnt tlow above the onset.
With regard to high EL quantum efficiency, it is especially important that the
barrier heights at both interfaces arc well balanced (sec Fig. 9-25) since each
charge carrier has to meet its counter charge inside the device in order to fom1 a
neutral excited species (see Section 9.6.5). Figure 9-25 shows that for devices
with a low baiTicr height the maximum efficiency occurs at significantly lower
operating voltages than for devices with higher ba1Tier height!';. The mobility does
not influence the EL efficiency as strong as the barrier height but the overall light
output for devices based on low mobility materials is expected to be considerably
lower due to the lower current flow through these materials compared to devices
with highly mobile carriers.
Any discrepancy between the measured and the calculated values for the cur-
rent in the model for field-induced tunneling can be discussed by (i) a back now
.....
...
c::
0.8 .,
u
!0:::
....
0.1>
.,
E
::>
c:
0.4
"'
::>
r::r
.,
. ::::
Ill
<5
.,
IX 0
0 10 2tl .10 40
Volaagc(V)
Figure 9-25. Field-induced aunncling: rcl:tlivc lJUanlum efticiencics o( organic LEOs calculatet.l for
various carrier mobililics and twrricr heights (I ... Jt
1
,= Jt., = Hr''. <1
1
1
,= <1
1
,.=0.2; 2 ... JI,,= 10--t' . Jt., = IU-11.
<1>,, =4'.,=0.2; 3 ... Jt,, =Jt., = 10 ". <1>,, =0.2, <J>H=0.4; 4 ... Jip=Jt,.= 10-
6
w,. = <J>,.=0.4). Rcpro<.lu<:eO from
Rd. (X:II.
9.6 /ccllvluminesn:llce and Models
291
the charge which were injected into the active layer, back to

f8_1 ], (11) the poor adhesion of the dcctrodes, or (iii) oxida-
tion at the mterfaces f83]. On taking this tirst effect into account and also
cons1denng a flow due to thermionic emission (j,,), the ovemll cunent
flow through (JIJ) ol ITO/MEH-PPV/AI devices, which was assumed to be domi-
nated by holes, was well described by Davids eta/. l8 1, 84]:

for charge carrier injection are the height of the poten-
tial bamet at the mterlace polymer/hole injection contact and the hole mobilit of
y
Accor?ing_ to that model, the net cwTent flow in the device therefore can be in-
creased blayer using a hole-transport layer, which possess higher
hole n!_obll .. ty_ than the :u.:t1vc polymer layer and which t.:hanges the hei ght of the
potenual barner at the mtcrface tr.tnsport layer/hole contact [HI].
have been other models presented over the last few years, which
descnbe t.:harge transport 111 LEOs based on soluble PPVs (H51 and in Alq3 (82f.
Blom et a/. l8S] stated that the /IV characteristics in LEOs based on lTO/di-
alkoxy-PPVs/Ca arc determined by the bulk conductivity and not by the h
. . c argc
earner lllJeCtlon, wluch is attributed to the low barrier hdght s at the interlace
and They that the current !low in so call ed hole-only
dev1ces ltW], the work function of electrodes arc close to the valence band
of the P?lymer, wtth 11D and Au a!'; the electrodes, depends quadmtically on the
Ill l?glllogV plot and can be described with following equation. which
IS charactenst1c for a space-charge-limited current (SCL) flow (s. Fig. 9-26):
(9.15)
where F.if.r is permittivity of the polymer, J.lp the hole mobility, and d the thick-
ness of the act1ve polymer layer {85).
In contrast to the hole-only devices, the elec:mm-only devices (where Ca is
used a!'; the bottom top electrode), a current flow is observed, which is sev-
eral orders _of magmtude lower than the current now in the hole-only devices
Fig. _9-26 and Fig. 9-27). This is in agreement with results from time-
ex.penments performed by Antoniadcs et a/. 1861. who ascribe the lower
mob1hty ot compared to holes as elli!t:tivc tr.tpping of elect rons in PPV .
In the. /IV plot _ot the device.<; two different regimes are observed
(see 9-27): tn the first rcg1me the current is trJp limited and shows an ohmic
behavwr, so that the current im:rca..;es lincmly with the voltage according to:
. v
J = lJ"ult, -
c/
(9. 16) '
292
9 Solid-state Aspects of Conjugated SemicOiuh.tcwrs
10
10'
1
NE
<
-,
Vbias (V)
Figure 9-26 Experimental ancJ calculatetl (solilllines) IN charociCriSiics of
. : . . M:S ,_ The current now in all devices is dc...crbcld by SLC w1t 1 a o c mo 1 -
vices and with a d ielectric w nMant of 3. in:.ct shows the_ chemical structure of
11
Y Jl,,- c . CH " - C H. ) Rcproducetl frorn Rei. (K5(.
the PPV investigatcol 1n that stully (I{ r = ,, " 2- 10 . I
1o2
10
1
10
10"'

10'
2
"'
E

10'
3
-,
10-4
10'
5
10-6
10'
7
0.1
100
Vbias (V)
Fi
"
27
o nl (''Ois) and theoretical (solill line) IN characteristics of. a Ca!PPV/Ca clec-
li:Ure y Cl((lCfllllC "' u ' otJ ed ' nP an Cltpo-
. ' . th" k L., or 310 nm. The thcorcllcal curve IS taiO c
tron-only deviCe With a c ness, n -
0
.
1
h
1
0
n Tt = 1500
distribution with a trap density
the hole SLC accord-

K and an equilibrium clcclron dcns1ty nu= . em -
to Eq. (9.13). Reproduced from Rd. lK5J.
he J1 is the electron mobility and no is the equilibrium electron density.
a"critical voltage, after all traps the PPY are with
filled limit) [87]the current flow greatly mcreases. In_ second c_ur
rent now is space charge limited and it can be quahtattvcly descnbcd assumlllg
an exponential distribution of ll<tps [85):
9.6 Electroluminelcellce Devices cmd Models 293
{9. 17}
where Nc is the effective density of states in the conduction band, N, the total
density of tr.1ps, T, the trap distribution parameter, and r=
For higher barrier heights at the interface (c.P
8
>0.2 eV) [85}the overall current
flow in the device injection-limited current tlow is strOngly determined by the in-
jection, especially at low applied voltages (see Fig. 9-27).
One has to consider that in Eqs. (9. 15)-(9. 17) the mobility J1 occurs as a pa-
ran"leter. As it wi ll be pointed out below, 11 shows a dependence on
the applied electric field typi cal for the type of organic material and for its intrin-
sic charge u-anspon mechanisms. For the hole mobility, J1
1
,. Blom et a/. obtained a
similar J dependency H91 from their device modeling for
dialkoxy PPV as it is often observed for organic semiconductors (see below).
The same equ<ttions as for the dectron-only devices can be applied to descri be
the IN characteristics for organic LEOs based on Alq3 (in single and mullihctero
layer devices) IK21.
For the same the single layer devices based on Alq3. Pcyghambarian eta/. [83j
found that the IN characteristics can also be described by an SCL current tlow in
the low cutTent regime. However, in the low current regi me the IN char.1cteristics
can be qualitatively modeled by the Fowler-Nordheim equation (even if, quantita-
tively, the real device cutTent diiTers from the calculated by seven orders of mag-
nitude) [83] and thennionic emission 1781.
In contrast to the solid slate concepts presented above, loannidis et ul. [90] de-
scribe the organic materials as amorphous molecules. This model is suitable to lit
W char.1cterislics of LEOs based on Alq3 and PPVs with a low mobility (}.1
taW cm
2
y - l s-
1
) . Essentially, they found that the current flow through these mate-
rials can be auributed to the increase in the mobility (sec Eq. (9. 18)) with the applied
voltage, which has been observed to r many conjugated polymers [91 ]. In the case that
the mobility exponentially increases with the electric tield, the current flow reads:
(9.18)
Such a log J1 J dependency is observed fur many organic semiconductors
[92- 98]. For other polrmers with an extraordinarily high mobility, such as m-
LPPP (j.t::::; 10- J cm
2
v- s-
1
) (99). which is at least one order of magnitude higher
than the highest mobility observed in PPV and its derivatives (3H, 100, 10 I], only
a weak dependence Jt() is observed (991.
Over.1ll, an unambiguous deM:ription of the current tlow to a certain injection
and tr.mspon model can not be obtained, as demonstrated by the example of
LEOs based on AllJ3. Si mi lar to the organic molecule Alq3 and also the conju-
gated oligomer hexaphenyl. it has been observed that many models presented
above seem to describe the /IV chamctetistics corn:ctly 11021.
The reason for that ambiguity is the fact that the IN characteristics are fitted
with equations (see above) consisting of various fit parameters in a rather re-
stricted voltage range, so that many different curves can model the IN curves
within a moderate variance range.
In summary, a fundamental model for the current flow in organic LED does
not exist but there are several different models which seem to describe the IN
characteristics of the various different organic LEOs reasonably well.
The presented results show that the properties and perfommncc of the various
organic OLEOs are quite different from each other. This is due to the different
types of the active organic layer, the electrodes, the device architecture, and the
preparation conditions:
The most important parameters characteri zing the active layer are the position
of the energetic levels (relative to those of the electrodes). the nature of the inter-
faces, the energy gap and its morphology, its mobil ity (for electrons and hol es),
the impurity concentration, and the free charge canier concentration. Whereas, the
first two pammeters determine the charge injection from the electrodes into the
polymer, the Iauer three inlluencc the charge transport of the injected charge car-
riers in the organic layer. Additionally, it has to be taken into account that many
of the above listed par..uneters arc dependent on each other. For example, the mo-
bility is strongly influenced by the impurity concentration due to tmpping of
charge carriers, and the impurity concentration also strongly influences the free
charge canier concentr..1tion of the organic material.
The metallic electrode materials are char..1cterized by their Fem1i levels. The
position of the Fem1i level relative to the energetic levels of the organic layer de-
tennines the potential barrier for charge carrier injection. The workfunction of
most metal electrodes relative to vacuum arc tabulated [103]. However, this nom-
inal value will usually strongly differ from the effective workfunction in the de-
vice due to interactions of the metallic- with the organic material, which can be of
physical or chemical nature 1104--106). Therefore, to calculate the potential banicr
height at the interface, the effective work function of the metal and the effective
ionization potential and electron affinity of the organic material at the interface
have to be measured [55, I 07j.
As stated above, the overall perfonnance of the LED is strongly influenced by
the nature of the interface layer and also by its extension. Due to diffusion pro-
cesses the electrode material can be extended far into the active layer.
By changing the device architecture e.g. by building multi- instead of single
layer structures the physical and chemical processes in the LED can be greatly al-
tered. For that reason the fundamental properties of the LED. such as threshold
voltage, efficiency, emission color, brightness, and lifetime can be optimized in
multilayer structures (43j.
The set-up or an organic LED at first sight appc<1n; to be very simple. How-
ever, in actuality the preparation of LEOs is r..1ther sophisticated and requires care-
ful and clean processing where many steps have to be performed in a dust- and
oxygen-free environment. The performance of the LEOs strongly depends on the
prepamtion conditions and this therefore complicates any comparisons made of
different groups on the same LEOs. This must be taken into account as well <IS
9.6 Electrolumiuesc:enc:e Devices and Models
295
the different properties of tl .
devices, when comparing and the set-up of the
9.6.5
Charge Recombination and Efliciency
1be_ efficient fonnation of singlet excitons from the . . . .
camers, are injected via the metallic contact _postllve and negattve
and negattve polarons (p+ and PI . th I s and transported as posttJve
nation of these singlet excitons e the efficient radiative recombi-
ficien_t clectroluminescence aa: cructal processes for the function of ef-
Dnven by the electric field p md a ro h
fonn neutral slates wh,cl . ' h. . PP ac each other. Upon meetin they

1
are en er smglet- or tri 1 o
charges forming the exciton tre bound I th . p et In both C<l!ies the
binding cner<Jy, which is to be a etr charged partner by a
gated polymers II 08 ). Directly after th . f ot volt for conju-
combinarion of a ')Qsir,vc . ,1. ' a tle . ,. c nl a snglct .cxc.ton by the
t " u g,t IVC po "\fUll ( . . "b
singlet cxcitons created b char e .. . . . . ' . .' IS le to disti ngui sh
rectly formed by ll rot.ll1 ' eXCiton, which w:s di-
. lc p 1oto ununesccncc q .
1
ld ,,, .
one lmponant parameter in the elect ol . . . uan um yle 'Pf IS
. . 1 ununescence )rocess A
1

1
.
empmcal expression for the electro! . . rc alive y s1mple
ummescence quantum effi
mtroduccd by Tsuto;ui et a/. I I 09 J; ICicncy has been
1
1<1> = Y
1
1rcJ>f (9. 19)
where Y is a double chame in e ( f: .
of a singlet
'{;-quantifies of the for-

gives a good qualitative picture of lhe rk" . _sunple, this expression
y is detennincd by the
_of an llle pa-

ue IS unity. Y= I is obtained a bal ccd and Its maximum val-
positive carriers = number r : d an . c lllJCCllon (number of injected
. o lllJecte negallve eamcrs) . . h" cd .
s1on layer of the device Th . . IS ac rev mto the emis-
cters, such as the 'lr a number of_ different param-
and the existence of space chul!e zon/' 0 P.P . g detmppmg mechanisms,
unity if p and p- are co fi d- . s. ne can consider that 1/r will approach
(see below). n me to each other by an imelligent device an:hitecrurc
According to Eq. (9.17) a hi h ho
1
. , -
tive material is required in io tum of the ac-
mcthods exist yielding the absolute h . rg_h Sever..tl
Slate or solution Howevc. p otol.umrncsccnce quantum ettrctency in solid
determined that the measured absolute values are
live efficiency values under devi an . _1encc c:m diller from the ellec-
quenching, and polanmic Ire quenching, temperature
Th d , . . .. . o c eels must , consrdcrcd I 541
c cslgn of the orgat11c LEOs should be . . . d - .
injection factor and the probability .fo . I so that the double ch;rrge
r smg et excuon formation is ncar to unirv
296 9 Solid-state Aspects of Conjugated Semiconductor!.
The theory of charge recombination in organic LEOs has been elaborated recently
[110-113].
Bassler e1 al. [110-1131 treated charge recombination in organic LEOs in terms
of chemical kinetics. The probability of recombination depends on the ratio of re-
combination rate ynP.nJY (where y represents a bimolecular rate constant) and the
transition time (1
1
r=dl J) of the charge carriers through the device.
The recombination rate Pr-x which is defined as the number of generated exci-
tons in 111 divided by the number of generated excitons in 11 1 plus the number of
minority carriers passing through the device in 111, for an unbalanced LED (where
j(x) j"(x) j
11
(x) and J.i,, J1
11
) is given by the following equation:
p = = I + .J!.E_
(
E ) -
1
y p d
(9.20}
where p is the density of positive charge carriers.
Obviously, the recombination rate increases with decreasing lrclllsition time of
the minority charge c.miers.
Jn the case that the current tlow of the majority charge carriers is space charge
limited, the recombination mte and hence the EL quantum efficiency is deter-
mined by the minority current (consider that every charge carrier which does not
meet a counter-charge before reaching the elecmx.le is lost for the r..tdiati ve recom-
bination process). The recombination etriciency is detem1ined by the minority cur-
rent in case the majority current is space charge li mited (II OJ. If both type of car-
riers are SCL each charge should meet a counter-charge and hence the efficiency
would approach unity [II 0].
The efficiency of LEOs can be improved if the transition time and hence the
mobility of the charge carriers is decreased, because then the steady state carrier
concentration of both type of charges within the device is increased. This can be
realized by blending the active layer with an insulating polyml!r ( 1141 or by other
additives. However, one has to bear in mind that, by decreasing the mobility of
the carriers, the overall current flow through the device is also decreased, so that
higher bias voltages are necessary to obtain the same brightness level as for the
undiluted polymer LED.
Jn bilayer LEOs the field distribution within the device can be modified and
the transport of the carriers can be controlled so that, in principle, higher efficien-
cies can be achieved. On considering the influence of the field modilication, one
has Lo bear in mind that the overall field drop over the whole device is given by
the etfective voltage divided by the device thickness. If therefore a hole-blocking
layer (electron trclllsp<>rting layer) is introduced to a hole-dominated device, then
the electron injection and hence the efticiency of the device can be improved due
to the electric field enhancement at the interface to the electron-injection contact,
but only at expense of the field drop at the interface to the hole injection contact
This disadv<llltage can be pa111y overcome, if thrcl! l<tyer- instead of two layer de-
vices are used, so that ohmic contacts arc formed at the interfaces (1121.
9
7
Highly Excited Conjugated Films
10-
1
20
. 100A
.. ?

10-3 .
200A ...
i
..
JOOA
.. ?
c 10 ?
400A
.

10-5
..
600A
... ?
::J

-
0
<(
-

...
10-
7
c
..

....
::J
10-9
0
1o-t t
D 100AA1q
10-tJ
0.01 0.1 1
10
Voltage (V)
297
Figure 9-211. Trap-limited .:urn:ot llow: lits (solid lines) to the c .
ttcs of two typical dc\'io.:o.:s with .
1
'l()() . . (")(). . xpcruncntal (symbols) IN
sho lW '
0 111
.mu " mn tluo.:k pon 1 .
ws for diiTcrc nt Alul-thio.:,
1
. , R rod . s aycr :mu Allj3. lnM:t
.,. " o:p Ul'Cu lmm Ref. fll:!l.
The thickness of lhc or<;mic h , . . .
1
. . . . . . . .
ficiency. FotTI!St t!l a/. 182J rc t S(.) 'lor ;m optimum cr.
and a hole tmnspon layer, a .on applying Alq3
of 370 lllll, whereas the ?bserved for an
thckn.ess ol the hole transpol1 layer (sec Fig. 9-28) Th d Y . . o.f the
for thmner Alq3 Ia ers (in h . , . . . . e ecreasc m the effictency
[115] . . . .b Y . . t e range of the lhffuslon length of holes in Alq3)
out attn utcd mcrc.tscd fr..tctioo of holes re<tching the electrodes w. th
m wt1ve recombmahon whereas h k -
1
-
into Alq3 arc trJppcd in bulk
0
j 'Alo; cr hlms, injected
that the probability for non-radiative mterlace zone so
A characteristic dependence of the cflicicnc . -
layer has also been observed f . I I Y on lhe thickness ot the acti ve
attributed to reflection of the t
LEOs. This etlect has been

in characteristic interference ma" t,g. .a d e. m_ctal electrodes resulting
th
. " n.t an muuma depcndmg on th h' k .
e acti ve layer and its rctiactivc index [116). c t tc ness ot
9.7
Highly Excited Conjugated Films
It has been shown by various groups that lilm . . d I . . .
conductors show a decrcsc j
11
PL . _:U
1

of COnJugated scmi-
c:- . emlsston me Width (sec Fil' . 9-2Q) fir
high excitation dens ities of approximately 1 kW/cm
2
As the precise physical ori-
gin was unclear, this phenomenon was called spectral narrowi ng. Since the first
reports on spectral narrowing in neat films of conjugated polymers [ 117- 12 1 J and
the realization of optically pumped microcavities [122, 123), the lasing properties
of this class of materials have received considerable attention. TI1e lasing proper-
tics of conj ugated polymers in solution are comparable or even exceeding r 124,
I 25] those of organic laser dyes indicating excellent intrinsic emissive properties.
By careful selection of the method of chemical synthesis and film processing, it is
possible to achieve negligible concentration quenching for pure films of conj u-
gated polymers as compared to organic dyes. Values of up to 62% for the photo-
luminescence quantum yields (PLQY) in neal tilms are reported [ 126). In addi-
tion, high values of the cross-section for stimulated emission l0-
1
s cm
2
) can
also be observed in neat conjugated polymer films [ 118]. One of the most effi-
cient way:. to couple the process of emission between the chromophores in a film
is the introducti on of a waveguide geometry. We have recently used m-LPPP
waveguides I I 21 J to investigate the emission propc11ics of this material under
high excitation densities. The waveguides, which con:-.ist of spin-cast m-LPPP
films, were exci ted through the glass substmte, wluch minimizes the photodegra-
dation since the hi ghly exci ted polymer layer is situated between the substrate and
the residual polymer, which itself is n01 excited. The length of the excited area
can be varied by an adjul>Lable slir. 1l1c cxpcrimemal set-up is depicted in Figure
9-30. The waveguides studied consisted of three dielectric layers (subslr..ue, poly-
mer and cladding = surrounding air) forming asymmetric waveguides. If the refrac-
ti ve index of the polymer (n
1
,) is higher than the refracti ve index of the substrate
(n.,) and the cladding layer (n,.
1
), thl!n the waveguide can support a limitl!d number
of guided modes, with two different polarizations: transverse electric modes (TE),
which arc polarit.cd pamllcl to the polymer/substrate interface, :.md transverse
magnetic modes (rM), which arc polarized perpendicular to the waveguide plane.
Below the cut-off, the wave propagation in the waveguide is genemlly described
by leaky waves representing guided modes beyond the cut-off. The cut-off thick-
ness de for both the lowest TM and TE anodes of an asymmetric waveguide (TEo,
TM
0
) is given by [ 127]:
dc-.TM., =
2n
). arctan{
-
{ (
2
). nt,
arctan -
112 - /(2
p s
(9.21)
(9.22)
where ). is the wavelength of the mode. Leaky arc expected to be guided
with a successive energy loss into the surrounding media. For a film thickness be-
9.7 Highly Ex<.ited Co11jugated Films
299
e
0 1.0
c:
0.8
:::J
.i 0.6
0.4
u;
0 .2
0.0
..J
(a)

f
; 1
--- E" 51JJ
I

,. !

(
..
,,_
"
''/"tiW.-.;
.'(,...

a.. 460 480 500 520 540
Wavelength [nm]
....... 489 30
E 488 l!(b)
.s 487
25
c: \ 2oE
2486 0 - - .s
(/) 485 \ - - 15
_e. 484 0 10
I!ICII 483 5 LL.
'o

0 50 100 150 200
Pump pulse energy (JJJ]
9-
29
(a) EnnS. \1<111 of IIJ U'PP al tliiTcn:m ex . . . .
lllaXJ mum ;mt.l peak (lOsllion uf lhc m-LPPP ... CllCfl:JCS. (b) Full wi<llh Ul hair
CllliSs1on versus cxcJIOJhun laser pulse energy.
low the cut-o!T, the propag:ltion losses for I,. k . . . . . . . . .
dccreusino lilm thickness lx>th lo . TE. ' TcMa y llllXks lllc.:lease dramatteally wnh
o . I anu modes 11 27 J
Spectral has been observed in neat films ol: conu atcd I
120. 1-31. where the samples well.' excil Ll hy . . . r po
m the polymer film provides the necessarv V:tadvegmdmg
spectral . . J
0
e- xc1 e area so
The . narrow_mg to amphficd spomancous emission (ASE) can be b .
. of a d1stmct directionality, as it would be ex ted
0

IS explmned by scattering in the >I mer liln . . for
detectable perpendicular to t p< y - 1. Thus, narrowmg IS even
low cut-ofT n r . polymer film [Jl7j. For films with a thickness be-
' o me narrowmg could be detected due to . dd.t" .
losses, so ahe could nut be obtained. a I IOnal propagation
The problem ol the divergent output can be o . . r . . .
is applied, where the film thickness of lla
Thas waveguide structure consist" ol a gl . .. b . y s below cut-of! .
fil
. . ass su strate (11 = 1 52) and . LPPP
I m With a thickness in the ranoe or I 00 200 ' . a m-
suremcnts on m-LPPP I I ""J o d nm .. on waveguide mca-
-o we etcmune an ellect
1
.
"err::::: 1.58 for TE-modcs and " ...... I 55 r TM ' tve re mctlve mdex of
ciT..... or -moues for th 1 h.
ncsscs at a wavelength at 490 nm. Accordinu to 8 9 2 121 . ose po ymer t lck-
a cut-off thickness of about 220 nm for the TJ:: - . . . ) and 9.22J. we calculate
respectivel y. '-<
1
mode and 390 nm lor TM
0
-mode,
la.ser beam a strong spectral
c ueh.:ctetl. The recorded spectra
300 9 Solid-state of Conjugated Semiconductors
are depicted in Figure 9-29a. The emission peak shifts with increasing pump
power to shorter wavelengths, bealuse ASE occurs faster than the spectral relaxa-
tion [1 23). The degree of polarization above the threshold is high as it is
expected for ASE. A plot of the peak shift and the line width dependence on the
pump pulse energy is shown in Figure 9-29 b. For excitation above a threshold of
3 kW/cm
2
, a highly directed, completely linear polarized output can be detected.
However, the final line width of the emission depends on the film prepamtion,
especially on the solvent which has also been observed for other conjugated poly-
mers [1 17, 123]. This effect can be attributed to a solvent-dependent fil m mor-
phology which leads to different broadening mechanisms due to the ordering ef-
fects of the molecules during the film preparation.
The observation of spectral narrowing of m-LPPP films below the cut-off thick-
ness implies that m-LPPP has a high gain, because the propagation losses due to
leaky modes are higher compared to waveguides supporting guided modes. To
quantify the net-gain that can be obtained in such a waveguide structure, we mea-
sured the net-gain g of a m-LPPP/glass waveguide by varying the excitation
length and detecting the light intensity along the z-axis of the excited waveguide
area. If the net-gain, g, experienced by the light, is g=g'-a, where g' is the gain
coefficient and a the propagation loss coellicient, then the detected light intensity
I (z. A.) is [ 129]:
I(z, A.) = c(A.)eii(A)l . (9.23)
The net-gain for a of 490 nm was about 40 em- for an excitation
power density of I I kW/cm , and up to 50 em- for an excitation power density
of 22 kW/cm
2
For higher excitation power densities the net-gain decreased to a
value of about 30 em- , probably due to heating and photodcgradation. Surpris-
ingly, there was no significant difference in the threshold for spectrdl narrowing in
a waveguide structure above cut-off (fused sil icalm-LPPP) and a waveguide struc-
ture below cut-off (glass/m-LPPP) where additional propagation losses should rc
suit in a decrease of the net-gain. This can only be explained if the influence of
ncullal density cylindrical
filler lens
exci1ation

X y

fiber
10 spcclrom elcr
adjustable
slil
... 9-30. Gcumcuy fur lhc gain-length determination expcnmenl in waveguides.
9. 7 Higltly Excited Conjugated Films
301

AE>C;459nm
1523cm

:J
<0
....._
>.
;t::
Aoc=457nm
C/)
c
2
Aoc=455nm c
c
co
E
AE>c=453nm co
a:
AE>c:=452nm
1605cm.
1573crn'1
spontaneous
13t 4cm'' "
Raman spectrum
1J!9cm.
800 1000 1200 1400 1600
Ramanshi ft [em
1
]
9-31. Raman spcclm in m-LPPP wave uides ohla l . . .
J)lctcd tn the llgurc. The bottom spcctru h g
11 00
al d,flcrcm laser wavelengths as cJc-.
from Ref. 11471. . m s OWlo !he rc,uJt of a cunvcmiunnl cw Raman experiment -
the propagation losses, due to leaky modes can be n I d
loss mechanisms. ' t:g cctc compared to other
The losses in a planar waveguide can be . . . . .
radiation losses due to of the to surface scaueri ng losses.
sorption losses. Surface scatterin . . wavegu structure, and residual ab-
elcctric til m waveguides {1 10j the loss mechanism in di-
. - n e assume t at thas as al 1 bl
waveguides, which is supported b the observ . . so app aca. e polymer
films also perpendicular to the I . d allan of lr nc n;mowmg m polymer
prepared from u.c scauerin.g {117] .. For
an the geometry must be co .. d y . a so . osscs due to amperfecuons
m-LPPP layers showed a macroscopic of
on the solvent used. Considerin th I e fi lm _homogencaty depending
field just below cut-off are smatYer actt.al prop:_rgallon losses of the optical
ky modes description {1 3 1] theaJ ey arc predicted by a conventional lea-
we assume tint the losse . d ,
1
k
are compared to other loss mechanisn;s which i _s . Ut: to ea y modes
scrvauon of a simibr threshold v;!luc for wavc;uilics abov .s. by ob-
o c anu ow cuf-nlf
302
9 Solid-state Aspects of Conjugated Semicv11ductors
The line narrowing due to ASE is, however, not the only effect observed in
polymer waveguides under high excitation densities, as_ in Figure 9-31. We
detected narrow emission lines with a wavelength pos1t1on d1rectly related to the
exciting laser wavelength. In a Raman-acti ve incident
with a frequency Wt. inter.tcts with a Raman-acltve vtbrauon w,, resultmg 111 a
Stokes mode with a frequency of w
5
= wc-w,. If the incident laser beam fre-
quency wL is chosen to be resonant to an absorption then this i_s referred to
as the resonant Raman effect. The spontaneous Raman s1gnal can be mcreased by
3-4 orders of magnitude by using dielectric waveguides (waveguide spec-
troscopy) [132]. Also sti mulated Raman scattering benefits from the opltcal
finement and the large interaction length, so large signal levels can be obtatncd
even for monolayers by using waveguide-coherent anti-Stokes Raman scattering
{133} or waveguide-stimulated Raman spectroscopy l 134J. .
Due to the small dimensions of a waveguide, large elcctnc field strengths can
be obtained over large distances. In combination with a medi um, which exhibits_ a
large non-linear Ratnan cross-section x
01
, ab_<we a threshold Stok_cs mode wtll
experience a gain, g, due to stimulated emtsston along the tntcr.lctton length d.
The Stokes intensity, 1
5
, can be written as 11351:
Is = ls(O) ff d
(9.24)
where
(9.25;
and 1, is the pump intensity. The excitation wavelength the ASE
has been chosen at 445 nm. If this is changed to the maxtmum of absorptton at
453 nm, then the typical spectml narrowing within the inhomogeneous broadeneu
0-1 tmnsition band can be observed at low excitation energies. Above a threshok
of about 400 kW/cm
2
additional strong Stokes modes can be observed accompa
nying or even completely overwhelming the ASE l_"he study of the intensit)
dependence of the Stokes modes shows an exponential as
SRS until a saturation regime is reached. The output charactensucs ot the mvesu-
gated waveguides docs not change in terms of polarization, ruld
beam divergence. Whereas the threshold for SRS was the for
different m-LPPP films, the result ing spectra strongly dtiTered m tenus of mten-
sity mtios and can be observed as Stokes modes at diflcrent investigated positions
for a sample.
We assume that this results from morphology effects due to the film prepara-
tion. A set of spectra for a varied excitation wavelength is depicted in Figure 9-
31. The narrow lines at 1280cm-
1
, 1523cm-
1
, and 1562cm-
1
are the Stokl.'"S
modes partly accompanied by the broader ASE peak. A. spontaneous Raman spec-
trum of planarized LPPP is depicted at the bottom of Ftgure 9-31.. The two peaks
near 1600 cm-
1
can be attributed to the aromatic ring C- C strctchmg modes. 1be
peaks located at 1300 em
1
can be au.ributcd to inter-ring stretching 11361. A com-
References 303
of the spontaneous Raman spectrum with the SRS Jines shows that these
hnes correspond_
1
to the spontaneous Raman modes. The slight deviation
of about em can be .atln_buted to the insufficient resolution and accuracy of
our detection sys!cm. wluch ts optimized for visible PL experiments. SRS only
can be_ 111 m-LPPP waveguides excited by a line focus but neither in a
geometry nor in solution. The effect could be observed in the range
of exctlahon between 450 nm up to 465 nm. For excitation wavelengths below
450 nm no SRS _was detl!ctablc, probably due to self-absorption effects. The
strong self-absorption also prevents anti-Stokes modes.
9.8 Conclusions
In w_c have treated seveml aspecLo; of conjugated semiconductors, with
the cmpl_Jasts on the structurc-propCit y relationships. Structure in this group
:>f matcnals obv10usly (I) chemical structure of the building blocks, (2) the
way these clements are linked together, (3) the number of the elements li nked and
the 111m w_hich intluences the state of order achieved in the organ-
IC All factors 111flucnce the optical- and charge transport properties of
Both in order to achieve a basic understanding of the
of these matenals but also for a successful development of dcvice-cngin-
x nng, a clear and weii developed picture of their chemistry is essential.
\cknowledgeutellts
We to thank the coJleagues in the group at Graz, especially Barbara
Herz, Chns11an Zenz, Egbert Zojer, Emil List, Markus Wuchse. Christian Hochfil-
zcr, Fmnz-Pctcr Wenzl, Leonhard Holzer. Klaus Pctritsch, Gerald Meinhardt Ger-
ald _Kr.10zclbinder, Markus Moser, S_tcfan Edcr. Roland Reset, and Faaidch Mcgh-
1adt.. Furthermore, we would also hke tu acknowledge exciting discussions with
Gughclmo Giulio Cerullo, Mauro Nisoli, Sandro De Silvestri, Valy Var-
dcny, Joseph Slunar, and Alan Hecger. It was a pleasure to work with our chcmis-
uy especially with Franz Stelt-er, Walter Fischer, Berthold Winkler,
Ullnch Scher!, Yves Geetts. and Klaus MUllen.
References
I. such an: us..d a.' a primer layer fur the galvanic
uon m m th1s ca.'iC lhc long tcm1 of the coujugatC<.I poly-
n.:r 1s no 1-.uc.
2. J. S. Miller. llt/1: Mat. l'J'JJ . 5. 671.
304
9 Solid-state of Conjugated Semiconductors
A. D. Schliiter in Handbook of Clmduc/inll Polymers (Eds.: T. Skotheim, R. L. J. R.
3
' Reynolds), Marcel Dekker New York
1997
p.
209
Skoth R L Elscnbaumcr J R Rey-
4. U Scherf in Hw1dbook of Conduc1i11g Polymers (Eds.: T e1m,
Ids) Marcel Dekker New YOlk 1997, p. 363.
9
.,.. " 33
no . .. F M ghdad' G Leisins l Athouel G. Froyer, Adv. MUI. 1 :n, "
5. S. Tru;ch, C. Brandstaucr, . e
and Refs. therein. . . 1997 82 4177
6. A. Niko, C. Brandstattcr, S. Tasch._ G. lesn_g: J. APt'' Pflys. P. . U Rohr Y. Geerts.
7. S. Tasch, C. Hochlilzer, E. J. W. l.ist,997G. Quante, . J tmg, .
u. Scherf, K. Miillen, Pltys. Rev. B
1
. . Schf ch u Rohr Y Geerts,
8. S. Tru;ch, E. J. W. List, 0 . Ekstrom, W. Graupncr71 2G8.83leismg, P. hng, . .
U Scherf K. Miillen, ApJJI. Phys. ulf. 1997. . "''-... J R
. . ' p. I (Eds T Skotheim, R L
9. M J Winokur in H(llldbook of Ctmduclmg o ymers
R .. Ill!) Marcel Dekker New Y()ri( 19'n, p. 707. Pol
eyno . . T R I H C Knachel W. W. Adams, E. P. Socci., B. l . Farmer. y-
10. K. N. Baker, A. V. . c:.c I ,
mer 1993, 34, 1571. dad' G Le'. N Unzog K Reichmann Thill Solid Films 1997,
11 . R. Rescl, N. Koch, F. Mesh . 1smg,
305, 2;2. J. A. Majcwsl.i. P. Vugl . G. Phys. Rtv. B 1995,51, 661!.
12. Y. N. Ganstcin, Php. Hel. Leu_. _1994, 73, 2504; S_VIIIil . 61\:ll..:ditzky, B.
:!: G. Grem, G. L..cditl.ky, B. Ulhich, G. Adv. Mul. 1992 4, 6, . reu .
Ullrich, G. Leising, Sylllh. Mt!l.

3
1!
3
. PI H<'v B 191!4 lY 6761.

1wi. 12. 4!!9. ,
11. G. Lan1.ani e/ a/., this book. . . .
4
66
9
18. G. Meinhardt, A. Horvath. G.
Scientific, Si11ga
19. D. Moses, A. J. Hccger, in Nelctxalim 111 ro ymers ..
pore . 'Kf . M A Abkowitz M. Stolka, Pol)?ner Preprinls 1992, 31, 414. and
20. B.R. Hs1ch, H. AniOn 1s,
Refs. . . . . A , 1 Pil "' Lett. 1994. 65. 2030.
2 1. H. Antomads, M. A. B. R. IHse;,l I: .n H Friend, A. B. Holmes, J. Phys.: Coml.
22. K. Pichler, D. A. Halhday, D. C. Brad ey, . u 1, -
Maller 1993, 5, 7 155. 1995 69 41 9
S Edcr M. Maui . G. l..clSing, U. Scherf, Synt/L Mel. :
23. W. Gmupner, . n G Le' . J Hube( U Scherf C/..,,istry of Mwenals 1995, 7, 2.
24. G. Grcm, c. P..JarKre. J. F K u. Sch.:rr. Adv. Mat. 1995, 7, 292.
25. J. Grimme, M. yensc .. .
1h GA. R.t-1. Bubc. Phys. Rev. 1967, 155,
. M. Onoda D. H. Park. K. Yoshino, J. Phys. C: Soltd Swte Pltys. 198'J, I, 113.
27. G . l..ediuk G. Leising, J. Phys. D: ApJ1l. Phys. 1994. 27, 2185.
28
i Varden:.J. Orenstein. G. L Baker, J. de PllysitJue. Colloque C3 1983, 44. 325.
P. O'Connor, J. Tauc, Pilys. Nev. B G Leising U Scherf K. Miillcn, Mol.
3 1. w. Gr.1upncr, M. Mauri, J. merw '
Cryst. Liq. Crysl. 1994, . I. y Sun K Manoha( A. G. MacDiarmid, A. J.
32. J. M. Leng. R. P. McCall. . . romac
Pllyr Rev B 1993, 4H, 15119. 46 3008
C. S. Luzzati, R. Tubino, A. llorghesi. Pily.. He. B 1992. I .
EA. Si linsh, Pllys. Stal. Sui. (n) l 'nO, 40 1112
p D Town,cnd R. ll. Friend. Phys. Hev. ,..o,., .
35. M $ + .. D 'Muses A. J. liceger. Solid Cmnmwl. 19H6, 5Y, :143. 1990 65 100
36
L R T M. )cJju, P. D. TownSClld, S. Etemad, G. L Baker, Pltys. Rev. L<'ll.
37
H. il<,urcr, H. Hev:_ B 1995:2,25117.
G. Lcditzky, PIID
in Hwdbouk of
40. J. Kanieki, Polymcne crncon uc . . y. rk 1986
Cuuducti11g Polymer.; (Ed.: T.
K R. ll. Frknd, P. L Bums.

41. J. H. Burroughcs, D. C. lk.Jdley. A. K. rown, '
A. B. Holmes, Nature 1990, 347, 539.
References 305
42. M. H. Pilkuhn, W. Schairer. Lighl mi11i11g in of Stmiccmdl.wors (Serit:l; Ed.:
T. S. Mos..._ Volume Ed.: C. Hilsum) Vol. 4, Nonh Hulland, Elsevier 1993.
43. G. Leising, S. Tasch. W. Graupncr. of Elcctrolumine:.ccnce in ParJphenyll!ne-Type
Conjugated Polymers and Oligomers, in Ha11dbook of Couductiug Polymers (Eds.: T. SkOihcim.
R. J. Reynolds). Marcel Dekker, New Yorl. I'J97.
44. A. R. Brown, D.C. Br.Jdlcy, J. H. R. H. Friend, N. C. Grc.:nham, P.l. Bum, A. B.
Holmes. A .Kmft. Appl. Phys. Leu. 1992, 61. 2793: R.H. Friend, Polymer LED's in Htmd/xxJk of
Conducting Polymers, 2nd <.'tin (&Is.: T. Sk01heim, R. Elsenbaumcr. J. Reynolds). Dekker, New
York 1996.
45. D. Br.IUn, A. J. Heeger. Atpl. Pl.ys. Leu. 1991, 5H, 19l!2.
46. V. Ohmori. M. Uchida. K. Muro, K. YO!>hino, Jul' J. of Appl. Phys. 1991,10, L 1941.
47. M. S. Sze, PIJ.I'Yics tJf :Semimuductar Deices, New York 19!!1; B. l. Shanna
(Ed) S<Jumky IJurriu Juuclimu uud Tlldr Applicalions, Plenum Pres.-;,
New Yorl. 19114.
4l!. Q. Pci, A. J. H<."t!!_!cr, Scit'ucr 1995, 26Y, 101!6.
49. A. J. Hc.:gcr. S. Kivclsun. J. R. Schricfn. W. l'. Su. H<'l: of Mod. l'Jil!l, 60, 71! 1.
50. D. B. Romero. M. Scha<lcr. L Zuppiroli. B. B. Fr.mcois, A
1
>pl. Phys. Leu. 19'J5. 67. lbS'J.
51. W. 0 . ln!!:lllas, Syulh. Mtl. l9'J7, X7. 5.
52. F. Huang, A. G. MacDi:mnid, B. R. Hsieh, Appl. Pl1y.f. L<u. l'J'J7. 71, 2415.
53. W. Briiuing, M. Meier. M. l lcrnld, S. Karg, M. Cll<'m. 19911, 227, 243.
54. G. Lei, mg. S. 'la-.:h, W. Gr..mpncr, Fundame111als of in Paraphenylcne-Type
Conjugated Polymc.-,. and OlignnlCr.>, in Hwullmok of OmcluniuK Pt>/.l'lll<' f'S (Ed.: T. SkOIIlCim).
Marcel Dcl.ker, New York I'J97.
55. I. H. Camphcll. D.l. Smith. Ferr.1ris, App/. Pl.ys. L<u. 1995, 66, 3030.
56. E. M. Conwell, Symh. Mtl. 19%. HJ. 102.
57. P. Dannctun, M. Liigdlund. C. Frcdriksson. R. La7.Z<Ironi. C. FautJUO.:t, S. St:1fs1rtim. C. W. Sp:mg-
lcr. J.L. W. R. Salaneck, Cl.em. P/n.r. 1994, /00, 6765.
58. I. D. Parker, H. H. Kim, App/. Phy.r. Leu. I W4, 64, 1774.
59. H. H. Kim. T. M. Miller. E. H. Wcto.:rwid, Y. O. Kim, E. w. Kwock, M. D. Morris, M. Cerullo, J.
Ligh1wave Techuo/. 19'J4, 12. ::!107.
60. R. N. Marks. F. Biscarini, T. Virgili, M. Muccini . R. Z:uuboni. C. Phil. Trtm.r. H. Soc.
Ltmd A (submillcd).
61. Y.-E. Kim, H. P..Jrl:, J.-J. Koo, App/. Phys. LC'/1. 1996. 69, 2:145.
62. H. Tang. F. li. J. Shinar, Appl. P/1.1'.r. Leu. i 9'n. 71, 2560.
63. R. Payrlcitner, DiJJ/oma TU Gr..v. 1999.
64. LS. Hung. C. W. T;mg. M. G. M;L.,.III , ApJI/. PII,\W. Leu. 1997, 70. 152.
65. E. Ellcdgui, H. R;u.afitrimo, Y. Gao. B. R. Hsieh, A11f1f. Plt.(s. u'/1. i'J95, 67, 2705 .
66. P. Brum,., J. N. JolmS.'iOJI, M. Uiglund, W. R. Sai:Ulccl., Symh. Me1. 1995, 74, l7'J.
67. J. S. Scon. J. H. KauiTmann. P. J. Brock. R. DiPcuu. J. Salo.:m, J. A. Goitia, J. Appl. Pllys. 1996,
79,2745.
68. S. Karg. J. S. Sc011. J. R. Salem. M. S1111h. Mel. (in
t/). Q. Pci. F. Klavcucr, U. S. Pal<'lll OR 261! 763. 1994.
70. Q. Pei, G. Yu, C. Zang. Y. Yang. A.J. Sl'il'nn.- l9'J5, 269, 101i6.
71. Y. Yang, Q. Pci . J. App/. Plly.r. 1997, HI, 3294.
72. D.-11. Hwang. B.S. Chuah. X.-C. Li . S. T. Kim, S. C. Mor.uti, A. B. Holmes. J. C. de Mello, R. H.
Friend. Mucromu/. Symp. 1997, 125, Ill.
73. L. 1-loll.cr, B. Winkler. F. P. S. l iL-..:h. L. Dai. A. W. ll. Mau. (i . Symfl. Met. (iu
print).
74. D. L. Smith. J. Appl. Pflys. 19'J7, XI. :!ll(>'J.
75. J. C. de Mclin, N. Tessler. S.C. Gr:dtam, lUi. Friend, P111s. Ht. B 19911. 57, 12 951.
76. M. Samp1etm, R. F.P. L. Hnlt.cr, S. Tasch: G. (unpublished).
n. S. M. Meier, W. Riess. J. Appl. 1997. H2, 195 1.
78. M. Matsumura. T. Ak:.i. M. Saitn. '[ Kimum. J. Appl. 1'/ty.r. I')'J(I. 711. :!(>4.
79. R. IJ. Fowler. L. N\>rdlh:im. l'mc. H. Sc>t'. Lmulmt Stt: A l 'J21!, II'), 173.
!!0. I. D. Parker, J. Appl. l'ilys. 199-l. 75, 1657.
Ill. P.S. Davids, Sh. M. Kogart, I. D. Parl;cr, D. L. Smith, AJ'JI/. Pllys. Leu. 1996, 69. 2270.
306 9 Solid-state of Conjugured Semiconductors
82. P. E. Burrows, S. R. Forrcsl. Appl. Phys. Lm. 1994, 64, 2285.
83. Y. Kawabe, G. E. Jabbour, S. E. Shaheen. B. Kippclen, N. Pey&IJ:unbarian, Appl. Phys. utt.
1997, 71, 1290.
84. B. K. Crone, 1. H. Campbell, P. S. Davids, D. L. Smith, Appl. Pllys. u/1. 1998, 73,3 162.
85. P. W. M. Blom, M.J. M. de Jong, J. J. Vlcggaar, Appl. Phys. Lett. 1996, 6H, 3308.
86. H. Antoniadis, M. A. Abkowitz, B. R. Hsieh, AtlfJI. Pllys. Leu. 1994, 65. 2030.
87. M. A. Lambert, P. Mark. Current l11jectiot1 i11 Svlid.f, Academic Pre.o;s. New York 1970.
88. P. W. M. Blom, M. J. M. de JOng, M. G. van Munster Phys. Rev. B 1997, 55, 656.
89. P.W.M. Blom, M. C. J. M. Visscnbcrg, Phys. Re1( Lett. 1998,80.3819.
90. A. loannidis, E. ForsylllC, Y. Gao, M. W. Wu, E.M. CoowcJI, AppL Pllys. Lett. 1998, 72, 3038.
91. U. Wolf, H. Bassler, M. Deussen. S. Heun, U. Lemmer, R. F. Mahrt, Z. Pllys. Cllem. 1994, IH4,
233.
92. D. Gi ll, J. Appl. Pl1ys. 1972, 43, 5033.
93. E. Mullcr-Horsche, D. Haarer, H. Scher, Phys. Rev. B 1989, 35, 1273.
94. P.M. Dor.;cnbger, L. Puutmcicr, H. J. Chem. Phys. 1991, 94, 5447.
95. M. Abkowitz. M. Stolka. Leu. 1988, 58, 239.
96. P. M. Dorscnbcrgcr, J. Appl. Phys. 1990, 6H. 5682.
97. D. M. P..ti, J. F. Yanus, M. Stolka. D. Rcnfer, W. W. Limburg, Pili/. Mug. B l '}gJ, 4H, 505.
98. II. Meyer, D. Haarcr, I I. Naannann, H. H. HUrhokl, Pllys. B 1995, 52, 2587
99. D. l lcrtcl, U. Bassler, U. Scherf (in print).
I 00. S. Hcun, R. F. Maim, A. Greiner, U. Lemmer, . U;L..,ler, D.A. Halliday, D. C. P. L
Bums, A. B. Holmes, J. Phys. Cmulet1.retl Muller 1993, 5, 247.
101. E. Lcbcdcv. T. Dittrich, V. Pctrova-Knch, S. Karg, W. Driitting, Appl. Phy.r. Leu. 1997, /, 2686.
102. M. Wuchse, A. Pogantsch, S. Tasch. G. Leising (unpublished).
103. H. B. Michaclsou, J. Appl. Pllys. 1977, 1.'1, 4729.
104. W. R. Salancck, J. L. Br&.las, Adv. Mut. 1996, H, 41!.
105. N. Koch, L.-M. Yu, J.-L. Guyaux, Y. Morciaux, G. Leising, J.-J. Pireaux, G. Dcmoustier.
Res. Svc. Sym(J. Proc. 1998, 4HH, 509.
I 06. N. Koch, Li.-M. Yu, V. P...lfCnlc, R. Laz:zarooi. R. J. Johnson, G. Leising, J. J. Pireaux, J. L. Bre-
das, Adv. Mut. 1998, 10 (in pnnt).
107. K. Seki, U.O. Karlson, R. Engelhardt, E.-E. Koch, W. SchmidL, C/Jem. Plty:r. 191!4, 91, 458.
108. J. L. Bredas, J. Cornil, A. J. Hccger, Adv. Mut. 1996. H. 447.
109. 1: Ts ulsui, S. Saito, llllrinsicully Cmuluctit111 Polymers: An Emerging Tedmology (Ed.: M. Al-
di:.si), NATO AS/ Series: Appl. Sciet1ces 1993, 246, 123.
11 0. U. Albrecht, H. Bassler, Ch11m. Pltys. LC'II. 1995, 199, 207.
Ill. H. Bassler, Pllys. Bull. 1997.
112. D. V. Khr.muchenkov, V. l Arkhipov. H. Bas.slcr, J. Atpl. Pflys. 1997, HI, 6954.
11 3. Y.-Jt Tak, H. Bassler, J. Appl. Phys. 1997, HI. 6963.
114. A. R. Brown, J. H. Burroughes. N. Grecnham, R. H. Friend, D. C. Bradlo.:y, P. L Bum, A. Krafl,
A. B. Holmes. Appl. Pflys. Leu. 1992, 6/, 2793.
115. C. W. Tang. S.A. VanSlyke, AfJIII. P/Jys. Leu. 1987, 51. 9 13.
116. A. J. Heeger invited talk at Lhe tntemutimwl Cm!{creuce uf Symlletic Metals, Mompcllier, 1998.
117. F. Hide, M. A. Diaz.-Garcia, B. J. Schwartz. M. R Q. Pci , A. J. Hcegcr, Science
1996, 273, 1822.
11 8. S. V. Frolov, W. Gcllcnnann, M. O.wki, K. YOlohino. Z. V. Vanlcny. Plly.v. Nev. Leu. 1997, 78,
729.
119. G. H. Gclinck. J. W. Warman, M. Remmers. D. NellCr, P/Jys. uu. 1997, 265. 320.
120. ll. J. Brouwer, V. V. Km!>niknv, A. Hilbcrcr, G. HadLJiuannou, Mat. 1996, X. 925.
121. C. Zcnz., W. S. Tasch, G. Leising, K. Mullen, U. Scherf, Aptl. Plrys. Leu. 1997, 71,
2566 and Rck therein.
122. N. Tessler, G. J. Denton, R.H. Friend, Nature 1996, JH2, 695.
123. M. A. Diaz-Garciu, F. Hide, B. J. Schwanz. M. It Q. Pt:i, A. J. Hccgcr, Syntll. Met
1997, H4, 445.
124. D. Moses, Appl. Plrys. Lett. 1992, 60, 3215.
125. W. lloiLCr, A. Penzkofa-, S. f-1. Gong, A. B1cycr, D. C. Ur.tdlcy, Ad1( Mat. 1996, H, 974.
126. M. K. Andcr.;son, G. Yu, A.J. Hccgcr, Syutll. Met. 1991, '<5. 1275.
Rcft! t!1/et'.\' 307
127. D. 111 'nuory of Dielr(tric I. Academic New York 1974.
128. J. Stunn. S. Tascll. A. Niko, G. Leising, E. Tuussacrc, J. Zyss, T.C. Kowalc-Lyk, K. D. Singer,
U. ScllCrf. J. Huber, Tl1in Sol. FifuLv 1997, 298, IJ8.
129. K. L. Shaldce, R. E. Nahory, R. F. Lehcny, J. of Lmnie.>c. 1973, 7, 2ll4.
130. R. G. Optics, Springer, Berlin 1995.
131. R. E. Smith, S. N. Houde-Waller, Opt. Lett. 1995, 20, 1133.
132. J. E Rahuh, J. D. Swalen, Spt(/m.>eotY <1 Swfaas. In Atll'llnus iu Sp('<"tW.f<"Ofl)', Wiley, 0
1
i-
chcstcr 1988.
133. G. I. Stegemann, R. F011enberry, C. R. W. M. Hetherington Ill, N. E.
van Wyck, J. E. Sipc. Op1. Lt-11. 1983. 8, 2\15.
134. J. S. Kangcr. T. W. Tucker. C. Otto, J. Greeve, Opt. uu. 1996, 2/, 671.
135. J. S. Kangcr, C. Ouo, J. Grccvc, 0111. Lrtt. 1995. 20, 2231.
136. L. Cuff, M. Kcncst. Synth. Met. 1995, 69, 683.
137. K.D. Aichholzer. Pftl) 'ntc.ri.<, 1lJ Gr..IZ, Au,tria 1994.
138. E. Zojc r, M. Knupfer, R. Rcscl, E Mcghdadi, G. Leising, J. Fink, Phys. Re11. B 1997, 56.
10138.
139. A. Niko, E Mcghdaoi, C. Amhrosch D(axl. P. Vogl, G. LciJ>ing, Syuth. Met. 1996, 76, 177.
140. K. Pclritsch, Diplomn Tltc.n.v, TU Groll, Austria 1996.
14 1. G. Cerullo, S. Stagira, M. NiMJii. S. De Silvo.tri, G. Lanl4lni, G. Kr.mzclbindcr, W.
G. Lcbmg, P/J.n . Rc- B 1998, 57, 12l!06.
142. W. Gr..10pncr. T. Just, K. PctritJ>ch, S. Tasch, G. Leising, M. Graupna-, A. Hcmlcuer. Soc. of
PlaM. &n .. Tt:cll. Papa.> XLIII, 1997. 1449.
143. M. Muscr, S. Tas.:h, G. Leising. Syutft. Mt/ . 1997 '14. 6.5 I.
144. W. Cr01upncr. S. EdcJ", K. Pctrit,ch, G. Lci,ing. U. Scherf. S.wult. Mn 1991, M , 507.
145. W. Graupncr, E Mcghdadi, G. Leising. G. Lanzani, M. Nisoli, S. De SilvcsLri. W. f-ischer. F.
Stcb.cr, Pity.\ . Rcv. B 1997. 5(1, 1012!!.
146. T. G. P. R. Hammond, J. Am. Clrem. Soc 1914, 96, 656!!.
147. C. Zenz. W. Gr.wpncr, S. l'a.'iCh, G. Leising, K. lskr.J, J. T. Ncgcr, J. cif Aftl. Plns.
1998,84, 5445. .
14!!. R. Menon. C. O. Yuon, D. MOM:,, A.J. Hccger, p. 27 in 1/mul/xxJk <1 ColldUI'titl/1 Polymc-rs
(EdJo.: T. Sk01heim. R.L. Elscnbaumcr. J.R. Reynolds), Marcel Dekka-. New Yo1i;, 1997.
149. G. Leising, Pftys. Rcr. B 1988, .f<J. 10313.
150. R. S. l}{lhlman, A. J. Epstein, p. 85 in flwullx>ok of Cmulutting Polymers (l:Us.: T. Sko1hcim.
R. L. Elscnbaumcr, J.R. Reynolds), Marcel Dckka-, New York 1997.
151. Y. Yang, Q. Pci, A. J. Ho.:cgcr, J. Afltl. Plly.<. 1996, 79, 934.
152. S. 1lts,h. A. Ni ko. G. Lei,ing, U. Scherf, Af11>1. Pl1ys. Leu. 1996, 6H, 1090.
10 Lasing tn Conjugated Polymers
Uli Lemmer, Andreas Haugeneder, Christian Kallinger,
and Jochcn Feldmann
10.1 Introduction
The enormous progress in the field of electroluminescent conjugated polymers has
led to performances of organic light-emining devices (LEOs) that are comparable
and in some aspects superior to thl!ir inorganic counte.rparts I 1). Quantum efficien-
cies in excess of 5% have been demonstr..tted l21 and show that a high fraction of
the injected carriers in a polymeric electrolumincscence (EL) device form elec-
tronic excitations which recombine radiatively.
Most of the optical and electronic properties of conjugated polymers can be un-
derstood within a model that regards these materials as armys of chromophores
that are formed by fully conjugated segments of the polymer backbone [3, 4 ).
Thesl! segment-; comprise only a small number (n I 0) of fundamental repeat
units. The optical properties of conjugated arc very similar to those of
organic molccuks with a n-clcctron system of finite size. Many of such molecules
arc highly luminescent in solution and arc successfully applied as emitters in dye
lasers for more than 30 years (5).
The combination of the two above mentioned properties, namely high EL-
yields and the strong similarities to laser dye molecules, make conjugated poly-
mers promising candidates for a solid state organic injection laser. However, it
was not until 1992 that conjugated polymers were used as an active laser material
in liquid solution L61 and 1996 that optically induced gain-narrowing processes in
a solid conjugated polymer were demonstrated l7). This is particularly worthwhile
mentioning since optically pumped solid state organic dye lasers had been rea-
lized long before in the form of dye molecules doped into different matrices [g-
Il]. Even in organic molecular crystals lasing was demonstrated more than 25
years ago [12]. These two classes of materials, however, have significant draw-
backs as far as applications are concemcd. While the doped matrices do not offer
any prospect for electrical injection (due to the absence of etlicicnt charge trJns-
port), organic molecular crystals in gener..tl suffer from problems and the
difficulties in preparing devices. Conjugated polymers as well as evapomted small
organic molecules may be a route to avoid these problems in the ncar future.
Both classes of materials can be deposited as thin films on a large variety of sub-
strates and both exhibit charge carrier transport. In this chapter we focus on conju-
gated polymers. Much of the underlying physics, however, is the same for solid
thin Jihns of small evaporated organic molecules [ 13- 15 j .
310
/0 Lasing i11 Conjugated Polymers
We will review some of the experiments in the field of optical
(i.e. time-resolved spectroscopy) that have the nature of
tations in conjugated polymers. In particular, we Will be able to lasmg
in solid state conjugated polymers is not as str..tightforward as the sumlanty to la-
ser dyes might suggest. The second part of the review presents a summary an? a
brief analysis of the tremendous progress that has. been ma?e over the lew
years in the field of optically pumped lasing and gam narrowmg processes m con-
jugated polymers.
10.2 Stimulated Emission in Organic Materials
A key ingredient for any laser is a sufficiently high efTcctive emission
cross-section in the excited state. Figure I 0- 1 presents a companson of the
tronic structure of laser dye molecules and conjugated polymers. In the of a
dye molecule (sec Fig. 10-1 a) laser action depends ma_inly on three d1fferent
electronic states S
0
, S., and T
1
TI1e most important optical transitiOn connects the
So electronic ground state and the first excited singlet S 1 _Due to the
coupling of the electronic system to the motiOn, sublevels ot the
two involved electronic levels have to be cons1dered. Add1Uonal spcct.r.tl
ing of the transitions is caused by the rotational of freedom
geneous broadening mechanisms. Thus, a quas1-contmuum _of _'S
Optical pumping of dye lasers is usually via pumpmg .'nto lymg
vibronic levels of the s ,-state. After relaxation Into the lowest lymg Vlbromc level
of the s,-manifold, the excitat ions can undergo a mdiative transition_ into higher
lying vibronic levels of the electronic This can happen m a sponta-
neous way giving rise to fluorescence or m a stimulated manner when another
photon of the specific wavelength interacts with the molecule. In terms of laser
physics the situation described here corresponds to _a where _the
lasing transi tion connects two levels that are not d1rectly mvolved m the optical
pumping process. _
Sti mulated emission is quantified by the (wavelength dependent) exc1ted state
asc In the case that no other processes are important, stimulated
emission leads directly to amplification of light. In a material with a volume den-
sity N.,_Ac of excited S
1
-states this amplification can be described by
lw
1
= 1;
0
Ne>.c L)
( 10.1)
where /;, and foul are the intensity of the incoming and the outgoing beam,
tively, and Lis the length of the light path in the sample. The term g
gain coefficient of the material. The wavelength dependence of
detennined by the spectral dependence a,..,(A) of the cross-section_ tor stunulated
emission. It is in most cases very similar to the PL-spcctrum and g1ven by
I 0.2 Slimulated Emi.uitm in Organic Mwcrials
311
Fq:_urc 10-1. En.:rgy >chcm.: of tlu: relevant clet:lronic kvels lh;Jt arc in
an u.yc molecule in soluliun in :1 conjugaJcd polymer (b). In bolh systems
of a phOion mduccs :1 tr.mslllOn from lhc smslct ground state S,
1
10 :1 cxc11ed sl:Uc within
the S,-manilild. Aflcr vibrunic n:la).aJinn. a nxl-shiftcd cmis.\iun can be obs.:rved. TI1is tr.m,ition cau
ocrur a as wdl a> in :1 ulilltncr. A lJhOioinduet:d may occur as
pCO<:c'scs .'" bolh 'YSicm' (PIA) due lu the pnpulaliun nf lhe triplet slate T
1
A pair of up-
poMcly lGP) .. -.m 1-..: in the eunjugatcd pulymer due to of the
TI!is C:lll lead hi i!dditiun:!l phutuinJuccd ilhSOI]ltion h;md, tlmt Cllllll><:le with the >timul:ucd
CUUSS!Oll.
(10.2)
where f(J..) is the normalized spectral distribution of the photoluminescence, 11 is
the refractive index, c0 is the vacuum light speed and r is the radiative lifetime of
the involved optkal transition. The cross-section for stimulated emission in conju-
polymers can be from this relation. With a typical radiative life-
lime of 1.5 ns I 16] and a wavelength of 500 nm, values in the range of w-t
6
cm
2
are calculated. Recent mea<>uremems confinn this estimate (17, 18].
Gain narrowing, i.e. changes in the emission spectrum of a photocxcited mate-
rial due to gain by stimulmcd emission, occurs even in the absence of a resonator
when the condition g I is fullilled for light that propagates inside Lhe sam-
exponential term in Eq. ( 10. 1) leads to a prelercntial ampl itication of
hght wuh the wavelength having the maximum gain g (A). The linewidth of the
emission decreases with an increasing density of excitations Ncxc
. Even in a dye molecule other can occur that compete with
stunulated emiSSIOn. So absoq)tion from the s,-slate to levels al higher energies
attenuates rather than amplities the incoming light. Extinction can also be due to
?ther like a residual absorption and scattering losses. Further compet-
mg absorption processes of excited molecules can arise from those molecules that
i!1tcrsystem crossing and populate the triplet state (see Fig. 10- 1 ). The ab-
sorptiOn from the T1-state to higher lying triplet states is particularly import<tnl for
continuous wave operation of dye lasers since population in tile T
1
-level may ac-
cumulate due to the long liiCtime of the triplet state. Due to these competing pro-
312 10 Lasing in Conjugated Polymers
cesses a more correct expression for the net gain coefficient in a solution of ex-
cited dye molecules can be written as:
8nca = Ncxc Gs;:. - Nexc GuiJs, t - Nr Or
(10.3}
Here Oub . t is the cross-section for an absorption from the S,-levcl to lying
states. Nr is the density of triplet excitations and or is the corrcspondmg cross-
section for absorption into higher lying triplet levels. Since the first two terms on
the right hand side both depend linearly on the density Ncxc of excited S,-states
an effective stimulated emission cross-section o,c.cn= Osc-<Tabs.t can be de.fined. A
quantitati ve treatment of the triplet absorption is more complicated since the den-
sity of molecules in the Tt-slate has to be known.
In conjugated polymers all the mechanisms discussed for dye molecules occur.
ln addition, processes due to charge tmnsfer and charge transport have to be con-
side::red in these materials. Photoexcited S
1
-states can not only decay into the
ground state or undef'.,;o intcr..ystcm cwssing T
1
-stah: .. As an additional
process one has to consider the creation of a patr ol two charged
si-pa.rticlcs that are located on different conjugated segments. In Fagurc I 0-1 b
is schematically indicated by the formation of a geminate pair (GP) from the pn-
mary excited state S
1
Although there is still some scicntilic controversy abou_t !he
nature and the formation mechanism of this precursor state for photoconduCtiVIty,
there is ample evidence that these excitations give rise to strong photoinduced ab-
sorption bands ll9-22}. To explore the possibility of lasing in conjugated poly-
mers it is mandatory to understand the dynamics of the different excitations de-
picted in Figure 10-lb and their respective quantum efticiencies. Some of the key
experiments will be discussed in the next few pamgraphs.
A suitable method for a detail ed investigation of stimulated emission and com-
peti ng exci ted state absorption processes is the technique of transient absorption
spectroscopy. Figure 10-2 shows a scheme of this technique. A strong femtose-
cond laser pulse (pump) is focused onto the sample_ A second ultrashort
pulse (probe) then interrogates the transmission changes due to
tions created by the pump pulse. The signal is rc..'Corded as a funcllon of tu1_1e de-
lay between the two pulse.<;. Therefore the dynamics of excited state absorption as
Whitelight-Probe
Figure IIJ-2. Experimental setup for pump and probe measurements. Two femtosecond puls.:s arc_ f()-
cuscd onto the same spot of th.: san1ple. 1lle pump pulse-induced .:hanges llTffu of the nomtahzcd
uf the probe pul:.e are measured as a function of the time delay between the two pulo;cs.
10.2 Stimulated Emission in Orga11ic Materials
313
well as the magnitude of stimulated emission can be monitored. The signal mea-
sured on a sample with thickness d is approximately
ll.T
70
= - ll.a d .
( 10.4)
Here To is the unperturbed transmission of the sample and ll.T is the transmission
change. !he absorption change ll.a is positive when photoinduced absorption is
the mechanisn_1. It is negative when stimulated emission (gain) or
bleachmg gtve the most unportam contributions. The Iauer process describes de-
of ground-state population and is not considered here since optical
gam lfl organtc molecules typically occurs for photon energies below the onset of
linear absorption.
The fi rst observation or stinutlatl!d emission in solid slate-conjugated polymer
was prc..o;cntcd by Yan ,,, a/. for poly(p-phenylcncvinylcnc) (PPV) J23J. The sil!n
of the tran:.utis:-.iun change:-. a11d lhc stm11g s imihuity uf its spccu-al sha()l! with tlle
fluorcscetll:e spectrum of PPV indicated stimulaJcd emission due to excitations
photogenerated by the pump pulse. From the absolute amount of stimul ated emis-
sion the authors concludetl that only a small fraction (about 12%) of the photons
absorbed from the pump pulse g:.tve rise to neutJ-al S
1
-excitations that could under-
go a sti mulated mdiative deactivation and thus amplify the probe pulse. They con-
cluded the excitations gener-..ttes a photoinduced absorption there-
by reducmg_ the gam tn . the sample. This finding was attributed to the pres-
cnre of spati ally 111d1rcct excllons (or geminate pairs keeping with the terminology
of Figure 10- 1 b) that arc gener-..Jtcd immediately after absorpt ion of the pump
pulse.
Direct evidence for U1c competition of two counteracting contributions to the
transient absorption changl!s stems from the temporal evolution of the transmis-
_change at 560 nm. From Figure 10-3 it can be seen that the positive tmns-
change due to the stimulated emission decays very fast. on a time scale
of piCOseconds. On the other hand the typical li fetime or excitations in the s
. . . I
state IS m the order of several hundred picoseconds. Therefore. one has to con-
the emission decay is not due to the decay of the s ,-popula-
llon (as ts typ1cally the case in dye solutions). The decay is instead aHributed to
the transict.t huild-up of spatially separated charged excitations that absorb at this
wavelength.
_Since a and long-lived stimul ated emission is required for
gam narrowmg and lasmg these experimental findings indicate why these phe-
nomena have not been found for a long time in conjugated polymers. In most
conjugated polymers stimulated emission is rather weak and only very shOJt
lived due to competing photoinduced absorption processes.
stronger longer li ved stimulated emission effects were subsequently
found 111 soluble conJugated polymers blended into inet1 matrix polymers. As an
example Figure I 0-4 displays the tmnsient transmission changes in a ladder-type
(LPPP) diluted in a polycarbonate matrix 124). Depending
on the wavelength of the probe pube a difi"crent sign is observed for the transmis-
314 JU in Conjugated Polymers
-2 0 2 4 6 8 10
Delay Time (ps)
Figure lCJ-3. Time-resolved photoinduccc.l changes in PPV probed at 560 nm for
photon energies (460 nm: open 4110 nm: solid circles, 500 nm; open squares, 510 nm; sohd
squares) {afler Ref. 1231).
sion change. The dotted line in Figure 10-4 depicts the _measurement for a
wavelength close to the PL-maximum of LPPP. At th1s wavelength a
tmnsmission change due to sti mulated emission is observed. As can be seen m
Figure 10-4 stimulated emission is still observed at a time delay of 50 ps after the
pump pulse. Rothberg et a/. made similar observations in_ dil_uted blends of a solu-
ble PPV (251. As a general result it was found that the d1lut1on of the polymer re-
duces the amount of photoinduced absorption that competes with the stimulated
emission. The amplitude as well as the lifetime of the stimulated emission is in-
creased in diluted systems and also in soluble polymers with well separ.1ted
chains [26, 27]. .
The positive effect of diluting the conjugated polymer can be understood m the
model proposed by Rothberg et a/. who suggested th<;U spatial_ly indirect
(geminate pairs) give rise to the that s
stimulated emission (23]. Upon d&luuon of the conJugated polymer tn an mcrt ma
trix polymer the majority of chains become isolated and therefore separa-
tion is suppressed and photoinduced absorption due to charged spec1es IS reduced.
An alternative explanation for the photoinduced absorption in the bulk polynx:r
has been discussed by the Cambridge group [28). It was shown that the amount
of stimulated emission depends critically on the degree of photooxidation of the
conjugated polymer. Figure I 0-5 compares the stimulated emission pristine
ppy (sec Fig. I 0-5 a) and its heavily photooxidizcd counterp;ut (sec Fig. 10-5 b).
10.2 Stimulated Emission in Organic Materials
315
1,0

c:
:::J
..ci
(ij
0,5
SE@2.48eV .......
t-
..
/

<l
PIA@ 1 91 ev
0.0
0 10 20 30 40 50
Time (ps)

(b)
F"=

-
v- . ;,_-: J
f--
-
30
v
....-..
-l i--
!.- 1--
- -
...... ,
.lA
'--"
f.- ---
....._,

_...,_
1.8 2.0 2 .. 2 2.4 1..8 2.0 2.2 2 .. 4
Energy {eV)
Energy {eV)
1-'igurc 10-4. behavior of the
photoinduccU 1r.111smission changes in LPPP
after excitation wi th a femtosecond pump
al 400 nm. 'The two curves correspond
to probe photon energies of 2.48 eV (dotted
line) and 1.91 eV (solid line). AI 2.48 eV
the change is positive due to
Mimulatcd emission (SE) while a photoin-
du..:cd ahl.orptiou (PIA) is obsaved at
1.\1 I cV (ac..:ording 10 Rcf.J24J).
(ps)
400
100
50
10
5
-1
Figure ICJ-5. Tmnsien1 Jransmission .:hangc,. 6 '/lf
0
in PPV for diiTcn:nt time delay" between the
and pulse. 'The pump pulse a 100 fs la:i4:r pul.sc al 325 nm obtained by frequency dou-
of amphlicd dye laser pulo;c,, (a) and (b) .:um:spund to dlli:rcnl sides of a PPV-film. The spec-
lrJ m (a) were obtained for the unoxidizcd side of the sample while the set of in (b) was mea-
sured for the oxidired side of the same sample. n1e main dillcrcu-.-cs observed are a much lower stim-
ulated cf!'cct_ for the oxidize<J_ side. The two buuom '[x:.:tr.J depict the PL-spectr.J for compari-
son. 'The hnc mchcates the opllcal absorption (a..:cortling to Ref. 1211J).
Significant stimulated emission is only found ftll' the pristine side of the sample.
From these results it was concluded that the photoinduced absorption that sup-
presses the stimulated emission is directly or inuirectly caused by the presence of
oxygen-related defects. It was shown earlit!r that the cll'cct of photooxidation on
the emission properties of PPV can be explained by the fonnation of carbonyl-
groups that act il.'i strong electron acceptors le:.tding to an eflicicnt dissociation of
the_ phol slate 1291. It can be concluded that 1hc dissociatcd pair ncar the
delccl leads to the strong photoinduced ab:.uq)tion. l11e observation 1hat
316 10 Lusiug iu Conjugated Polymers
photooxidation strongly quenches the stimulated emission is in accordance with
the result of enhancement of optical gain in diluted systems. The photoexcitations
in these materials are less efficiently quenched by defects because the diffusion to
the defect sites is reduced [ 16).
Generally, photooxidation has an even stronger negative effect on lasing and
stimulated emission in conjugated polymers than it has on the EL-pcrfonnance. It
not only reduces the number of excited S
1
states but additionally creates charged
absorbing species that partly compensate the stimulated emission due to the neu-
tml excited states.
In summary, two effects mai nly conllibute to an enhancement of stimulated
emission in conjugated polymers. Photooxidation of the materials has to be
avoided for maximum gain. In addition, di lution of the polymer in a matrix mate-
rial can be used to increase the net gain. The applicability of the 'dilution-
approach' for future electrically pumped devices, however, might be questioned
since the charge transport in such diluted systems is also much worse than in a
bulk polymer. Therefore, the high excitation densities necessary for lasing opera-
tion might not be reached via carrier injection in blend materials. For optical
pumped applications, however, a conjugated polymer blended in a solid non-con-
jugated matrix polymer might be a promising solid-state approach to replace the
liquid solution in a dye laser [30-32].
One of the promising polymers that fulfils the requirements of exhibiting mther
hi gh mobility as well as high stimul ated emission is the methyl-substituted ladder-
type poly(pam-phenylcnevinylene) [33-35 ). The chemical structure of this poly-
mer is shown in Figure For a more detailed discussion of the main spectral
characteristics of optical gai n in conjugated polymers the differential transmission
(DT) lipcclrum of this LPPP is presented in f-igure 10-7c for a pump pulse energy
of nJ and a negligible ti me delay.
The maximum trdllsmission changes are observed at the low enei'JY side of the 0-
0 transition peak. In this spectral range around 455 nm the photoinduced positive
tr.lflsmission change is a superposition of bleaching due to ground-state depletion
and amplification of the probe pulse by stimulated deactivation of exci ted conju-
gated segments. In this spectral range, however, a positive tmnsmission change is
not synonymous with net optical gain since the sample absorption hall to be compen-
sated firs!. At longer wavelengths (around 490 nm) the DT-spectrum exhibits a sec-
ond peak corresponding to the first vibronic sideband observed in the PL-spectrum
that is shown in Figure I 0-7 b for comparison. As seen in Figure I 0-7 a, the sample
absorption in this spectr.ll range is very low (due to a negligible population in the
first excited vibronic state of the S
0
-manifold). Thus, the tr . .msmission enhancement
is attributed to optical gain caused by stimulated emission. Incoming photons of the
R x R'

Figure l0-6. Otemieal slruclure or lhc ladOcr-lypc poly(/J<Iru-phcny-
lcnc). X rcprcscnL' a m.:lhyl-gruup ami R and R" arc and 1,4-
decylphcnyl. rcsJll....:Livcly.
10.3 Gain Narrvwiug i11 Conjugated Polymer Thin Films
317

::l

...J

350 400 450 500 550 600
Wavelength (nm)
Figure l0-7. (a) Absorplion spectrum of
LPPP. The arrow indicates che spectral po-
sicion of lhc elicitation puiM: in lhc cimc- rc-
M>Ivcd measurements. {b) PL specuum foe
LPPP for low ellcication pulse energies. (c)
Oi llcrcncial ob-
served in LPPP afler pholocllcitation wich
a lcmlnsccond pulse having a pulse energy
uf !10 uJ al a wavelengch or 400 nm. nx:
a1Tow indicates chc spcccral poe;ilion of the
probe puiM:s used for a more detailed in-
of che gain dynamic1>.
probe pulse a rad_iative transition from the vibronic ground state of
the first electrOillc exc1ted stateS, Into vibronically excited states of the electronic So
ground state .. From the absolute value of the tr.msmission change and the assumption
that 100% ol the absorbed photons create S
1
exci tations, we can derive the effective
cross-section a.., . .:1r for stimulated emission in LPPP. A value of 1.51 o-
16
cm
2
is ob-
tained for a wavelength ).=490 nm. As seen in Figure I0-7c the transmission
changes wavelengths exceeding 550 nm arc negative. Titis is auri butcd 10 a
an Sn <- S 1 excited state absorption and the absorption due to
charged cxolalluns (polarons) lh;ll arc funned by spolli<Ulcuus (ll<cp-assisted) disso-
ciation of the neutml S
1
state (22, 24].
10.3 Gain Narrowing in Conjugated Polymer Thin Films
The various to s_timulated emission (SE) in conjugated poly-
mers by means oJ tmns1ent absorption spectroscopy have revealed the absolute
amount of SE. its spectr.1l dependence, as well as its life.time in different materi-
als._ Addition_ally, these experiments have pointed out the important role of com-
photoinduced absorption processes that may reduce or even inhibit gain in
The experiments discussed so far. however, were only
111 terms. o! an ensemble of non-interacting chromophores. Upon illumina-
tion, the lransm1ss1on of the material changes and stimulated emission can be de-
tected as an of a probe beam. The next step towards a conjugated
polymer laser _device measure the emission or the material and to investigate
whether e_m1s.s1on. i.e. gain na1Towing of the spectrum, oc-
cur.-; for Intense_ opllcal_ cxcnauon. These experiments arc l<.llher straightlorwanl
and c.m he C<tmcd out 111 the same geometry as simple PL-mcasuremcnts. Since
318
/0 Lasing u1 Conjugated Polymers
high excitation phenomena arc investigated, however, the laser has to
be powerful enough. As the conjugated polymers do not (yet) W_Ithstand ex-
c itation levels in cw-operation. the experiments have to be earned out with laser
pulses with a typical dumtion of only a or shorter. . .
The first observation of gain narrowmg 1n a conjugated polymer m the solid
state was accomplished by the Santa Barbara group using free standing films of
blend systems consisting of a soluble PPV namely MEH-PPV, polystyrene, and
nanoparticles (7}. Figure I 0-8 shows the measured emission for two
different excitation intensities. As seen in this figure the broad emiSSIOn spectrum
collapses into a narrow emission line when the pump intensity is increased above
a certain threshold. This result was interpreted in terms of gain narrowing due to
stimulated emission. The Ti0
2
particles act as scattering centers in the optically
pumped material thereby increasing the length pho!on
propagate inside the sample (36). 11ms, the I for gam narrowm.g
in the sample is fullilled for lower pump energu..:s than m the absence of these
particles. Although the usc of scaucring partidcs is an appealing way to
the threshold for gain narrowing. this approach hears some severe dmwbacks lor
applications. l11c radiation, which is emitted by the docs not show any
directionality and has therefore only limited usc in dcvtccs. .
Major advances into geometries that arc potential candidates for an
driven lasing device with a highly directional emission were then reported mdc-
pendently by three diiTcrcnt groups l37- 39). It _is to note that the sub-
mission dates of the lirst three papers on th1s subject d1ffcr by less than two
.
The results in the references (37] and l38] were obtained for simple spm
coated films being deposited on glass substrates. The basic observation of line
narrowing through stimulated emission is shown in Figure I 0-9 for a 210 nm
thick film of a soluble PPV (BuEH-PPV) deposited on a glass substrate l37).
Upon increasing the pump pulse energy from 0. 1 to 0.62 the emission
spectrum collapses into a narrow emission line. There are two maJOr advances
c
0
u;
1/)
. E
w
..
..
..
..
\.r-.1/60
.
-........
.................
... .......................
600 650 700 750
Wavelength (nm)
lo"igure 10-8. Emission spectr.t of a
free Mantling litm of a blend system
of 0.9% MEH-PPV in
polystyrene with ca. 10
11
em- l 1i0r
partides. The nanoparticlcs act as op-
tieal scaucring center"). The emission
spectrum is depicted for two different
excitation puiM: energies. Optical ex-
citation was accomplbh.:d with laser
pulses of dur.uion 10 ns and w.tvc-
lcngth 532 nm (acconling lo Ref.
(71>.
7
2
6
c:
:::J
5
.e
4
?;-
iii
3 c
Q)
c
2
..J
!l.
10.3 Gain Narrowing in Conjugated Polymer Thill Films
319
-0.091JJ
,.
.......... 0.251JJ
I
I
("1/1.2)
I

___ 0.62)JJ
t\
(*1/2.2)
t\ _10.01JJ
\ . (*1160)
--
525 575 625
Wavelength (nm)
675
lo'igurc 10-9. spcctrJ for a
210 nm thick film of BuEH-PPV spin-
olllo a glass for differ-
ent excitation pulse Optical
cxcit:uion was ilCCOmplishcd with laser
of duration I 0 ns (acconling to
Hef. f37J).
compared the . results from the same group lor the sample contai ning the
Ti02 firstly. the threshold for line nan"Owing was decreased by
three ordcn; ot magmludc. this result was obtained for a bulk polymer
that also shows htgh clectrolumtnesccnce e fliciencies. Similar drastic chauges of
the at oomparablc excitation intensities were reported in the references
(38, 40} lor the solubk DO<:?-roly(para-phcnylenc vinylene). The experimental
results, however. were not attnhmcd to gain nanowing due to stimulated emission
Instead und supert1uorescencc were invoked for the explana-
tion of the findings. These etrects re ly on a coherent coupling of a
large numbe_r .o.t enutters that participate in a coopcmtive emission process (41 ).
thc:o;e tnl!tal reports other groups have n:portcd on spectml twnow-
mg m thm ttlms (35. 42, 43]. It can be concluded that spec-
tral narrowtng ?t the at . high excit<t tion levels is mther a geneml phe-
for Ctll lsstve cOnjugated polymers tlwn the exception. The pro-
gress synthests _and tech.n?logy has led to the development of conjugated poly-
mers wuh de!ect dens111es and much higher PL-quantum yields than in those
polymers 111 the early 90's with transient absorption spectroscopy. The dif-
resuiLo; and threshold values for spectral narrowing in thin con-
JUgated polymer hlms are summari zed in Appendix 1.
. a detailed photophysics underlying gain narrowing in con-
JUgated polymer thm ftlms, femtosecond spectroscopy can be used as a power-
ful tool. We have performed tune-resolved measuremento; at a probe wavelength of
nm to th_e and its relation to the emission proper-
ties under excuatton mtensucs. As seen in Figure 10-7 c the tr.tnsmission
change at th1s wavelength is due to optical guin by stimulated deactivation of S
states. It reveals the dynamic.o; of the St population. Figure 10- IOa
the lr.lnsmtsston changes at 500 nm for various excitation pulse energies for the
LPPP-film coated onto For the lowest excitation pulse energy of
6 nJ observe a fast nse 10 the Mgnal and a subsettucnt decay marked by a 1/e
decay-t1mc constant of 36 ps. When the excitation pulse energy is graduall y in-
320
/0 Lasing in Conjugated Polymel"$
(a) (b)
f :--_1(" _--
0.1f t -

0.1 . -- --- :- 25 nJ ---- - ---- -- --- c::
.__
0.01 c::
0.1 f-r -- ; _____
::rr -..
0
01
0 20 40 450 500
Time (ps) Wavelength (nm)
11}..10. (a) Semilugarithmic plot of the stimulated emission tr.msients for various excitation
pulse c:nergics for LPPP on glass. The cxcitatiun pulses have a of 150 fs :m:
centered at 400nm. The probe pulse were filteral (Ao= 500nm, 6A= I0nm). (b)
speclr.! recorded for the same excitation conditions. The s(le(:tra arc nlll1lklli:ted at the purdy electroniC
cmiss1on band (:.ccording to Ref. I 181).
creased an additional much faster component becomes more and more prominent
whi le the 1/e-<iecay time constant of the slower part of the curve remains almost
the same. For comparison Figure I 0-10 b shows the intensity dependence of the cor-
responding emission spectra measured for the same excitation conditions.- The
are strongly intensity dependent and exhibit significant changes start.'ng. at exca-
tation levels of approximately 10 nJ . This corresponds exactly to the excttatmn
where the ultrafast component becomes apparent in the .low. exct-
tation levels the first vibronic sideband around 490 nm is lower m emtssaon anten-
sity than 0-0 band at 453 nm. Its spectral width amounts to 35 nm at
half maximum (FWHM)). The behavior for increasing excitation pulse energaes p
is distinctly different. The li rst vibronic sideband at 490 nm increasingly promi-
nent and additionally undergoes a significant spectml narrowtng. For /,=65 nJ the
spectrum is dominated by the emission band at 490 nm having a width ?f
9 nm (FWHM). The intensity-dependent emission can be cxplamcd by gam
narrowing due to amplilied spontaneous emission (ASE). that an: sponta-
neously emitted at some position in the LPPP film are coupled mto the wa-
veguide mode (see Figure 10- 11 for the calculated mode pa_uern). can st1mulate
fua1her mdiativc processes of other photoexc1tcd OOnJugated segments
during their propagation through the film. These fa-
vor the emission of photons with the highest net gam coclltcJent. When the sumu-
lated emission becomes the dominant pathway, the emission is spectmlly narrower
than the spomaneous mdiation. Since ASE is a collecti ve eflect of an ensemble of
excited emitters it depends on the coupling of the different emitters through
tromagnetic field. The conjugated polymer on glass forms a planar waveguade wath
10.4 Lasing in Conjugated Polymers
321
.... :he a 290 nm thin film of LPPP d!!po.\itcd on a BK7 substr.stc. A planar
rormcd smce the polymer film ha.' the highc.\t index of refraction. The
mtcns1ty prohlc of lhc guided TE waveguide mode fur the sample is shown on 1hc righ1
hand s1de. Only one guided mode is supponcd.
its a:nooe mainly in the conjugated polymer lilm. Thus, the different photo-
exct!ed conjugated polymer segments are efliciently to each other and ASE
by la_terally photons is observed at low excitation pulse ener-
ultrafast component m the pump/probe measurements observed at the same
levels. the emission spectra exhibit spectral narrowing, can be ex-
pl_runed by the depl?tion of the excited state due to the enhanced probability lor
sumulated etmssaon the ASE-process. This dynamics can be quantitati vely
understood by companng the experimental results with a numerical solution of
tl_JC <:<>upled rate equations for the tcmpomlly and spatially dependent density of ex-
catatJons and photons II Kl .
The first combine gain nan-owing under high excitation with a resonator
thatyrov1des feedback in order to achieve true lasing action, were canied
out group 139). used a microcavuy resonator in their experi-
As seen scheme the material PPV was spin-
coated on t_op of a ht ghly rellcctave d1stnbutcd Bragg reflector. The second mirror
for the structure accomplished by evaporati ng a silver layer as a
rnetalmm'Qr. fhe two nmrors confine the electromagnetic wave and lead to discrete
modes inside the cavity 1441. As seen in the in figure 10- 12 the line-
Width ts already spectrally narrow at low.e_xcitation intensities where gain narrowing
does not yet play a role. At low mtcnst!les the emission is due to three different
modes that are well scparJt_ed from each other. The occurrence of lasing action
by a non-lmear behavior of the diiTcrcnt modes. At high energy
the was fully concentrated nllo the mode with th.: highest
l111S no_n-ltnear wus accompanied by an enhancement of the dircctional-
uy of the emu.ted Both etlects were attributed to lasing at high excitation
In a _mtcrocavuy structure the rat her low ovemll gai n per roundtrip leads to
htgh threshold values, i.e. when a rather lossy metal mirror is used us
one ot the renecting surfaces. Much lower threshold energiL-s arc observed in the
322
10 Lasing in Conjugated Polymers
High

..
energy
.0:::
Silver
5
I
60nm
I
e
11
: > t !

-100nm
. .- -
-
PPV

'
' I
ji i !

. : : ;
i : i i
OBR
. : , '
.' . .
Excitation
355rvn
500 520 540 560 580 600 620
Wavelength (nm)
Figure 10-12. L.dt h<tnd side: Structure of a PPV microcavity. A thin film of the conjugated IJ'?Iymer
deposited ou top of a highly reflc.:tive distributed Br.sgg reflector (00R). The marror as lhen
by ev;apor.stion of a layer. Right hand E.mi,.sion spcc!r.s o( the nm:roeav.lly a!
d talion of 0.05 j.l1 lme) and 1.1 J.1l hm:). ro.p:c.:tivcly. Lil:\Cr puiM!.' ot dur.staon
200-300 and a wavelength of 355 nm were u,.etl for optical excitation (aaortlmg 1\1 Ref. (JI)j).
case of highly rellcctivc dielectric mirrors at both sides of the cavity 145, 46]. Other
interesting gcometnes comprise microdisk and mi croring_ lasers 147, 48). .
An alternati ve route to low threshold polymer lasers ts to use a geometry wtlh
the lasing process occurring in the lateml direction. A very promising way to
achieve optical feedback in the horizontal is the uS:C of_ a structured _su?-
strate providing distributed feedback (DFB) m the lateml by
modulation of the refmctive index. This approach can be easrly combmed wrth
the techniques for depositing the organic emission layer can be readily used
for large-area geometries. Organics in general the addttto?al degree of free-
dom given by the mechanical flexibility. When thts advantage rs to be conserved,
standard semiconductor technologies using rigid substrates are ruled Tile
most promising str.1tegy is the realization of an all-plastic DFB-resonator usmg an
organic emitter as the active laser medium (49, 50). . . . .
Distributed feedback relics on the diffraction of wavegutded ltght by a penod1c
modulation of either the refractive index or the gain coellicient. Starting with a
flat substrate made of poly( ethylene terephthalatc) with a of I J.1tU, a
periodic height modul ation with a period A =300 nm s rmrlar amplitude has
been introduced into an acrylic coaling by a UV embossmg process. The stamp
for the embossing process has been produced by holographic of a
ti vc photoresist and subsequent tr.msfer of the surface-relief mto a ntckel
stamp by electroforming. We stress that our approach the laser
not involve any lithographic step and is therefore sulled to be used 1_n
combi nati on with spin-coated and other low-cost technologtes that fotm the basts
for organic thin tilm deposition. On top of thi s flexible,
we have spin-coated a Jilm of LPPP. The average as d.ctermm_cd
from absorption measurements, is 400 nm. Atomtc Ioree r111croscoptc stud1cs
323
show the _of the conjugated film exhibits a height modulation with the
same penod but stgntticantly smaller amplitude (< 10 nm) than the substrate un-
derneath. Figure I 0-13 shows a scheme of our device and illustmtes the distribu-
ted feedback mechanism. In our film only the fundamental TEo and TMo modes
are supported by the planar waveguide formed by the higher index LPPP-film em-
between .the two lo":er index materials (substrate and air/vacuum). The
penod of the hetght modulatton A was chosen to correspond to one full wave-
length where ndT denotes the effective refmctive index of the considered
wavegu_tded and Acm the vacuum emission wavelength of LPPP. The first
of the mo<.les at Anr = A11,.
1
r is coupled out into a di-
recll?n to the frlm. Optical feedback is realized by second order dif
fraction w.hrch co_upl_es the two counter-propagating waves [5 1].
For of device we have used the frequency-doubled output of
a Ti : sapphire laser. The full emission spec-
trum of our devtce lor_ low exct tallon pulse energies,, is shown as an inset in Figure
I 0- 14. The photolununesccncc spectrum consists of the purely electroni c emission
at nm its vibronic si.de bands at. longer wavelengths. 1l1e main part
?fFtgurc 0- 1 the cmrssron spcctm 111 the range concspond-
.ng to the band at490 nm with high spcctml resolution (ca. 0.3 nm)
three drlferent. pulse energies ,. As discussed above, the highest net
gam and thus act ton arc expected in thi s wavelength mngc. Figure 10- 14 a
shows .the cm_tsston spectrum measured for an excitation pulse energy of 0.35 nJ.
t:-s _an rnterestrng. we observe a characteri stic dip at 488 nm which precisely
mdtcates the posttt on ot the Bragg wavelength in the waveguide. For a threshold
pump of 1.5 nJ we observe the emission spectrum displayed in Figure I0-
14_b .. For thrs energy a peak evolves near Au, and additionall y a number of charac-
tensllc narrow around the PL-maximum is superimposed on the broad PL-
spectrum. The emtsston changes drasti cally when the pump energy is in-
to 5_ nJ: As m Ftgurc 10- 14c the spectrum is completely dominated by
a hne very close ... This spcctml oollapse is accompanied by a
change tn the angular emtsston pauem as illustrated in Figure 10-15. The
for pumpmg conditions exhibits a very small divergence of less than
0. 1.5 perpcndrcular the .gmting lines. Additionally, the emitted light is hi ghly po-
lanzed along the grat mg lrnes.
m=l
*
I
LPPP
PET with acrylic coating
10- U . nf ah.: lkxibk: <.Ji,lrihuacd
Jl.:cdha..:k la,.o;r tlcvi.:c. The pcriutlk heithl mudu-
lahuu ul ahl Mlh,u;n.: ..:aus.:s <lill.rm:aiuu uf th.: wa
llllkh:.,. 111e Ji rsa urJcr-ditrr.scrctl light
(m= I) is .:uupl.:tl uu1 rrom the wavcguiJ.: uutl
perpcutlicular lu lhc tihn. The l>Ceuntl
ortJc.r Oilrr:lCllllll (m: 2) is reo i1110 lhe I:UUIIh:T
pmpagauug wavo: autl intlu.:e" Lhc ll-..:<.1-
hO!Ck lir la,ing
324 /0 Lasing in Conjugwed Polymers
-
(/)

c

..0
.....
ro
-
>-
......
Cii
c
Q)
......
c
c
0
.Cii
(/)
.E
w
>-
e>
Q)
c
w
nJ
480 485 490 495 500
Wavelength (nm)
Figure 10 14. Inset: PhOlolumincscence
trum for low cxcililtioo pulse Ep
Main part: (a) displays the spectrum !or
pump pubc well below the
thrc.,hold while (b) shows the spectrum ob-
t;lincd for exdtation with a pump I.'OC'l;Y
do....: to the thrc:.OOid; (c) prcscnlls the
mode-lasing spl.'Ctrum emiued when
the device is pumped well above threshold.
The dashed indicate the zero line which
is arbitr;uily shilicd in case of (b) and (c).
0
y 0
Mnv\ii .
1

...
#

... .

2 3 4 5 6
Pump Energy (nJ)
l' igure 10-15. Output vs. input en-
ergy char.1cteristic of our laser
vice. The horizontal dashetl curve m-
dicatcs the zero line. A dear laser
threshold behavior at an excitation
pulse energy of 1.5 nJ is obsc'"':ed-
Below the lasing threshold only tso-
tropic photoluminescence .
Above threshold the dev1cc emitS
low divergence mode laser
perpendicular to the SU"
face, as schematic;lly shown in the
inscL The la...cr liglu is pol;u-izcd par-
allel to the grJting lines.
10.5 Outlook 325
.
Figure I 0- 15 shows the output vs. input energy relation with a clear threshold
at a pump pulse energy of approximately 1.5 nJ. This value is an order of magni-
tude lower than the threshold for the observation of ASE in simple planar wave-
guides, i.e. without distributed feedback but prepared with the same conjugated
polymer.
All features are clear indications for laser action within the optically excited re-
gion of the DFB-structure. Lasing of the TEo-mode propagating perpendicular to
the gmting lines is achi eved through the feedback provided by second-prder
Bmgg rellection. Laser light is transferred from a waveguided mode into a free
space radiation mode, propagating perpendicular to the film, vio first order diffrac-
tion. Single mode emission is observed for pump energies above threshold .
The flexibil ity of the substrate, the ease, and the low costs of fabrication of this
DFB-polymer laser offer a very promising way to novel surface-emitti ng laser
devices which take full advantage of the properties of conjugated polymers.
10.5 Outlook
A brief overview of lhe experimental work on stimulated emission and lao; ing in
thin films of conj ugated polymers was given. The mpid development over the
pasl years has shown that combined efforts of improved chemistry and detailed
optical investigations (i.e. femtosecond spectroscopy) and novel geometries offer
promising prospects towards future devices. By improved synthetic methods, ad-
vances in the polymer design, and an improved technology, the photolumines-
cence yield as well as the gai n under optical pumping has been enhanced. As far
as lasing appli cations are concemed this was not only a quantitati ve step but a
qualilati ve one that has opened a new field of research. The tremendous progress
is also documented by way of many publications on this subject in the last two
years. The properties of some or the different conj ugated polymer lasers reported
so far are summari zed in Appendix II.
The key question with regard to appl ications is whelher electrically pumped
laser opemtion can be achieved or not. Threshold values below 100 W/cm
2
for
gain narrowing under optical pumping in an organic waveguide structure were
reported {52]. Provided lhc quantum efficiencies for radiative recombinat ion are
high enough lhis the corresponding lhreshold values for the injection
current below 100 A/em-. This current value has ulrca<.l y been exceeded in pulsed
electrical operation of polymer LEOs [53, 541. Further experiments, however,
have to clarify the role of the charged cxcitutions as well as the triplet excited
states, which arc inevitably present under electrical pumping. In addition, the
unavoidable contacts lcud to much h.ighcr losses in structures where catTier
injection is possi ble. The invcstigatilm of suitable hctcrosllllctures and the search
for new advantageous geometries and materials, which provide lower threshold
values, wi ll be a ti.tscinating fidLI for ncar future work. As far as arc
326 I 0 Lasing in CvnjugtJJed Polymcr.f
concerned it will be most interesting whether organic solid state lasers will have a
chance to compete with their inorganic counterparts, i.e. the GaN-based
semiconductor lasers. It might even be that organic/inorganic hybrid solutions, as
recently demonstrated for EL-<.levices 155], will play an important role for future
solid state emitting devices. The usc of a mechanically flexible substrate
introduces a new feature into laser technology and might lead to completely novel
applications in measurement instrumentation and display technology which rely
on large area emitters and geometries not accessible to conventional inorganic
laser materials.
Acknowledgetnetlls
We would like to thank M. Hilmer, M. Pemer, and W. Spirkl for their contribu-
tions. We thank U. Sche.rf and K. Mullen, Max-Planck-Insti tut fiir Polymer-
forschung, Mainz, Germany for supplying the high-quality conjugated polymer
LPPP. We also gratefully acknowledge A. Gombct1 and Y. Wiuwcr, Fraunhofer
ISE, Freiburg, Germany for the fruitful collaborJtion on the DFB-substmtcs. Our
work is financiall y suppot1cd by the Stihung Yolkswagenwerk and the Bayrische
Forschungsstiftung.
Appmdix I 327
Appendix I
t'ulltfitimrJ> tlrrr.lwltf wrlur. far xuiu uanwl"illl( ill tlifferem tvJtjuxutetl JHII\'Iners. Note
lhai
IS

cvsl!:'' /iJ ' 'IIIIIJ'tlll! the Willie. tlue 10 tlrl! tliffercllt /user pulse tlu,.;timr usetl ;
11
lhe expenml!Jrt. . .A, .... 111</tt:mt.< tlte wtwtltngtlr ji1r e.1ciuuimr. T
1
,
1
,.. i. tift pulse tlrmuiotr of tire exdtiug
laser pulse t111tl A tlte lllt'tl of tire Sf'tll o11 the .wmt11e.
Reference Material
Exci"uion conditions
Threshold for gain
(71 MEH-PPV blended in
;..,._=532 nm
9mJII:m
2
polystyrene with
T,..t-. .,= 10 ns

A ::::: (1.5 mm)
2
1371 BuEH-PPV
nm 40J.LIIcm
2
T
1
,...,...= t0 ns
(401 000-PPV
A:::::( l mm)
2
)., . , =!'5:12 nm
.:w J.LIIcm
2
(421 PPJ VE
r
1
..,
1
.._ = 12() ps
.\,._.=337 1111\
:::::500 J.LIIcm
2
T put..: = 1!00 ps
(431
A= 1.2xCl.5 cnl
Si-PPV
;..,._ =355 nm
I mJ/cm
2
T,.,1,.,= 15ns
A= 5><2.5 mnl
1561 PPV
nm
t3 J.LIIcm
2
!35j LPPP
T fl"l"' = 20Q-J()()
J.., .,=400nm
25 J.LIIcm
2
T
1
,ut.;c= 150 fs
A:::::(0.2mml
MEH-PPV: -cthylhcxykxy)- t.4-phcnylcnc vinytcnc)
000-PPV: PPV wllh R
2
_, =0C..H
17
BuEH-PPV: Poly(2-butyl-5-(2'-cthylhcxyt)-IA-phenytcne vinylc
11
e)
copolymer coru:aimng phenytcnc, vinylcue and non-COlljugatcd cthytidcne units
Sa-PPV. Poly(dnncthylslylcnc-lxtrttphcnylcncvinylcnc-(2.5-di-n-octyl-paru-pi1Cnylcnc)-vinylenc-
1
mm-
phcnylcnc)
LPPP: ladder type l>olublc poty(pam-phcnytcnc)
328
10 LA.fing in Conjuguted Polymers
Appendix ll
I fi I iu itl clifferetll ccmjugctled [Htlymers. Dijfert'tll reso-
Excitumm cmulitimiS am/ tlrreslw/cl VCI ues ur m 8
1
. . . oses clirru:u/l IV cumpcln! the
ed
/ . eo/ /oslllg Note t lUI II IS Ul SCHlie C 'JJ'
tltltOr structures are us to ac rwve " . . . ,
111
. A.. . imlicutes tire wuvdeu!;lh
clue IV tire c.Jiffereul lu.ver pul.>e

A ;,.e Ul'(!(l of the spul un d1e
for excautiull, is llle pulse c/uramm OJ I I! exciting as
.rnmple.
Reference
MuiCrial ruxl resonator
Excitutton conditions
1391
PPV microcuvity
.A.:..c=355 nm
r,-..=200-300 ps
1451
BEH-PPV microeuvity
A.,...., = 555 nm
r,., .... = 100 fs
A::::(IUO

[571
BuH-PPV 1nierocavity
An, =435 IIIli
Tpua ... = 10 ,
,\ "' ( 1.5 nnnr
{461
I'DOPT mn:roc:tvaty
i-.;-. = 53() nm
r puh< =lSII- IIlii b ,
A:::; (211-ltXl
!481
BEII-PJ>V micrunng
.<.,.. = 53:?. 11111
r,......, : 10
i. .... : 555 0111
r""1,.. = lllO
1471
DO<H'PV
.A.,,."' 5J2 nm
micruring
r
1
.,
1
..c"' 100 ps
r,....a,.,"' 100
microdisk

1581
BuEH-PPV
)..,..,=435 nm
distributed fecuback
r.,..,.,= 10 ns
2
A mm)
1501
LJ>J>P
J..,,. =400nm
distributed lecuback
r
1
1Ubc= 150 fs
2
(Oexiblc)
mm)
B EH-PPV: J>oly(2,5-bas(2' -cthylhex ylox y )-paru-phenylcne vinylenc)
PDOPT: subslituteJ polythiophcne
References
Thrc.o;ho!J for

0. 12
I

100 pJ/pulsc
100 pJ/pubc
:::::

3.7
I. Polymeric und Electronic and Applications. MHS-IJuflctill 1991, 22, 6.
2 COT flll(l :l/www.cdtltcl.cfl.uk, 1999. Ex -
1
rs"' band dc-cri"'ion of the
..
0 0
C Bradlc M Henncc,;e. c1 on vc ...
3. U. Ruu..:her. H. . y, . . , in lenc). Ph s. Re1( 8, 199tl. 42, 91!30.
ahsorption and lununesccnce Ill poly(t-phcnyk::v . y B R F Mahrt. II. Kurz. H.
S
.
1
dl u Lemmer R. Kersting. S. Karg. W. "'a", . . . -' diss0-
4. M. c lCJ cr. M C
1
.
1
dy of picosecond excaton rclax<Illllll atou
B!ll.slcr, E. 0 . GObel, P. Thoma.'>, onte ar o s u ' 551
ciation in poly(phenylencvmyknc), 54, V.nl I Springer Berlin Hcidclbcrg
5. F. J>. Schafer (f..d. ) Dye Lasers. Topics 111 Apphcd . .
New Yurk 1973.
References 329
6. D. Mosc.,, High qu:tntum efficiency luminescence from a c01mucting polymer in solution: a novel
polymer laser dye, Apt11. Phys. Lm. 1992, 60, 3215.
7. F. Hide, B. J. Schw:utz. M. A. Di:u.-Garcia, A. J. Hccgcr. emission from solutions and films
CtJOtaining semiconducting pulym.:r mad litunium uiuxide nunOCI)'Niuls, Cltl'lll. Plays. ull. 1996,
256.424.
8. H. P. Weller, R. Ulrich .. A thin-fi lm ring la.o;c( IIppi. Plt.1s. LC'll. 1971, /9., 3ts.
9. T. W. Hansch., M. J>cmicr, A. L. Schawlow, acrion or dyes in gelatin. / J. of Quwumn
Elemrmks 1971, QE-7. 45.
10. H. Kogdmk, C. V. Shank. Stimulated ennssiun in a periodic strociUre. Af'tJI. Pltys. utt. 1971, 18,
152.
I I. R. Reisleld. D. Brusilovsky, M. Eyal, E. Miron. Z. Burstein. J . lvri, A new solid-sute tunable !u-
ser in the visible, Claem. Pltn. Lm. 1989. IW. 43.
12. N. Kurt. La...er an orguutc mulc.:ular l'by.,im SwliiJ Sulitli A 1972, /J,
65 1.
13. V. G. Ko7Jov. V. Hulovic, P. E. Bum1w,, M. Buldo. V. B. Khullin, G. P..u1hasurathy, S. R. Forrest,
Y. You. M. E. fulmtNNI , StuJy or la.,ing actiun OO:;cU 011 For.;ter energy transfer in optically
pumped organic semiconductor thin films. J. Appl. Pltys. I \191!. 84, 4096.
14. V. G. Ko1Jnv, V. Bulovic. P. E. Uurrows. S. R La...cr action in orgunic scmaconductor
waveguidc anJ Juuhk-hctcmstrut:IUn: devices, Na1t11l! 1\197. JHII, 362.
15. A. Dudaba!.tllUr, M. It L:. Slusher, z. B:au, A. limko. J>. Schao11ino. E. Laskowski.
H. E. Kat/. 0 . Nulama.,u. Rc.,unaturs und materials fuc urgank based on energy tr.111sfe1;
lt:t:t: J. uf Selt!<'ll'tl1it'iC'.\ i11 Quwrmm E/cc-tmnic.r 1998, -1, 67.
16. U. Lemmer. R. F. Mahr1. Y. Wada. A. Grcin.:r. H. E. 0 . Good, Time resolved luminc:.-
ceu<.:e stuJy of rc.:ombiuation in dccrrolunuOL'!II:Cllt polymers, Appl. Pftyl. u11. 1993,
62. 2!\27.
17. W. Hol1:o!r, A. Pcll/1-ofcr, S.-H. Gong. A. Blcycr, D.O. C. Br.sdky, La....:r Aclion in Poly(m-phcny-
lcnevinylene-co-25-diuctoxy-f' Phcnylcncvinyknc). Aclv. Muter. 1\1%, 8, 914
18. A. Haug.:ncdcr. M. C. Kallinger, W. Spirkl. U. Lemmer. J. FeWmann, U. Scherf, Non-lin-
cur a111.l ra :omhinution in conjugatetl polyniCT wavegu1dcs. J. At'l'' Pftys. l\1119, 85.
1124.
19. J . M. Lcng. S. Jcglinski. X. Wei, R. E. Benner, z. V. Vardcny. F. Guo, S. MUZ11mdar, Optical
probes of excited in poly(/1-phcnylcncvinylcnc). Pllys. Hev. Ull. 1994, 72. 156.
20. K. J>khkr, D. A. Hallid:ay. D. C. Bum. R. H. Faicnu. A. B. Hulmcs. Optio.:al
copy of highly onk.rcd pulytJI phenylenevinyl.:ne), J. of Pllysic.f : Cmulersecl Maller 1993, 5,
7 155.
21. A. J. Hccger, D. Moses, M. Sinclair. Semiconducting polynlCrs: fast response non-linear optical
nl<ltcriuls. S)11llr. Mn, 1986. 15, 'J5.
22. W. Gr.supncr, G. Cerullo. M. Lautaui, M. Nisoli, E. J. W. Li.\t, G. Lci.,ing. S. De Silvestri, Darcel
observatinn 1.1f ultr..tfa.\1 charge genemtion in ladder-type poly(p<Ira-phenylene). Pftys.
Rc'V. um. 1998, 81, 3259.
23. M. Yan. L. J. Rothberg. F. P;ipadimitrul-opoulns. M. E. Galvin, 'I: M. Miller. Spatially indirect ex-
citons prinl:ll)' photoexcitutions in cunjug:ttcu polymers, Plry.f . Rev. Lc!ll. 1994, 72, 1104.
24. T J>auck, R HL'Ilnig. M. Pcmcr, U. Lcnuncr. U. Siegner. R. F. Muhn, U. Scherf, K. Mullen., H.
E. 0 . GObel, Fe mwsc-c<md dynamics of emission :IHJ phutoinuu.:cd absorption
in a J>J>P-typc ladder polymc1; Ocm. Pltys. &11. 1995, 244, 171.
25. M. Yun. L. J. Rothhcrg, E. W. Kwock, T. M. Miller, lntcrchain excitations in conjugated polymer.;,
Plrys. Rev. Lm. I \1115, 75. I 9<J2.
26. B. J . Schwartl., F. Hide. M. R. A. J. He .. -gu. stuuics o f stimulated emission
and guin in films or conjugmcd polym.:rs. Clr<'lll. Pflys. l..m. 1\197. 265, 327.
27. W. Grotupncr, G. Leising. G. Lunzmti, M. S. De U. Scherf, Femtosecond relaxa-
tion or pholltexcitutions in u puly(parot-phcuylcncHypc lauocr pulymCl; Pltp. R1m Lc/1. 1\1\16, 76.
847.
28. G .. Denton, N. Tcl....ter, N. T. Ham,;m. R. H. 1-'ricnu. inllucm:ing stimulatcd emission rrom
pol)'(/1-pheuylcnevinylcnc). Plt.rs. 1997, 78. 733.
29. M. Yan. L. J . RothhcJ-g, F. M. E. G:alvin, T.M. Miller, Defect quenching of
conjugarcJ polymer luminc:.o.:cncc. /'fry.. Uri\ u/1. 19<J4, 73, 744.
330 /0 Lasing in Coujugllled Polymers
30. G. Wegmann. H. Giesscn, D. He.te.l, R. F. Mahn, Blue-green laser- from a solid conju-
gated polymer, Svl. Stat. Cumm. 1997, 104, 159.
31. D. N. Kumar, J. D. Bhawalkar, P. N. Prasad. F. E. Karosz, B. Hu, Solid-stale tunable cavity
in a poly(para-phcnylcnc vinylcnc) derivative a hcmating block co-polymet Appl. Pllys. Lett
1997, 71. 999.
32. D. N. Kumar. J.D. N. Prasad, cavity lasing from poly(p-phenylencvinyl-
cne)-si lica nanocomposile bulk. Applied Optics 1998, 37, 510.
33. J. Huber, K. Mi.illcn, J. Salhccl., H. Schcnk, U. Scherf, T. Stehlin, R. Stem, Acu Polymer 1994,
45, 244.
34. S. A. Niko. G. Lciing, U. Scherf, Highly cfficicm ek:ctrolumifl(."l.CCOCC of new wide band
gap ladder-type poly(par.! phcnylene.), AppL Phys. Lm. 1996, 68, 1090.
35. A. Haugencder. M. Hil mer, C. Kallinger, M. Pcrncr, W. Spirkl, U. Lemmer, J. Feldmann, U.
Schc.rf. Mechanism of gain 0<1rrowing in conjugated polymer thin films, Appl. Pflys. JJ 1998, 66,
31!9.
36. N. M. Lawandy, A. M. Baladtandran, A. S. L. Gomes, E. Sauvain, act ion in strongly :;QI(ter-
ing media. Nmure 1994, 368, 436.
37. t'. Hide, M.A. U. J. Schw..n-'. M. R. Andcn....on. P. Qibing. A. J. Hccgcr, Scmicon-
du.:ling polymers: a ucw cla.'>S of wlid-slale laser matcri<lls. Science 1996. 27.1, 11!33.
31!. S. V. Frolov. M. Ozaki. W. Gcllcnnann, Z. V. Vardcny. K. Yoshino, Mirrorlel.l> lasing in coodud
ing polymer poly(2,5-dioctyloxy-p-phcnylcnevinylcnc) films. JpiL J. Aflt'l. PIJys. 1996. 35,
Ll 371.
39. N. Tessler, G. J. Dcn1on. R. H. Friend, La.\ing from conjugated-polymer microcavitics. Nuturt
1996. Jb'2, <>95.
40. S. V. Frolov, W. Gellcrnmun, M. K. Yoshino. Z. V. Vankny, Coopcr.tlivc emission in pi-
polymer thin lilms. Phy.f. Re1. u/1. 1997, 711, 729.
4 1. A. E. Siegman. Luser.r. Science Books. Mill CA. USA 191!6.
42. G. H. Gclinck, J.M. Warman, M. Remmers, D. Neher. Narrow-band emissions from conj ugated-
polymer iihns. Cltt:IIL Pllys. Let/. 1997, 265, 320.
43. H. J. Brouwer, V. V. Kra.,nikov, A. Hilbcn:r, G. Hadziioannou. Blue from neal scm
conducting allemaling copolymer films. Adv. Mult!r. 1996, 8, 935.
44. U. Lemmer, R. Hennig, W. Cuss, A. Ochsc, J. PomnlCrehnc. R. Sander. A. Greiner, R. F. Malut,
H. Cassler. J. Feldmann, E.O. Gtibcl. Microc;wily effects in a spin-cuilloo polymer two-layer sys-
tCII\ Appl. Pllys. Lett. 1995, 66, 1301.
45. A. Schulzgen. C. Spiegelberg. M. M. Morrell, S. C. Mendes, C. Kippclen, N. Pcyghambarian.
M. F. Nabor. E. A. Mash, P. M. Allemand, Ncar diffmction-Jimited laser emission from a polymer
in a high lincsse planar Apfl/. Pllys. Leu., 19911. 72. 269.
46. T. Granlund. M. Thc-.mdcr. M. Berggren. M. AndcN.,on, A. Ru:teeka.. V. Sundstrom, G. Bjork,
M. Granstrom. 0 . lngana.s, A polythiophcnc microcavity lase( CIJt'nt. Phys. Leu. 1991!, 288, 879.
47. S. V. Frolov, A. Fujii, D. Chinn, Z. V. Vardeny. K. Yoshino, R. V. Gregory. Cylindrical microlasers
and light cmiuing devices from conducting polymers. Appl. Pllys. Leu. 1998, 72, 2!111.
4!1. Y. Kawabc. C. Spiegelberg, A. Schulzgen. M. F. Nabor, B. Kippclcn, E. A. Mai>lt. P. M. AllenlOIIld,
M. Kuwilla-Gonokarlli, K. Tukcda, N. Peyghambarian. Whispering-gallery-mode microring laser
using a conjugated polymet Appl. Pll_vs. u'll. 19!18. 72, 141.
49. M. llcrggrcn, A. Dodabalapur, R. E. Slusher, wiU1 imprinted gr.Jtings oo
plastic substrates. ApJJ/. Pltys. Leu. 19911. 72, 4 10.
50. C. Killlinger. M. Hilmer, A. Haugcncder, M. Pc.mcr. W. Spirkt, U. Lemmer. J. Feldmann, U.
Scherf. K. Mullen, A. Gomben, V. Wiuwcr. Aexibt..: conjugillcd polymer laser. Atlv. Matt'r. 1998,
10. 920.
51. J. E. Ujorkholm, C. V. Shilnk, Higher-order distributed feedback ocillalors, Appl. Pltys. Le1L
1972, 20. 306.
52. M. Berggren, A. R. E. Slusher, Z. Light amplification in organic thin fil ms
using ca!.C<Ide energy tmnslcr. Nuwrc 1997, 381J, 466.
53. N. N. T. Harrison, R. H. Friend, High peak briglnnes.. polymer light-cmiuing diodes. Mv.
Mt11er., 19911. /0, M.
54. H. Otaya. R. Pogrcb. D. Davidov, uv clcctrolumincsccoce from poly(p-phcnylcnevinyl
enc) polymer induced by strong voltage pul:.c' Phys. Hl'll. JJ 1997, 56. Rt2702.
References 331
55.
F. P. DcnBaarl>, A. J. Hccger, White light. from lnGaN/coujugalcd polymer
hybnd hght-emnung diodes. Appl. Pll.vs. Leu. 1997, 70, 2664.
56. G. J. Denton, N. :c.'ililer. R. H. Friend, Spcctr;tl narrowing in opliCillly pumped
hl01s, Af/1: Matt!r. 1997. 9. 547.
Hide, B. J. M.D. McGehee, M. R. Anders.wn. A. J. Hccgcr. Plas-
tiC companson ot gam ll<lrruwmg wrlh a soluble semiconducting polymer in waveguides
57.
and nucrocaVIliCS. Appl. Pfl_r.<. Len. am. 70. 3191.
51!. M. McGehee. M. A. Diaz-Garcia, E Hide, R. E. K. Miller. D. Moses A J Hcegcr,
Scnm:onducting polymer di:.tributcd Appl. Plty.v.. u.-
11
19911, 72, 1536.
11 Physics of Polymer Light-Emitting Diodes
I. H. Campbell and D. L. Smith
11.1 Introduction
Polymer light-emiuing diodes (LEOs) have the potential to revolutionize display
technology by enabling low cost, color tlat panel di splays with viewing properties
compar.tble to conventional cathode ray tubes {I). Polymer LEOs have been dem-
onstrated with emission wavelengths throughout the visible spectrum (2]. adequate
luminous efficiency for large area displays and device operating lifetimes exceeding
7000 hours 131. In spi te of these impressive results the intrinsic limits or polymer
LED performance and operating lifdiml.! have not yet been reached. It now appears
that polymer LEOs will soon be uti lired in a wide variety of display products.
Polymer light-cmiuing diodes were first reported in 1990 (41. The polymer
used in these first devices was poly(para-phenylene vinylene) (PPV). The chemi-
cal structure of PPV and the device structure of an early polymer LED are shown
in Figure 11 -1. Poly(pam-phenylene vinylene) is a conjugated polymer with an
energy gap of roughly 2.7 eV which emits in the green region of the spectrum at
about 2.3 eV. The device structure is a metaVundopcd polymer/metal structure em-
ploying indium tin oxide (ITO) as a transparent anode and aluminum as the cath-
ode. In forward bias. electrons arc injected from aluminum and holes from ITO.
1be injected electrons and holes recombine in the polymer emitting light. The
polymer layer is thin, typically I 00 nm, to allow efficient charge injection into
and transport through the undoped polymer film.
The current-voltage and luminance-voltage characteristics of a state of the art
polymer LED [ ~ are shown in Figure 11 -2. The luminance of this device is
roughly 650 cd/m at 4 V and the luminous efficiency C<\n reach 2 lm/W. This lu-
minance is more than adequate for display purposes. For comparison, the lumi-
nance of the white display on a color cathode my tube is about 500 cdlm
2
l5]. The
luminous etliciency, 2 lm/W, is comparable to other emissive electronic di splay
technologies f5 j. The device structure of this state of the art LED is similar to the
frrst device although a modified polymer and ditTercnt metallic contacts are used
to improve the efficiency and stability of the diode. Reference {2] provides a re-
view of the history of the development of polymer LEOs.
The operating principles of polymer light-emitting diodes are fundamentally
distinct from conventional inor.;anic semiconductor-based LEOs. The rcctilicatinn
and light-emitting properties of inorganic LEOs arc due to the electrical junction
. between oppositdy doped, J> and 11 type regions of the inorganic semiconductor
[6]. In contrast, polymer light-cmiui ng diodes arc formed using un undopcd, insu-
334
II Physics of Polymer light-Emitting Diodes
- PPV ( 100 nm) Polymer Emissive Layer
!J ITO (200 nm) . . . . Tr-.111sparcnt Contact
n Glass Substrate
AI <oonm>mTopMetalcontacl
Poly (p-phcnylcne vmylcnc) Lighl Emission
Figure 11-1. Chemical structure of poly(Jxlra phenylenc vinylene) (PPV) 0111d schematic polymer LED
device structure.
150
1500

.. e
r"

- rnAJcm'
c
<
- - cdlm2 1000
.!.
100
:::0
..
:::0

0
;;;
n
c
0
..
Q
500
c.
50
3
i:
...J
..
t:
:::0
u
2 3 4
Bias (V)
Figure 11-2. Current-volt.age 010d Juminanc.:e-voltage characteristics of a state of the an polymer LED.
lating polymer. The rectitication and light-emitting properties of the LED
are caused by the use of asymmetric metal contacts. One .contact 1s only
able to inject electrons efficientl y and the only IOJCCts holes ef!i-
ciently. The injected electrons and holes recombme m the polymer enut-
ting light. High work function metals more clfic1ently electrons
and, similarly, low work function metals Inject electrons more effictently than
holes. Therefore, the hi gh work function metal is the anode and "':'ark
function metal is the calhode. This defines the forward and drecta.ons
of the diode and leads to current rectitication, bipolar charge IOJCCtJon, and hgh1
emission in polymer LEOs. The essential physical to be un-
derstood to describe polymer LEDs are therefore charge 11110 the un-
doped polymer from the metallic contacts, charge transport m the polymer fi lm
and electron-hole recombination processes in the polymer. _ .
Polymer LEOs are similar to thin film organic molecular LEOs hrs.l reported m
1987 [7 ). Organic molecular LEOs uti lize thin lilms of small
rc1ther than polymer films as the light-emitting The films ol small organac
molecules are undoped and have electronic propcrtte:,. comparable 10 the
lilms used in polymer LEOs. In geneml, 1he device physics of polymer LEOs IS
11.2 Thin Films of Elcctmlumil!esccllt Polymers
335
similar to that of molecular LEOs. The understanding of lhe device
phys1cs of these two types of LEOs has proceeded in parallel and the conclusions
here a_re applicable to both molcculur and polymer LEOs.
Thas ch:1pter 1s orgamzed as follows: in Section 11 .2 the relevant properties of
elcctrolummesccm polymer films are summarized; in Section 11.3 the electronic
properties of metaVp.olymer are described; in Section 1 1 .4 single layer
LEOs dascussed; 111 Secllon 11 .5 multi-layer polymer LEDs are con-
sadered; and Sectaon 11.6 summarizes the conclusions.
11.2 Thin Films of Electroluminescent Polymers
Electroluminescent polymer thin lilms are typically prepared using spin casting
. . that aa:e .soluble in common organic solvents arc spun cast
from soluuons about I% polymer by weight. Poly(pClm-pheny-
lcne vmylene) and polymers are typically prepared using precursor
polymer rou1es. !_\ thm him 1_s by spin casting 1hc precursor polymer
then convertmg the resultmg thm him to the desired polymer. The two tcch-
naques produce tilms simil_ar propenies. Poly(pam-phenylene vinylene) tilms
With crystall ite sizes of :.ahou1 5 nm 21. Polymers
wath large sade ch:.ams, ollcn mldw to improve lhe polymer solubil ity, are typical-
ly an:'orphous. To polymer films have been produced using a wide variety of
and processmg conditions, i.e. different solvents, polymer concentm-
uons, spm speeds, and convers ion tcmpemtures. Therefore, two nominally identi-
cal films of the poly.mer often have somewhat different physical properties.
polymer lllms cons1s1 of a large number of polymer chai ns each consisting of
hundred monomer repeat units. TI1e electronic sl ructure of the poly-
mer IS not darectly related to the physical length of the polymer chains. Electronical-
ly, the polymer chain may be to consist of a number of conjugated poly-
mer segmems separated by tw1sts or kinks that disrupt the 1C bonds between ditTerent
segments of same physical polymer chain 1M). The 1erm 'conjugati on length' is
used to dcscnbe the mean length of these conjugalcd segments. The electronic struc-
of the film is lhen similar to a dis1ribu1ion of oligomer molecules of
lengths. the electronic energy slructure of oligomer molecules is a
the oligomer !ength the distribution of conjugation lengths produces
a dastnbutaon of elcc1ron1c slales an lhe polymt!r film. There is also di sorder in the
electronic of the polymer lilm due to variati ons in the local arr.mgement
of I he f I 0). Titc electronic energy struclure of a conjugated polymer
1s by the surrounding polymer chains because lhe electronic po-
ol surrounding medium vmi es and because or local dipole interac-
tions bc1ween nc1ghbori ng polymer chains. The combincu cl1oct of the distribution
of conjug<uion lengths and the disorder in the arrangement of polymer chains broad-
ens the electronic density of stales by about 0. 1-0.2 cV.
336 I I Physics vf Polymer Li8ht-Emitting Diodes
11.2.1 Electronic Energy Structure
One of the fund<Imental processes occurring in polymer LEOs is charge injection
from the metal contacts into the electroluminescent polymer film. This charge in-
jection can be <.juaJitatively understood by considering the electronic energy struc-
ture of the thin polymer film. The electronic energy structure of a PPV film [11,
12] is shown in Figure 11-3 along with the work function of various metals used
as contacts in polymer LEOs [13]. The ionization potential (Ev) of PPV. i.e. the
energy re4uired to remove an electron from the highest occupied state to vacuum,
is roughly 5.2 eV. The electron aftinity (l:.'c-), i.e. the energy gained when adding
an electron to the lowest energy unoccupied state from vacuum, is roughly 2.5 eV.
The energy gap. is about 2.7 eV. To inject electrons the contact must be
able to donate electrons into the lowest unoccupied state 2.5 e V below vacuum.
Similarly, to inject holes (remove electnms) the contact must be able to accept
electrons from an energy 5.2 eV below vacuum. In the limit of no interaction be-
tween a metal and a polymer in physical contact, their relative energies arc deter-
mined by the work function of the metal and the electron affinity and ionization
potential of the polymer. 'Ibis limit is the ideal Schottky model (14 J. In this mod-
el, the energy barrier to electron (hole) injection is
cj)r(lr) = IE,.()- WI ( 11.1)
where W is the work funttion of the metal contact. The ideal Schottky model is
found to apply to PPV-based polymers. lberefore, to inject electrons imo PPV, a
metal contact should have a work function close to or less thM 2.5 eV and to in-
ject holes, the metal should have a work function close to or greater than 5.2 eV.
This is the basis for the use of high work function metals as anodes and low
work function metals as cathodes. l11c eflccl-; of using different metal contacts
will be discussed in Sections 11.3 and 11 .4.
11.2.2 Optical Properties
The optical absorption Md electroluminescence emission spectra of a soluble PPV
derivative, poly(2-methoxy, 5-(2' -ethyl-hexyloxy)- 1 ,4-phenylene vinylene] (MEH-
PPV), arc shown in Figure 11-4. The absorption and emission spectra arc typical
of PPV-based polymers. TI1e maximum absorption coellicicnt is about
2.5xl 0
5
em- . The absorption has a broad peak, which is roughly O.S cV wide
with vibronic features evident at ubout 2.2 cV and 2.4 eV. The energy gap of
MEH-PPV is about 2.4 eV ( ISJ. The energy gap is larger than the optical absorp-
tion onset because of the exciton binding energy. The exciton binding energy in
conjugated polymers is typically a few tenths of an electron volt r 16]. Tile electro-
luminescence emission spectrum peaks at about 2 cV anJ also contains seveml vi-
bronic peaks allhough the highest energy peak is dominant. The diode elcctrolu-
Vacuwn Level
Elcclron A!Ciniry (Ec>
1/.2 T11i11 FiluL\ of Poly111ers
PPV
Worl: Funcoons of Metal Comacts
- -- - - ---- OcV
-2.5cV
Sm 2.7 eV
Ca 2.9cV
Mg 3.7cV
AJ, Ag 4.3cV
-- Cu. ITO 4.6 cV
toniurion POicntial (Ev> ---
5
_
2
cV Au5. t cV
1'1 5.7cV
337
Fq:ure 11-3. Et.:,tron energy kvd diagr.un uf Prv
00
rk
in JXllym.:r lt.r... '
1
wo Ulll:tnms uf scb:lcd t:ontu:l used
..
.....
0.4
;:;
:>
0.8
'
- .0
...
0. 3

0
., 0. 6 . ;a
..,
'.
;:;
c
.. .,
u
0. 2
"' 0.4
.
0 .,
c A
e
'
"' '
'

:>
-<
g
'
0. 2 0. 1
u
.,
iij
2.0
2. 5
0. 0
3. 0
Phoron Energy (cV)
Figure 11-4. ElcclrolumincS(.'Cncc a 11 p1 1 b

1
' u " SJl<.'Cirum uf the soluble polymer MEH-PPV.
spectrum is broad, roughly 50 nm wide. The width of th b
and emtsston spectra is partially due to the disorder in the ,- lttl Ladde a sol rpuon
that t . r k" . . cr po ymers
abrln _n tng groups th?t preserve the structure or the polymer chain have
const em y sharper spectral teatur 1111 Tl 1 1
h . . . . es 1..: P toto unnnescence spectrum (not
s_ s the spectrum indiGlling that the excita-
tions optically dectncally ;u-c illcntical. The red shift in enl!r> be-
tween opucal absorptron ;utd emission pcaks of about o ') . y . .. 1 ..
trolununescent polymers. - c s typ1c.J ol elc.:c-
A cri_tical parameter in determining the ellicicncy of polym r LED .
of singlet cxciruns in the polymer i.; the
t uy t tat .r smgkt cxnton wtll <b:ay r<rdi;rti vcly. Tit.: quantum clli-
33H II Physics of Polymer Light-Emitting Diodes
ciency of the singlet exciton is detem1ined by measuring the photoluminescence
quantu m efficiency. In this measurement, optical absorption produces singlet exci-
tons and the fraction of those that recombine radiatively is measured. In an LED,
the singlet excitons are produced by injecting charge from each contact rather than
through optical absorption. The recombination probability for singlet excitons pro-
duced optically and eleclricaJly is assumed to be identical. The li rst polymer films
used in LEDs had photoluminescence quantum efficiencies of roughly 30% fl8j.
Improvements in synthesis and polymer design have increased thi s to more than
80% [3] and it appears that films with photoluminescence efficiencies approaching
I 00% can be produced. The photoluminescence quantum efficiency does not then
significantly limit the maximum operating efficiency of polymer LED.;.
11.2.3 Electrical Transport Properties
Conjugated polymers which emit in the of the optical spectrum
have energy gaps in excess of 2 cY and therefore negligible intrinsic carrier
concentrations (< 10
5
cm-
3
) at room temperature. Although the polymers may be
electronically doped, the dopant countcrions signilicantly perturb the intrinsic
properties of the undopcd polymer gcncmlly making the carrier mobilities, which
arc dctcnnined in doped lilms, not relevant to the undopcd films used in LEOs.
Adding an electronic charge to the undopcd polymer cn.:ates an accompanying tat
lice deformation. The charge and the accompanying lattice deformation is called a
polaron I 19). For convenience, electron polarons and hole polarons arc referred to
simply as electrons and holes in this chapter.
'Ibere are two methods currently in wide usc to describe the clccuical transport
properties of undoped conjugated polymers. Both attempt to account for the ener-
getic disorder characteristic of polymer thin films but using diO"ercnt fom1alisms.
One approach describes charge tmnsport in the polymer by an electric field-depen-
dent mobility [20- 241. This description arose from related work on charge trans-
port in molecularly doped polymers. Another technique typically uses a field-inde-
pendent mobility but considers trapping eftects, particularly the energy distribu-
tion or the trapping sites, within the polymer film !25, 261. TI1is approach arose
from tmnsport studies of disordered inorganic semiconductor Because of
the disorder in the polymer and the different methods of accounting for the disor-
der it is difficult to rigorously dcline the carrier mobility of the polymer films.
For example, with a fteld-dcpcnuent mobility, the mobility varies hy about two or-
ders of magnitude for the electric liclds typical of polymer LEOs while in the
trapping approach the mobility is nominally well delincd but the charge transport
properties of the film depend strongly on the densi ty of the injected charge.
Two main methods have been used to measure the charge carrier mobility in elec-
troluminescent polymers: time of flight ( f OF) carrier tmnsittime measurements and
analysis of the current-voltage (1-V) chamcteristics of single carrier device::; in the
::;p;tcc charge-limited current (SCLC) regime. A summary of the results for the hole
mobility of PPV and PPV-relatcd polymers is given in Table I 1- I 124, 27- 32]. For
11.3 Device l:.'lectnmic Structure
339
Table 11-1. Hole mobilily of u1l<loped PPV-ba.'iCd polymers dclcnnincd by various methods.
Polymer
PPV
PPV
PPV
PPV
PPV
Dialkoxy-PPV
MEH-PPV
IO'K
10
7
- JU"'
Jxro "- ro-
7
2xto-<>
Ill tt-sxro-x
.lxi0-4>
Sxt()
1
'
Mclhod
TOF 1241
Tr..msislor I 21\l
Tr.u1sien1 EL 1301
SCLC 1291
SCLC 1311
SCLC [26, 271
/- Vanalysis 1321
PPV, the values range from a few times l0-
6
to l n-H
0111
2
y - 's- ' n. d f a1
. . . . . . . u . 11US sprea o v -
u_es a of elcctnc fields and carrier densities which accounts for a
ol At arc few measurements of the
electron 1s d11f1cult to measure by time of flight
tcchn1qucs because 11 1s extremely scns1t1vc to small numbers of extrinsic Lr.1pping
and electron tr.tps are predomin:.mt in conjugated polymers [33 1. It is also
t_o mobility using current-voltage analysis because of a
combma_L1on ol and the use of reactive, low work function metals
effic1ent uycct_JOn. The mobilities 1ablc .11 - 1 arc typical of cunju-
_arc seven to ten ol magnitude smaller than inorganic
mobillll':-'i . low mob1hty of the polymer plays a critical role in
dctenn1mng 111JCCtlon and tr.mspon ch:mu.:teristics of polymer LED .
. :he rest ol th1s chapter will focus pri marily on results using the soluble
MEH-PPY. _The :csulrs obtaincu for MEH-PPV are typical or the
polymers m LEOs. l11e_ and results presented arc gener-
ally appltca_blc. l11ey the operatton ol a wide ranoe of polymer LED . f
r.he appropnate polymer lrlm properties an:: used. e s I
11.3 Device Electronic Structure
In th1s section the electronic structure of metal/pol)' mcr/mctal dev
1
ce . . . d
ered Tl . h . . s 1s cons1 -
. us 1s _I _c to describe the operating characteristics of
LEOs. TI1e hrst scctton dcscnbcs 1ntemal photoemission measurements of metaU
Schottky in device structures. The second section . rc-
measurements ol bUtlt-m potentials which occur in device stru .
1
. PI
1 t 1 . h ..
1
- . c ures cmp oy-
ng me a Wit energy barriers. The Schottky energy banicrs
and the d1odc butlr-m potcntral largely determine the electrical cha ... , . . . t'
polymer LEOs. lactenstJcs o
340 11 Physics of Polymer Lisllt-Emitting Diodes
11.3.1 Internal Photoemission Measurements
of Schottky Energy Barriers
The electrical injection properties of metal/polymer contacts arc detennined by the
magnitude of the Schottky energy barrier to charge injection into the polymer
film. The Schottky energy banicr to electron (hole) injection is the energy differ-
ence between the Fermi energy in the metal and the lowest energy unoccupied
state (highest energy occupied state) of the polymer at the contact. To understand
the operation of the device quantitati vely, the magnitude of the metal/polymer
Schottky energy barriers must be known. The most direct way to measure the
Schottky energy barrier is to usc internal photoemission. In internal photocmis-
sion, optically genemted hot electrons (or holes) in a metal yield a photocurrcnt
as they traverse a metal/insulator interface. The photocurrent yield is [34]
( 11.2)
where ltv is the photon energy. The Schottky barrier is determined by extmpolat-
ing the photocurrent as a function of photon energy. Depending upon the di rec-
tion of the electric lield in the structure either the electron or hole Schottky en-
ergy barrier is measured.
Figure l l -5a is a plot of the square root of the photocurrent yield as a function
of photon energy for an AVMEH-PPV /Ca structure in reverse bias. In reverse
bias, the photocurrent is due to electrons exci ted over the electron Schottky bar
rier as depicted in the inset of Figure 11-5 a. The solid line is a least squares fit to
the photocurrent, which extrc1polates to a Schottky energy barrier of 1.0 eV. Fig-
ure 11-5 b is a plot of the square root of the photocurrent yield as a function of
photon energy for the same AI/MEH-PPV/Ca structure as in Figure ll -5a and
also for a Cu/MEH-PPV/Ca structure both in forward bias. In forward bias, the
photocurrent is due to hot holes excited over the hole Schottky barrier as depicted
in the inset in Figure I I -5 b. The solid lines are least square fits to the photocur-
renL<;, which extmpol alc to Schouk y energy barriers of 1.07 c V and 0.80 e V for AI
and Cu, respectively. This difference in Schottky barrier height is consistent with
the difference in work function between Cu and AI.
These Schottky energy barriers are measured in the presence of an electric field in
the structure which b necessary to be able to collect the photocurrcnt. The photocur-
rentthresholds arc not the zero electric field Schouky barriers because of the electric
field in the polymer and the image charge potential created when the electron leaves
the metal. This effect results in a lowering of the Schottky energy barrier given by (341
( 11.3)
where is the electric field in the polymer and e is the static dielectric constant. The
Schouky energy barrier is lowered by 0.1 eV for an electric field of V/cm
using a typical polymer dielectric constant c=3. There ure two contributions to the
...... 0.3

oi.05
-5
-...... 0.2 0.95
g F- 2 6 10
o F!Ckl( IO' Vk:m)
.c

g 0.1

@
1.1 1.2 1.3
PhOton Energy (eV)
0.8
......
M
0
s ....
0.6
c:
0
0
0.4 .c

c:
0
::
0.2
u
<)
iii
.......
e AI
1.4
0.9 1.0 1.1 1.2 1.3 1.4
Photon Energy (cV)
1/.J Device Elettronic Structure
341
figun 11-5. ph<Jinemission rcspnn.-;c a funct ion of ph<llon energy for (a) an AUMEH-PPV/
Ca structure bra. .... -d to collect ei\."Cirons and (b) for the same AUMEH-PPV/Ca slrtK:turc and a Cui
MEH-PPV/Ca struclun: bmsct.l In cullcct lnM:I in (;r) the .:lcctric ricld t.lcpcnt.lcncc of the
photoccspotL\C thn::<l10kl for the AUMEH-PPV/Ca slrtK:turc biasecJ to collect electrons.
electric l'ield in structure; the external hias applied to the struc-
ture _the bu1lt-m potcnttal caused by the use of asynmlCtric metal comacts. The
held d?pendence of the photoemission threshold, including the effects of the
below), agrees with thi s expression as shown by comparino it
w1th b1as-dependent data in the upper ten inset of Figure ll -5a. o
lt Is dJ (hcult _ to mctaVpolymer Scholll\y energy barriers smaller than
about 0.5 e'! mtcrnal photocmission. Small Schollky energy b:u..-iers lead to
em1ss10n prouuccd by the absorption of light in the metal which
are 10 trom photm:uncms 1341. 1 f the structure is cooled
10
try to_ Improve th1s ll 1s often found that the signilicant decrease in the
of the polymer f27 J makes it dillicult to measure the
_cunent. To overcome this limitation, internal photoemis-
Sion and measurements arc combi ncd to measure small Schouky
energy burners, as dcscnbed bcluw.
342 11 Plrysic:s of Polymer Uglu-l:.iJJilling Diodes
11.3.2 Built-In Potentials in Device Structures
Schematic energy level diagrams of a metal/polymer/metal structure before and
after the layers are in contact are shown in the Lop two drawings of Figure 11-6.
Before contact, the metals and the polymer have relative energies determined by
the metal work functions and the electron affinity and ionization potential of the
polymer. After contact there is a built-in electric field in the structure due to the
dif'terent Schottky energy barriers of the asymmetric metal contacts. Capacitance-
voltage measurements demonstrate that the metal/polymer/metal structures are
fully depleted and therefore the electric field is constant throughout the bulk of
the structure 131, 35]. The built-in potential, vh/. i.e. the product of the constant
built-in electric field and the layer thickness may be written
( 11.4)
where <P.,
1
<
21
is the electron Schottky energy barrier between metal 1(2) and the
polymer anti W
1
<
21
is the work function of metal I (2). The buill-in potential is
equal to the di fference between the work functions of the two metal contacts
(equation in brackets) only if there is negligible charge trans!Cr between the me-
tals and either intrinsic or extrinsic eiC4:tronic states in the polymer lilm.
There are two widely used methods to measure built-in potentials in metaV
polymer/metal structures: electroabsorption [ 15] and photocurrcnt [36, 37). The
photocurrent or the electroabsorption signal is measured as a function of DC bias
applied to the structure. Both techniques rely on a signal that is proportional to
the electric fieltl in the polymer fi lm. In the electroabsorption measurement, an
AC bias at frequency, f, is appl ied to the device in addi tion to the DC bias. 1be
electroabsorption signal measured at the fundamental frequency, f, of the applied
AC bias is proportional to the static electric ticld in the polymer. In the photocur-
rent measurement only a DC bias is applied. The photocurrent signal depends on
the electric field in the polymer layer because the optically generated carriers are
separated efliciently and .contribute to a photocurrent only in the presence of an
electric field. In both techniques, the appl ied DC bias at which the signal is
nulled is the built-in potential of the structure. 'Ille signal is nulled when the ap-
plied bias cancels the built-in electric field in the polymer as showl'l in the bottom
diagmm of Figure 11-6.
Table 11-2 shows the built-in potential in metai!MEH-PPV/metal structures
measured by either clectroabsorption [ 15) or photocurrent techniques 137] for a
variety of contact metals. The uncertainty in both the work function differences
and the built-in potential measurements is about 0. 1 eV. For all or the structures
except the Pt-Ca and AI-Sm devices there is good agreement between the metal
work function dillcrcnce, LlW, and the bui lt-in potential, Vhi This indicates that
for a wide range of metal contaclo.; the Schottky energy barrier between the metal
and MEH-PPV is well approximated by the ideal Schottky model <llltl that stale
charging, which pins the Schottky energy barrier, is not significant. A built-in po-
tential smaller than the diJTerence between the contact work functions implies that
Before Contact
Ec
Ev
D
Polymer
Metal. w
2
Metal, w
1
After Contact

e2
Melai.W
1
Applied Bias= Vbi
+ e2
Polymer
Metal. W
2
Metai,W
1
1 /.J Device Efet'lrOJtic: Strucwre
343
I I -(. Sd1cma1ic energy diagnuns of mclal/
lruclurcs. 1l1c slluclurcs arc shown before
(upper panel). aflcr conlacl in e4ui lihrium (l'Cllll".tl
p;.uld). <IIlli. conlacl wi1h a hias c4ual Ill 1hc buill-in po-
lcnllal applu:d lu lh.: SlruLJurc llowcr Jl:lllCI).
1a_ble ll-2. Wurk funclion 6lV. and buill-in pulcnlial v, fur a of mclal C"III"ICI
pau-s 10 MEH-PPV. . v
Coni acts
61
(MEii-PPV)
A I-Sm
I.Cl
u
AI-Ca
1.4
1.3
AgC:1
1.4
1.-1
Cu-Ca
1.7
1.7
Au-Ca
2.:!
2.11
1'101
:!.X
2. 1
rro.cu
().()
0.0
TfO.MJ;
(). I)
1.1
344 II Physics of Polymer Light-Emitting Diodes
electronic state charging has occurred [38]. A smaller built-in potential could be
due to charging either intrinsic states of the polymer or metal/polymer interface
states. If small built-in potentials, which are not related to intrinsic charged excita-
tion energies, are observed, then this is a clear indication that interface slate
charging is the limiting process. 'n1is is the case for the common semi-
conductors such as Si and GaAs. By contrast, for most electrolununescent poly-
mers investigated, the built-in potentials scale directly with the metal work func-
tions over a wide mnge and built-in potentials nearly as large as the polymer en-
ergy gap can be observed. .
Tile satumtion of the built-in potential in the Pt-Ca and the AI-Sm structures IS
caused by charging intrinsic states in the MEH-PPV film. The energy gap of
MEH-PPV is about 2.4 eV with the electron and hole energy levels at about
2.9 e V and 5.3 e V, respectively [ 15]. The work function of Pt is larger than the
hole energy level of MEH-PPV. When Pt is in contact with MEH-PPV, electrons
are transferred from the polymer to the metal pinning the electrochemical poten-
tial close to the hole energy level of MEH-PPV. Similarly, Sm h<IS a work func-
tion smaller than the electron energy level of MEH-PPV so that electrons are
transferred from Sm to MEH-PPV pinni ng the electrochemical potential ncar the
electron energy level of MEH-PPV. Figure 11 -7 shows the calculated built-in po-
tential (39j across an MEH-PPV lilm sandwiched between two metal contacts as
a function of the difference in work function between the high work function me-
tal and the fixed Ca contact. The relevant experimental built-in potentials taken
from Table 11-2 arc also shown in Figure 11-7. The work functions of the metals
used in the calculation are shown in Figure 11-3. The measurements and calcula-
tions were carried out for room temperature conditions. Because of the thermal
2.0
MIMEH-PPV/Ca

0.0 0.5 1.0 1.5 2.0 2.5
Work Function Difference (WwWc.) (eV)
Figur e 11-7. und measured bu111-in polcnllal as a funo.:ti<lll or rnelal work func1ion differ-
ence fur mclaVMEII-PPV/Ca The calcul:llcd buill-in pulcnlials for lhc unJup..-d Mcii-PPV
struciUrcs arc in guud ugrccmcnl wilh lhc mcasurcJ huill-in
I I . .J SinKft: fayer DI!Vicl!s 345
occupation of the energy levels, essentially no built-in potential occurs unti l the
work function is about 0.2 eV below the electron energy level in the undoped
polymer. The built-i n potential then increases <tpproximatcly linearly with increas-
mg work function until it saturates at about 2. 1 V. The saturation value of the
::JUilt-in potential is somewhat smaller than the energy gap because of thermal oc-
cupancy of the energy levels.
The built-in potential in the structure is a measure of the difference between
the Schottky energy barriers of the two contacts. Combining built-in potential
measurement-; with intcmal photoemission results , which directly measure: the
Schottky energy barrier, allows a wide range of Schottky energy barriers to be de-
termined. many conjugated polymers the ideal Schottky model provides a
good descnptwn of the electronic structure of mctal/polymcr/mct;tl stn1ctures. The
bar:_iers arc given by Eq. ( 11. 1 ). The Schottky barriers and built-
m potenlmls lor MEH-PPV detennincd from this combination of measurements
are used in the next section desc1ibing single-layer devices.
11.4 Single-layer Devices
In this singlc-luyer polymer devices consisting of one conjugated polymer
layer sandw1ched between two metallic electrodes urc considered. A device model
is used to describe the operation of polymer LEOs and the results of the model
calculations arc compurcd with experiment al obscrvutions. TI1c first section dis-
c_usscs structures in which the energy banicr to inj ection of one ear-
ner type 1s slglllhcantly larger than for the other so that the cun-cm tlow in the
device is dominated by a single carrier type. Although such single-carrier struc-
do not function as LEOs. they provide a compamtively simple situation in
wh1ch to study the operating p1inciples of polymer dioc.lcs. The second section
lhen considers two-canicr structures in which both carrier types arc injected and .
which function as LEOs.
Since the first report of polymer LEOs in 1990 there has been considemble
the opcr.tti ng principles of the devices [2, 40]. System-
atJc mvest1gat1on of the charge injection properties of different metal contacts in
single-layer polymer LEOs W<IS first rcpo11ed in [41]. Sp<1ce charge-li mited hole
from an electrical contact with a small Schonky energy barTier were re-
ported 1n Ref. [27]. Etlicient devices employing both electron and hole contact<>
with small Schottky energy barriers have also been reponed 1421. These results
provide the essential foundation for the device model described below.
346 I 1 Physics of Polymer l.iglu-Emilling Diodes
11.4.1 Single-carrier Structures
The device model describes transport in the organic device by the time-dependent
continuity equation, with a c.lrift-dillusion form for the current density, coupled to
Poisson's equation. To be specilic, consider single-carrier structures with holes as
the dominant carrier type. In this case,
( 11.5)
where
( 11.6)
Here, pis the hole density, J
1
, is the hole current density, G(R) is the carrier genera-
tion (recombination) r.uc, p
1
, is the hole mobility, e is the magnitude of the electron
charge. is the electric field, k is Boltzmann's constant, Tis the temperature, and the
diffusivity has been written in terms of the mobility using Einstein's relation. Re-
combination does not occur in a single-carrier device and generation is negligible
at room tcmpcmturc for the comparatively large energy gap polymers being consid-
ered. 1l1e right hand side of Eq. ( 11 .5) therefore vanishes for single-carrier devices.
The model uses licld-cJcpendcnt canicr mobilities given by L20-241
( 11.7)
where is the eleclric field and p
0
and Eo arc material parameters. The charge in-
side the polymer is dominated by the injected carriers and the electric field is de-
tennined by Poisson's equation with the charge given by the hole density.
The boundary conditions are given by specifying the particle currents at the
boundaries. Holes can be injected into the polymer by thcnnionic emission and tun-
neling 1321. Holes in the polymer at the contact interface can also fall back into the
metal, a process usually call ed interface rccombina1ion. Interface recombi nation is
the time-reversed process of thermionic emission. At thcnnodynamil.: equilibrium
the rates for these two time-reversed processes arc the same by detailed balam:e.
Thus, there arc three current components to the hole current at a contact: thcnnionic
emission, a backflowing interface recombination current that is the time-reversed
process of thcnnionic emission, and tunneling. Specifically, take the contact at
x=O as the hole injecting contact and consider the hole current density at this contact,
( 11.8)
where 1,
11
is the thcnnionic emission current density, 1;, is the back flowing inter-
face recombination current density, and 1,, is the tunneling current density. A sim-
ple model for the thennionic cmis.-;ion current density is
I 1.4 Single-layer Det>ices 347
where A is Richanlson's constant. Because of the image force. the Schottky en-
ergy banicr to hole injection <J>It depends on the electric field at the interface as
described by Eq. ( 11.3). The image force ha1Tier lowering tenn is only includeJ if
the electric field has the correct sign. The interface recombination cum:nt density
is proportional to the hole density at the interface
l ;r = vp(O) .
(I 1.1 0)
The ki netic coc.:flicient ,, is determined by detailed balancing between thermionic
emission and interface recombination. The tunneling current density is calculated
using the WKB approximation for tunneli ng through a potential given by the im-
age force model. Tunneling is only possible if the electric field at the interface
has the COITCCt sign.
To dctenninc the kinetic coefficient ,. it is necessary to specify an equilibrium
model for the polymer. For the e4uilibrium description. the polymer is considered
to be made up of a series of conjugated chain segments. Non-degenerate cases are
considered so that the occupation probability of a conjugated chain segment by elec-
trons or holes is much less than unity. Let u
0
be the densi ty of conj ugated seg-
mento; multiplied hy the numher of ways that a chain segment can be occupied by an
electron or hole (i.e., its dcgcncmcy). The equilibrium hole density is
(11.1 1)
where r/J(x) is the position-dependent potential and If/ is the Fermi en-
a the Fermi energy is detcm1incd by the metal. Because the po-
tenl!al 1s continuous across the interface, the equili brium hole density is
( 11 . 12)
where the equilibrium value for the electric licld at the contact is used to evaluate
</>ft. &juating the thermionic emission cun-cnt density. E4. ( 11.9), and the interface
recombination current density. &(. ( 11.10), at equilibri um determines the kinetic
coefficient ''
AT
2
1' =--.
llu
With this value for a, the thermionic cum.:nt density can he written as
(11.13)
( 11.14)
where p,,r{(0)) is the quasi-equilibrium hole density at the comact inclUt.ling the
barrier lowering l.luc to the electric field. (0).
348 II Physics of Polymer light-Emitting Diodes
The net hole current density at x=O can be written as
J,..(O) = v[p.,r(((0)) - p(O)] +11u ( 11.15)
where vp(O) is the interface recombination current and vpq .. (E(O)) is the ther-
mionic emission current density. At steady state the total particle current does not
depend on position. For si ngle-carrier devices there is only one component to the
particle current and therefore that component can nor depend on position. For a
hole-only device the hole current is independent of position and J
1
,(0) is equal lo
the net device current density. Eq. (11.15) can be solved for p(O)
)
l w -J,/
p(O) = Pq.-(E(O ) + -'----'-
v
( 11.16)
where is the net dcvke current density. For polymer diodes the device cunent
density is negligible compared to the sum of the thennionic and tunneling current
densities so that can be dropped in the above e4uation. the device
current is too small to significamly alter the hole at the comact. There are
therefore two limiting regimes: one in which the thermionic emi ssion current den-
sity is large compared to the tunneling current density so that p(U) =p,
1
,.(E(0)) and
one in which the tunneling cum!nt densi ty i!> large compared to the thermionic
emission current density so that p(O) =J,/1'. The lirst limit often occurs in poly-
mer LEDs under their usual opcn.lling conditions. It provides a particularly si mple
case because the contact region is in quasi-equilibrium and all the complexities of
the actual injection processes drop out.
Intuitively one expects that for small energy barrier contacts, current llow in a
si ngle-carrier device wi ll be limited by charge eflccts and for large energy
barrier contacts, current flow will be limited by the contacts. To investigate the
transition between space charge-limited and contact-limited current flow, we con-
sider organic diodes fabricated using MEH-PPV with injection barriers such that
holes dominate the CUITCilt now. We take a device I 00 nm thick, ti x the cathode
barrier for electron injection at 2.2 cV com:sponding to a Au contact (at this large
value for the barrier few electrons arc injected), and vary the anode barrier for
hole injection from 0. 1 to 0.6 eV in 0. 1 eV steps. We usc a dielectric constant
and take II()= 10
21
cm-
1
. By comparing with experimental results we usc
p.(
1
= 1.7 10-
7
cm
2
V
1
s-
1
and 1::.(
1
=7.5 10 .. V/cm for the hole mobility par.1metcrs.
The calculations arc carried out for room tcmpcmture conditions. The upper panel
of Figure 11-8 shows a linear-linear plot and the lower panel a log-linear plot of
the calculated /- V curves. The C<tlcul ated results for 0. 1. 0.2, ami 0.3 c V barriers
are nearly the same. For these cases, the current now is space charge limited. As
the energy barrier is further increased the current is decreased indicating that the
current now becomes contact limited. These results show that, for typical organic
LED device parameters, it is important that injection ba1Tiers be kept less thtm
about 0.4 e V.
Figure 11-9 compares measured (solid lines) and calculated (dotted lines) 1- V
curves for MEH-PPV devices of about 11 0 nm in thickness, in which the cathode
1/ . .J Sillgie-/ayer Devices 349
0.10
0.08
0.06
0.04
N'
0.02
E
0

..,
1o2
10-3
0
Bias (V)
foigurc ll-8. Lim:ar-lin.:ar (upp.:r panel) and log-linear (lower p:u1cl) plots of c:akulmcd current den-
sity a.\ a function or bias vnhage lor 100 nm MEH-PPV devices with a 2.2 cV batTu:r 10 clcc:lron in-
jection and 0. 1. 0.2, O.J, 0.-t. 0.5. ami 0.6 eV baiTier.. 1u hole injection.
Al4.3 cV-
Cu4.6cV-
AuS. I cV-
1'1 S.7cV-
- --- - AuS. I cV

0.1Sr--......,---,cr-- -.----.-.-.
N'
E 0.10

.., 0.05
Bias (V)
fo' igurr 11-9. Measured l'olid hnc') and calculated (Ja,l-...xl lin.:') c.:um:nt dcn,ity a.' a function 11( volt-
age bias for MEI-I -PPV devices of ahnul I 10 11111 in tlli.:l-nc'' with 1\u a.' I he clcclron injecting oontacl
and PI, 1\u. Cu. and AI the hole injL-.:ti ng cuntac1. l11c: upper panel 'huws a M:hcmatic energy level
diagr.un li>r the sli1J<:Iun:s.
contact is fixed to be Au and the anode contuct is varied between Pt, Au, Cu, and
AI. A schematic energy level diagram of the structures is shown in the upper pan-
el of the ligure. Due to the large energy batTier for clct:tron injection from Au
into MEH-PPV, there are very few electrons injected into the device. The mobility
parameters Jlo and 0 given above were detennined by lilting to these data. The
same mobility parameters were used for the cakulati on of all four devices. The
350 11 Physics of Polymer Lighr-Emittiug Diodes
energy barriers for hole injection into MEH-PPV were: essentially zero for Pt,
0_2 eV for Au, 0.6 eV for Cu and 1.1 eV for AI. These results are in reasonably
good agreement with the previously determined values. The 1- V curves for the de-
vices with hole injection from Pt and from Au are essentially the same. This is
expected because the energy baniers for injection in both cases is small enough
that the current is space charge limited. When the energy barrier is increased in
the device with a Cu contact, the current at a given bias voltage is much reduced
showing that the contact limits the current flow. The current is fUJther reduced
when an AI contact with a even larger banier is used.
The magnitude of the three components of the injected current, that is the
thermionic (dotted line), interface recombination (solid line), and tunneling (dotted
line) current components, together with the net device current (dashed line) for
the devices with Pt. Cu, and AI contacts is shown in Figure I 1-10. The upper
panel shows the case of a Pt-injecting contact, where the energy banicr to injec-
tion is essentially zero (0.05 eV was used in the calculation) and the current now
is space charge limited. In this case the magnitude of the thermionic emission and
interface recombination currents arc very large and they almost exactly cancel
each other out. The net device currem, which is the difference in magnitude be-
tween the thermionic emission and interface recombination currents, is much
smaller than either of these two components sepamtely. There is no tunneling cur-
rent because the electric field as the contact has the wrong sign for tunneling. The
thermionic emission current and interface recombination currents are independent
of bias because the applied electric field is completely screened by a large carrier
density at the inte1face and the electric field at the inte1face has the wrong sign
for image force barrier lowering. The injection current components for the case of
a Au injecting contact (not shown), which has a 0.2 eV energy barrier, arc qualita-
tively similar to that for a Pt contact. The absolute value for the thermionic emis-
sion and interface recombination components are smaller than for the Pt contact
device and they have some bias dependence because the applied electric field is
not completely screened at the interface. The magnitudes of the thennionic emis-
sion and inte1face recombination currents arc still much larger than the net device
current.
The middle panel of Figure 11 -10 shows results for the device with a Cu con-
tact where the energy barrier is increased to 0.6 eV and the current tlow is contact
limited. The magnitude of the thermionic emission and interface recombination
components are still much larger than the net device current in this case. The elec-
tric field ncar the contact is no longer screened by a high density of carriers near
to the interface as is the case for the device with a Pt contact and there is image
force lowering of the barrier. Therefore, the them1ionic emission cu1Tcnt is bias
dependent and in addition tunneling is possible. Over most or the bias range
shown, them1ionic emission is much larger than tunneling. but tunneling is a
stronger function of bias than thermionic emission is and at the highest bias
shown these two current components become comparable.
The lower panel of Figure 11-10 shows results for a device with an AI contact
where the barrier has been increased to 1.1 eV. All current components are
strongly reduced by the larger energy barrier and it is necessary to go to a much
.........
C\1
E
(..)

.._..
--,
106
1 o3 ThJmionic lnlertace Recombination
1
Pt/ Au Device Curren!
_____ ! __________ _
------
10-3

1o2
1
10-2
10-4
5
20
Bias (V)
10 15 20
Bias (V)
.... -"-
,,,'' --
_ .. -
,
" Thermionic . ,
. , .
bneling 0 Current
25 30
Bias (V)
35 40
11.4 Single-layer Devices 351
Figure 11-10. Calcul<ttcd valu.:s or the injc"ion current culllll<Uu:nts ;md the total device current as a
function of bias for lhc Pt (upper panel), Cu (ccntr:1l panel), and AI (lower panel) hole injecting con-
tact devices.
greater bias to get a reasonably large current. Because tunneling is a more rapidly
increasing function of bias than thermionic emission, tunneling is larger than
thermionic emission at the bias rcr1uired for significant current flow in this device
with a large energy barrier. Interface recombination nearly cancels out the tunnel-
ing injection current anJ the net device cmTent is much smaller than the tunneling
component. The net device current is approximately proportional to the tunneling
component but is much smaller in absolute magnitude [32j.
For typical polymer LED device parameters, current is space charge limited if
the energy barrier to injection is less than about 0.3- 0.4 eV <md contact limited if
it is lar<;er than that. Injection currents have a component due to thennionic emis-
sion and a component due to tunneling. Both thermionic emission and tunneling
352 1 I Physics of Polymer Liglu-Emirting Dicxles
are field dependent; tunneli ng is a more rapidly increasing function of field than
thermionic emission. For typical polymer LED parameters the thermionic emis-
sion current is larger than the tunneling current for electric fields less than about
2 1 0
6
V /em and tunneling is dominant at larger electric fields. At the lower fields
where thermionic emission dominates, a combination of emission and
interface recombination establishes a quasi-equilibrium carrier density at the inter-
face. This is a comparatively simple regime because the carrier density at the con-
tacts is determined entirely by statistical considemtions and the complexities of
the actual injection process arc not present. At higher fields where tunneling dom-
inates, a combination of tunneling and interface recombination establishes the car-
rier density at the interface. 'Ibis regime is more complex than when thennionic
emission dominates because the interface carrier density depends on the details of
thl! injection processes and can not be found from statistical resul ts alone. In all
cases the net dl!vice current is small compared to the largest injection component
Interface al most exactly cancels the injection current; that is, most
carriers that are injected into the polymer fall back into the metal contact. As a re-
sult of the very low mobilities of conjugated polymers, only a very small fmction
of the injected carriers arc cxtr.1cted from the contact region.
11.4.2 1\vo-carrier Structures
Carrier injection in a two-carrier structure works the same as for a single carrier
structure except that in the two-carrier structure the energy baniers to injection
arc small enough for both carrier types that they can be effectively injected. Car-
rier injection depends on the electric tield al the injecting contact. lf the density
of injected carriers is small enough that space charge etlects are unimportant,
which requires that the energy barrier for both carrier types is greater than about
0.3-0.4 eV, there will not be an interaction between injection at the two contacts.
If one of the barriers is lower than this so that space charge effects change the
electric fields at the contacts, there wi ll be an intemction between inj ection at the
two contacts because carriers inj ected at one contact will modify the electric field
at the other.
Carrier recombination occurs in a two-caTicr structure and whe1i it is radiative
leads to light emission of the polymer LEOs. In polymer LEOs the carriers that
are injected from the separ.ue contacts join to form an exciton which then recom-
bines. Either a singlet or triplet exciton can be fonned when an electron and hole
bind together. Only the singlet exciton has an allowed optical transition to the
ground state. The branching mtio for formi ng si nglet or triplet excitons is nOI
known but if it is governed by statistics alone, three triplets woul d be formed for
every singlet. Non-radiative recombination can occur in addition to radiative re-
combination. It appears that the non-r..tdiative recombination of singlet excitons at
low density is primarily defect rdated and may be 1n<1de insignificant in many
conjugated polymers. In contmst to singlet excitons, the intrinsic lifetime of an
isolated triplet exciton is probably mther long and their recombination may be
1/.4 Single-lilycr Devices 353
dominated by defect-related non-mdiative recombination. Assuming that all triplet
excitons recombine non-mdiatively and that the singlet/triplet fonnation bmnching
ratio is given by statistics alone, the existence of triplet exci tons would reduce the
possible polymer LED clliciency by a factOr of four. The consequences of triplet
excitons in polymer LEOs arc not clearly understood however. In inorganic LEOs
made from Ill- V semiconductors there is a comparatively large spin-orbit interac-
tion so thai spin is not a good quantum number and there is no loss in elliciency
due to tri plet excitons.
A device model to descri be two-carrier structures is basically simi lar 10 that
used for one canier structures except that continuity equations for both carrier
types are solved. 1lte additional process that must be considered is charge carrier
recombination. The recombination is bimolecular, R= )' (np), where the recombina-
tion coefficient is given hy 1431
4TCc' Jl
111
y = --
r.
( 11.1 7)
where Jt, is the lar<Jer of Jl, or Jlw This fonn for the recombinati on coetrident <IS-
sumes that exciton fomt<ltion is the rate limiting step for recombination and that
the exciton recombines rapidly after it is fonncd. The limiting step to exciton for-
mation is the approach of the two cm-riers under their mutual Coulomb attraction
in a low mobility material.
An accurate description of a single-layer LED should be obtained by using the
injection and transport prope11ies of electrons and holes, detennined indepen-
dently from the Schottky energy barrier and si ngle-carrier device measurements.
to describe the two carrier LED structure. To test this procedure consider struc-
tures fabricated from the conjugated oligomer 2 -methox y-S-(2' -ethy I hex ylox y )-
1,4-bis(4-styrylstyryl)/bcnzene (MEH-DSB) with electron and hole energy levels
at about 2.35 eV and 5.1 eV, respectively 144]. TI1e Schollky energy barriers are
given by the ideal Schottky model. Hole-only devices are made using an Au and
an AI contact. The Au contact has essentially no barrier to hole injection and the
AI conwct has roughly a 2 cV bmTier to electron injection. Electron-only devices
are fabricated using Sm and Ca cont:u:ts. Both Sm and Ca inject electrons into
MEH-DSB, but the injection barrier is too large lor ellicient hole injection from
either contact. The mobili ty pammeters for electrons and holes are separately
found by fiuing the /- V characteristics of the single-carrier devices. Figure 11- 11
shows a comparison or the measured and calculated 1- V chamcteristics for the
two single carrier structures. The solid lines are the measured results and the
dashed lines arc the calculated results. Tite show log-linear plots of the re-
sults. The hole-only device is about nm thick and the electron only device is
about 90 nm thick. The electron-only device is biased such that Ca injects elec-
trons. A two carrier device was fabricated using a Ca contact to inject electrons
and an Au contact to inject holes. The device was about HO nm thick. Figure 11-
12 shows a comparison of the /- V charac.:teristics of the two-carrier device with a
calculation using the mobility parameters detennincd from the single-carrier struc-
tures. The solid line is the measured result and the dashed line is the calculated
354 /1 Physics of Polymer LiJSht-Emiuing Diodes
Sm I MEH-DSB I Ca
0.10
10"
1
..........
0.08
C\1
E
0.06 10-2
(.)
-<(
0.04
-
....,
10-3
0.02
5
0
0 5 10 15
Bias (V)
AI I MEH-DSB I Au
0.3
..........
10-1
C\1
E 0.2
(.)
1o2
-<(
-
1()'3
...., 0.1
1o4
1
0
0 2 3 4 5
Bias (V)
Figure 11-11. Comparison of measured an<.l calculated current d.:nsity as a funcuon of for an
electron-only Sm/MEH-I'PV/D :.truciUre (upper panel) and a hole-only AUMEH-DSB/Au struCture
(lower panel). The main part:> of the fi gure are linear-linear plots and the in!>Cb arc log-linear plots.
result. The inset shows a log-linear plot of the results. There is reasonably good
agreement between the measured and calculated cu':es. .
The hole current in this LED is space charge limtted and the electron current tS
contact limited. There are many more holes than electrons in the device and all of
the injected electrons recombine in the device. The measured external quamum ef-
ficiency of the device is about 0.5% al a current density of 0. 1 Ncm
2
. The
bination current calculated from the device model is in reasonable agreement wtth
the observed quamum efliciency. The quantum efficiency of this device is limited
by the asymmetric charge injection. Most of the injected holes traverse the structure
without recombining because there are lew electrons available to form excitons.
An efficient LED has two essential characteristics: (I) all of the injected car-
riers recombine in the llevicc and (2) the opemting voltage is as low as possible.
To prolluce light cflicicntly, all of the current shoulll lead to recombination. This
0.3
N'
0.2
10- 1
E
10-2
1o3
..,
0.1 10 2
00
2 4
Bias (V)
6
11.5 Multi-layer Devit:es 355
figurc 11-12. Comparison of tneasurcd and
calculated current density a.o; a function of
for a two carrier Ca/MEH-PPV/Au
8 tructure. lliC main part of the figure is fin-
c:Jr-lincar plob an<.l the in,;ct is fog-linear
phlls.
requires the electron anll hole currents to be equal. It can be difficult to balance
injection in layer structures because the Schottky barriers to charge
lnJCCllon and the camer mobilities arc ditlicult to control. Carriers injected into
the polymer can either recombine in the film or they can uaverse the structure
and reach the other contact without recombining. A C<trrier that u-averses the de-
recombining is wasted and structures musr be designed to minimize
thts posstbthty. To produce LEDs with high power efliciency the operatin<> volt-
age be as low as_ possible. To reduce the operating voltage in a
0
single
layer dcvtcc the polymer I Jim shoulll be as thin as possible. From these considera-
tions, the polymer layer should then be the minimum thickness that allows com-
recombination of the carriers injected into the polymer lilm. lf both contacts
lllject carriers efficiently it is possible to achieve ellicicm recombination and low
drive voltage in single layer structures. In practice this is often difficult to
polymer diodes employing two or three polymer layers with
dtfferent elcctromc energy structures and diO.ercnt charge carrier mobilities allow
these criteria to be more readily satisliell.
11.5 Multi-layer Devices
In this section multi-layer polymer diodes consisting of two or three conjugated
layers _are_considcred. Multi-layer llcviccs are usually llesigncll so that ra-
dtallve takes place primarily in one or the polymer layers. n1ere
arc two pnnctple functwns that the additional layers can have: rhey can block in-
jected carriers from traversing the structure anu reaching the other contact without
and they can enhance current llow into the luminescent layer by
servmg as transport layers. The reh.tlivc energy levels and 1hc mobilities of the
electrons and holes in the polymer layers arc impot1<ull llcvice design parameters.
356 I I Physics vf Polymer Light-Emiuing Diodes
The values of these parameters in the polymer layers making up a multi-layer
structure plays an important role in the operation of the device_
The util ity and importance of multi-layer device structures was demonstmted in
the first report of organic molecular LEOs [7]. Since then, their use has been
widespread in both organic molecular and polymer LEOs [45, 46]. The details of
the ope1ating principles of many multi-layer structures continue to be investigated
[47-49}. The relative importance of chat'.;e carrier blocking versus improved car-
rier transport of the additional, non-luminescent layers is often unclear_ The dra-
matic improvefl'lents in diode performance and, in many cases, device lifetime
make a detai led understanding of multi-layer device physics essential.
11.5.1 Blocking Layers
It is possible that injected carriers traverse an LED structure and reach the other
contact without recombining. This is a parasitic process that is desir..tble to avoid.
The use of a blocking layer, whidl provides an energy barrier that injected car-
riers must overcome to reach the othl.!r contact, is a method of preventing this
pamsitic process. It is often the case that the current !low in an LED strudurc is
carried pri marily by one carrier type either because that canier type has a lower
energy barrier 10 injection or because it has a higher mobility. This was the case
for the MEH-DSB structure di:scusscd in the previous section in which holes
dominated the curn.:nt flow. In devices with unbalanced current flow, the effi-
ciency can be significantly improved by providing an energy barrier to the domi-
nant carrier type.
As an example, consider the structure schematically illustrated at flat band bias
in the upper panel of Figure 11- 13. It consists of two 50 nm polymer layers. The
layer on the right has an energy gap of 2.4 eY. The electron energy levels of the
two layers arc the same and there is a hole barrier which can be varied in the
layer on the right. First consider a hole-only device in which the energy barrier at
the hole injecting comact on the left is 0. 1 eY and the energy barrier to electron
injection from the contact on the right is 1.2 eV. The lower panel of Figure 11 - 13
shows calculated current-voltage chamcteristics when there is no hole barrier, a
0.3 eV hole barrier, and a 0.5 eV hole barrier. The mobility parameters arc those
used for holes in MEH-PPV in the previous section. With no barrier the current is
space charge limited. The 0.3 eV hole barrier significantly n.xluccs the device cur-
rent and the 0.5 e V banier almost completely blocks the hole current. A barrier of
about 0.3 eV is required for effective blocking, a 0.2 eV barrier for example has
only a marginal effect.
Figure 11 - 14 shows the calculated hole density (upper panel) and the electric
field (lower panel) as a function or position lor the three structures. For the de-
vices with a hole barrier there is a large accumulation of holes at the interface.
The spike in the hole density at the interface causes a rapid chang!! in the electric
fidd at the interface. The lield in the hole barrier layer is significantly larger than
in the hole injection layer. for the 0.5 eV hole banier stmcture, almost all of the
1/.5 Multi-layer Devices
357
I 24eV
-1 I
Hole Barrier t
50nm
0.10
0.08
I
-
I
(\J
No Barrier
I
E
0.06
I
0.3ev
1

I
0.04
I
I
-
I
.,
0.02
I
,
,
o.sev ,
0 --
-
--------
0 5
10 15 20
Bias (V)
_H-IJ. \:UITCill d.:nsity a fU114: liun uf hi;l, fur tWU Iayer huleunly Slrtl4:tun:s
(O. t cV IIIJCCtlun O..mer lur with a 0.0. ll.3, and 0.5 eV Clli!J1tY harrier fur hul.:.' at the intcrlia.:c
the polymer layers. Th.: upper panel is a xhcm;all.: of the energy kvcl diagram fur the
elcctr:c fic_ld i_n th_l! hole layer. 1l1c electric licld is approximately inde-
pendent ol m each ol the two layers. The electric lield in the middle of
the blockang layer and the luminescent layer is ploucd as a function of bias
Figure II : 15. As the bias is increased, the electric field in the blocking layer
r..tptdly. In_ contrast, the electric field in the luminescent layer remains re-
latavely _and with bias. The addition of a blocking layer
_two tmponam etlects; II causes an accumulation of charge at the block-
mg . because of this charge m:cumulation, it changes the electric
field dtstnbutton Ill the structure.
TI1e eflect of accumulation at a blocking layer in a polymer device
has du:cctly ob:-;crvet.l using elcctruabswplion h:clmiqucs 150]. The
structure consastcd of a large-energy-gap electron-blocking layer (P30A) and a
smaller energy gap lununcscent layer (MEH-PPV) e<tch 100
11111
thick sandwiched
betwcer_l Ca contacb. The internal electron energy barril!r was about 1 cV. 11
1
c
layer contact has a negligible Schonky energy barrier and the C<JJ
blockang layer contact has large electron and hole Schonky ener"y baniers. ri -
ure 11 - 16 shows the electric lldt.l in each of the layers as a of
358
E'
0
.._
>
L{)
0
::::::..
"0
iD
u:
0
;::
0
Q)
w
Jl Physics of Polymer Ughl-Emitting Diodes
10 V Bias

-----------1
\
I
- 0.3 oV
\ ------
0.5
0
20 40 60 80
Position (nm)
100
Calc:ulat<:J hole J cn:.ity
(upper p;md) ano.l ckctric liciJ (lower
a.' a fw1,tion uf P'"itiun for the three
turc' of F1g. II - L\ at 01 I 0 V I.J1a.'i.
20
15
10
5
LunVnescentLayor
0
0
4
6 8
10
Bias (V)
f.' i):III'C 11-15. electric Jic(J ;1 fu nction bi;L'i in lhC cc_nter of the blucking layer ;md in
the center of the layer oi the 0.5 cV barncr structure of l'lg. 11- 13.
.
0
t 1.he luminescent layer. This is an analogous situa-
in Figure 11_- 15 except in
arc blocked rather than holes. These expenmcntal demonstrate t_ e e, ec_
f block in , layers by directl y measuring the redtstnbuuon o_f the electnc . 10
due to the accumulation of charge al the blockmg layer/lummc.scent
layer interface.
8
6
5
>
"b 4
3
2
11.5 Muft1-fllyer Devices 359
Layer
Ot:----- -:-- - - --:-- - ----j Figure ll- 16. Measured electric licld as a
0 2 4
6
fum:1ion of bm' in the blocking layer
Bias (V)
11.5.2 Transport Layers
(P30A) ami in the luminescent layer
(MEi t-t>PV) uf ;m clcctron-only stru.:turc.
A polymer layer al a can enhance c.:UITenl fl ow by serving as a t.ransport layl! r.
The transport layer could have an increased canier mobili ty or a reduced Schottky
barrier. For example, consider an electron-only device made from the two-polymer-
layer structure! in the top panel of Figure 11- 13 but. using an electron contact on the
left with a 0.5 eV injection barrier and a hole contact on the right with a 1.2 eV in-
jection barrier. For this case the current is contact limited and thermionic
emission is the dominant injection mechanism for a bias less than about 20 V.
The electron density ncar the electron injecting contact is therefore given by
(I !.I S)
where the electric licld at the contact is used to evaluate (/), .. 1l1e electron current
is conti nuous at steady slate for this structure. The electron current
is dominat.cd by the dri ft. wmponem. i.e. the dinusion current is comparatively
small, so the electron current is
1,. = t'Jl(E(O) )E(O)nue
<J>,ft.T
(11.19)
Increasing the electron mobility in the layer ncar to the electron contact propor-
tionall y increases the net injected electron current. The current may nol change by
exactly the same amount that the mobi lily is increased by if the density of in-
jected electrons is large enough to change the electric field disttibution.
The upper panel of Figure 11 - 17 shows the or increasing the electron mo-
bility in the layer ncar to l.hc electron contact of the lwo-polymer-laycr electron-only
device. The solid line is the calculated 1- V characteristic when the electron mobili-
ties of the two layers arc the same and givcn hy the value used ahovc. 1l1e dolled li ne
360
J 1 Physics of Polymer Lig/lt-Emitting Diodes
0.10
.
.
.
.
.
0.08
.
.
.
- C\1
E
0.06
u

___.
....,
?:"
'i!!
Q)
0
c
e
0
Q)
jjj
0.04
.
.
.
.
.
0.02
.
.
.
.
.
...
.
0
_ .. _ ..
0
2
4 6
12
Bias (V)
2.0
1.5
1.0
0.5
0
12 v ..
: ..
Enhanced mobility i ..
. -..
0
. -
i ................ ..
. .
! .
.
.
20 40 60 80
Position (nm)
100
Fl urc 11-11. Calculated current density as a function of (upper p:mcl) and electron dcn:'it.y
ru:!ction or position at 12 v Oower panel) for a two-layer electron-only electron IRJC::tl()n
cr device with the energy level diagram ror the two polymer layers shown tn fag. 11_- !3. The 1110-
=y the h:ft hand polymer is increased by a fac10r of ten in the enhanced mobthly structure
(dolled line).
. the calculated 1- y characteristic when the electron mobility in the layer to the
injecting contact is increased by a factor of The panel ot
11- 17 shows the calculated electron density as a f uncuon of posataon at a 12 Y
The electron current is constant across the structure. Because e_leclrOn
changes abruptly at the interface beL ween polymer laye:-', e h.:cta.on density must
also change abruptly at this intcafacc. The electron dcnstty as larger an the mo-
bi.lity polymer at the right of the device. In a two-carrier structure, the holes wall al.so
be concentrated in the right polymer layer .. Thus, the enhanced
helps to concentr.1Lc the in the regaon where the hole densaty as hagh an
therefore increase carrier recombmataon.
11.5 Multi-layer Devices 361
11.5.3 Two-carrier Multi-layer Devices
Next, consider a two-canier device made from the two-polymer-layer structure in
the top panel of Figure 11- 13 but using an electron contact on the left with a
0.5 eY injection bmTier and a hole contact on the right with a 0. 1 eV injection bar-
rier. If there is no hole barrier, the hole current will be space charge limited be-
cause of the small energy barrier to hole injection. The electron current, however,
is contact limited because of the comparatively large energy barrier to electron in-
jection. If the electron and hole mobilities are the same, the device cu!Tent will be
dominated by holes. Such a stn.acture will not be an eflicient LED because most
of the holes injected into it will traverse the device without recombining with the
compamtivcly small number of electrons in the structure. If an energy barrier for
holes is included at the inte1face between diOcrent polymer layers, the holes are
confined in the layer on the right by this barrier and the loss of holes by travers-
ing the device is reduced. If, in addition, the polymer layer on the left has an in-
creased electron mobi lity, the electron current will be increased and the voltage
necessary to reach a given cuaTent will be decrease(.(.
Figure 11-18 shows the calculated cuaTcnt density (solid lines) and recombination
current density (dashed lines) as a function of bias for a single-layer stn.acture, a
structure with a 0.3 eY hole banicr, and a slrUcturc with a 0.3 eY hole barrier and
also with a factor of ten enhanced electron mobility in the left polymer layer. The
recombination current density is calculated by integrating the recombination rate
across the length of the device. The mtio of recombination current density to total
current density gives the fraction of total current that leads to carrier recombina-
tion. Multiplying this ratio by the efficiency of r.1dia1ive recombination, that is,
the fr.1ction of total recombination events that are radiative, gives the internal quan-
tum efficiency of the device. For the single-layer device, the recombination current
density is only about a fifth of the total device current. In this stn.acturc in which the
current is dominated by holes, only about a firth of the holes recombine in the struc-
ture. 1l1e other four lifths of the holes tr.tversc the device without recombining and
are lost at the electron injecting contact. When the 0.3 cY hole-blocking layer is in-
cluded, the holes can not easily cross the cner<JY batTier. The recombination current
density is now nearly equal to the total current density meaning that essentially all
the carriers injected into the device recombine. In this case the device efficiency is
only limited by the efficiency of mdiative recombination. However, the bias neces-
sary to reach a given cun"Cnt density has been increased by the hole-blocki ng layer.
When the electron mobility of the polymcr layer on the left is also increased, so that
it serves as both a hole hhx:king layer ;md also ;1s an electron tr;ansport hoth I he
total cum:nt amlthc cunent ia11.:n.:aseu. The enhancc<l electron mo-
bility ha'\ increased the electron cuaTcnt. In this structure tl1c cuJTcnt in the left poly-
mer layer is carried only by electrons, the hoks are blocked from this
layer. 1l1e electrons recombine when they enter the polymer layer on the right
which has a large density of holes. It is not necessary LO use an elt:ctron-blocking
layer in this structure because the hole injcclion is high so that there arc a large num-
ber of holes in the slruclut-c with whid1 the dcctrons c;m recombine.
362 II Physics vf Polymer Light-Emillillg Divdes
0.08
-
(\J
E 0.06

SlngleLaye
.._..
0.04
0.02
00
2
4 6
Bias (V)
8
10
Figure 11- 18. C.tkul;uctl current (soliJ line) ;uul tc.:omhin;UtOO current (Ja,hcd line) <lcnsi1y a
function of voh;tgc bia.\ for a single-layer structun:. a two-layer with a hoh:-blocking layer
and a two-layer structure in which the hoh.:-blocl..ing layer abo an .:lcctron tr.lll.,pun layer.
Recent work wi th multi-layer polymer LEOs h<l)) achieved impressive results
and highlights the importance of multi-layer structures [46}. Single-layer, two-
layer and three-layer devices were fabricated using a soluble PPV-based polymer
as the lumincscent layer. The external quantum eflicicncics of the single-layer,
two-layer, and three-layer devices were 0.08%, 0.55%, and I%. respectively, with
luminous efliciencics of about 0.5 hn!W, 3 lm/W, and 6 hn!W. These results
clearly demonstrate improvement in the recombination current because of the in-
crease in quantum etliciency. The corresponding increase in luminous efticiency
demonstrates that the improvement in recombination efficiency was achieved
without a significant increase in the operating bias.
11.6 Conclusion
Since the fi rst repmt of polymer LEOs in 1990 there has been dramatic improve--
ment both in their operating chamcteristics and in umlcrstamling their device
physics. Single-layer polymer LEOs are becoming quantitatively understood.
Charge injection from different metal contacts, carrier tmnsport in the polymer
film, anti electron-hole recombination arc beginni ng to be tlcscibetl 4uantitatively.
The understanding of multi-layer LEOs has also seen dramatic progress although
the results are more qualitative than in single-layer devices. The centr.1l issues in
multi-layer device physics, i.e. the relative electronic energy structure and trans-
port properties of the polymer layers, arc now becoming dear.
Despite the tremendous progress that has been uchicvetl there remain a number
of critical 4uestions that need to be In :-.ingk-layer structures, a detailed
References 363
.
understanding of the charne c .1. b. .
tn
.
1
. . t:> at aer recom mall on process is lacking The rol f
P et excttons whach may . [I e o
nation events is n . . account or as as three qumters of the recombi-
tons may For. a _fraction of the triplet exci-
tum cflicicncy hl lll ult. -oduce smglct exctlons thus mcreasing the device quan-
. - ayer structures a nd . . d. f .
ergy ban-iers in the d , . I . . u crstan mg o the mtemal en-
. cvtce e cctromc structure and th t - . .
constituent layers is required In man . . . h, . e _ansport propett tes of the
obtained by further d, .led . .. . y cases: t ese multt-laycr properties may be
slituent layers. ctat mt:asurcments ol the properties of the individual cpn-
State-of-thc-aJ1 polymer LED . h .
ciencies suitable for a wi , . now ave ope:aung lifclimes and luminous effi-
clcar that the appt_lications. Furthcnnorc, it is
cached . per ormance have not yel b
r . . . Wtth. in matetial synthesis, fabri cation techni u, . . d eden
vtce dcstgn, sagnahcant increases in LED ' f . q cs, an e-
imp. to tile _expe l_ cted.d!hese
apphcauons. s Ill uwre tsplay
References
I. J.lt H. AntoniaJis, M. Hucso.:hen. w. L..:onart.l J . .
mg. SmJtct' 191XI, 27.1. !!114. ' . Mlll<:r, R. Moon, D. R01unan, A. Stocl..-
2. N.C. R. H. friend. in Solid Swtt Pfl .,., . EO, . .
Press. New Ymt 19\15. (l. 1. ' ' -' ( H. E Spacpen). Ac:.u.t.:mic
3. J._C. Can.:r. I. Griu.i. S.K. !leeks. D.J. Lace S G Lath .
C.R. Towns, I I.E Willnlimn. AJIJII. pr,rx." 0 . RuiL de los P..mos. K.
4. J.ll. Burroughcs. D. D. C. Uradlcy, A. It R.N. . K . . .. . .
Bum.,, A. B. Holmes, Natun 19'JO, .147, 539. . . M<K:k.ly, R. H. FnenJ, P. L
5. S. Malsun\010, in L::lcctrmril' DiSflla Dt!t'ices (EJ . S M ) ol .
Yotk 19'JO. Ch<t
1
w,! 1. J
111
W1lcy & Sons. New
6. S.M. Sz.:. in Plty.ricv II/ Semin mtluctur Devins 2nJ ct.l J I W'l & So
1981, 2. '
0 111 1
ey New York.. USA
7. W. Tang: S.A. VanSlyke, Appl. Pltys. Len. 1987. 51. 91 3.
8. . E. Kohler, I. D. W. Samuel. J. Appl. Pltys. 191)5 /01 6248
9. B. Tran G Zerbi R Sd K .. '
.' . . . ten .. , . Mullen, J. Clttm. Pill'S. 19\11 95 319 1
10. in Organic Mo/C'ntlar AlP New York 1994 Cha 1, 3
I I. 1m1 AnJcn.on, D. Dunphy T W I . . . K ' ' p cr
tcr. 1995,7. 72'!.. Mullen, N.R. Annsmmg, Ma-
12 K. Scki. S. A!o:l<l;t, T. Mori H lnnl..u h I M . T. 0 . .
1990, 74. ()77. ' "
1
' ur.tsc, hm,lu. T. Noguchi. Solie/ Stall' Cm
111111111

13. PH. n._ MBich:teiMIIl, in 1/mull>tHJk tif Cfltmistry "'"' 1'11\>iO. 62nt.l ctl ('"' . t> c
re,s, l iC<t R;unn. 1"1. t91ll. "-" ' V.'ca,l). CI{C
14 E. II. RhoJcricl.., W. R. rt\!n,lcy. M. p Sh I . . .
Plty.ticr (Ed.: C. Hiburn). Nunh-llollai;J, Stm,.muluctors. V.l. -1. Drlin
15. 1.11. Campbell T w lh lr f) L s J . . p.
16. J L B..W J . C. : g c . nul h .. I'. /'ltn R<'t: / .I'll. 111'.16 76 (')()()
. " . unul. A.J. IIL'-1!cr. t\,ft: 111,11, ." IY'.I(l ,'1 4-17
17. G. Kr.nllclhiuJcr II J Hym. s II II . S I . ' .
16:\'!.. . . c. . "cut. . {uth, (,. Lc.-ing. U. Schclf. 1'/ty.r. I'J\17, U.'fl.
364 J I Physics of Polymer Ligllt-Emilling Diodes
G I I D W S
. nucl G R II ayes R T Phillips Y. A. l{. R. Kcscncr, S.C. Moruui,
18. N. C. rcen 1um, . . aJ '
A B Hol cs R H Friend C/tem Pltys. Lerr. 1995, 241, 89.
. . m ' . s' B tl ' . J. L Br<!das R Silhcy in 1/umlfmok of f>III,VIIII'rX,
19. R. R. Chance. D. . ou rcaux. .- .
(Ed.: T.A. Skothcim), Marcel Dekker, New York 19116, Chapter 24.
20. D. M. Pai, J. Chem. Pf1ys. 1970, 52, 2285.
21. H. Bassler, Phys. Swt. Sol. 1993, 8175. 15.
Y. N. Gartstein, E. M. Conwell. Chem. Pl1y.v. Lett. 1996. 255, 93.
22
D H Dunlap P. E. P..mis, V.M. Kenkre. Pltys. Rev. Lett. 1996. 77. 542.
23
II: Meyer. D.' lia;lrcr, II. Na;annann. H. H. liorhold, Plly.v. Rev. 1995, 1152, 25!\7.
24
' P. E. Burrows, S. R. Forrest, Appl. Ph)((. Leu. 1994, 64,
2285

25. P. W M Blom, M. J. M. de Jong, J.J. M. Vleggaar, Appl. Plty.v. Leu. 1996, 68, 3308.
i6. P. W:M: Blom. M. J. M. de Jong, M. G. van Rei\ 1997, 855, R656. 7 35'>3
7. K. Pichler, C. P. Jarrett, R. H. Friend, B. Rher, A. J. Appl. Phys. 7 dov y
V. N. Savvate'ev, M. Tarabia, H. Crutycl . E.-Z. FarrJgl, G.-B. Cohen. S. Ktrsleln. D. Davl .
Avny, R. Neum;mn. Sylllft. Mtt. 1997. 1269. , 994 67 l tlS
30 s. K;trg. v. Dyakonov, M. Meier. W. R1css, G. P:r.ISCh, Sy11tiL M<t. 1 ..,
. A J C D D C Bmdley D G LidL.Cy, J. IIppi. Pill's . 1997, 82, 63-6.
3
1. r.'s' M I. D.' D. L Smith, Allli l'fty.f. u ll. 19'J6. tiY, 22711.
3:!. ,lVI S, ..> I. . <> ' . I . 1"'' 4 fl5 ?QJO
H
. A.
1
d'
1
M A AbkowiiL U. R. H,ich, llftpl. Pl1ys. u.'ll. n -
33. . n om.t s, . . .. . PI\: . 1970 Vol 6 Chotptcr 2.
3 R. WillianlS, in S(miconductors w1d 5eiii11111Nuls, Ac.ttlcnm: ss
4
II D L S
1
11 J p Fcrr.1ris Ap
1
tl. Pllvs. Leu. 1995, 66. 3030.
J. J. M .. D: D.C. BmJ.Icy. K. H. Fti cnd. A.B. Holmes. J. l'ltys.: Coudens. Mat
t l!r 1994, 6. 1379. X5 121'\
37. X. Wei , S. A. Jcglinski, Z. V. Vankny, M('/.
1
9')7, ' :. . J A I Pl1 s 199'7, 81.
38. c. M. Heller. 1. H. CaJnpbcll. D. L. Smllh, N. N. 13arotsht...ov. J. P. Fcrr.1ns, PP )
39. A. Saxena. D. L. Smith. J. IIppi.

4
24-4.
40. E. M. Conwell , M. W. Wu, Al>pl. l'ltys. Leu. I
4 1 I. D. Parker, J. Apl>l. Pltys. 1994, 75. 1656: " <
. M Btom M. J. M. de Jong, S. BrccdiJk,llpp/. Ph>s. Leu. 1997, . . .
42. P. W. . V I Pcrel I N Yassievich in NUJiradiativt Recombmawm Ill Scuucnnducton ,
43. V. N. Abakumov, . . '
North-Holland, Amsterdam, 1991. p. lOll. . .
996 80
'>1\83
M. D. Joswick, 1. H. Campbell. N. N. Bar.tshkov. J. P. Ferrans, J. Pltys. 1 -
44
' S A VanSI ke, C. H. Chen. C. W. T'..lng, Al'fll. Pl1y.\. Lt:11. 1996. _69. -160.
45. D C)' Bric/ A. Olcycr. D. G. Lid:t..:y. D. D.C. Br.tdlcy, T. Tsutsut. J. IIppi. 19'.17. X2, 2662.
46. D: V. H. Bassler. V. I. Arkhipuv. J. App/. Pllys. 1996, 79, 9-83.
47. D. V. Khr.smtchcnkov. V.I. Arkhi pov. H. Bassler, J. IIppi. Phys. 1997, 81, 6954.
:: y H Tak H Bassler J. Appl. Plays. 1997.8/, 6963.
50. I.H. M. D: Joswick, 1. D. P'.u-ker, Appl. Pltys. Leu. 1995, 67, 3171.
12 Charge Transport
in Random Organic Semiconductors
Heinz Bassler
12.1 Introduction
Until now elcctropho10gmphic image recording has been the only technique that
exploited the electric propet1ies of organic solids on a broad industrial scale. This
will hopefull y change when organic light-emitting diodes (LEOs) reach a level of
maturity required for commercial applications. As a result, current research is fo-
cused on the charge inj ection, transpmt, and recombination propenies of random
organic, notably conj ugated, solids under the conditions existing in LEOs under
operation. lt is the purpose or this chapter to down a com:eptual framework
for understanding transpon in LED-related including charge in-
jection from electrodes, which is the essential charge-dcliveting process.
Organic solids diller rrom inorganic in two essential aspects. First, the
electronic interaction between the molecules constituting the lattice is weak, and,
second, the relative dielectric constant (l:) is low. values for an organic
solid arc 3 to 4 compared, for instance, with 1: = II for silicon. The first implies
that tr.mspolt bands in molecular crystals, i.e., valence and conduction bands as
well as exciton bands, arc nam>w. Typical bandwidths range fmm 10 to 100 meY
l l , 2}. As a consequence, the mean free paths of charge carriers and excitons are
of the order of the lauice spacing. This renders coherence effects in transport un-
impOitant except at low temperatures. The low dielectric constant, which is a con-
sequence of the molecules retaining their electronic identity, leads to coulombic
effects being imponant. Recall that the binding energy of'a Wannier-typc exciton
varies as m*!t?, where m* is the eflectivc electron mass. For m*=O. l of lhe free
electron mass and relevant for silicon. a binding energy in the order of
25 meV is obtained, implying thai charge carriers generated viu a thenually or op-
tically driven valence-to-conduction-band transition are essentially free at room
temperature. On the ot her hand, the coulombic binding energy of an elecuon-hole
pair locate<.l at nearest-neighbor sites in a mol ecular crystal wilh 3 is O.K eV.
The lowest excited states in molecular crystals are singlet and triplet exdtons
(3]. Since it costs coulombk energy to lransl'cr an electron that has been excited
optically from the HOMO (highest occupied moktular orbital) to the LUMO
366 12 Charge Transport in Random Orgunic Semicvnc/u('tors
(lowest unoccupied molecular orbital) of an adjacent neutral
transfer (CT) transitions in single-component molecular crystals are h1ghcr Ill en-
ergy than S
1
.-So tmnsitions. In view of their lower oscillator strength they are
buried underneath the vibronic progression of the Iauer and can be recovered only
by employing clcctromodulation in which to po-
lar states, such as CT states, are sclccti vcly enhanced. Usmg th1s tcchnaquc, Sebas-
tian et al. measured cr absorption spectnt of polycrystalline anthmcene, tetmccne,
and pentacene (4]. For anthr.tccnc the lowest Cf tr.msition involving the two
. ecules in the monoclinic unit cell is located eV above the S
1
.-So tranSition
and carries about 3% of the oscillator strength of the latter (see Fig. 12-9). With
increasing size of tht! n-electron system the energy off-se.t from the si nglet exciton
transition becomes smaller and the oscillator strength increases.
The position of the valence band, or, more generally, of the
state in a non-crystalline solid, can be located by photoelectron or photoenuss1on
spectroscopy l5]. Typical values for the ionization arc between 5 and
6 eV. In view of the negligibly small oscillator strength tor d1rect
duction-band transitions, the location of the latter as well as the band gap IS
not amenable to direct optical probing. A useful estimate is, however, by
the approximate relation ), where /
11
and arc the 10n1zat1on
energy and electron affinity in the gas phase, respectivelY_. and p+ and the
electronic polarization energies of a positive and a negauvc charge earner 111 the
solid. While p+ is the difference between the ionization energy in the gas phase
and the crystal, respectively, p- cannot be measured directly but has to be calcu-
lated. To zero-order approximation p+;::; r. typically 1.3 e Y. a rule
thumb E exceeds the optical gap, set by the lowest dipole-allowed smglet tmnsl-
tion, by :oughly I cY. The difference is a measure of exciton binding
". In crystalline polydiacetylcnc eY as detern1med by electroreflecuon
spectroscopy indicating that increasing the size of a n-electron system lowers Eb
.
Upon contacting a semiconductor with metallic the Femu levels oo
both sides of either contact have to equilibrate. This is accomplished by chaq,>e
exchange across the interface. In doped inorganic semiconduct<?rs charges are
delivered via impurity ionil.ation. This gives rise to the fonnat1on of a Schottky-
type depletion layer whose thickness is

N., being the of do-
nor/acceptor states and V Lhe interfacial potential (7 j. TI> obtam a
in the order of w-
5
em at V= l, N., needs to be 10
7
cm-
3
. Dopant dens1t1es ot
that order of magnitude that arc able to act as electron donors or acceptors, i.e.
have HOMOs close to the conduction band or LUMOs close to the valence band,
are difiicult if not possible to incorpor..ate in molecular crystals. An exception is
poly(para-phenylenc vinylene) (PPV) prepared via a special precursor route l8)
that leads to inadvertent doping. In molecular crystals and modestly dean poly-
mers, donor/acceptor concenlmtions arc too low for of thin de-
pletion layers. Band bending in the vicinity of the contacts IS, thercl ore, 111 most
cases, negligible. . .
In the absence of cithc.:r surface states, which may pin the Femu level at the In-
terface between the dielectric and the electrode, the energy barriers, which in tum
12.2 C/wrge Currier lnjeclion
367
control hol e and electron iniection 6
1
, = 1-<1> .. and 6 = f" -A [91 '"
1
s the
'.J unbuC , ""'carhc.x.Jc ""' .
workfunct1on of and 1=1
11
- P+ and A =A
11
+P- arc the ionization en-
ergy athn1ty of the organic dielectric, respectively, which indicate the
encrg.1es at wh1ch hole and electron transport occurs .
. Dcpcnd_ing the magnitude of 6. the current llowing through a device can
e1!her be lllJI.!ct_lon _ or 1ransport. i.e. spm:c charge limited. 111c latter whkh
will be deal! wnh Ill Section 12.3. requires one of the electrodes to be ohmic, i.e.
to be to s_uppl_y d1arge caniers per unit time than the sample can trans-
pelt V1olat1ng Po1sson's law. Otherwise char<6e carrier injection will be the
rate-hmatmg step.
12.2 Charge Carrier Injection
12.2.1 Concepts
The text book to injection into a dielectric at high electric field'i arc
the Fowler Nordheun (FN) model lor tunneling injection and the Richardson
Schottky. (RS) of thermionic emission liO]. The FN model ignores image
and mvokes of electrons fiom the metal through a
gular baaner 11110 unbound contmuum st:1tes. It predicLo;:
, 4 /2m,ffll
3
1
2
j(F) = BF- exp - ---=- V __ _
3heF
( 12. 1)
is or temperature. Here, m,
11
is the effective mass of the carrier
ans1de the d1clectnc. The essential assumption of the RS model is that an electron
from the metal be once it has acquired a thermal energy sutricient to
cross potenual max1mum that rcsulLo; from the superposition of the external
and '.he_ 1111age charge P?tential. nor inclao;tic scattering of the
hot tmversmg the potential maxunum arc considered. The j(f) char-
actenstlc IS pred1cted as follows:
( 12.2)
The shm\coming of either of these approaches is obvious. At an electric field be-
10 V/cm and 2xto<> Y/cmthe baiTier lowering in a dielectric with a dielcc-
tnc constant 3.5 to between ().06 cV and cV and the maximum of
the 1s located between 3 nm and 0.7 nm away from the in-
terface. Barner _may, Lherelon!, be comparable to the barrier height itself
and the of tunneling 1s problematic ao; arc the tacit assumptions of a trian-
gular barner and the existence of " conti nuum or unbound states into which car-
368 12 Charge Transport in Random Organic Semiconductors
riers can tunnel. The application of the RS concept, on the other hand, suffers
from the neglect of inelastic carrier scattering inside the potential well which is of
crucial importance in organic solids in which tr..tnspot1 is an incoherent process
and the mean free path is compamble to the intermolecular distance, i.e. ;;;;;; I nm.
The importance of this problem has been recognized long ago within the context
of photoionization in Inolecular solids and it is genemlly accepted that Onsager's
theory of Brownian motion within a coulombic potential represents the appropri-
ate theoretical fnuncwork to model photocarrier generation as a function of elec-
tric field and temperature [I 0-13).
Despite those deficiencies both the FN and the RS concept have been applied
to charge catTier injection into light-emitting diodes, the motivation being the suc-
cess of, for instance, the FN model to yield reasonable values for the barrier
height-; and to account for the tempcmture-independcnt j (F) chamcteristics at high
fields [ 14-16 ). It has been noted, though. that absolute currents arc orders of mag-
nitude lower than expected on the basis of Eq. (I) [ 17). This has recently been ac-
counted for by considering back How of caiTiers towards the 116, 17)
although it is hard to justify the reasons why carriers that have tunndcd into a re-
gion beyond the maximum or the potential should return to the dectrude wi thout
being impeded by the same energy batTier which they had just passed.
Abkowitz et a/. [ 18 J developed an altemative molld based on thennally as-
sisted tunneling that takes proper account of the hopping chamcter of canier mo-
tion inside the dielectric but ignores both the coulombic potential and the ener-
getic disorder of the system. They showed that experimental j(F) curves can be
fiued with a reasonable set of parameters provided that non-ne<trcst neighbor, i.e.
tunneling, transitions are invoked. A more sophisticated version of this injection
concept has been presented by Gartstcin and Conwell [19) employi ng Monte Car-
lo simulation techniques. Their model takes full <tccount of both the energetic dis-
order of any non-crystalline hopping system and the image charge potential and
allows the evaluation of the probability of a canier to avoid geminate recombina-
tion with its sibling image charge without considering the initial injection process.
This procedure cannot, per se, yield the temperature dependence of the entire in-
jection process since the initial and energetically most costly injection event is
disregarded in that treatment.
It is obvious that a complete description of the field and temper..tture depen-
dence of the injection current has to consider the field and temperature dependen-
cies of the primary injection event and of the subsequent r..tndom walk of the car-
riers with the superimposed external and image charge potential and must take
proper care of peculiarities of charge carrier hopping in a mndom medium [20].
This problem has recently been treated analytically by Arkhipov t:t a/. [21 J. The
system considered was an energetically as well as positionally r.mdom hopping
system in contact with a metallic electrode. Charge trJnspon was assumed to oc-
cur among localized sites of a Gaussian distribution g() of states (DOS) of vari-
ance a and centered about the energy =0 and off-set from the Fenni level of the
metal contact by a zero field banier !!.. The initial event is the transfer of a charge
carrier from the Penni level to a localized state in a surface layer of the dielectric
located at a distance x
11
equal or in excess of the average intersite distance a. The
12.2 Clutrge Carrier Injection
369
potential energy of a carrier at a di t . . . .
the Fermi level of a metal i . . s ance _away. from. the mterf ace and relative to
potential, and the site cnerg; of the Image potential, the extemal
' e-
U(x, ) = L\ - - eFx+

( 12.3)
The primary injection evem is the result of an optimization proccd .th
to the trade-on between activation ene . ure. WI respect
tor states on the other. Once injected
of accep-
the electrode or to overcome th, . . . ' e l P 1on Cit er Lo return to
electric ti ld Th. . . I potcnllal and be collected by the external
c . Is mvo vcs a (h1Jus1v. nml . I' . . .
that th d. I t l: om w.J " .unong U1e llK:ahled sues
c te ec nc Is composed of and whi I , . . . .
e
onfea conjuatcd polymer. chain with
Bem" a St"'"lla t " " s

., s c process tl IS not amenable to ri"or . . .
ment. However, considcri n\! tbat the il t" I . . . . . ., ous analytiC treat-
within the tail of tl
11 1
'
1
lllJedlon process populates a state
ready C.'>tablished th;u thermal quasi-equilibrium is al-
. l:aiTlcr st.lrts 1s random walk u d
11
. .
caped. recombination with it s ima<>e charge. ca; l'"cllastepdremdl se, ehs-
con 111ons ot the
1
111
- 1
1
b .
0
un er t e
a equl I num. The simplest way to do tl . . . . .
ID of Onsnt's tllco
01
. . . . lis IS 1n tenns ot the
. . ry genu nate patr dl . .. . . .
escape probability is: prcd1ctmg that the
'"
j
. dxexp[- .!!- (I'O.r + _ e -)]
kT 16m:
0
t.:x
lt'f".\c' = _u;:-- ,._ ------------
1
dr exp [- !!_ + t: ) ]
kT 167rt"I:X
ll "1)
(1::!.4)
ElaborJ tinn these id . . A ..
1

. f . o ,.. . . . I" llpov t:l a/. calculated the dependence of lh .
JCC o? cunent on clectnc held temperature of the DOS . d . . . e _n-
couplmg. ' In sllength of mterstte
Fioure P-1 shows a . t fi
. .- . . :;cncs o current- ICld ch<cr..tctcristi . . . . '
field IOJCClton baiTicr L\.. calculated tor a DOS . h . cs par..tmetnc Ill the zero
site distance a=0.6 nm, and T=
3
00 K Th .

. eV, an inter-
creasin L\ and . . - , . . . c lllJCcllon cunent Increases with de-
. g Wllh held as IOtUill vely expected. AI hi oh r ld . . . .
!J., J(F) tends to satur..ttion. Otherw. h .
1
. . ., 1e . s and small
tse I e s ope ol I J versus I F .
creases monotonously. In nencral the CLlt""CIIl t "s t e- . . g . curves 111-
Fi <:> emperature d d
tg. 12_-2), not following An11enius' law, thou h (sec Fiu P- cpcn enl (see
coefficient decreases strongly with incr . . . , g
1
. . _.,. - 3). The temperature
high electric fields f' . _ . easmg e held and reverses sign at
23x I 06 VI The. or the pat amcters chosen this happens at a field of about
on the b h temper..tture dependence is significantly weaker than ex,......cred
asls o t e zero field bamcr L\=0 4 V At T- 300 .
the tangents of lnj versus r'
1
. . ." c .. -:- - . K and F= 10 Vcm
1
p Ob ytdd pp.ucnt ;u:tlvatmn energies of 0.15 eV
370
12 Charge Trunspon in Rundom Orgunic Semiconductors
1E-5

t E-7
tE-8

tE-9
.e tE-10
E
tE-11 (I)
t:
t E-12 ::::1
(,)
c
tE-13
0
u
tE-14
(I)
c:
tE-15
tE-16
1E-t7
tE-18
-o-0.3oV
V O.hV
o-
- 0 0.7oV
10
Field, V/m
10-3 .?;-
;;;
10 .. c
(I)
10-5
"0
E
tO""
(I)
t
to'
::::1
(,)
c
10 .. 0
to
"g
c:
to-
trr"
Fi, 12-1 A c.:ompari.o;on of thcorctic-.11 and experimental injection cum:m:. into typically lUll
conjugated pOlymers :.andwichc.:d between UJ\ rro_ am.! _an AI cathode. Open sym-
bols refer to calculated j(F} characteri:.tics. /lts the zen> field lllJCCIIOO barncr (Ref. 1211).
10-5
10 ..
10"
7
t ... . .... ., . ! . , . . : _ .. ,:: ..
A - 0 4 eV ; ; '"''''''" u, .. ,. 0
- ."'!"
o = 0.08eV
...
a =0.6nm
::i
10 ..
ro
10-Q
_.j
c
Q)
10"'0
....
....
y = 10" em'
..
::J
10"" <..>
c
0
ti
10"
12
........ T =200 K
Q)
10""
c- ----- T = 150 K
10"
14
1015
. .... .. ..
....... ,., .... , ....... .
10
Field, V/m
a:lgurc
1
2-
2
Temperature dependent j(F) char.1c.: tcristi.:s for injection into a hopping syMctn charucter-
iLCd by /l:0.4 cV ;md o =ll.OK cV (Ref. 121 1).
mll
- : v =0.08 eV
- -- :v=0.16eV
10
-12
,.-..,.

t:
::s
.D
m-n
F (VIcm)
.....
l
.._,
--.
10
-1r.
10
5
VIcm

_ _... __ ___._ __ _..___.
0 5 10 15
w 3rr(KJ
12.2 Clwrge Carrier l11jecrio11 371
12-3. T.:utpcraturc-l.lepcndcnce of the
injc.:tiun current :1t different electric ;md
widths or thc OOS. The lkt!-oltcd line rcprcsems
the pn:tli.:tion of law for a rero
licld bamcr 6=0.4 eV (Ref. [21]).
(a=O.l6 eV) and 0. 11 eV (a=O.l6 cV), respectively. At T= 100 K the correspond-
ing values are 0.06 eV and 0.05 eV.
Disorder has a promoting efl"ect on the injection efficiency as borne out by Fig-
ure 12-4. The cun-cnt im.:reases significantly as the width of the distribution in-
crca.-;e.-;, the more the is the larger the injection batTier. This is a plausible
result since the larger U1e spread of the site energies, the more likely it becomes
for a carrier to lind an acceptor site at an energy less than 6. An electric field
will further deca-case the a-e4uircd thermal energy. This concurs with our previous
simulation (22) as well as experimental (231 work concerning intrinsic as well as
electrode-sensitized photogeneration of charge caniers in random organic solids .
Increasing me intersite distance is wunterproducti ve for carrier inj ection be-
cause lor a given distance from the electrode to a hopping site the probability of
finding the next hopping neighbor in the bulk decreases with decreasing concen-
tration. This means that in diluted systems hopping sites that are too close to the
surface cannot act as acceptors since caniCl-s arc li kely to retum to me electrode.
Therefore, the eiJective distance from the electrode to the nearest active acceptors
increases with decreasi ng concentration. lt is straightlorward that an increase in
the wavcfunction localization length }' has the opposite effect.
372
::>
ro
c
G.>
t
::J
0
c:
.Q
ti
G.>
c:
I 2 Charge Trall.f{HJrt in Ru11dom Organic Semicmulucton
10'
7
10 ..
F lri'VI<m
T 300K
10 .. " O.linm
Hr"'
y a lrfan'

10'
11

10'
12
10'"
""
10 ...
10-15

10'
16
- - o 0.04 oV
10"
17
-e-o. ooeev

10'
11 - ... -o 0.16eV
10''
8
.......
0.2 0.3 0.4 0.5 0.6 0.7 0.8
Barrier height, eV
12-4. Dependence nf lhe injco.:1ion
currcnl 011 1hc 'lCFO field barrier hcighl ll
fur v;uiablc widlhs uf 1hc dcnsily of hop
ping s i:IICS (Rei. (2JJ).
The above treatment neither includes long-range tr.:msitions nor tunneling tmnsi-
tions except for the first jump whose r'.lte depends exponentially on the product of
the jump distance and the wavefunction localization length. Since the distance be-
tween the first acceptor layer and the eleclrode is always less rhan its dislance from
the maximum of the superimposed image and external potenlials, subsequenl escape
of the carrier from that layer has been trc<ltcd as being diffusive. Bearing in mind this
basic feature of the model, it is instructive to compare the calculated field dependen-
cies of the injection current with the predictions of either the Fowler Nordheim tun-
neling model or the Richardson-Schouky thermionic emission model. Figure 12-5
presents the analytic data in a representation In j versus r
1
The plots arc curved
but extrapolate to straight sections at high electric field..; that extend over more than
one decade. It is particularly noteworthy that the asymptotic slopes -yield injection
barriers that arc approximately 3/4 of the input barrier if analyzed in tenllS of the
Fowler Nordheim tunneling theory (Eq. ( 12. 1)) taking the effective mass as being
equal to the free electron mass. This indicates that j(F) characteristics of injec-
tion-limited currents approach FN-tunneling. like behavior although FN-tunncling,
is not involved at all. One can, therefore, usc asymptotit: FN-plots in an opcr:.ational
way for obtaining crude estimates for the injection baniers considering, however,
that the functional agreement is accidental. Data fitting in tenns of Richardson-
Schottky appears to be even more successful. Figure 12-6 shows semilogarithmic
plots of the current versus Ft
12
For ll=O.S eY and 0.6 eY perfect straight lines
are obtained h!Hh are noted smaller Analyzin
the slopes (d hljlclf
2
) 111 terms of &J. (12.2) yadds (d4m:4J) '-II>.T=1.1xl(J
10" 7.--- ------
l(fl()
;:
::0
-e
..

IIT'I
l!T'l
10""

f l l to-7 cm/V)
12.2 Charge Cllrrier Jujec:tion
373
1_2-S. R:frcscnl:n_mn or the injcc1iun cum;:lll
on a lnJ t scale. n.c line imlic:ucs the
prclltl:lo.:d by tuwkr Nordheim ltuuu:ling lhl.'Ory for fl =O.!l cV
assunung 1ha1 thc clli:o.:tivc mass the rrcc electron m;tS.,.
(
(
2
ca)n!Y)'
12
1
-d and

for ll = 0.8 cY and 0.6 eY, while Eq
wou prcdtct I.IOxiO-- (cm/V)
112
.
The . for the success of this type of data liuino is that for modcrutel
large II unimpoalant escape the image potential
treated walhtn the of the Onsager or the RS model. An indication that
Onsager descnpllon as. ncvCJthclcss. more apprupliatc is the intersection of
J(F) curves for van able temperature at hi<>h electric f"teld., Tha .
1
s a h
1

r . . ' ., c ar.tc cnstac
cature ol Onsager prllCCsses 124].
12.2.2 Comparison wi th Experiment
Cua:cn. li_cld. ncasun:u with polymers sanuwichcd be-
twee.n .an mdtum-tm oxade (ITO) anode :md an :tluminum cathode are usually hole
and arc .. consequent ly, appruprialc for testing injection/Jranspol1 models
?r of untpolar CUITCnt now. Data shown in Figure 12- 1 refer to in'ec-
currents recorded typically 100 nm thick spin-coated films oF Jcri-
vatt,vcs nl (PPV) and a planatiLcu poly(pam-phen _
lenc) cmploymg a Kealhley uni t. The polymcn; werl.!: y
374
12 Clwrge Trcmsrwn in Random Orgwtic Semicmtclucrors
PPV-iminc
a PPV-ether
n
a ladder type poly(para-phenylene)
R' : -n-Cq-113
phenylsubstitutcd PPV,
and diphenylaminostyrylbenzene (DASMB)
,.....
!!l
a
::l
12.2 C/wrge Currier /ujectimt 375
.e 1012
"'
'-'
.......
10"'3
lligurc 12--6. Reprcscmmion of the calculaacd
tion on a lnj vs Fin :.calc. appropriah: for
lcsung th.:nnionic injc.:tion following Rit;hanlson-
Scholtky 1heory.
For PPV-imine and PPV-ether the oxidation potential, measured by cyclic voltam-
metry using Ag/AgCl as a reference are E .. x=0.8 cV and 0.92 eV, respecti vely. By
adopting the values 4.6 eV and 4.8 eV for the work functions of a Ag/AgCI and
an ITO electrode, respectively, one arrives at zero field injection of 0.4
and 0.55 eV. These values represent lower bounds because cyclic voltammetry is
carried out in polar solvents in which the stabilization energy of radical ions ex-
ceeds that in a polymer film, where only electronic polarization takes place. E,x
values for LPPP and PPPV are not available but in theory they should exceed
those of PPV-imine and PPV-ether.
The shapes of experimental and theoretical j (F) curves are in mutual agree-
ment. By comparison one arrives at injection barriers ranging from 0.4 eV (PPV
imine) to 0.7 eV (PPPV). The agreement between theory and experiment is simi-
larly good as far as the tempemture dependence is concerned. Data shown in Fig-
ure 12-7 were taken with DASMB and confirm the analytic results for
High brightness of electroluminescent diodes requires efficient carrier injection.
To achieve this goal one should select hole-transporti ng materials with low-lying
LUMO the final goal being to establish ohmic contacts (sec Section 12.3 ). How-
ever, chemical constraints and the desire to achieve emi ssion in the blue spectr.1l
region usually require a compromise in the selection of active compounds solely
on the basis of energy level arguments. l11is problem can be overcome by insert-
ing a thin layer with pa11icularly low oxidation potential between ITO and the
hole-transporting layer, which may act as the emitter layer. This alleviate.-; the re-
376 12 Charge Transport in Random Organic Semico11ducturs
10
8
10"$ 10
2
10
1

10
0

10"
1

u;
10 ..
::;
10"
7
1
-r=JOOKI
a= 0.08 ev : ....... r ; 100 K
Ill c
Q)
..... , ......
1 I
10-2
"0
..
c
10-3
:; .. ...
6

298K
10 ..
c

223K
0
:
:e

173K
. .
10"
5
Q)

123K s
10
8

::I
10
4 0
c
0
13
1010 Q)
E
I
10"
11

88K
10 ..
1012 10"
7
10
8
Fie ld, V/m
Figure 12-7. j(F) for a 100 11111 lhid tiln1 uf diphcnylaminustyryll-,.,:nL.cnc (DASMB)
sandwiched between lTO ;md Al-clcclwdcs, paramclric in tcmpcr.llurc. The salunuion at high ch.:ctric
fields is due to lhc rcsi,wnce of the ITO.
quirement of having a high electric field at the anode to accomplish efficient hole
injection. The same principle is involved in the expetimcnts of Antoniadis et al.
[25] showing that insertion of a PPV layer between an ITO anode and a molecu-
larly doped polymer containi ng diaryldiaminc dispersed in polycarbonates im-
proves hole injection. It may also explain the successful use of polyaniline as an
anode material in LEOs 126]. If the interface between the injection-promoting layer
and the hole-tr.msporting layer is not a sharp boundary the energy gap between the
two layen; will be somewhat smeared out and can be compensated for by the poten-
tial energy a carrier gains when hopping along a large potential gradient.
The above strategy was tested [27] with a 3-layer LED consisting of a
poly(2,5-thienylene vinylene) (PTV) layer, known to have particularly low oxida-
tion potential 128], followed by a layer of 1,4-bis-(4' -diphenylaminostyryl)-2,5-di-
methoxy-ben:tene (OASMI3) [291 and a layer of 2-(4-biphcnyl)-5-(4-tert-butyl-
phecnyl)-1,3,4-oxadiazol (PBO) dispersed in polystyrene (PS) in a 20: 80 ratio.
Films of poly-(2,5-thienylene-a-bromoethylene) were obtained by vapor phase
pyrolysis of 2,5-bis-(bromomethyl)thiophenc and subsequent vapor deposition of
the quinoid monomers onto a cold substrate following a previously published pro-
cedure [30]. They were converted to PTV by temperature-induced diminution of
HBr.
Figure 12-8 summarizes the inronnation available as far as the HOMO/LUMO
positions of the compounds is concerned. Being inferred from oxidation/reduction
potentials measured by cydic vohantmctry in polar solution and from HOMO/
LUMO gaps, absolute values should be viewed with some caution.
12.2 Currier flljec:ricm 377
One can, nevertheless, conclude that (i) there is only a very small barrier for hole
injection from ITO to PTV, if any barrier at all, (ii) a linite energy should exist
for hole tnmsport across the PTVIOASMB interface, and (iii) PBD should act as
an efficient internal blockade for hole tr.u1sport towards the cathode.
The j(F) characteristics measured with 80 nm to 160 nm thick single layer
ITOIPTVIAI diodes arc highly superlinear and bear out a strong thickness depen-
dence at constant external electric field. This is suggestive of space charge-limited
hole transport in the trapping regime (see Section 12.3) as expected on the premise
of the small energy barrier for hole injection from an ITO anode. Figure 12-9 COJll-
pares the current-field dependencies of (i) an evaporated, I 00 nm thick single layer
.lf I ,4-bi.\' (4'diphenylaminostyryl)-2,5-dimethoxybenzcne (OASMB) diode, (ii) a
bilayer device consisting of a 20 nm thick DASMB layer and a 60 nm thick
PBD:PS layer and (ii i) a trilayer assembly consisting of a 15 nm thick PTV layer,
a 20 nm thick DASMB layer and a 40 nm thick Pl30 : PS layer. It is obvious that
insertion of a PBO: PS layer suhstamially reduces the current flow across a
DASMB diode. This is due to hole accumulation at the interface between both
layers because or the mismatch of the HOMO levels [31 I and the concomitant
screening of the electric licld in the anodic cell compartment [32, 33 J. In fact, this
lisplaccmcnt of the injection limitedj(F) characteristics in a double logarithmic re-
:->resentation provides a direct measure for the factor by which the electric field act-
ing on the injecting ITO anode is diminished compared to the value V/L. The neg-
ative effect of interfacial space charge accumulation as far as the majority carrier
injection is concerned can, however, be overcompensated by insening a thin PTV
' >UtTer layer between ITO and the hole transporting emitting layer. In a PTV layer
vacuum level
0 - -
-1
-2
-3
-6
-7
2.0
LUMO
2.3 - 2.4
LUMO
LUMO

4
8
4 9S
__.:.:..;. .:.......:__ S . I S
ITO
. 6.3
PlV OASMB PBD.PS
H
AI
IZ H. Encrl,\y level of a trilaycr
LED of polylhicnylvinylcnc WI'V},

hcnJ.cnc (l)I\SMIIJ an<l 2-(4-hiphcnyl}-:'i-(4-t.:n -
(PilD) (Ref. (2711.
378
/2 Charge Transport in Random Organic Semiconductorl
10
1
10
:f;
10"
1
10"
2
10"
3
-
// "'
E
00 "' 0

0 "'
0 A
-
oo
A
0
10-4
0
"'
0
"'
10"
1
0 A
0
"'
A
10-6 A
0
A
10-11
0
..
10
5
10
6
E (V/cm)
J:o'igurc 129. j() plols of tliO<lcs contaimng a 100 11111 thick DASMO layer (open _circles), a J:?ASMB/
POD: PS layer of total 80 nm (open anti a trilayer ol a 15 nm thiCk PTY
lnycr, a 20 nm I hick DASM B layer anti a 40 11111 thick POD: PS layer (open :.quarcs).
as thin as 15 nm, trapping effects are unimportant and one can fully exploit the ad-
vantage of the ohmicity of the ITO/PTV contact as far as hole injection is concerned.
In Lhis case the majority carrier current is solely limited by Lhe rate of the processes
by which the internal space decays charge, i.e. leakage of
across the internal energy barrier and loss due to recombmatton w1th electrons ul
jectcd from the cathode. . . _ _ _
It is obvious that the str.llegy to enhance hole lfiJCCtJon mto the em1tter layer
by inserting a low work function material between the ITO anode and the latter
can only work if the energy barrier between the two layers docs not prevent holes
from migrating into the emitter layer. !he reason for to_ happen relates to
charge cmTier hopping in a random med1um. unphes
broadening of the density of hopping states. typ1cal vanances bemg m _the
of 0.1 eV (see Section 12.4). Be.1ring in mind that (i) interface.-; are.
never ideally sharp and (ii) the gain in potential energy when a earner_
across a distance of 2 nm in a field or 10
6
V/cm is 0.2 eV, it is easy to reahzc
a 0.2- 0.3 eV gap between the centers or Lhe man!fold of of
cent layers will effectively be washed out in a h1gh elcdnc held: Th1s
why the j(l-} curve of the LED approaches that of a thm enutter
layer at high fields hut ralls oil sharply at (external) fields below 5xl o- V/cm.
12.3 Space limited (SCL) Currents 379
12.3 Space Charge Limitt>d (SCL) Currents
12.3.1 The Concept
Suppose that a semiconductor of thickness L is contacted wi th an electrode that,
by virtue of a low-energy banier at the interface, is able to supply an unlimited
number of one type of carrier. The current is then limited by its own space charge
which, in the extreme case, reduces the electric field at the injecting contact to
zero. This is realized when the number of carriers per unit area inside Lhe sample
approaches the capacitor charge, i.e. 1.:(/e. It is Lhis number of carriers that can be
transported per tmnsit time t,r=dlp. Hence, the maximum cunent is
d. A more ri gorous treatment has to take into account the non-uniform distribu-
tion of space charge and, concomitantly, electric field [34]. Starting with Pois-
son's equation and the continuity equation.
. 9 v
2
JSCL = g teoJt L3
( 12.5)
is obtained for tmp-frce SCL conduction (Child's law). The charge carriers den-
si ty decreases with increasing distance from Lhc injection contact according to
(
) _ 3 a.:
0
V (L)
112
II\ -- - - -
. 4 ' L
2
X
while Lhe local electric field increases according to
F(x) = 1/ 2
2 L L
The average space charge density (per unit volume) becomes
3 v
n =-- -:;.
2 e L-
( 12.6)
(12.7)
( 12.8)
Tile increase or the ela:tric field with increasing distance rrom the injecting elec-
trode has an important consequence lor the time dependence of a tmnsient SCL-
Iimited current after applying a rectangular voltage pulse. Since the leading edge
of the ensemble of carriers moves faster as it approaches tlte exit contact, the cur-
. rent increases with time and features a cusp at a time t=0.7B t,r [35j, where
is the carrier transit time under space charge-free conditions.
380
12 Charge Tru11sport ill RC111dom Orga11ic Semicmrducwrs
The situation becomes more complicated in the presence of tmps. In geneml,
( 12.9)
where e is lhe ratio of free to total space charge.
In the case of an energeticall y discrete trapping level, the functional depen-
dence j(V,L) remains unaltered but the current becomes activated; lhe activation
energy being equal to the trap depth. However, in cases of practical interest traps
are usually distributed in energy. In lhat case traps will be filled from lhe bottom
to the top of the distribution as the applied electric tield increases. This is equiva-
lent to an upward-shift in lhe quasi-Fermi with clecuic field. As a consequence,
e increases with electric licld and the j(V) or, equivalently, lhe j(F) characteris-
tics becomes steeper to finally merge into Child's law if the total number of traps
avai lable is less than the number of charges the sample can accommodate on the
premise of Poisson's law. The only case that can be handled in a simple analytic
way is that of an exponential distribution of tmps, lr .. cxp
where II (E) is the number of traps per unit volume and umt energy 111terval, H 1S
the total tr.1p density and T, . is a chamcteristic temperature. The SCL-currcnt then
becomes 135 I
. ( aol )t(21+ ')H'p+l
] SCL = NcJJJlf! He(/ + I ) T+T U
( 12.10)
where I= T./f. Neg is the density of transport states and F = V/L. Of greater relevance
for random organic solids like conjugated polyn1t:rs or molecularly polymers
appears to be a Gaussian distribution of tr.1pping states [36). Under th1s Ci rcumstance
the problem can only be solved numeric.ally. In !he slope .of j(f)
plots in double logarithmic representation increases w1th mcreasmg clcctnc field
while it is constant in the case of an exponential distribution. However, lhe strong
thickness dependence of j (SCLJ is retained. It provides an unambiguous clue for dis-
tinguishing between trap-modulated SCL-conduction and.
tion (see Section 12.2). On the basis of thej(.F) chamctenst1cs alone 11 can be diffi-
cult if not impossible to discriminate between both possibilities. .
In the above consider.1tion it has been tacitly assumed that the charge camcr
mobility docs not depend on the electric licld. This is a good approximation for
molecular crystals yet not lor disordered systems in which transport occurs via
hopping. Abkowitz et al. (371 have solved that for a .licld of
Jl of the form p:=Jto (F/F
0
) and tmp-free SCL conduct1on. The1r treatment pred1cts
. F" a2 II/ (n + 2) + 1]" '2
Jsn =
1
:
1
:,p11 L. Fj;(n + 2)
( 12.11)
A gcneml, albeit implicit solution for arbitmry licld dependence of Jl has beer
presented by Young
12.3 Space CI1C1rge Limi1ed (SCL) Currems 381
.
12.3.2 Experimental Results
There is of SCL current !low in molecular crys-
tals, albeit med1ated by trappmg ellects [I}. Trap-free SCL conduction has been
with molecular glasses and molecularly doped polymers [39}. In these
stud1es the charge carrying moieties have been selected or the premise of them
having a low oxidation potential, i.e. a high lying HOMO. The lower lhe excita-
tion potential of the bulk transport material is the less likely it becomes lhat inad-
vertent impurities with an even smaller oxidation potential, act as traps for holes.
111Cn, only SlllJCtural tmps can capture charge carriers. This results in a lower
overall mobil ity o.r charge as compared to single crystals and is concep-
tually accoumed lor by hoppmg theories lor random media as discussed in Sec-
tion 12 .. 4. it to here that the mobility becomes tcmperclture depen-
dent often teatunng a held dependence of the fonn lncc F
112
, where the slope de-
pends on the degree of fro;t.cn-in disorder. Evidence for the occurrence of tr.tp-frcc
SCL hole transpo11 in the system mentioned above has been (i) the anreement of
experimental j sn.(F) data with values calculated from Eq. ( 12.5) on b;L-;is of
charge carrier mobility under space-charne-frce conditions and (ii) ob-
. . 0 .
servallon ot a cusp in trall!>icm SCL-signals that monitors canicr anival at the
exit contact.
. SCL-conduction has also been observed with LEOs 1401. A textbook example
ts .the worl-. of Blum et a/. 1411 on alkoxy-substituted PPV carrying either an oh-
rruc lor hole injcdion (ITO) or an ohmic electrode for electron injection
the second electrode serving as an exit contact only. In the case of hole
lhcj(V,L) characteristic is in accord with trap-free SCL conduction obey-
mg 0'1ld's law (Eq. (12.5)) and yielding a hole mobility of Sxto-
7
cm
2
y-
1
5-
1
(sec F1g .. I 0). The clcl:tron current observed at appropriate bias is also space
charge lnn1ted but trap-cnntrull ed as evidenced by the steep j( V) characteristic in
combination with its dependence on sample thickness. Applying the methodolony
of Ref. [351 the concentration of electron traps was obtained as H=5xt0
17
cm':.
1
.
Candidates are oxidation products [42, 431.
Figures 12- 12 and 12- 13 document that trap-free SCL-conduction can, in fact,
also be observed in the case of electron transport. Data in Finurc 12- 12 were ob-
for a single layer of poly!>tyrene with a vinylquaterphenyl
chain copolymer, s.mdwichcd between an 11D anode and a calcium cathode and
given lhat oxidation and reduction potentials of the matenal majnrity cani ers
only be electrons. Data analysis in terms of Eq. (12.5) yields an electron mobility
f 8 10
_.., 2 y - 1 - 1 T .
o x em s . he rather low value 1s due to the dilution of the charuc
carrying moiety. The obvious reason why in this case no tr.1p-limited SCL
duction is observed is that the ('F ,-quatcrphcnyl substituent is not susceplihle 10
chemical 1lxidation.
Figure 12-.13 comp<Jrcs j (F) characteristics for a single layer diode of polylluor-
cnone sandwiched between an ITO anodl' and either an al uminum or an maunc-
sium cathode l45 1. The increase of the CUITcnt upon replacing AI by Mg
that in the latter case the m;tiority of the carriers must be electrons. At the same
382
12 Charge Transport ;, Rundm11 Orgtmic Semicmuluctor.r

VbiasM
Figure 12-10. j(V) char-JCtcrislics of ITOIPPVIAu hole nnly devices with L=O. I31JOI
(squarcs)=31im (Uiangles). and 0.70 11m (dills). Full liues represem the predit1ion of Child's law (Eq.
(12.5) for a hole mobility of 5xl0 ' 1:01! v s ' and a ..Jiclccuic mnstam c=3. The im;el shuws the
PPV used wilh X
1
=CII.l and X2 =Caot-l21 (Rei'. 14111.
1o0
1()''
10"'
1:

-,

1o-0
.

1041
10 100
VbiasM
Figure 12-11. Thickness dependence of the electro1r unly j(V) characteristics :.u L=0.22, 0.31 , and
0.37 IJm. Solid lines have been calculated for an cxponemial distribution of electron u-.s.ps or the loUI
densily tO'" cm l and a temperature 1500 K (Ref. 14111.
time the j(F) chamcteristic approaches Child's law yielding an electron mobili ty
of l.2xl0-6 cm
2
y - l s-
1
. ll is of the same order of magnitude as measured with
different electron transporting materials applying the time of ll ight technique [46,
47). This confirms the notion that hole and electron mobility-conjugated polymers
become comparable in magnitude if trapping Ciln be excluded.
12.3 Space Chlll'l:l' Umitetl ( SCL) Currellls 3H3
10''
N
.E
10 ..
u
<(
::>
c

.... 10
6

::J
u

10 ..
1o' 10
electric field/ Vern
Fillurc 12-12. }IF) characlcri'll'' rdkllillt( SCL d cclmn lluw a 1110 IIIII thick film ur CF,-PQJ>
copolyn\Cr hclwccn a <"lkiulll l':llhudc ami an ITO anoclc. TIIC full lin.: .. slop.:
of 2 (Ref. 14411. .

NE

Fluorenon -Mg o Fluorenon -AI
10-r-------------.
10''
10-l

10-
3
10 ..
10'
5
10-6
10'7
10-e
0
10'
9
......

0
0
0
0
0
0
0
0
10
6
field (V/crn)
0
0
00
0
0
0
12-l.l. j(J.") dlarac:lcli,lic f11r a thin llhll ur
pulylluurcnon.: ,'(;lllllwio.:hcd hclwccn an ITO
mlc tllltl a Mg full MIUarc ur an AI calhu..Jc
lul'k:ll MIUan.:s). The Mg cathode inject, a SCL
ckclrun cun-cnl ut1eying law.
384 12 C/wrge Transport in Rundum Orgtmic Semiconductors
12.4 Charge Carrier Transport
12.4.1 Concepts
Charge carrier transport in molecular crystals has been stu.dicd em-
ploying the time of flight (fOF) method. Mobi lity values arc m the or-
der of 0.1 to 1 cm
2
v- s- and weakly temperature dependent tf measured near
room temperature. At lower temperatures J1(1) often approaches acti vated behav-
ior. With the advent of extremely clean samples it became clear, however, that
this is due to tmpping. ln its absence, Jl (1) approaches a power law dependence,
/l (1) a:. l". In crystalline naphthalene, values in the onler of 10
2
cm
2
v- s- have
been reported at T-;;: 30 K indicative of band-li ke motion limited by at:oustic pho-
non scatterinn 1481. At higher tcmpcrc1tures, carrier mean free paths become com
pardblc to intermolecular spacing, the com:omitant superposition of hopping
and coherence cOccts representing a challenge for any theoretical description. The
most advanced theoretical treatment available to date is that of Silinsh and Capek
[491.
The s ituation is considerably simpler in molecular glasses and mokcularly
doped polymers, because the presence of disonlcr eliminates any involvement of
coherence eiTccts. Molecularly doped polymers are widely used as trc1nspoat layers
in the photoreceptor assemblies of photocopying machines. A brief account of the
recent achievements conceming the understanding of charge tmnsport in these
systems will be given in this secti on. For details the reader is referred to previous
reviews [50, 51) as well as to the monogrc1ph by Borsenberger and Wetss [521.
Most of lhe experi mental work has been carried out on both neat glasses of deri-
vatives of triphenylamine, hydmzone, pyrc1zoli ne, and their molecular dispersions
in polymeric binders like polystyrene and polycarbonate. By virtue or their low
oxidation potential they are hole conductors. A few reports on electron-transport-
ing molecularly doped polymers have recentl y appeared in the literature [53, 54).
Conventional TOF studies, performed on sandwich-type structures, yield sig
nal s with anomalously broad tails. At lower tcmpemtures they tend to loose their
inflection point, which marks the arrival of the carrier sheet at the exi t contact,
i.e. become dispersive [55]. Mobility values rc10ge from 2: 10- o to 2: I

em\
v- s- (TAPCIPS) [56] at 295 K and electric fields in the order of 10 Vern- .
The catTier mobility is notoriously temperc1ture activated yielding activation ener-
gies between 0.7 and 0.2eV and Jl(T-+oo) values, in the order of 10 to
1000 cm
2
y-t s-
1
i.e. much larger than crystal values if analyzed in terms of the
Arrhenius equati on. Although the polymer host docs not, by virtue or its energy
level structure, participate directly in charge transport, it may have a profound et:
teet on the absolute magnitude of J1. as well as its T-depcndence as illustrated in
Figure 12- 14 for TAPC, which is present a.-; an amorphous film and doped into
PS and PC, respecti vely. In general, increasing polarity of the binder reduces Jl.
Another ubiquitous feature observed in charge transport studies in molecularly
doped polymers relates to the field dcpcndetll:e of '' obeying a In Jl
112
law
TAPC: polystyrene
TAPC: polycarbonate
10 6

{1000/T)
2
K-
2
12.-1 Charge Carrier Tnmsport
385
ll-t4. Lug:rihm of the zcro-
li.:kl muhitity "' for TIWC-dopcd
polystyrene. TAf>C-dnpcd pulycarbonale.
anJ pure TAPC. (Rd . (6:'iJ).
a quite large range of fi elds (sec Fig. 12- 15). Orten, albeit not always, tlevia-
ttons arc noted at low liclds.
. hat! become practice to analyze the /l (T, F) behavior in terms of Gi ll's em-
ptncal equation 150):
Jl(T, F) = J1exp[- (6o - fJFt f
2
)jkT,.gj
( 12. 12)
where l/T-1/T*. T* is tcmpcr.tture at which Arrhenius plots of Jl(1) in-
tersect, and JIQ=Jt(T=T*). Thts suggests that tmnsport is controlled hy traps that
are charged when empty. Sevcrc1l problems arc encountered when applying Eq.
(12. 12):
l. Introduction of an cfrective temperature has no theoretical found:uion
2. It is um:catistit: .to assume systems of different chemical anti prc-
''Ill ehemtcally vety dtll ercnt mutes, contain a similar amount of impuri-
ttcs that arc chargt.'tl when empty;
3. P can deviate from the value predicted by Poole-Frenkcl (PF) theory
P
_ (".lF.'',. n) 112
I'F- L " II ;
4. PF cannot explai n why the licld dependence of Jl is reversed at T> T*
as venlled hy experiment.
386
12 Clrarge Tronspun in Random Organic: Scmicumlucrors

::l..
T(K)
329
319
309
299
289
279
269
259
249
239
229
Figure 12-15. Hole mohilily in .mok.'CU
lar <lb1x:r..iun of 75% (hy cJ
1
o-7L _ __] _ _ TAPC in polycaa:bonatc a.' a funcuon of
00 IZ thl! Cl<:ctric field par.Jmctric ill lCIIlpcr.l
turc (Ref. 1561>.
Composi tion has a marked effect on p .. Dilution can Jl to orders
llla litude. The functional dependence 1s often expressed m tcnns ol an cxponen
ti algJdependencc on intersite distance R=m:-
113
as _suggested by
lattice gas model, p(c:)cx.lf- cxp l- (2ya)l. Here IS the mtcr:-1te
h . a
1
lute' system and 2ya is a measure ol the clectromc mters1tc couphng.
11\ t e unu u
1
d. 'cp ndcnce
. 11 2 - 10 One should also note that the exponenua u e
typlCI y, ya = . . . h ld f . t port
of intcrsite coupling precludcs observing a pcrcolallon thres o m r.1ns
I 2.4 Clwrge Ct1rrier 1hmspurt 387
There have been attempts to correlate Jl with properties of the charge transport-
ing molecules in molecularly doped polymers. No systematic variation wi th the
ionization potential in the case of hole-tmnsporting systems was found. This con-
curs with the absence of any dependence of charge canicr mobility in molecular
crystals on the absolute position of either the valence or the conduction band.
However, dclocali zation of the excess charge within the tmnsport molecule seems
to have a positi ve effect on transport while large dipole moments act in an oppo-
site way. The ract that the functional features or the mobility are independent of
chemical constitution calls for an interpretation in terms of underlying physical
rather than chemical principles. The most obvious one relates to the disorder pre-
sent in these systems and invoked previously by Scher and Montroll (551 to ex-
plam the occuiTencc of dispersion. TI1e disorder model developed by the Marburg
group [50j to treat charge carrier motion in random organic solid-; is a micro-
scopic model as opposed to the continuous time mndom walk concept based on a
heuristic wai ting-lime distribution. It rests on the following assumptions:
I. Because of the randomness of the intermolccular intemctions in a non-crys-
talline organic solid, the electronic polarization energy of a charge carrier located
on a transp011 molecule is subject to some tluctuation. A manifestation of this ef-
fect in optical spectroscopy is the inhomogeneous broadening of absorption lines
of chromophorcs embedded in orgunic glasses 157 j as well as those of bulk poly-
mers.
2. Gi ven the !.h011 mean free path or charge C<Irriers in molecular crystals due
to narrow energy bands, the introduction or disorder in the above magnitude
causes complete localization. Transport is thus described in terms of hopping
among localized states. In chemical terms it is a redox process among chemically
identical dopants that diiTcr physically. In analogy to optical absorption profiles
the density-of-states (DOS) profile is assumed to be a Gaussian of vari ance a, the
quant ity ii=alkT being a measure of the degree of energetic di sorder.
3. Polaronic ell'ects arc of secondary imp011ance only.
4. Charge transport is an incoherent random walk desctibed by a generalized
master equation and transition rates arc or the Miller-Abr.1ham lorm:
( 12.13)
where 6R;i is the intersite distuncc and &iJ is the dillerence of the site energies
including the electric lidd tem1!..
5. In addition to the energetic disorder or the hopping sites, geomeuic (posi-
tional) disorder can be taken into account by lclling 2 }'1 lluctuate randomly ac-
cording to a Gaussian distribution of variance E (ojf-diagmwl disvrder) thus mi-
micking the variation in intersite distance and/or ovcrl<tp due to variation of the
mutual molccular 01icnta1ions.
The model has been treated analytkally emJ>Ioying the ellcctive mcdium
approach [5HJ and by Monte Carlo simulation. It makes the lo llowing predictions:
A dilute ensemble or charge caniers, initially generated at random
within the DOS, tend!. to relax lowanl the wit Males and ultimately equilibrates at
388
12 Charge Trwrspon in Ram/om Organic Semicmuluctors
. Prgy -cl-!kT below the center of the DOS, the variance of the occupational
an enr . lf R 1 d
DOS being equal to that of the DOS llse . elaxat10n u:ans aLes_ a tunc-. e-
d
nt cmTenL reflecting l.hc time dependence of the earner mobthty. A TOF stg-
pen e ' f RC f h
1
ill therefore carry a spike at short ttmes trrespccllve o -lime o t c ctr-
or not the photocurrcnl will _to _a depends on
or l.he carrier transit time exceeds the eqUJhbnum tune. the Iauer m-
faster with increasing disorder l.han l.he former, TOF s1gnals must even-
become dispersive. For a 10-J.Im-thick sample l.he critical . value of rr is
i-mplying Lhat the transition occurs at 230 K for 100-meV-wtde DOS.
pven if iT< 5, TOF signals carry tails that arc much broader l.han expected m
ever, . of diffusive broadening of an initially b-shaped packet of carriers that obeys
law relating mobility and diffusivity via eD=pkT [59). The reason for
the distribution of jump mtes implied by the character of hop-
. , fransport. If a drain licld acts on any ensemble ol random walkers whose
rJ.te is subject to a dil>tribution, the packet will spread faster with time than
JUlllp .o . . I I .
in the' absence uf disorder 1601. The 1. e ectnc
fi ld
. md degree of disorder 1611. Fur a =4, wh1ch tums nut to be a realtsttc value
IC c .o h (
,. any systems near room tempemture, the cumputauuns mutcate t <tl t 1e ap-
'or 111- . -
1
f. 1
1 D incrc<rses linearly Wtth lied anu urstance rom I te lnJect-
parenr " ' "'''" . . . . . .
in, e#ectrode. This causes universality of 1!on-d1spers1ve TOF s!gnals
l
g t k fi eld and sample thickness. For a = 4, the tall sprc.rdmg, expressed 111
eecrr . h
1
-
1
1 h
terms of the dispersion w=(l
1
rr t
11
)/t
112
, where t w. _s 1 e t_une a ter ':"' l ll: 1 t e cur-
was decayed to 1/2 of iL'i plateau value and Iu s the lime at wh1ch asymptotes
rent lT
intcrs,ect, is predicted to be :;:0.4. . .
Sirlce the mean energy of the c.,, vanes as 1
1
, the mean
. tion energy that a camcr has to overcome m order to execute a hop must
actJ v.,. r - ld) b.l.
also .;ary as I . As a consequence, the T-dependence ot the (low-he mo 1 1ty
is predicted to follow
J1(T) = p
0
cxpj- (2af3kT)
2
J = p
0
expj- (2fr/3fJ. (1 2. 14)
If
plolled J1(7) in an Arrhenius dianram and detcnninctl the apparent acti va-
onr o. .
s;:nergy 11 from the tangent at a g1vcn tempemture T, one would obtam
For a =O.I eV and T=295 K, 11=0.35 eV. 11 is, l.hus, always a mul-
ti ple of a. On t_he since '.lny S enter
h' sollzmann I actor lor the JUmp rate as E,)2 Ill the low-field llnlll, the disorder
t c rJbution to 11 would dominate even if a and ,, were comparJ.blc.
and geometric. disorder must rise tu a field or Jl, al-
beit in an opposing way. T1lting an encrgellcally mh?mogeneous. DOS Ill an elec-
tric field lowers, on average, the fur forward JUmp_s. Therefore,
st increase with f: At very h1gh hclds, 1.c. when the dtsorder effect
Jl mu . . .
1
. .
1
,.-1
. vanish and a earner w1ll acqUire a constant vc octy, cqUJva ent w JICX. r ,
must . b d.
as
00
rne out by f-i gure 12-16. the separallon, y 1-
1
1 depresses l.hc threshold held above wh1ch J' begms to decrease w1th field
UtiOI'
I62J because backward jumps arc eliminated at ..
on the ot her hand, can generate dead ends lor the d11lusmg camcr. Smce
000
200
2.50
300
J so
c = 1 00
12.4 Cltarge Currier Transport
389
12-16. Field dependence of
the charge canicr mobility in an un
dilulcd hupping syslcm al various
Of the disurdcr parameter
ir = rr/kT (Rd. 167)).
may involve jumps against the licld direction, Jl(F) will decrease
With f!' m a_ system where a:;;O and where there is large geomct1ic disorder. Upon
and positional disorder, the Iauer ell'ect will prevail at
lower llclds wh1lc at h1ghcr fields the gradual elimination of the e llcct of ener-
getic begins dominate rise to a sigmoidal 11 (F) relationship.
The sunulahons predtct In ft. F
1
- Within a fi nite lield range the slope
S
/"F' r . . . , . .
= v nJt u - changmg stgn when positional disorder exceeds cneroetic disor-
der. Functionally, Jt(T.F) can be expressed as b
Jl(T,F) = 11
11
expj-(2af3)
2
J ex ) 1.5
{
p( ., ,-2 F ' / 2 r
cxp (a--2.25)F
1
1-,r 5 1.5
( 12. 15)
where /4t is a function of concentration, I: is the geometric disorder par.unetcr
and (cnl!V)
1
r- is an empirical constant. F should be replaced by
effective held F"ll :;;eFal2kT in Eq. (12. 15). This, however, has little e ffect on data
if restricted _to expcrimemally realistic temperature regimes [ 621. Note
that Eq. that the field dependence dtanges sign if E>a/J.:T. The
phenomenologically ddmcd Gill temperature P is, thus, related to the disorder
parameters of the system P=alki:. Fora:;;(). l eV <utd =3, K.
There is abundant evidence that the ahove fonnalism pmvides a framework lor
explaining the. majori_ty of including the temperature and field
dependence o l nmb1hty. albe11 nut m the entire lido reuime, notahly (i) the tem-
d:P.endem:e ol the P<lr;uneter of lnX F{h plots, (ii) the prefactor
mob1hty, (11 1) the mllucnce of randomly dipoks on the width of the
390 12 . Charge Tra11sport ill Ra11dom Orgwric Semicoucluc:tors
DOS and, concomitantly, on f.J [63-66], and, (iv) the temporal features of TOF
signals, notably the universality of non-dispersive signals at variable sample
length and electric field, and the transition to dispersive transport which, remark-
ably, does not bear out universality [67).
In molecular doped polymers the variance of the disorder potential that follows
from a plot of In f.J versus r
2
is typically 0. 1 eV, comprising contributions from
the interaction of a charge carrier with induced as well as with permanent dipoles
In molecules that suffer a major structural relaxation after removal or ad-
dition of an electron, the polaron contribution to the activation energy has to be
taken into account in addition to the (temperature-dependent) disorder effect In
the weak-field limit it gives rise to an extra Boltzmann factor in the expression
for p(7). More generally, Marcus-type rates may have to be invoked tor the ele>
mentury jump process 167).
The shortcoming of the Monte Carlo simulations of Ref. [50) has been the way
in which positional disorder has been incorporated. Contmry to real systems in
which the electronic coupling between a given molecule and its diiTerent neigh-
bors is din'crent, because of the difference in typology, the simul<ttion classitied a
site as being good, W'erage, or hac/ as fur as coupling to all its neighbors was
concerned. Subsequent simulat ion work by Gartstcin and Conwell 168- 70) re-
placed this ovcrsimplistic assumption by a more realistic bond approach involving
positive correlations among the encrgic.'> of neighboring hopping sites. They
showed that this has a profound effect on the field dependence of the carrier mobil-
ity. Introducing spatial correlations causes the range of velocity of the In f.J<XF
1
n
law to extend further towards lower fields and, concomitantly, improves agree-
ment with experi ment. Conceptually a strong field dependence of the mobility
should occur when the potential drop, eF/, across a relevant length of the system
is comparable to kT. With uncorrelated energies the only length scale of relevance
is the mean intersite spacing u. Correlations introduce a new length scale, namely
the correlation length associated with the energetic disorder, thereby decreasing
the critical electric field. Du.<;e<J upon these ideas Dunlap et aL (71 J developed an
analytic model, albeit premised upon a I D treatment, which is able to explain ex-
perimental Jl(F) data on the ba.o; is of values lor the width of the DOS consistent
with those inferred from the tempemture dependence of the carrier mobility.
12.4.2 Transport in the Presence of Extrinsic Traps
Recently the effect of intrinsic traps on hopping transport in mndom organic sys-
tems was studied both in simulation and experiment [72]. In the computation it
has been assumed that the energy distri bution of the tmps features the same Gaus-
sian profile as that of bulk states.
Figure.-; 12- 17 and 12-1 show the temperature dependencies of the mobi lily in
a hoppi ng system with a Gaussian DOS of variance a:;0.065 eY as a function of
the relative concentration c of Imps of average depth , = 0.25 eY and as a func
tion of the trap depth , at a fixed concentration c=(}.(}3, respectively. For c=O
o=0.06SeV
E,= 0.25eV
c
1.0 X l o-J
3.0 xlo-1
x 1cr
2
12.4 Clwrge Carrier 1hmspurt

0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5
(1 OOO!T)2 (K)-2
391
Frgure 12-17. lllc lempcralurc d pc1' .. r h '
. <: IUCIJ<:Ic.s o 1 c """Hilly lor 17=0.065 eV for dn
COOCl.'Olr:lliOns ol 11\C dcplh was 0.25 c V aJld Ilk: licld 2x l()l V . J . . . .' crcnl
responds 10 lhc
of (Rd. I?21J. <:Ill The dashed hnc c..-or-

:s recovered: 'I?e presence of tmps lowers the mobility as expected
12-17 and 12-18 is that, to a first order
0
. Eq. ( mamtatns the tcmpcr..rturc dependency of the mobility if one
rep
1
. laces the .ds?rder parameter by <m cflccti ve disorder pammctcr a or cq .
emly, an cllecLJ VC width or the DOS that dcn.nds on hoth II . r:Jl ' . UIVa-
the de lh r 1 . . . . . 1e conccntratton and
come f. o .'11.:: Devtallons I rom the behavior predicted by Eq. ( 12.14) be-
th gh

tor eV, notably at lower temper.llurcs. It is noteworthy

ou , t at tle T-+ co Intercepts of It (1), if ploucd as In 'l versus r2 va b ,
no more than a fact r" ,. ' ry Y
1
. . . . . or
0
:- upon tr.1p deplh <Utd concentration.
lr:l n e vanallon wrth Imp IS presented in Figure 12- 19. The elfect of
ps on the mobrhty, rellcctcd 10 an increase of be . bl
Jbo . . "tT comes noLrcea e only
a cnucal trap that depends on concentrat ion. Above that cri ti-
cal value, c?.tJ mcreases approxrmately linearly with r
1
gure 12 20 h
P
leme t r . ,. - s ows com-
. n ary rn onnaiJon concemmg the cllcct of the trap com:cntration on a . 1
d.cpth .. The data _us <r ()f parallel straight lines :f.
1
:,
Ca&u> vc1sus In plot. Thetr mtcrscciiOII wrllt tl1c 1 - 1 1 d.
. . 1 "c:JJ I'T- I lie Ill I CUtes the
c,. ot tr.tps of depth E, needed to effcl:l the mobility (sec
392 I 2 Charge Transport i11 Rullllom Orgw1ic: Semic:ou.ductors
E.(eV)
"O:"i""C)
0.18
0.25
0.30
0.35
1 o-oL-_ _ _._ _ _._ ___ __,_ _ ___.
0.0
4
3
2.5 5.0 7.5 10.0 12.5 15.0 17.5
(1 ooorrp (K)-2
c
3.0 X l()J
1.0 X 1o-J
1.0 X 10'
1

0.10 0.15 0.20 0.25 0.30 0.35

l'igurc: 12-U!. 1l1c tcmpcraiUrc ..cpcn
dcncies of !he mobility simulme<.l for
diffcn:m trap dep!hs. TIIC tr..tp concen-
tr..ttions were and the field
2><10
5
V em ' (Ref. (72]).
l'' ignn 12-19. TI1c (f1<Jfoi
vs. Imp depth. par.unctric in the 113(
cmu:cmr.llion (Ref. (721).
/ 2.4 Charge Currier 1i'tmsport
393
4
E,(eV)
0.30
0.25
0.20
3 0.15
N

CD 2
0
tl
-
c

0. 10 0. 15 0.20 0.25 0.30 0.35 0.40
E
1
(eV)
Figure: 12-20. The pat';lti\Ctcr (o,
1
jf1/
vs. l.'tltiCcmmtion, paraniCtric in the tr.tp
depth 1::, (Ref. 172 ().
1' igurc: 12-21. 'lliC nitical cunccmra-
tilltl c,. ahuvc which ntodil"y the
width of tile DOS. It is delined the
l'OIICCntr.ttllltl at which tit.: >traight
lin,es in Fig. I intersect the ta,J
at "' I l111c (Rd. (721).
394 12 Charge Transport in Random Orgcmic Semicmuluctors
It is obvious, and verified by experiment [73), that above a cri tical trap concen-
tration the mobi lity increases wi th concentration. This is due to the onset of inter-
Imp transfer that alleviates thermal detrapping of a carrier as a necessary step for
charge transport. The simulation results presented in Figure 12-22 are in accord
with this notion. The data for JJ(c) at ,=0. 195 eV, i.e. E/a=3. pass through a
minimum at a tmp conccntmtion c= I o-. Location of the minimum on a conccn-
trdtion scale depends, of course, on
1
since the competition between thermal de-
tmpping and inter-trap transport scales exponentiaJiy with ,. The field depen-
dence of the mobility in a trap containing system characterized by an effective
width is similar to that of a trap-free system with the same width of the DOS.
Figure 12-23 shows simulation of time-of-flight photocurrent transients a1 vari-
able tenfCrature for a system containing 0.25 eY tmps at a concentration
c=3xl0- . This translates into a,:g=0.080 eV. The current decays monotonously
by several orders of magnitude to finally merge into a plateau followed by a rapid
fall-off that retlccts discharge of the carriers at the exit contact. This is in accord
with experiment [741.
In phenomenological terms, the presence of a distribution of traps is equivalent
to an increase of the number of tail states of the DOS and, concomitantly, opens
additional pathways to the relaxation of charge carriers towards steeper states. A
zero order analytic description of the effect can be based upon the Hocstercy and
Letson [75) fom1alism. The Iauer is premised on the argument that the carrier mo-
.--.
(/)

c
1()0......--------------.
10
1
.0

<tS
-:1.
1 02 L-.J.....J...J..I.J.IJIJ..--I....U..L.U.II.L-...L-I...u.JWIJ.--1....U..L.lllll
10
4
103 1 02 10
1
100
c
Figu.-c 12-22. 1ne dependence of the
mobilily on 1rap conccnlr:nion. The
width of Ill<! DOS 0.065 cV, the
1r.1p depth 0. I 95 c V, 1hc lcmpcrature
400 K, and Ill<! licld 2x I OS V cnC
1
(IM. 1721>.
I-
I I
1\
o..,
3. 10
3.57
3. 71
3.87
12.4 Carrier 1hmsport
395
..
log t (arb units)
t' lgur-c 12-23. SimulalcJ pholtlt:UITelll lr . .lllsi-
c_ms lor JiiTcrcnl values of a lf For she simula-
a =0.065 cV, r = Jxlo- S, anti E,=0.2.'i eV.
Fur darily tho! curves have been vcr-
ucally and holl:t.Omally (Ref. 176]).
in a "".ith relati ve trap c _is the product of the mobility
lll the trap-free systt:m p(c==O) multsphcd by a tmppmg factor.
[I + cexp(E,fkT)r',
( 12. 16)
that accounts for the time spent by a carrier in tmps. In the presence of traps, the
mobi lity is thus
(12. 17)
. . [ (2ir )]2
Conssdenng that Jt(c) = Jlu exp - ;ff , where a,
1
l = a(c)la(c==0), and
Jt(c = 0) = Jlu ]
2
it follows that
(
a :lf(c))
2
( 3 )
2
[ (E)]
= I + Ur In I + c cxp k;. . ( 12. 18)
396 12 Charge Transport in Random Organic Semiconductors
For c exp (E/k1) 1,
(12. 19)
Eq. (12. 19) predicts that a family of su-aight lines should be obtained on plotting
aeJ!a versus In c: at variable trap depth and versus , parametric in concentration.
It implies, however, an incorrect temperature scaling. Due to the a term on the
right hand side of Eq. ( 12.18), the slopes of a<'J!a versus , and In c: plots are pre-
dicted to depend on temperature, contrary to both simulation results and experi-
ment. Formally this is a consequence of the error introduced by describing the re-
tardation as an ensemble of charge carriers in tem1s of Eq. ( 12. 16 ), which is ap-
propriate for a system devoid of disorder. In physical terms this assumption ne-
glects the opening of new relaxation pathways for an ensemble of caJTiers brought
about by the additional states at the tail of the DOS. This causes the temperature
dependence of the tmpping fm.: tor to deviate from a simple An11Cnius form. De
spite this shor1coming, Eqs. (12.18) and ( 12.19) are helpful for an assessment of
the effect of a deliberately added trap distribution on the transport properties. This
is illustmted in Figure 12-24 as far as the variation or a,'l)la where Inc can be de-
rived for measurements of the hole mobility in mokcular glasses of tri-p-tolyl-
amine (ITA) doped with vaaious concentrations or di-p-tolyl-p-anisylamine
(DTA), di-p-anisyl-p-tolylamine (DAT), and tri-p-anisylamine (TAA) [76]. The
successive substit ution of I, 2 or 3 methyl-groups in ITA by methoxy-functional-
itics lowers the oxidation potential relative to ITA by 0.08 eV (DTA), 0.15 eV
(DAT), and 0.22 eV (TAA), respectively. In the case of no additional polaronic ef-
fect these numbers should be equal to the averc1ge trap depths for holes.
"'
,._

"'
.9.
2.5
Et(eV)
0.22
2.0 0.15
o.oe
1.5
1.0

l<'igure 12-24. The par.tmctcr a, nfa versus tr.tp oon
........ ........... 1ui.0-3-'-...........W1CJ'2"-L..U.J,J,...W10 CCUlr.JtKIIl ror 'ITA dopct.l with DTA. DA1: and
TAA. The tr.tp mccnl!ation is &ivcn in molc/111ole
Ct(moVmol) 1TA cRd. 17fl>.
12.4 Charge Currier 1/unsport
397
Figure 12-25 shows the tempemture dependencies of the zero-field mobilities.
The temperature dependence predicted from Eq. (12. 14) is recovered. Analyzing
the data using Eq. (12. 14) yields a.,g==0.083, 0.084, 0.101, and 0. 117 eV for ITA
and ITA doped with DTA, DAT, and TAA. The correspondino values of Jlo are
2.3, 2.6, 3. 1, and 2.2 in 10-
2
cm
2
y - s- t uni ts. o
The effect of traps on charge carrier motion does not become noticeable until
the tmp conccntr.uion reaches a threshold value. One can define a critical concen-
lmlion c,/2 at which the mobility has decreased to one half of the value of the
tmp-free system. Eq. ( 12. 19) predict<; that
Ct f 2 = exp(') .
kT
( 12.20)
The confirm the notion that the basic features of trapping due to extrinsic
tmps 111 a random organic hopping system can be accounted for within the frame-
of the _ronnalism. The cll'txt of traps can be dealt with by introduc-
mg an dcnstty. n.:ason for the success of this simplistic approach is
that supenmposang a trap distribution of aver.tge trap depth E
omo a Gaussian-shaped imrinsic DOS of the same width yields a
DOS that features a Gaussian tai l whose cll'ectivc width agrees with Eq. ( 12. 18)
as long as , S0.3 eV. For deeper traps the temperature dependence of the mobili-
ty becomes Arrhenius-like [77).
It is that the of tmpping is comparable to that in a sys-
tem devotd ol dtsordcr. In tact. the critical concemration above which the effect
of traps becomes_ is the same. i.e. In c,. 1:./kT, which follows from Eq.
(12. 17). The_ baste dtltcrcncc between a disordered and a disorder-free system is
TTA
TTA:DTA
TTA:OAT
TTA:TAA
l'igurc 12-25. lltc tcmpcr;uurc dependencies of
the L.cro-rtetll mobility for TrA anll TrA dup.:c.J
with DTA. OAT. and TAA. The TTA wm.:cnamtion
wa" 40%. the hi1Kicr material was polystyn:1te. l ltc
l>TA. OAT and TAA to TI'A were
I.Uxlll
1
111ullmul TI'A (Hd. J7C.J).
398 I 2 Charge Transport in Uuudom Organic Semicouductors
that in the former the phenomenology of canier transport, expressed via J.t(T,E,c),
is distinguishable from a trap-free system while in the Iauer an Arrhenius tem-
perature dependence of p(7) is an unambiguous signature of trapping. Since the
width of the DOS is not a priori known, one cannot, a priori, distinguish trap-af-
fected from trap-free transport. Hole mobility measurements on polyvinylcarba-
zole (PVK) illustr.ue this ambiguity. Photoluminescence specu-oscopy [78, 79] in-
dicates that PVK comains incipient dimers at a concentration in the order of 10-
3
that are traps for singlet excitations and give rise to excimer emission. It is known
that these sites are hole traps [80]. This is not a priori obvious ti-om hole trans-
port measurements. Gill's [81] original data for PVK: TNF mixtures with low
TNF were interpreted in terms of what became known as the Gill formalism for
tmnsport in PV K and related systems. leaving the interpretation of the activation
energy open to conjecture. Replotting the Gill data on a In 11 versus r
2
scale
leads to a family of straight lines intersecting at T-+ ro, yielding
Jt(T-+ oo)=5xl0-
2
cm
2
y - t s-
1
and a=0. 142 eV in conformity wi th the notion of
hopping motion in a Gaussian-shaped DOS. Tr.msicnt photocurrcnt measurements
by Muller-Horschc et a/. (741 over a period of eight decades revealed a tcmporJI
pauern of exactly the kind as shown in Figure 12-23. In quantitative terms, one
can explain hole transport in PY K by considering the polym..:r having an intrinsic
DOS of width a= e V and containing 0. I% or 0.4 c V tmps.
12.4.3 Charge Carrier Transport in Conjugated Polymers
12.4.3.1 Time-of-Flight Studies
There is no reason why the ideas developed in the preceding section should not
apply to transport in LEOs notably if these arc based upon vapor deposited low
molecular weight materials. They should in principle pertain to conjugated poly-
mers also since there is good evidence that a polymer, in electronic tenns, can be
considered as an ensemble of subunits of statb.tically varying length, refened to
as the effective conjugation length which, by virtue of simple particle in the box
arguments, translates into statistically varying site t:nergy, i.e. HOMO and LUMO
posi tions. Electronic interrupt ion is caused by topological defects like chain kinks
or twists. Those segments should act as the elementary chargc-carTying moieties
among which charge caniers move by hopping. It is less dear that the disuibu-
tion or site energies is Gaussian :IIlli there is good reason to suspect that trapping
clTects due to impurities arc more severe than in low molecular
weight glasses l941.
Experimental infonnation for polymeric LED is sparse. A key problem for con-
ventional time-of-llight studies is that the condition of generating a sheet or car-
riers whose spatial extension is small compared to the thickness of a I 00 nm
film is difficult to meet. On the other hand, thick films fabricated, for instance, by
solvent casting mthcr than by spin coati ng, may Jiffer regarding their morphology
and, concomitantly, the built-in-disorder. On the fundamental side, tmnsport in
12.4 Charge Currier Trumport
399
th
r.lnddom systems is a relaxation phenomena Charge came I . h.
e enstty of ho . . . rs re ax wtt m
d ti . . ppmg wh1le mtgrating and their mobility becom . .
11
quantuy not unlll relaxation has been com letd T , - . . a we
bthty measurements on a thick n _ . . c . hc!elore tesults of mo-
time-of-tlight signals, i e TOF .
01
. not. pcnatn thm ltlms. Non-dispersive
the leading edge of kmk the anival of
measured typi cally on 10 thick fitn!e been
poly(phenylphcnylene vinylene) (PPPV f
821
. denvauves, n.amely
oxyphenylvinylene) (DPOP-PPV) lSJJ ) H
1
and . ,4-phenylene-1,2-dtphen-
of 10-4 cm2 y - 1 s- 1 at 295 . -...... _o c . Ill pppy are in the order
. th K and dcctc.tse Wllh tncrcasmo electric field A J .
mg e tempemturc dependence within th. . . <> na yz-
sian density of localiwd ield
17
_
0 09
y eli r-.uncwmk hoppmg wtthm a Gaus-
Jlo (T-+ 2x 10-2 y- t .-1 .TOe Gausstan wtdth of the DOS and
DPOP Ppv
ed
s . F-expcllmcnts by Meyer el a/ [83] on
- cover a dy 1 . f . .
in time. Experimental o six decades m amplitude and eight decades
appropriate for testing whi.ch is

1 111
1gwe - -.!. Whtle at
10 ..
10""
T z 2341(
E = 7 .Sxlo' V!cm
10 ..
10 ..
T a 2961(
E 7.5xiO' Vlan
10 ....
T = 3501<
T s 3SOK
E ; 7.5x10' Vlcm
E a 5xi O' V/cm
1o 10' 1o o> 10 , 1o lo' 1o IO 10"'
t(s}
12-.26. 'limc uf-liJ;hl fen hole llloliun in DPOI'-I'J>V . tl" ..
Inc: licit!.,. ll1c s.cmplc lllid,
11
c,, w"'
4 11111
A . .. _, . .. tffcl\:111 lcmpcr.uun.-, anc.J dec-
. ITUws lllulc"lc the tr;111, 11 lnnc (HI!f. IH.ll).
400 12 Charge Transport in Random Organic ScmiconduciVrs
10-2
350K 300K 270K 230K
500 kV/cm
10-
3 350 kV/cm
200 kvtcm
75 kvtcm
10 ...
4 OkV/cm
';;;'
N<:.. 10-
E

.:.:
10 ... 10 --

::)
10-' :o... --
10
, 0 2 .. 0 6

2.5 3.0 3.5 4.0 4.5
1 rr 11 OOOIKJ
lo'igurc 12-27. l c mJl<!ralure of the hole mobiluy an at different clectri.e
Dale for T= O have been obtuincll by exlmpolation. The inset the of Arrhemus plots
at Tc
1
=465 K (Ref. )831).
K the tmnsient photocuncnt, exci ted by 35 ps pulses of a frequency-
tripled laser (A_.x . =355 nm), seulcs to a plateau and at times shorter than the mean
carrier transit time tmnsport becomes dispersive at lower temRCratures. Room tem-
perature values of the hole mobility arc in the order of I O-' cm
2
v-.' s- t . compar.Ible
to values reported for PPPY. Plouing Jt(7)-data on an Arrhcmus (see
Fig. 12-27) yields a family of stmight intersecting at T0 =465 K and
ing to values mnging from I to 10 em y- t s-t forT-+ ro. The calculated acl!vauon
time energies arc between 350 meV and 220 meV for electric fields between 0 and
5xi0
5
V/cm. Interpretation has been given in terms of multiple tmpping by hole
tmps employing a Fourier tr.msfonn technique to calculate the density of localized
states. TI1e results indicated that almost every monomer rnust act as a trap. The mes-
sage, on the other hand, may be taken as an indication lhat a hopping as
outlined in Section 12.3. 1 is more appropriate for data analysis. Segments ol tre
PPV-chain, comprising between 5 and 10 repeat units, can be considc.red I?
as hopping sites for charge carriers and as optical absorbers responstble for the .m-
homogencous broadened absoq)tion band and its vibronic I:eplica. In
the of 12-27 on a In Jl versus r
2
diagmm
of stnught hnes that extmpolate to Jln (T-+ oo) 2x I 0 em V s . are
noted for T<250 K, i.e. alkT>4.1 which coincides with the value of the dtsordcr
parameter at which Monte Carlo simulations to dispersive
transport to occur l601. Their slope yields an cllecllvc wu.lth ol lhc DOS of
95 meY at F =7.5x l0
4
V/cm. II decreases monotonously to H4 meY at F=5xlcf
V/cm. Extmpolation tu F -+ 0 yields a= 100 ml'V. Since it 4uitc
tious if 1wo PPV-derivatives that were synthcsit.cd ia completely different chcnucal
F {V/cmJ ofmeVJ
84
15 10
5
frl
2 10
5
91
7.5 10' 95
lll
Figure I 2-.!8. Temperature dependence
of the hole mobility in DPOP-I'PV
plotlcd Oil it In Jl vs. "r
2
M:ale.

:;;
.!!.
c
..
t:
;;;J
0
0

c.
12.4 Charge Currier Transpor1
40
l.t
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0. 1
0.0
-o. l
2.0 0.0
E-4x to' vtan
T 290K
2.0 4.0 6.0 8.0 10.0 12.0
t (j!S)
Figure 12-29. l'hutocurrcut Jr:msicnt of the IT01
McLPPP/AI smnple otfter exdwtion through the ITO an-
ode with light pulses of 45() nm ;u 21){) K ;md an ;spplicJ
uf 4x10
4
V em
1
The hule mobi lity j,
XxJ(}
1
s
1

routes contai ned the same amount of traps or the same depth relative to the position
of the hole level of the bulk material, it seems straighllorward to assume
hole .values for PPPV and DPOP-PPV retlcct a bulk prop-
erty, :e. mollon among COnJugated of the PPV chain. This intcr-
IS supported the agreement between the a and Jlu values with the rcspcc-
value measured w!lh molecular weight glasses in which charge tmnsport is
kno-:.vn to be solely detenmned by the built-in disorder of the bulk hopping sites (sec
&:chon I ). _Pu shoukl in this case be identified as the mobility dctcr-
mmed by Jumps m a hopping system at tcmpcmlures such that kT>a. It is
W?I1h rccalhng lhat t.he prcsenL-e or shallow traps would only modify the effective
wtdth of.thc DOS w!lhout changi ng the basic phenomenology of charge lr.tnsport
(see SectiOn 12.4.2).
TOF expctimems on 7 J.lll1 thit.:k smnples of unsubstitutcd PPV fabricated
1
ia
the route liB I yielded signals that Jid not even reveal a kink in double
loganthnuc. representation. the high t.:ontcnt of accidental dopants. in-
ti/Ct these prcparalton techniques, transport highly dispersive.
Iccently, Lchcdev "' a/. I I suct.:ecdcd 111 obt<1ining TOF si<>nals on thinner
PPV (0.7 to 1.5 J.ltn) fabrit.:alcd Pi" an improvcJ precut-:;;. route that did
a lonk .m double_ log<trithmic representation. The S111<tller degree or dispcr-
allnhuted to sample qualily. At room tempcmllm: ;md when
F -_ 10 Y/cm, lhe hole mubthty was aboUI 10-1 cn1
2
y - t s and was tcmpcmt url'
acuvalcd. f-rom An11cnius plot an aclivmiun l'llergy uf 0.75 eY was inkrred. It
has at S<ll1ll' tunc been altribllled to trapping by a Gaussian di stribulion or
offset from lhe hole transp011 level by 0.35- 0.5 eY :md having a width of
402 12 Churge Trunspurt in f<uudom Orgunic Semiccmductors
0. 13-0.16 eV, and lO lhe break-up of bipolarons into polarons (rcquiling an en-
ergy of 0.6 eV) followed by tempcmture activated (0.15 eV) polaron tr.msport.
The latter hypothesis will be commented upon in Section 12.4.5.
lnfomlation concerning charge carrier motion is also available from space
charge limited (SCL) conduction as discussed in greater detai l in Section 12.3.2.
Bolh the time-of-flight technique as well as lhe SCL technique monitor transport
of charge carriers across lhe entire sample. Bearing in mind that coupling among
adjacent polymer segments is weak as compared to covalent coupling along the
chain it is straightforward to consider interchain hoppi ng as being rate li miti ng.
The only technique that can, in principle, shed light on the veloci ty of charge
transport along an uninterrupted chain is photoinduced or electron beam-induced
microwave conductivity (H6). In lhat case one probes lhe oscillatory motion of a
charge carrier, the maximum displacement being ax;;;: I0-
12
11F em for a 30 GHz
microwave field. For ps;2xl0
2
cm
2
v-
1
s- , reported to be an upper boundary for
charge C<Jrrier motion in crystalline polydiacctylcne, F= 10
2
V/cm, !1s;0.2 nm
Similar experiments have been perfonned on poly(2-(3,7-dimelhyloctoxy)-5-mclh-
oxy-1,4-phenylene vinylene) whi ch f01ms a gel in benzene solution at tempera-
tures below 35"C [87]. The experimentally accessible quantity is the mdiation-in-
duced conductivi ty, i.e. the product of the number of carriers produced, i.e., the gen-
eration efticiency , and the sum of the electron and hole mobilities. For the gel,
.!jt=(2.00.3)xl0-4cm
2
v-
1
s-
1
has been found. The corresponding value for the
isolated chain was (2.00.5f
5
cm
2
v- s '. Estimating ,ps; for intrinsic charge
carrier formation at an electric microwave field of 10
2
V/cm [881, lhen
p"?:.2 cm
2
v-
1
s for lhe intm-scgmental mobi lity of a charge C<Jrrier on a PPV-chain.
Recently it has been demonstmted that TOF signals in n-conjugated polymers
are not necessari ly dispersive. The essential requirement for non-dispersive tr.ms-
port is a low degree of disorder in addi tion to a high degree of purity. A material
of choice is a ladder-type methyl-substit uted poly(para-phenylene) (McLPPP)
(89]. Its rigidity combined wi th its solubility gives rise to minimal disorder, testi-
tled by well structured absorption and fluorescence spectm and a concomitant
small Stokes shift [90). Figure 12-29 shows non-dispersive TOF hole transients
on I 11m thick MeLPPP films [91, 92). In Figure 12-30 the mobility is ploued
versus F
112
The mobility is only weakly tempcmture dependent and decreases by
a factor of three with decreasing temperature between 393 and 153 K. Extmpola-
tion to the limit 1/T-. 0 on the premise of an Arrhenius Jaw yields Jto= 3.7xl<r
3
cm
2
v-' s-
1
(F= 8xl0
4
Vcm-
1
). It is apparcm that lhe hole mobility in McLPPP is
almost field independent above a field of 6xJ0
4
Vcm-
1
.
The present results are remarkable as concerns the absolute magnitude of the
hole mobility, the Gaussian chamcter of the TOF signals. as well as the weak, if
not negligible tempcmture and electric field dependence of the charge carrier mo-
bi li ty. At 300 K and an applied licit! of 6x l0
4
Vcm-
1
the mobility reaches values
above w-:lcm
2
y - l s -
1
. This is at least two orders of magnitude higher than the
effective mobility in PPV and its derivatives [82, 83, 85[. The TOF signals of
MeLPPP feature chamcteristics of Gaussian transpo1t, which is in marked contmst
to the strong dispersive photocum:nt transients in PPV-type polymcn;. If ones as-
sumes the v;ilidity or Einstein's relation (eD=plkD the dispersion, w [93), of a
4xto

393 K
0 333 K

303 K
..,-,. ...
0 213 K

ISl K
"123K

ri' lA'?;.
etfl>.
"
200 300 400 500 bOO
E"' ((V/cm}"'J
12.4 Charge Carrier 1iml.lport
403
igure 12-JO. The dcctric field tlcpendcnce of
the hole mobility in McLPPP at tliiTcrcnt lem-
pcr.tlurcs.
of eaniers is prcdic_tcd to be 0. 14 at 290 K and an applied vollaoe of
U - 4 V (Eq_. ( 12.2)). Expl!n mcntally a value of 0.36 from a transit time t =J 1 .
and decay tunc /11.!=4.9 ps (sec Fig. wus obtained. tr liS
( 12.21)
dependence of the cha_rge carrier mobility of tempcmture and electric field in
McLPPP .that ol c'?'st<tls r.Jthcr than of convent ional conju-
gated the JllObihty IS twu orden; or magnitude lower. Appar-
hchavror 1s not with the disorder model at least in its prc-
must argument for this is the observation that the tem-
mobthty docs not sati sfy a log
11
...... 11f! relation follows
1110
01 less Arrhe I F h 1 re
_
4
.aw. 10111 t e asymptote in Figure 12-3
(-4xlO Vc.m ) one calculates an acttvatwn energy of 22 meV whi h .
less than tl e h . c 1s even
1 m omogcncous broadenmg of excited single st1tes Th
1

1
"
1
n 1 tl
tra . .. . ' S p JeS lUI
. Is. not hnutcd. Ohv1ously energy disorder is no longer the rate limit-
mg. factor lh.1s. hrghly <utd a new concept of hopping under
those 1s A sullllarly lu,gh value of hole mobility has been
reported on a Itlm ol polylluophcnc 1941.
12.4.4 Transient Absorption of Radical Cations
way obtainin_g informat ion on the timc-avcraued mobility of ctn ru ,.

0 11
<Icross a sample of arbitrary is, to
the and charge c<miers density Pia tnmsient absorp-
uon .tnt! to 1nkr th.c mob1hty f rom ) =enpF Such experiments have been per-
formed un hlcnlls ul conJugated oligomcrs lkrivcll from tris-slilhcnc amine and a
404
12 Clrurge Trwr.1110rl in Rumlum Orgwric Semiconductors
chemically similar polymer [ bis-( 4' -di ph en ylami nost yryl )-2,5-di methox ybenzene
(BOAD)] by employing a combinalion of conventional lock-in techniques and
modulation of the hole current injected fi-om an ITO anode upon application of a
periodic rec1angular vohage pulse ala repetition r.ue of 300Hz l95, 96). The
sient absorption is measured under this condition, which is due to the mobrle
charge carrier, i.e. carriers whose transit time is less than ms. Figure 12-31
compares the transient, i.e. current-modulated absory>tion spectrum ot: a tilm of
tris-(para-methoxystilbcnc)amine (MSA) blended w1th polysulfpne Wllh the air
sorption spectrum of the MSA cation produced by chemical oxidation of MSA.by
SbCis in llry chloroform solution under an argon aLmospherc. The concentrauon
of the MSA was 1.07x I o-s mol/1. The amount of oxidant was kept low in order
to enable coexistence of the cation and the neutml molecule ao; seen in the absorp-
tion spcclm. In such a case the energetically preferred species is the singly
charged r.1dical cation of MSA rather than the dication. The agreement of both
spectra not only tcstitics the sensitivity of the melhod to detect car-
riers inside the sample but it also proves that (i) the charge carrymg spcc1es 1s the
r.1dical cation mther lhan a dication (i.e . a bipolaron) and (ii) no olhcr species
giving rise to tmnsicnl absorption is present 1971. The implication of these results
will be elabomtcd upon in Section 12.4.5.
Chemical oxidation of the charge carrier moiety under controllcll conditions
provides a way to measure the absorption cross-section of the mdical calion and,
concomitantly, to determine the injccled charge-eanier density in lhc solid Jilm
upon applying an extemal voltage. Thi:. allows the calculation of the average mo-
bility of majority carriers without conside1ing dispersive transport. Figure 12-32
shows data for the hole mobility in BDAD blended with polysulfone at various
concentmtions (by weight) of BOAD. The expected decrease with decreasing con-
4.0x10"

i!
t
0.2
!!>
s
I
2.01t10"
o.o+----..-----r--......---,------r--'o.o
500 eoo 700 eoo
>.. (rm)
12-Jl. Abo;olfllion or Lhc MSA call\111 prepared by uxidauon clllurulunn solut_ion
1.07x 1 moi/L MSA (<.lolloo) compared to the room temperature of mJeclcd t:hargc camcn
in a MSA single-layer LED wmaini ng 20% MSA in PSu ('oh<.l) (Ref. 1961).
12.-J Charge Currier Trun.vport 405
centmtion, i.e. increasing inlem1olecular separation, is recovered. 1l1e method can
also be used to assess the import<Ulce of d wrge ciTccts in LEOs.
Finally the questions will be addressed as to whclher or not a transient elcctrolu-
mincscence experiment can yield complementary infonnation on charge carrier mo-
bilities in organic LEOs. Starting from a simplitied piclure that neglects any delayed
injection p-occsses, holes and electrons are injected into the LED from opposite
sides and move toward each other. If injection starts at t=O, the fronts of the hole
and electron clouds begin 10 interpcnetrJie at a time 1,
1
= d/E(J4+Jl_). For JL J4,
IJ approaches the hole transit rime across the sample. implying that lhc charge c:..Jr-
rier ft-ont approaches the cathode. Since I here will be no charge canier recombination
prior to this event, clcctmluminesccnce should not slm1 until the delay time t,
1
has
elapsed and should not rise further until lhc clecln>n cloud has spread lhroughout
the sample and slcady stale condi tions have been establ ished. The delay time should
therefore yield the hole mobility. However, the mobili ly Jala infe1Ted under this pre-
mise arc typically one order of magnitude smaller than those from rransient absorp-
lion (961. The acluallliscrepancy between both values is even bigger if one considers
lhat lransient optical ah:.orption yields the average hole mobility while tJ should re-
flect the a.JTival lime of lhc fastest caniers from an ensemble or caniers that moves
dispersively. On the other hanJ, the mobility values infenell from the time
lag of elcctroluminesccnce be the true hole mobilities because otherwise the
CUJTcnt should have been space charge limiled. The conclusion is that 1,
1
does not
reflect anival of the majmity at the c<llht>Ue. The reason why it docs not.
relates to lumincsccm.:c quenching in the vicinity of a metal. From earlier expeli-
ments on 11uore!>cence quenching in mewl-coverc:d antllrJccne crystals, the thick-
ness of the quenching zone has been estimated to be about 15-20 nm (9HI. Electro-
luminescence can only occur once the fmnt uf the cleclron doull has migrated across
l
1o4
}.
1
10 ...
1.0 1.5
l"[rm)
2.0 z.s
figure 12-32. Cuuccntt':lliun oc11Cutknc' of tho: hulo: mubitiry fur Ul)AI) in ubtaino:<.l frum
tr.msicm ;lbsorptiotl <.lma. n1c '-Calc the avcmgc tlbwucc between rhc 13DAD tuulc.:ulcs
(Hcf.[%f).
406
/2 Charge Transport in Randum Orgcmic Semiconductors
this distance away from the cathode. In such a case IJ=Sif1.E, where sis the mini-
mum mnge required to avoid electrolumincscence quenching by energy transfer to
metal electrons. Inserting s= IS nm yields JL=3xl0-
18
cm
2
v-' s- for electron mo-
tion across MSA molecules doped into PSu. In view of the high lying LUMOs of
MSA, electron transport is likely to be controlled by extrinsic e.g. oxygen,
seems to be plausible. The sluggish approach of the clectrolummcsccncc towards
final saturation, which is usually observed upon addressing an lED by a rectangular
voltage pulse, may be a signature of the broad distribution of transit times in
medium. The situation will be further complicated by the increase of the effic1ency
for electron injection because a positive charge layer next to the alumin.ur:n
builds up and enhances the catho<.lic electric field that. comrols electron In
essence the onset of EL will be governed by interfactal charge accumulauon rather
than by' the carrier transi t time. Recent advances concerning the rise behavior of bi-
layer LEOs arc mentioned in Refs. l99-10ll.
12.4.5 Some Concerning the Nature
of Charge Carrying Moieties
The famous Su-Schricffcr-Heeger-Hamiltonian 11021 is based upon the notion that
in conjugated polymers electron-electron intemction is. weak while electron-pho-
non intemction is strong. It predicts the elementary exc1tattons to be polarc>ns and
bipolarons. Conjugated polymers should, therefore, like one-dimensi?nal
semiconductors. Evidence in favor of this conceptual lmmework was denved
from tmnsicnt absorption following optical absorption. The model l l 031 predicts
that bipolarons should manifest themselves via two absorption features below the
opti cal gap, retlecting tmnsitions from the localized level to the. respec-
ti ve delocalizcd band states and among the doubly occupted and empty btpolaron
levels, respectively. Conversely, polarons should give rise to a
triplet. In the case of a positively charged polaron the three absorptton
rive from (i) a transition between valence band states and the polaron level, (u) a
lf',ltlsition between a singly occupied polaron level to the unocc.upied polar?n lev-
el split off the conduction band, and (iii) a trans.ition fron.l the stngly po-
laron level to conduction band states. Meanwlule there 1s abundant expenmcntal
and thcon!tical evidence [ I 041 that the neglect of electron-electron intemctions in
the SSH-Hamiltonian is unjustified and that, because or the impot1ance of Cou-
lomb interactions, optical excitations generate neutral excitations. often referred to
us exeitons despite the luck of tmnslational symmetry a mndom polymer, mther
than unbound charge carriers. Nevertheless, the trans1ent featun:s of
polurons and bipolarons is often still assigned the approach ol the_
ductor band model. Notably the fact that tmnstcnt absorptiOn spectra ol
systems features two bands ncar 0.6 cY and 1.6 cY has been taken as ev1dencc
favor of the notion that charge carriers do lonn bipolarons implying that the. gam
in lattice deformation energy is large enough to overcompensate the coulom?tc re-
pulsion of two lmmo-charges. However, both magndic resonance expenments
12.4 Churge Carrier Trcmspor1
407
llOS] as as the comparison between the absorption spectra of chemically, as
well charged species r I 06] :md those of charge curriers in
. gives unambiguous evidence tor these being singly
charged md1cal c;1llons/amons mther than dicationsldianions. The f01ct that the
modulation experiment to detect mobile charge caniers yields no evidence for the
occutTem:e of tr.msient spedes other than the mdic.:al cation c.:onfinns that the for-
mation of a. a pair or homo-charges is energetically unfavorable except
under condt!lons ot lugh charge densi ties where one chromophore has to uccom-
m<>?ate more. than charge cmTier. By the way, the appearance of a second oxi-
datton/rcducllon step 111 cyclic voltammetry conlirms that it requires extra energy
to rem.ove/add. a from/to a chromophorc (107, 108j. Assigning
the energy ol hole transport in PPV to the thermally activated
diSSOCIU!Ion ol a bipolaron into a pair or polamns IHSI is, therclore, incorrect.
There is another reason why it is problematic to adopt the semiconductor tcnni -
?ology for optical tmnsitions related to charge carriers. That concept
transthons among a polaron level and a delocalized band state, i.e. non-
transitions on a conliguration coordinate scheme. However, a radical cat-
IOn/anton represents a chemically ditrerent entity. Optical transitions occur be-
tween the orbitals of the mdical ions, whose equilibri um confiouration is of
dillcrent of the ncutml molecule, ruther than a conligur-
relaxed ton and a neutml molecule in its non-relaxed configura-
Ilona! .state. 1s, mdccd, clear evidence against the notion that the optical
ene'?y 1s ." of the polaron-binding energy: the structural reorga-
enef';tes ol ohgomers of PPV have been culculatoo to be around 0.15 eY
(with a tet.u.lcncy to decrease a." the oligomer increases in size) [ 1091 while the
lowest ubsor:rtion u.r mdical cations of ppy is ncar to 0.6 e y [ 110 ).
In the case ot a md1cal calion tillS trunsition is between the second li llcd molecu-
lar orbital and the singly occupied molecular orbital that derives from the HOMO
of the neutml pan!nt molecule. Would we interpn!l the mmsient 0.6 eV tcature in
terms of polaron binding enef'.;ies, one would not expect clcctrolumineseence to
occur because the energy or a pair of polarons would be less than the HOMO-
LUMO gap.
Acknowledgt'lltents
I am grateful toY. I. Arkhipov, K. Book, P.M. Borsenbcrger, D. He11el, M. Rcdecker.
Y. H. Tuk, U. Wolf rur their conllibutions to this work. Financial suppon came
from the Dc:lllsche (SFB 383 and projects 436 Rus 113/
9314 and Bu 411133) as well as from the Fonds cler Cllemi.1dten ltu/ustrie.
408 / 2 Charge in Random Organic Semiconductors
References
1. E. A. Silinsh, in Orgu11k Moleculttr Cry.fWlr. Springer, Berlin 1980.
2. M. Pope, C. L Swenberg, /ectronic Proc:eifSes in Organic Cryswls, Clarendon Press, Oxford
1982.
3. L. Sebastian, G. Weber, G. Peter, t-1. ChenL Phys. 1983, 75, 103.
4. L Sebastian, G. Weiser, H. Bassler, Cltem. Phys. 1981. 61, 125.
5. Sec, e.g., K. Scki, Pltoluclettroll spectrO.fCOf))' of polymers, in Opticttl Teclutiques to Clwructerize
Polymer S)'>1elltS (Ed. H. Bassler), Amsterdam 1989, Chapier 4.
6. L. Sebastian, G. Weiser. Phys. Rev. Le11. , 1981, 46, 1156.
7. S.M. Sze, Physics of Scmic:unducwr Devices, Wiley, New York 1981.
8. S. Kay. W. Riess, V. Dy:lkom>V, M. Schwoerer. Symll. Met. 1993, 54, 427.
9. G. V.wbcl. 1-l Pltys. u11. 1968, 2711, 328.
10. See e.g. C. Wcissmantel. C. Hamann. Gnmdlagen der Festk6rperpllysik, VEB, Deutscher Verlag
dcr Wi,.o,cnM:h:sflcn. llcrlin 1981.
II . K. Kato, C. L Br.sun. J. Clttm. I'IIJ'.r. 1980. 72, 172.
12. D. E llJo,!>ey. Rc1: IJ. 1974. Sl. 511!:\.
13. D.M. Pai. R. Em:k, P/11' l<cv. IJ. 1975. II . 5163.
14. J. D. P:1rker, J. IIppi. l'it.)W. 1994. 75, 16511.
15. A. J. Hcegcr. I. D. J':srkcr. Y. Yang. Syutlt. Mct. (J7. ::?.l.
16. H. Vc.lwcbcr. J. Pununerchnc, H. IU'. Malnl. A. Grcsncr. W. llcnJ.. H. Ua,slcr. Syutlr.
Mct. 1995. 6H. 263.
17. P.S. David,, Sh. M. K\lgun, I. D. Parl-er. D. L. Smith, AJit'l. /'h,s. l..c.11. l 'JW>, f1Si. 2::?711.
18. M. A. Abkowit7., II. A. Mi1.c,, F:K:ci , A(lpl. Lc11. 1995. (J(},
19. Y.N. Gartstein. N. Yu., E. M. Cunwcll, C/um. Pity:>. Lcu. 1996, 255. 93.
20. H. Bibslcr, Play.f . Stu/. Sol. (l1), 1993, /75. 15.
21. V.I. Arkhipov. E. V. Emcliunova. Y. l l. lak, H. lliis.,Jcr. J. IIppi. f'ltys. 1998. 84, H4H.
22. U. Albrecht. H. Chem. Plsys. u11., 1995. 235.
23. s. Barth, D. Hettel, Y. ll. Tak, II. Bassler, 1-1.11. Horhold, Cltem. Plays. Leu. 1997,274, 165.
24. B. Rics, G. Schiinhcrr. II . Bassler, M. Silver, Pili/. Mag. lJ. 19H3, 4X. l!7.
25. H. Antoni:Jdis, B. R. l lsich, M.A. Abkowitz. M. Stolka. Appl. Plrys. u11. 19!13. 62, 3167.
26. Y. Y:Jng. A.J. Hceger, 111'1'1 Plays. Leu. 1994. 64. 1245.
27. Y. l-l Tak, S. Many, A. Greiner, H. Bassler. S. Pfei iTer. H. H. Hor1mld, llctu l'ulym. 1997, 48,
450. .
28. H. Eckhanlt. L W. Shacklcue. K. Y. Jcn, R. L. Eheubaumcr, J. Cltcm. Pltys. 1989, 9/, 1303.
29. H. Rost. A. Teusche.l, S. PlciiTcr, H. I-I. 1-Ji\rhold, Met. 1997. 84. 269.
30. 0 . J. P\lnuncrcllnC, W. Gus:.. H. Votwcbcr, Y. H. Tak, V. Stiimpncn, J. H. Wendorff, S.
Spiegel. C. Moller, A. Grcinc.r. Symlt. Mn. 1996, 82, I.
31. J. P\lmmcrchnc. H. Vc:.twcbcr. W. Guss, R. F. Mahrt, H. M. Polli<:h, J. Daub, Acb-. Mut.
1995, 7, 551.
32. D. V. KhrJnnchcnkov, A. I. Arkhipov, 1.1. J. IIppi. /'lays. 1991.lll. 6954.
33. Y. H. Tak, H. J. Afltll. Plly.f. 1997, XI. 6963.
34. W. Helfrich. in 1'/nwic.\ uml Clst!mi.flry of tltt! Solid Swtc. Vol. Ill (&Is.) D. Fox, M. M.
E. Wiley. New Y\lrl. 19<>7.
35. A. Many, G. Rakavy, Plly:>. &v. 1%2, 126,
35. P. Mark. W. Hclfnch. J. IIppi. 1'/sy.f . 19(12, JJ, 2115.
36. S. Ncspurck. E.A. Silinsh, 1'/sy.f. Stu/. Sol. (11) 1976, 34, 747.
37. M. J.S. Facci, M. Slolk:s, Cllt!m. Phys. 1993, 177. 783.
Jl!. R.Young. Pili/. Mug. 8, 1994, 69, 577.
39. M.A. Abkowil"l, D. Pui. Pili/. Mug. 8 1986, 53. 193.
40. Y. H. lax, H. Vcslwebcr, H. Uiisslcr, A. Blcyer. R. Stock mann. H. H. Horl10ld, Clwm. Pllys. 1996,
212, 471.
41 P. W. M. Illom, M. J. M. dc Jung, J. J. M. Vlcgga.r, Apfll. Lc/1. 1996, 6ll,
Rejere11ces 409
42.
H. Amoniadis. L.J. Rothbcrg, F. PaJXtdimilmpoulos, M. Yan, M. E. Galvin M. A. Abk w
Pllys. Rev. 8 .1994. 50, 14911. '
0 117

43. F: Papadimitmkopoulos. K. Konslandimidis. T. M. Miller. R. Opila, E. A. Chandross M. E. Gal-
vm. Cltem. Mat. 1994. 6, 1563. '
45.
46.
47.
48.
49.
so.
51.
F. U.:kert. H. Y. Tal., K. Miillcn, H. Bassler. Ad1'- Mut.
P. M. Bor.<cnbcrgcr. E. H. Magin, M. van dcr Auwcr.scr E C de Schryver Ph)'S S .. t Sul (b)
1994, IH6, 217. . ' " . .., . . '
P. M. Borsenbcro.;cr, W. T. Grucnhaum. M. O. O'Rcgun. L.J. J. Pulwn. Sd. Pan B PtJ/
1111
Pltys. 1995, JJ, 214.l. '
W. Warta., N. Karl. Pltys. 8 191!5, 32. 1172.
E.A .. Si lin,.Jl, V. Capek, in 0Tganic Malt'cular Cry.ftal.s. AlP Press. New Yorl. 1994.
H. P!t.vs. Status S.1/idi IJ 1993. 175. 15.
P.M. llurscnl>crgc.r. E.l-1. Magin. M. van dcr Auweracr. E C. th: Schryver Pltvs Stuful S'alidt" A
1993. 1-JO, 9. ' . . .
52. P.M. Bun;cnhcrgcr. D. S. Weiss. in OfX<tllic PlwtaRtcttllors ji1r lmagi1111 Syslt'IILr Marcel Dekker
New Yurk 1993. '
53. P.M. Bmscnbcrgcr. R E. H. Magin, S1t11us Solicli 1J 1994, I H5, 465.
54. P.M. Ourscnbcrgcr, E. H. Magm. M. van dcr Anwcracr. f'. C. de Schryver I'Jsvs Stat Sui. (b)
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
61!.
tl).
70.
71.
n
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
1.'16. 217. . . .
II. Scher, E. W. Mummll. 1'/t.r.r. lJ 1975. 12, 24.'15.
P.M. Ourscnbcrger, L. Pauuncicr. K. Kichcrt, It .. Jcr, J. Cltc:m. Phys. 1991. w. 5447.
L. Kadur. J. Clwm. P!t.n. 1991. Sl5. 5574.
0. Muvaghar. M. <.iruncw:sld, U. Rics, H. Bassler, D. Wiim. 1'11\'.t. Rc
1
: lJ 1986 JJ S545
l. B. Schein. Pili/. fl .. 1992, 65, 795. ' '
P. M. Bursenbcrger. L. J>;sullllCIL'f, H. l'hn. Rtl: II 1997, .J6, 12145; ibsd 1993, 48, 3066
P.M. Oorscnbcrgcr, II. Uiis.,Jcr. J. llpfll. Plty.v. 75, %7.
U. H:srtcnstcm. II. Bit.'oslcr, S. Dcun, P.M. Omscnhcrger, M. van Jcr Auwer:scr, F. c. de
CIWIII. 1'/rys. 1995, lSI I . 321. '
P.M. Ourscs_sbcrgL;. R. Ridscn, II. Ua,slcr. l'lly.v. Rts. II 47, 4::?H9.
M. Sugsuc.Ju, J. Sc-i. Tcdmol., 1993, J7. 245.
P.M. llorscnbergcr, H. Biissler. J. Clwm. Pit)".<. I, 95, 5327.
P. M. E. H. Magin. J. Plty.rim lJ CmultJI.<. Malia 19g(,, 2/7, 212.
B. llanenstcm. H. Ba.,sJcr. S. I kun, P. Bor!ICnbcrgcr. M. van dcr Auwcmer R c de s J
011!111. Pity.<. 1995, I'JI. 321. . . L lryvcr,
N. Yu . E. M. Cunwcll. Cltt!m. Pltys. &11. 1994. 217, 41.
N. Yu., E.M. Conwdl, J. Cltem. Plty.1. 1994. 100. 9175.
GartMcin. N. Yu . E. M. Conwdl. Pity.<. lJ 1995. 51. 6947.
D. Dunlap, P. E. Paris, V. M. Kcnl.n:, Leu. 1996, 77. 542.
U. Wulf, H . P.M. Borscnbc.rgcr, W. T. Grucnbaum, Cllem. Plty.f. 1997, 222, 259.
D. M. Pas, J. F. Yanu.'. M. Stolka. J. Pltys. Cltcm., ,'Y/, 4714.
E. D. Haarcr. M. /'h1w. Rt' l'. JJ. 191n. 35. 1273.
D. C. Hoc,tcrey, G. M. LCI,on. J. l'frr.<. Cl1<m. Solie I.>, 1963, 2.J. 16119.
P.M. U\lrscnhergcr, W. ' J: Grucnhaum, U. Wnlf. H. Clt!!m. Pfr
1
.,, .. 1998. 2J.J, 277.
J. Veres/, C. Juha.z. Plti/. lJ 1971, 75, 377.
W. Klopffcr. in Electmnic PmJI<'rtic.s o/" (I !.tis. J Mon G Pfit r) w Jc N. v,,rk
19H2. ' . . . . . c ' I y, cw ..
U. HauM:hcr. H. Macrrmtolnule.\ 19')(1, 2.f, 39H.
M. K. AJ..ig:uno. N. Y:unanouri, H. Mikawa, !:>. J'ol)'lll. J. I\IH5 /7 545
W. Gsll, J. Appl. 1972, .JJ. 5033. ' ' .
M. Gailhergcr, H. Uasslcr. Pltys. l<e1: /J 1991, .J.J, 1{(>.13.
H. Meyer, D. Ha:1rcr, H. Naannann, H. H. Hiirhold, 1'1/y.,. R
1
s: 1J 1995, 52, 25H7.
B. Mollay, U. Lemmer. B. Kcr.ting. R. F. Mahrt, H. E Kanll"nmnn H U'isslc 1>1
1
R , 8. I""'
50, 10769. ' . . . y... cv. 7700
85. E. lchcdcv, n,. Ditui.:h, V. J>etruva-Koch, S. Karg, w. Uruuing. IIppi. l'lly.f. Lcu. 1997. 71.
2686.
410 J2 C/wrge Tra11spor1 in Randum Orgawc Sc:micmrducturs
86. G.P. van der Laan, M. P. de J. M. Wam1an, D. M. de Lccuw, J. in Polyuwric
Materials for Microelectronic llpplicatiuus (Eds.: H. ho, S. Tagawa, K. Hone), ACS Sympo
sium Series 579, American ChcmiC<JI S01.:icty. Wa...hington 1954, p. 316.
87. G. H. Gclim:k, J. M. Wam1an. t::.G. J. Slaring. J. Clrem. 19%, /00,5485.
8H. S. Barth, H. H. Rosl, H. H. Hilrhold. Pllys. Rev. B. 1991,56, 3844.
1!9. U. Scherf, A. Bohnen. K. MUII.:n, Mncrumol. Clttwr. 1992, 193, 1127.
90. R. F. Mahrt, T. Pauck, U. Lemma, U. Siegner, M. Hopmeicr, R. Hennig. H. E.J. GQ.
bel. P. J laring Bolivar, G. Wegmann, H. Kur;1 U. Schen, K. Mullen, P/lp. Rev. B 1996. 54,
1759.
91. D. Hertel, U. Schclf, H. Bassler, Adv. Mut. 1998, /0, 1119.
92. D. Hertel, H. Bassler, U. Scherf, H. H. Horhold, J. Clrem. Pltys. 1999, 110, 9214.
93. L. B. Schein, Plrilus. Plil. B 1992. 65, 795.
94. M. Redccker, D. D. C. Br:Klley, M. lnbasckamn. E. P. Woo, IIppi. Plrys. 1998, 73, 1565.
95. M. Redccker. H. llppL Plly.f . Leu. 1996, 69, 70.
96. M. Rcdccker, H. Bassler, H. II. Horhnkl, J. Plrys. Cltem. 1997, 101,7398.
97. A. R. Oruwn. K. l'ichlcr, N.C. Grccnh;uu, D. D. C. Or.Kllcy, R. H. Friend, A. 0. Holmes, C/u:m.
Plrys. Lm. 1993, 2/0, 61.
91!. H. Kur1.ccwska, 1-1. Bassler, J. Lumi11. 1977, /5, 261.
. 99. V. R. Nikitenku, Y.-H. Tak, H. Bassler. J. IIppi. l'il)'.f. l991S, 1>4. 2334.
100. V. R. Nikitenku, II. Bassler, J. llptl. /'fly.>. 1999, H5. 651 5. .
101. S. Barth, H. P. Muller, ll. Riehl. H. Vcslwcbcr, J>. F. Seidler. W. Riell. Plrp. 8, rn
pres.-;.
102. A.J. Hccger, S. Kivelson, R. J. Schricffcr, W. P. Su, Nev. Mod. Pflys. 1988, 00, 71!2.
103. K. Fcsser, A. R. Brshop, A. J. Campbell. l'lrys. Ht:l'. IJ. 19113, 27. 41!04. .
104. Sec, e.g., H. Bassler, in Primury Plrolocxr:itutimrx in Ccmjugut,d Po/ymcr.f: Mulemlur n;rton
1
usus Semicund1Ktur &uul Model (Ed. N. S. Sarici ftci) World St.:icntilic, Singapore 1997.
l OS. P. Brendel, A. Grupp, M. Mehring, R. Schenk, K. Miillen, W. Huber, Met. 1992, 45, 49.
106. M. Deusscn, H. Bassler, Cheur. Plrys. 1992. IM, 241.
107. J. Hcin:te, J. Mortensen, K. Mullen, R. Schenk, J. Clrcm. Sue. Clu:m. Cmumun . 191!7, 701.
108. K. Mccrholz, J. /e.kuochim. /lcru 1996. 41. 1839.
109. D. Bcljonnc, Z. Shuai, R. H. Friend, J. L J. Ch .. m. Phys. 1995, 102, 2042.
110. R. H. Fricno, D. D. C. Or.tdlcy, P. D. Townsend, J. Plry.f. D 191!7, 20, 1367.
13 The Chemistry, Physics and Engineering
of Organic Light-Emitting Diodes
John Campbell Scott and George G. Malliams
13.1 Introduction
The flat-panel display industry is currently dominated by liquid-crystal technol-
ogy. Staning in the 1970s with their introduction in watches. liquid crystal dis-
plays (LC0s) first took over most uf lhe instrument panel business, then nour-
ished as the laptop computer market grew, origi nally with monochrome screens
and now increasingly with color. LCOs were readily as the display of
choice for handhekl devices such as cellular phones and personal organizers.
'They are now making inroads into the miniature display market, as reflective
light-valves for projection displays and have even stm1cd to replace many cath-
ode-my tubes on the desktop. Several other nat -panel display technologies. which
Iracc their origins lt.:ast as far bad\ as LCOs, have either fallen by the wayside
or, at best, have penetrated only limited mmkct segment-;. For example, plasma
display manufacturers arc cum:ntly focused on high-end, lmge wall-mounted pa-
nels. Electrolumincsct.:nt and lidd emission displays have achieved only modest
commercial success in the instrument, medical, and military arenas. Will organic
light-emitting diodt.:s (OLEOs) fare any better against LCOs, which have at this
poinl become an entrenched technology with a large installed manufacturing base
and a well developed infrastructure for parts supply and integmtion?
In this we present a critit.:al evaluation of the advantages that OLEOs
might have relative to competing 1echnologics and assess the current state of pro-
gress in overcoming some of the dilliculties tltat have been perceived in commer-
cializing OLEO technology. It is generally accepLCd that the geometry of
OLEOs is virtually ideal l(lr 11at-panel display application: a layer of luminescent
material is placed between twu electrodes, in a sandwich geometry; light is
emitted on the passage of clecllic current, with a color that depends on lhe choice
of organic material. It is dillicult to imagine anything simpler, !latter, or with less
weight. The critical issues which must be addressed before OLEOs can be consid-
ered a viable technology are power efficiency, intcgmlion with d1ivc eleclronics,
opemting und storage lifetimes, environmental sensitivity, and the cost of manu-
faclure. We shall consider each of these issues in this with an
overview of the science of OLEOs as it is cun-cntly understood and of the tech-
nology as it is currently pmcticcd.
4 12 /3 Tire Chemistry, Physics tmd 111Ji11eering of Organic Light-Emitting Diodes
The organic materials which arc employed in must distinct
functions in the operation of the device: the conduct1on of and the
emission of light. The conduction process is analogous to that m a w1de band-gnp
semiconductor and involves the transport of injected charge, electrons and hol.es,
from each of the electrodes. When the electrons and holes meet, they
to form excitons, i.e., excited states of the organic molecules that may radmuvely
relax to their ground state. The light emission process is the same. as in
cence, the difference being that the exci ton is created by
rather than by optical pumping. As we shall see, in some dev1ce structures a
gle organic material is used to tmnsport holes and as well as. to emil
light. In other structures, the functions are perfom1ed by d1fferent orga_mc layers
so that one may scparJ.tely optimize electron and hole transport and
In Section 13.2, we introduce the materials used in OLEOs. The most obv1ous
cla.'isilication of the organic materials used in OLEOs is small molecule versus
polymer. This distinction relates more to the processing methods used. than to the
ba-.ic principles of of the final device. Small molecule matcnals arc typ-
ically coated by thermal cvapomtion in va_cuum, polymers usually
spin-coated from solutiun. V<ICUUill cvapurauon to easy coat111? suc-
cessive layers. With solution processing, one must consH.lcr the of
each layer with the solvents used for layer!i. lm:re<.ts mgly,
multilayered polymer devices arc being Jescnbcd Ill the literature and, naturally,
hybrid devices with layerli of both polymer and small molecule have made.
The fundamental operation of OLEO devices is the ol_the mo-
lecular architecture of the materials used. One may v1suahze the sohd 111m as .a
mndom array of si tes which may be occupied by an electron, a hol.e, or an exci-
ton. The movement of these species from site to site occurs by hoppmg .. The loca-
tion within the molecule, and the spatial extent of each site, depends on 1ts
tron structure and the same molecular unit may acl, at J ill'erent times, a.<; a sue
for either or electron or exci ton, albeit with different spatial distributions in
each case. The molecular architecture, dictated primarily by the a-bonding struc-
ture and with van der Waals' interactions providing cohesion in the solid, defirn:s
the arrJ.ngcmcnt and orientation of the n-conjugatcd sites. To a very .large 1t
is irrelevant to the motion of the charges and cxcitons whether the slles are on m-
dividual molecules in a glassy solid, on molecular dopants in a polymer
on side-groups tethered to a polymer backbone, or on monomers
beads along the polymer chain. Even in the case of a polymer that ! deally,
be fully conjugated there arc, in reality, defects which .break the and
limit the extent of each site to just a segment of the ent1rc polymer chmn. .
The paper is organized to descri be, first, the materials that been 10
OLEOs then the device structures that have been evaluated. Alter a descnpuon
of the used to characterize and evaluate mate1ials and devices, we sum-
marize the current stale of understanding of the physics of device operation, fol-
lowed by a di scussion of the mechanisms which lead to degradatio.n and failure.
Finally, we present the issues that must be addressed to develop a VIable
el display technology using OLEOs. Space and schctlulc prevent a
review of the vast lileratun: in this mpidly moving fidd. We h<tvc tned to present
13.2 Muteriu/.\ 4 13
a list of references which balances between Lhe original, seminal work. and the
most recent up-to-date contri butions, which generally contain their own extensive
ci tations. We realize that this results in the omission of many important papers
and for thai we apologize. in advance, to their authors.
13.2 Materials
13.2.1 Conjugated Polymers
Elcctroluminesccncc was first discovered in a conjugated polymer, namely poly
(pam-phenylcnc vinylenc) (PPV). hy workers at Cambridge University in 1990
ll]. Since that time, many derivatives of PPV have been synthesized and investi-
gated and mhcr classes of lumineS(.cnt conjugah:d pulym,:rs have lleen identified.
Some examples, showing the chemical structures. arc gi vcn in Table 13- 1. (The
litemturc is too vast to provide a comprehensive listing in this relatively brief re-
view.)
PPV itself is <111 insoluble polymer und thcrclorc must be coated in a soluble
unconjugatcd precursor form with subsequent thermal l'Onversion. The Buyreulh
group 12. 31 have carTicd out u thorough study of the conversion mechanism and
its dependence on processing conditions. PPV 1runsp011s both electrons and holes
and can therefore be used in single-layer devices 14. 5J. It emi ts yellow-green
light, wi th a peak wavelength or 510 nm.
Among the PPV-based polymers. the diulkoxy <.le rivativcs arc particularly note-
WOJthy. MEH-PPV (see Tallie 13-1) was introduced by the group at the Univer-
sity or California at Santa Barbara 161. Tin! side-group substi tucnL-; not only ren-
der the polymer soluble in common organic solvents such as xylene and anisole,
but they also change the electrical and optical charactc1istics. As we shall sec, this
pe1mits Lhe USC of specific electrodes to give nearly balmlcCd electron and hole in-
ject.ion, leading to high eiTicicncy. At the S<Jme time the emission is shifted into
the omnge-rcd region of the spectrum. Workers <II Philips Labs in the Netherlands
[7] have intmduccd a similar derivative, which they designate CICIO, indicating
the branched decyl chain mther than the octyl chain or MEH-PPV (in many of
their publications they refer to it merely as PPV).
A second major class of emi ssi vc polymer is based on polythiophcne 1 g).
Again, substitution in this case at the -3- positiun of the thiophene ring is used to
solubil ize the polymer a11d to tunc the emission wavelength 191. Other heterocy-
clic conjugated polymers arc represented by polypyridinc 1101 and polypyridincvi-
nylene llll. Since each of these contains clcctmn-dclicicnt aromatic groups, they
tend to be bcller electron 1ranspo11ers than their phcnylene analogs. They emil p1i -
marily in the blue.
Substitution al the vinylene carbon position of PPV dcrivativc.:s reduce their tcn-
dency to oxidation. Examplcs (sec Tallie 13- 1) arc C'N-PPV II :! I anJ DPOP-PPV
414
/3 17re Chemistry, Plrysic:s und E11gi11el!ring of Orgwric Ug/11-Emitting Diodes
Table 131. Chemical structures or luminescent conjugated
Commonly acronym and chemical name
PPV
poly(p-phcnylcnc vinylcnc)
MEH-PPV
polyl2 mcthoxy-5-(2' -cthyl hcxoxy)-
1,4-phenylene vinylene}
PJAT
poly(3-alkyhhiophcn.:}
PPyV
poly(p-pyridyl vinylcuc)
PPy
poly(p-pyridinc)
CN-PPV
(R
1
=R2 =Cc.Hil)
polyl2,5-biJ(hexylox y)-1,4-phcuylcnc-
( 1-cyanovinylene)]
DPOP-PPV
(R= phenyl)
poly( 1,4-phcnyle nc- 1,2-
diphenoxyphenyl vinylcnc)
PDPA
poly(diphenyl acetylene)
Chemical structure

MeO
OR
RO
Table 13-1. (continuctl)
Commonly acronym and chemical nank!
DHO-PPE
(R, = = hcxyl)
polyl1.4-(2,5-dihcxoxy)-phcnylcnc
elhynylcnc)
PPP
poly(paro-phcnylcc)
LPPP
"lalklcrctl poly(/lllm-phcnylcnc)''
POAF
poly(9,9-dialkyllluorcnc)
I 3.2 Materiuls 415
Chcmic01l SlC\11.."\UfC
OR,

A
1
0
R A'

[13}. The vinylenc linkage can be replaced wi th the ethylene group to foml PPE
and ils derivatives, maintaining conjugation and again improving stability [ 14).
Altemativcly, the aromalic groups can be removed entirely from the backbone
leaving the conjugation pattem of polyacctylenes II S ). Although the unsubslituted
parent polymer is not luminescent, many of ils aromatic derivatives show etlicient
blue or green emission (16 ).
A great deal of recent attention has focused on polyarylenes, where the direct
bonding between phenylene rings resulls in a much more stable chemical struc-
ture than the vinylene linkage of PPV. Among the earliest of this class were the
Jaddered poly-pcrra-phenylcncs (LPPP) synthesized as a result of collaboration be-
tween groups at Mainz in Gennany and Graz in Austria (17, 18). Such materials
are typically blue emillers. A related polyarylcne of great current interest is based
on fluorene (1 9--2 11. By dialkyl substitution at the -9- position, modemtely solu-
ble fluorene homopolymers can be prepared 1221. however, the chemical synthesis
of polyarylenes lends iLo;elf to the preparation or random or altemating copoly-
mers, as well as other interesting molecular architectures. Thus, groups at mM
[23) and Dow l241 were <thlc to synthesilC polymers with high solubil ity due to
the introduction uf conjugation hreaking co-monomers. Such an apprtmch also
permits color tuning :md auj t.-;tment of the glas!. tl"<lllsi tion tcmpcmturc. Most rc-
416 13 The Chemistry, Physics am/ Engineering of Organic Light-Emitting Diodes
cently, schemes have been introduced to terminate the polymer chains in order to
control the molecular weight and to introduce crosslinkable groups [25, 26].
Then, after the soluble polymer has been coated, it can be cured to convert it to a
form which wi ll not dissolve in the solvents used to coat subsequent layers.
13.2.2 Small Molecules
There are many organic compounds with useful electronic and/or optical proper-
ties and with sufficiently high volatility to be evaporable at a temperature well be-
low that at which decomposition occurs. Since thermal evaporation lends itself to
facile multilayering, organic compounds may be selected for usc in one or more
function: elccti\Jn injection, electron tmnsport, hole injection, hole tn.msport, and/
or emission. A complete list of matetials that have been used in OLEOs is too
vast to be included here. Rather, we list those that have been most extensively
studied.
Many organo-metallk chelatcs show bot h good electron transport behavior and
reasonably eflicient emission. One may distinguish between the cases where the
behavior is due to the ligand from those which arc metal-centered. The prototypi-
cal example of the former is aluminum triquinolate (Aiq
3
, sec Table 13-2), which
was used in the pioneering work at Kodak 1271. In the decade since then, many
other chelates have been characterized for their tmnsport and emission characteris-
tics 128). A wide range of colors, ranging from blue in, for example, a salicyli-
dene amine complex of Zn peaking at 460 nm, to green in Beb<h (Table 13-2) at
5 16 nm, to yellow in his-(8-oxyquinolato) zi nc at 568 nm, have been demon-
strated from materials of this type.
Metal-centered emission is found in several mre-earth complexes, for example
europium diketone chelatcs [29). These compounds emit relatively narrow spectra
associated with the d- f transitions of the metal ion. Relatively few comprehensive
studies of this class have been carried out to date, but the available evidence 130]
seems to indicate tltat the photoluminescent efficiencies are somewhat lower than
the ligand-centered emitters.
Another important class of electron-trnnsporti ng emitter is the distyryl-arylcnes.
These have been explored most extensively by workers at ldemitsu Kosan [31,
32], with the bulk of the published data focusing on a compound designated as
DPYBi (sec Table 13-2). This class of materials may be considered as small mole-
cule analogs of the PPY polymers, with distyrylbcnzcne and its derivatives (33)
as prototypical examples. Because of the short conjugation length they tend to be
blue emitters.
Among the electron transport agents, derivatives of oxadiazolc 134, 351 have
been extensively studied. (Oxadiazolcs do emit quite efficiently, but the W'i\Vc-
lengths (361 are genemlly too short to be useful for display By far
the most widely used hole tr.msport materials arc the aryl-aminl!s, exemplified by (
TPD [371 (sec Table 13-2). Because of their use in elcctrophntogr.Jjtlhic photocoq,.
ductors, dating back to the 1970s, there is an extensive; (:3H I on the
13.2 Materials 417
1ablc 13-2. Chemical slru..:lurcs or n:prt!St!nlalivc ::.mall molecule 1mnsport rnulcrials and luminc.sccnl
dyes.
Commonly used a.:mnym and dJCllJi.:al name
Alq or
(emiller, elcc1ron malCrial)
lris-{8-oxyquinol:uo) alummium
Bcbq2
(EM. ETMJ
his-( I 0-oxyhcn!.ol h Jquinulalo Jhcryllium
Eu(ITFA) 1l'hcn
(EM,l:.I'M)
tris (4.4.4 -tri lluun- 1-(2-thicnyl)- 1.3-
butanccJiono)- 1,10-phcnalllhrolinc
europium( I Ill
DPVBi
' EM. bipolar
1,4' bil (2.:!-diphcnylvinyl)hiphcnyl
PBD
(EM. ETMJ .
2-(4-biphcnyl) 5(4+buy1phcny1)
1,3,4-ox:x.liazolc
TPD orTAD
hole lr.mspon malcria1)
N,N" -diphcny1-N. N' -bis-(J-nJC!hylphcnyl)-
l. l' ) biphcnyi...J.4' diaminc

(HTM)
N,N'..cJiphcny1-N,N'-tlinaphlhy1-
' 1,1' )-biphcny1-4.4' ..cJiaminc
C'hcmi.:al Mru..:lun:
I {''j
)l ,._N 0 S
Y
Eu Q
J . ' o CF,
3
N N
I )-J!.. )\. { '"\ I
0
418
I 3 71
1
e Chemistry, Physics and Enginceriug vf Orga11ic Lig/u-Ei11itti11g Diodes
Table 13-2. (Continued)
Commonly used acronym anti chemical no.une
MTDATA
(HTM, example of a starburst amine)
spiro-2P
(the core of the )piro-<:ompountls)

pcrylcne
(EM. blue)
qumar.:ridonc
(EM, green)
PPCP
(EM, blue)
pcntaphenylcyclopcntadicne
DCM
(EM. ordngc-n:tl)
4-(dicyanomcthylenc)-2-nJCthyi-
)-4H-pymn
rubrcnc
(EM, yellow)
Chemical slrllcture
(()J
( ; \ )
CN
I
I

1
I 3.2 Mvlecularly Doped Polymers and Polymer Ble11ds 419
charge transport properties of these materials. When used as the hole transport
layer in OLEOs it is essential that they remain in their glassy form, hence exten-
sive molecular engineering has gone into the synthesis of aryl-amines with ever
higher glass transition tempcmtures. Some of the earliest replacements for TPO
were TAPC and NBP, introduced by the Kodak group {27, 39]. More recently,
Shirota el c1/. [40) have introduced the swrburs/ mnines with glass transition tem-
peratures as high as 160 "C.
The molecular structure, and the high molecular weight, of the starburst amines
places them in a category which straddles the division between small molecules
and polymers: oligomers. They can be thennally evaporated, but many of them
also form high optical quality films when cast from solution. Some starburst oxa-
diazole (41 J electron-tmnsporting materials have also been synthesized and fall
into this intermediate category. The spiro compounds of Salbeck e1 a/. [42, 43] re-
present an interesting new molecular architecture that incorporates the electrically
active molecular uniL-; into a structure which inhibits crystallization and therefore
exhibits high glass tnmsition temperatures. Emitters and electron-tmnsporting ex-
amples have been synthesized with this spiro architecture. A number of oligomers
have been studied as mo<lcl compounds for their corresponding polymers. This
work is reviewed by Hadziionanou et a/. elsewhere in this volume.
Fluorescent small molecules are used as dop:.mts in either electron- or hole-
transpot1ing bi nders. These emitters are selected for their high photoluminescent
quantum dlicicncy and for the color of their emission. Typical examples include
perylene and its derivatives 144], quinacridones {451. pcntaphenylcyclopcntcne
[46}, dicyanomcthylene pyrans {47, 4HJ, and rubrene 136. 49]. The emissive do-
pant is chosen to have a lower excited state energy than the host, such that if an
exciton fonns on a host molecule it will spontaneously tmnsfer to the dopant. Re-
latively small concentmtions of dopant are used, typically in the order of I%, in
order to avoid concentration quenchi ng of their luminescence.
13.2.3 Molecularly Doped Polymers and Polymer Blends
Small organic molecules doped into polymer binders have also been employed in
OLEO devices. Coating is done using inexpensive solution techniques. A com-
monly used polymer is polyvinylcarbazole {50-521. which is a hole transport ma-
terial with modemte mobility. Polysilane!. have also been used as hole tmnsport
agenl'> {531. Common laser dyes may he employed :1s the emissive molecular do-
pant, for example coumarins {50, 51). rhodamine.-; {501 or pymns 151, 53). Similar
consider.uions of energetics and concentmtion apply to doped polymers as to
small molecule dopant-host systems: the dopant should provide the lowest energy
site for the exciton and com;entration (jUenching should be minimized.
A small amount of work hw; been undertaken to explore polymer blends,
where one polymer is chosen for its charge tmnsport characteristics and the other
for iLo; luminescence. Best efliciencies an: obtained when small concentmtions of
the emitter arc present in the transporting polymer, e.g. blending one PPY deriva-
420 I 3 The Chemistry, Physics and Engineering of Organic Light-Emilling Diodes
live with another [54], P3HT in PVK [55] or poly(terphenyldiyl vinylene) in a
polysilylene [56]. Tasch et al. [571 have obtained white light emission by combin-
ing blue emitting m-LPPP with orange-red emitting poly(perylene-co-diethynyl-
benzene).
Doubly doped polymers can be used to enhance two functions. For example.
Wu et a/. [58] added Aiq
3
as an electron tr.msport agent and nile red as an emit-
ter to hole transporting PVK.
13.2.4 Self-Assembled Layers, Langmuir-Blodgett Layers,
and Liquid Crystals
Since multiple electrical and optical functionality must be combined in the fabrica-
tion of an OLED, many workers have turned to the techniques of molecular self-as-
sembly in order to optimize the microstructure of the materials used. In turn, such
approaches necessitate the incorporation of additional t.:hemical functionality into
the molecules. For example, the suc<.:essive dipping of a substrate into solutions of
polyanion and polycation leads to the deposition of poly-ionic bilaycrs 159, 60].
Since the precursor fonn of PPV is cationic, this is a very appealing way to tailor
its properties. Anionit.: polymer.; that have been studied include sulfonated polysty-
rene [59] and sulfonated polyaniline !59, 60]. Thermal conversion of the precursor
PPV then results in an electroluminescent blended polymer tilm.
Another approach to molecular assembly involves siloxane chemistry [61 ). In
this method, the electrically or optically active oligomers arc terminated with tri-
chlorosilane. Layers are built up by successive cycles of dip. rinse, and cure to
fonn hole transport, emissive, and electron transport layers of the desired thick-
nesses. Similar methods have also been used to deposit just a molet.:ular mono-
layer on the electrode surface, in order to modify its injection properties.
The long chain side groups, which are frequently used to solubilize conjugated
polymers, in some cases have the additional effect of making the resulting materi-
al amenable to coating by Langmuir-Blodgett (LB) tedmiques. A number of
groups [62, 631 have availed themselves of this phenomenon to deposit aligned
polymer films. In addition to orienting the polymer backbone along the dipping
direction, LB coating permits control of the film thickness at the molecular scale
since essentially one molecular monolayer is coated in each dip cycle. Among the
conjugated polymers that have been examined using these techniques are deriva-
tives of polythiophene !62] and poly(para-phenylene) [63, 641. each of which ex-
hibit polarized emission.
A related approat.:h to the alignment of molecular species is the usc of liquid crys-
tals. especially as char<6e transport materials 165-671. Here the motivation is to
achieve high mobility by ananging the molecules in stacks such that overlap of
the n-orbitals allows rapid tn.msfer from one to the next. Triphenylene derivatives
show discotic liquid crystal alignment and highly anisotropic hole mobility [66}.
The smectic phase of an oxadiazole derivative exhibits very high electron mobility
1671 and polarized dectroluminescencc, although only at very high voltages.
IJ.2 Mulemlllrl)' Doped Polymers and Polymer Blends 421
13.2.5 Electrodes and Interface Modification
13.2.5.1 Anodes
!he materials use<! as the electron and hole electrodes play a crucial role
the of the device and therefore cannot be neglected even
m a revtew ot the matc1ials used in OLEDs. The primary requirements for
the functiOn of the electrodes is that the work function of the cathode be suffi-
ciently low and that of the anode sul'ficicntly high, to enable good injection of
electrons and holes, respectively. In addition, at least one clet.:trode must be suffi-
ciently to permit the exit of light from the organic layer.
By lar the most prevalent material used li.>r the anode is indium-tin-oxide
has a high work function (4.5-5. 1 eV) and is trdnsparent
sn the v1s1ble. The w1de range of work function reflects the chemistry of ITO and
its electrical conduction. ITO is a nonstoichiometrie semiconducting
ox1de m wh1ch percent of the oxygen sites are vacant, resulting in degen-
erate n-typc doptng In order to the doping mechanism of ITO it
is useful to consider the parent compound.
which a complicated crystal

stmcture, but may be thought of as ln
2
0
3
1 where 0 represent-; a vacancy on the
oxygen trivalent indium is replaced by tetravalent tin, charge
compensation 1s mmntmncd by filling the corresponding number of vacancies
oxygen_ Titus, the fonnula becomes ln
2
c
1
__
0
Sn
2
,0.h_,0
1
_x, which is
Still . an mtnns1c senuconductor having low conductivity at room temperature.
Dopmg may now be thought of as removing oxygen to restore some of the va-
cancy sites: ht:w-x,Sn2.,.0.l+.-.. DHx-y) 1lte oxygen concentration can be controlled
during of tl_1e ITO tilm, for example by the partial pressure of oxygen
reacttvc 1691 or it may be later modilied by annealing in an oxi-
dlzmg or reducmg atmosphere 168]. 1lte lattice remains stable approximately to
the composition with the original concentmtion of vacancies, i.e. y=x. Each va-
cancy is an electron donor. providing two electrons (the difference in ch;
1
rge be-
tween an oxygen anion and the vacancy). For small values of y, the material acts
as an n-type semiconductor with the donor states contributing electrons to the
conductio1_1 band. As y the donor states fom1 a band which eventually
merges w1th the bottom of the conduction band. At this stage the material be-
comes a degenerate semiconductor with a metallic conductivity of order 10' S/cm.
The value of the conductivity, as well as the work function and the optical
absprpt1on spectrum, depend upon the degree of doping, i.e. upon the concentm-
tion of oxygen. Since ITO inherently contains a large number of defects. the tin
atoms and the mndomly located vacancies, the conductivity also depends on de-
tails of sample preparation and thennal history as well s on the de"rCC of c
1
ystal-
linity. "'
of ITO described in the previous paragraph make it a useful
matenal lor use as the anode in an OLED. At the same time, they arc the cause
which have been observed in the reproducibility and stability
of OLEO devtccs. We shall rctum to this topic in more detail later, hut it
422 I J 11ze Chemistry, Physics and Engineeri11g of Orga11ic Light-Emitting Diodes
to state for now that the extreme sensitivity of the work function and conductivity
of ITO to processing conditions and to history can lead to wide variations in the
opcmtion of the device unless extreme care is taken to ensure identical surface
stoichiometry and structure from batch to batch. In addition. ITO has been shown
[70, 7 1 1 to react with the hydrochloric acid produced during the tht:rmal conver-
sion of the PPV precursor, leading to the introduction of dopant ions, as
well as indium chloride crystals, in the bulk of the PPV layer.
Because of the variabi lity of ITO, several other tr..tnsparent inorganic conduc-
tors have been evaluated for possible use in OLEOs. Among the most promising
is zinc-indium oxide and the corresponding tin doped material (ZITO) [72]. In or-
der to eliminate PPV doping by lnCI4 Herold et al. [73) suggested the use of
fluorine-doped tin dioxide (fTO) a-; an anode. Although this material led to less
fluorescence quenching of the converted PPV, the injection voltages were rela-
tively high and the electroluminescent quantum efficiency similar to that of ITO
devices. Aluminum-doped zinc oxide can be deposited in thin film fonn, with rea-
sonably good conductivity and excellent tmnspal\!ncy in the visible. Unfortu-
nately, its use as an anode appears to lead to an opemting much higher
than ITO [74].
All of the materials discussed in the last paragraph arc non-stoichiometric
oxides and although thei r relative tendencies to act as a source of oxygen for oxi-
dation of the organic layer(s) is clearly di fferent, they all provoke concerns about
the ult imate opcmt ing lifetimes of OLEO devices. For this reason, more conven-
tional (elemental) metals have been examined. Even though they are inherently
absorbing and reflective in the visible, thin layers can be made to have sufficient
electrical conductivi ty and acceptable tmnsmission. Examples include gold [75,
76] and platinum [76] which have high work functions and therefore act as excel-
lent hole injectors. Moreover, being noble metals, they can yield ve1y stable de-
vices.
13.2.5.2 Cathodes
Since the functional requirement of the cathode is the injection of electrons, the
obvious choice of material is an electronegat ive metal. In geneml, charge injection
does indeed improve in going from AI to Mg to Ca, corresponding to the respec-
tive work functions of these metals. However, the very property which makes
them good cathodes also leads to their rapid oxidation or corrosion in air. Thus,
considerable energy is being expended to develop more stable cathodes, as well
as to provide hermetic encapsulation. Mg:Ag alloys [27, 771 arc somewhat more
stable than elemental Mg, and small concentr..stions of Li in AI [78, 79] reduce its
work function without much cost in resistance to oxidation. Allcmpts to identify
more novel cathode materials with greater stability, for example tr..snsi tion metal
carbides [80], have thus far yielded liLLie succc.-;s.
13.2 Molecularly Doped Polymas wzd Polymer Blends
423
13.2.5.3 Electrode Modification
A thin layer the electrode and the charge transport material can
be used to mod1fy the process. Some of these arc (relatively poor) con-
ductors and should be v1cwcd as electrode materials in their own right, tor exam-
ple the polymers polyaniline (PAni) (81- !>3 1 and polyethylenedioxythiophene
or PEDOT) 183 .. 841 .heavil y doped with anions to be intJinsically conduct-
mg. They have work lunct1ons of approxi mately 5.0 cV [751 and therefore are
used as typically on top of ITO, which is present to provide lat-
eral conduct1v1ty. Thm layers of transition metal oxide on ITO have also been
shown .174 I to. have injection properties than ITO itself. Again these materi -
als (Oxides ol. molybdenum or vunadium) have high work functions,
but ol thc1r low conductivity cannot he used ulonc ;L-; the electrode.
LangmUJr-Blodgeu ;md self-assembled monolayers have been deposited
on the ?_ottom tx:rorc t:..snsporting and emissive layers in an aucmpt
to m<Xhly the properties ol the mtCJ1acc. Alkanethiol lo nns self-assembled mono-
on noble metals. Titiols with an intlinsic dipole moment, such as
amme tcnmnatcd. or derivati ves, deposit1...-d on silver [851 and copper
have to the work function, raising or lowering it accord
mg to the d1rect1on ol the thpolc: if the dipole is oriented towards the interhc .
the ':"ork function is raised, and vice versa. A similar effect was observed
gr..sftmg a to the surfal:e of ITO (87(. Hole injection
the mod1hed anode a spm-co.ated PPP layer was found to occur a t a sig-
The dtpole moment of the carboxylic acid group
IS onented towards the mtertacc and therefore increases the work function. TI
1
c ef:.
feet of an .layer .can be seen by treatment with a protonic acid
vapor ac1d, wh1ch ra1scs the work function of ITO ( 88(.
. ol the .top may also be achieved. This was done by add-
mg a amount ot surlactant, as an ether phosphate or an ether sulfate
to spm-coat solution ol: the luminescent polymer 189]. The Jipophobic elhe;
at the surface of the (predominantly) hydrocarbon polymer, be-
commg ava1lable with the aluminum cathode which is deposited
on t.op. TI10s, th..: d1polc 111 the surfactant poinL'i away from the electrode and Jow-
ers 1ts work function to improve the injection of electrons.
13.2.5.4 Barrier Layers
lnter!'acial not only alter the electronic structure they also introduce a
burner layer. Thus, although the dipole effect may improve the energetic
ahgnmcnt between the Fcm1i level of the anode (cathode) and the HOMO
of .the organic an electrically inc11 molecule may also inhibit
d1arge IIIJectwn by rcdlll:mg the transition matrix clement for transfer between the
electronic states on either side 175(. Inorganic int..:rfacial ha1Tiers have also bL'Cil
used to int..:rfaces. for example LiF (90, I) 11 and AI:!OJ (921.
lor th1s work uppcars to hav..: been to prevent extr..sction of the
maJOnty camcr, thereby enlwncing the licld at the electrode and the injection of
424
J 3 7111! C1Je
11
ustry, Physics and engineering of Organic LighJ-Emiuing Dioclcs
the minority carrier. However, improvements in perfom1ance . observed for
both operating voltage and quantum_ efriciency, would mdtcate that the
mechanism actually involves changes 10 work functiOn 1931.
13.2.5.5 Transparent Cathodt.'S
OLEOs arc normally fabricated on a transparent and the.refore top
a transparent anode. However, several potential apphcattons, such as mtcro-dt:;-
plays integrated on a crystalline silicon chip or a totally transp:u-ent
for a heads-up display, require a transparent top electrode. There _has been
work published describing the development of tr..msparent cathodes. The most
vious approach is to use a very thin metal layer,_ as Mg:
a tmnsparcnt conductor, such as ITO [94). ts not _so tl appears,
si nce the cathode metal must survive the rcacttve sputtenng process employed to
de sit the ITO. Another approach uses no metal but rather a CuPc layer
Atq
3
and the 110 1951. h is suggested .that the oxtdattve
environment during ITO deposition results in heavy 1Hype dopmg ncar the CuPc
interface.
13.3 Device Structures
The materials described in the preceding section may be in an OLEO
vice in a variety of different geometries and compositions. The stmplesl of these ts a
single organic layer sandwiched between two cl_cctrodcs. In c.ontmst to the
lion used in surface science, it is customary to hst the layers order of depost-
tion. Thus, anode/organic/cathode (for example, 110/PPV/Al) uuphcs that the anode
(ITO) is deposited first on the (presumably su?stratc. . . ..
In a single-layer device, the organic must all l_unc.uons.
hole tmnsport, electron tr..msport, and (see .Ftg. 13-1 a
the energy level structure and device opcratton). In thts case, the lllJeCliOn _r.ues o
holes from the anode into the HOMO and of electrons from cathode snto the
LUMO must be roughly equal for eflicient operation. Otherwise the
. . of one sign will j ust pass through the organic layer without recombsnau.on,

10
the current but not to . . These arc_
and arc satisfied in just a few cases ol pradtcal Interest: (e:g.
MEH-PPV) arc found to have a HOMO that aligns well. w1th Fenm
of rro, gold L%1 and PEDOT [97), and a ts close 111 cal-
.
1
196) They also exhibit moderately h1gh moh1ht1es for both
1981. and have high luminescent yields {99], typically of omnge-rcd hghtso
the fully conjugated polymer. . . , , , . . ..
By using multiple layers one may tmmcdtately
imposed on u single material. This reali:tation was lllc breakthrough 111 the ltcld ac-
(a)

1

Anooe
(b)
) e
,.,.,--- I
I
I
J
1 J.J Device Smu:tures 425
(
c) '-;i e
,'/ ....... _
I

'...- I
Figure 13-l. Energy level diagr.uns under lorwanl bia.,. (a) Single-layer device both holes
and clcctrons <UJd emits; (h) two-layer deviL'C with hulc and clc.:tron lr.msport layers. one or blllh of
which may emil; (c) lhm:-taycr Jcvocc with cmllling dye doped (here) into a thin region or the elcc-
IIOO layer.
complishcd by the Kodak group in the early 19l:i0s 1271. For example, in the case of
two (sec Fig. 13- 1 b), one material (that to the anode) cau be selected
hole injection transport, while that adjacent to the cathode permits good
tnjCCt1on and tmnsport ol electrons. Emission may occur from ei ther or both materi-
als. The interface bt!twcen the two organic layers can have two additional ellects on
the of a bilayer .device. First is that the energy level offsets may present a
hamer lor electrons entcnng the hole transport layer, and vice versa. This tends to
prevent the loss of ctliciency caused by the passage of charge from one electrode
to the other without recombination. Secondly, because of the high density of carriers
on each side of the organic interface (holes in the HTL and electrons in the ETL)
recombination is most likely to occur near the interface and well away from the me-
tallic electrodes. This reduces the probability of exciton quenching by dissociation at
the. electrode. 1l1e exact nature of recombination and emission depends on the ener-
getiCS of holes, electrons, and excitons in each material. For example if, as illustmted
in Figmc 13-1 b, the harrier to holes is less than that for electrons, then holes will
enter E'!L and rccmnhinc there. In general, assuming comparable
exc1ton-bmdmg encrg1es 111 the two materials, the exciton has a lower cner"y on the
side of the interface where it funned anti will therefore emit there (in Fig. l3- l b the
HOMO.-LUMO gap is smaller in the ETL). 111crc is also the possibility of direct
rccombmation across the interface because the electron transport material (accep-
tor) and hole transport matc1ial (donor) form atl excited state charge-transfer com-
plex (cxciplcx) which can relax radiativcly to its ground state 11001.
Trilayer structures ofTer the additional possibility of selecting the emissive ma-
terial, independent of its transpon In the c:1sc of small molecules, the
emitter is typically added as a tlopant in either the HTL or the ETL. nc:r the in-
teiface bt!twecn them, and prcfcr..tbly on the side where recombination occurs (sec
Fig. 13- 1 c). ntc dopant is sclcccd to have an exciton energy less tlJan that of its
host, and a high luminescent yield. Its concentration is optimized to ensure exci-
ton capture, while minimi zi ng concentration As before, the details of
recombination and emission depend on the energetics of all the materials. The do-
pant may act :ts an electron or hoh; trap, or both, in its host. 1l1us, for example,
an ch.:ctron lmp in lhc ETL will eapllll\! and hold an electron until :1 hole is in-
jected nea.-hy from the I ITL. In this the dopant is the rccomhinalinn r '"'"r
426 /3 1l1e Physics and Engineering of Orgcmic Ug/11-Emitting Diodes
and little exciton migration occurs. In other cases, the charge barriers may favor
recombination on one side of the interface, while the dopant, with its lower exci
ton energy. is on the other side. Then the exciton will tend to migrate back acm;s
the interface, provided that its lifetime is sufficient.
Clearly additional layers may be used to accomplish other benefits, tailorine
the energy profiles and mobilities across the entire organic stack. Splitting the
tr.msport Iayer(s) into two sepamte layers permits the optimization of injectioo
into the layer nearest the electrode (sometimes called the injection layer), and
transport in the farther layer liO I]. layers of insulator (charge confinement
layers) have also been used in an attempt to control the motion of the charges and
ensure recombination in the dc:.ired region [I 02].
1l1ere is one added layer which deserves special mention, namely a thin copper
phlhalocyaninc layer, which has been placed I I 03) between an ITO anode and the
hole tmnsport layer. It is not an injection layer in the sense just discussed, be-
cause its HOMO is not well aligned with the ITO Fenni energy and it slightly
mises the opcr.lling voltage of the structure. It does, however, tlmmatil:ally im-
prove Lhe stability of the device appears to act as an adhesion layer for the or-
ganic materials above it. The mechanism(s) for these improvements is not yet
well understood.
Lastly in this section we describe a device structure LhaL is modilictl in situ by
the passage of electric cunent between the electrodes. It was named the light-
emitting electrochemical cell (LEC) by its inventors at Uniax (104). The organic
layer, in this case <I blend of conjugatctl and electrolyt ic polymers, contains mo-
bile anions and cations in the form of a saiL such as a quaternary ammonium or-
ganic sulfate. l11c mechanism of operation is illusLr.lletl in Figure 13-2 and was
described as follows I 104). On the ini ti al application of a voltage, the anions
move towards Lhe anode. At the same time. elecLrons are removed from the conju-
gated polymer (it is oxidized) to form a polycaLion, with the anions acting as
countcrions. The result is a heavily p-tloped polymer with (nearly) metallic con-
ductivity adjaccm LO the anode. Similarly, the polymer adjacent to the cathode is
reduced to give a heavily doped 11-type conductor, with the cations as counter-
charges. 1l1ese regions of conducting polymer may be compared to the anode
polymers dcscribctl in Section 13.2.5 and are presumed to make Ohmic conlad
with the metal elcctmtlcs [I 041 (but sec I I 051, discussed in Section 13.5.4, for an
alternative point of view). Further from the interfaces the concentmtion of ions de-
creases to give an intrinsic semiconducting zonr..: in the center. After the doped re-
gions are fom1ed the LEC operates in a manner similar to a single layer OLEO.
Electrons and holes are injected from opposi te sides of the semiconducting region
where they recombine to emit light. Now there is no abrupt for injection,
but mLher a gradual change from metal to semicontlul:tor. EIIicicnL charge injec-
tion is thus achieved regardless of the work functions of Lhe anode anti cathode
metals.
Additional advantages of this structure include Lhe possibility of using a rcla-.
tively thick layer of polymr..:r: in the order of I J.1 compared to I 00 nm or conven-
tional OLEOs. In turn, this permits the fabrication of in-plane structures where in-
terdigitated electrodes are deposited on thr..: suhstmtc anti ovcrcoatcd wi th the
13.4 C/Jaracterizatioll 427
(a)
(b) (c)
Figure IJ-2 .. Schcmatil dial,!ram of the ..
1
1
, ., L'"C 0 . .,. ' (
dopc
OO _' ' &:. IS <Ill (,lXIul l<.'U JH)'pc
. ) I> " rcdun:d <Hype duped) SJICt.:ICs, "' IS a neutral ckctrun-hulc pair. (a) The cell
bclon: :tpplymg a Vlllfal,!c: (hJ duping opposite >ik> as Hype and p-typc; (t.:) t:hargc migmtion and ra-
dtauvc dcc.1y. Adap!t:d l'mm [IOtj.
polymer layer . I I(K> 1. A disadvantage is that, over time after the voltage is re-
moved, the anaons anti r..:ations migrate back towards the cemer of the cell anti
be separated a?ain before currents will flow to produce emis-
Improvements 111 opcrataon of LECs include the usc of a t>Oiyr..:Lher phase
separated fr0111 the CllliSSIVC polymr..:r by atltJition Of <1 SUrfactant. l11e percoJa1ing
polymer ionic motion towards the electrodes 11071. This im-
proves the response of the cell, in that the cler..:tnx.:hemistry al the anode and
cathode ?Ccurs more quackly anti Lhc nonnal injection of electrons anti holes starts
quae_kly. _The Lime to form Lhe fJ anti n-tlopctl regions can be eliminated r..:n
fonmng Lhe doped regions just once when the cell is made, for example
tempcm_turc to_ mobilize the ions, then hx.:l..ing the structure in place,
usmg 10ns Lhat arc anunob1le at room tcmperatUI\! 11 og, 1091.
13.4 Characterization
Before any mo.tt_c::rial c.:un be consitl..:retl for application in
OLEOs,_ a of 1ts pr..:rfurmance in motld device structures is neces-
sary. Ot mtc::rest urc thr..: relationships between the voltage, current, ratli -
and c_tiiCICilCy, or the emitted light. Thesl! jJhy.viml quanti-
lies Lhe s oper.1tmg d1arac.:teristic.:s m1d depend not only
011
the
of thl: organic, but ulso on the tll!vice energetics, i.e. the
vanous energy barners at the of the organic.: with the metal eb:trodcs,
428
13 Tile Chemistry, Physics a11d Engineering of Orga11ic Light-Emitting Diodes
and between organic layers in the case of multilayer devices. The_refore,
of a candidate material for OLEOs includes ? f 1ts and
on properties and chamcterization of dev1ce energettcs and ln
we review the basic characterization methods; results are given m th:
section that follows.
13.4.1 Device Characteristics
Tile device characteristics arc measured in model devices, where o.ne or_ or
ganic materials are sandwiched between two well known electrodes, a
arcnt high work function anode (ITO, Au, etc.) and an opaque, o_ .
' 1 od (C Mg AI ct) The thickne:-..' of the 1s typ1cally m
uon cat 1 c a, . , . . . , . . . . . .
the order of 100 nm and, for experi mental the IS
th d
01
- a l"ew
111
m 2 The preparat1011 and charactcnlA.Itlon
111 c or er . . . d , . 1 tl low
lace in the of oxygen and hunud1ty, <trc t_o. 1e .
p rk function electrodes and possibly to the Of'6;mic. The stability
wo . . nditions is usually first, in order to make sure that 1_10 slgml
operatmg co . .. . . Tl . . . by lor exam
ic-mt de radation takes place dunng charadt:IIZ:.tll on. 11s uonc . .
PI
C the of tht: c.:urrt:lll and undel
' t d radmnce as a unc-
volta e drive. Subsequently, measurements ol t c cun\;n . an : .
ti on an applied voltage, and the spedral depcnden< .. ol the
.. ed out. Tlte mdiance b measured w1th a C<thbrated or_ by
sample at the input port of an integmting sphere. ln th1s way, hght
II
to _to
Au/MEH-PPV/Ca
/
f)
p
-it-

-5 0
Voltage {V)
5
I
I
. .o olta of an MEH-PPV-bascd
Figure 13-3. Typical curwn-vollagc anu r;rulallCc-v gc
OLEO with ;sn Au anoc.lc and an ITO cathode.
Before Coo1ac1
E. ---
- E.
E.- ___ _
E.

I i
----: ---r-

/ 3.4 Characterizotiutl 429
J

Jo'igurc 13-4. Energy level diagmm of a inglc- layer OLEO, where the org;u1il: mate rial is dcpiciCd iiS
a fully depleted scmicooduclor. The valence band v corresponds 10 the HOMO and the conduction
band 1:.(- corrcspunds In rhc LUMO. lllc Fermi levels ni lhc two metal un: marked ""
Upon a buill-in pmcrllial is and 11<.-ctb to be culllpcns:u..:d fOf'. hcfurc the device
will begin to opcr.ni ng.
tmpped in the layered structure and guided to the edges is discarded and only
light that is emitted from the front side of the is detected.
Typicul results from a Au/MEH-PPV/Ca diode are shown in Figure 13-3. Under
forward bias, the current and the r.tdiance ;.tre mpidly increasing with voltage, while
under reverse bias there is little current and no radiance. A qualitative unden;tanding
of the devic.:c charuc.:teristics is obtained wi th the hdp or the simplified energy level
diagr.s.m in Figure 13-4. Since the renni levels of the two metals must align at z.cro
bias, a buil t-in potentiul ( V,;) is established across the organic layer. For an applied
bias (V,,
1
,
1
,
1
) of than V,;, the electric lidd inside the polymer opposes charge in-
jection and forward dril't cun-cnt. When the <tppl kd voltage V
1
,
1
, the current
and the radiance im:re;.tsc rapidly. Under bias, the b;m-icrs for charge injec-
tion arc high and little cun-cnt flows through the device.
13.4.2 Figures-of-Merit
The processes of ch;.u-gc injection, transpo11, and recombination dictate the recom-
bination efficiency b(f). which is the fmction of injected electrons that recombine
to give an exciton. The recombination eiTicieney, which is a function of the de-
vice cun-cnt, plays a pri mary role in detcm1ining the amount of emitted light,
therefore detern1ining the OLEO tigurcs-of-merit. For example. the quantum efli-
cicncy '/u(J) (fmction of injcctcc.l electrons that results in the emission of a
photon from the device) is, to a fin;t approximation, given by:
( 13. 1)
where t/>J. is the nuorcscence yield of the organic layer (usually ussumcd to be
equal to 1/4 of the photoluminescence yield of the lihn, though this is not always
the case [II OJ) and fhx r is the extemal coupling efficiency, usually approxi mated
to be equal to 112n
2
(whe1-c 11 is the refmctive index of the organic layer) for an
organic whe1-c the transition arc r..tndomly oriented 11111.
430
13 The Chemistry, Physics and Engineering of Orgcmic Light-Emitting Diodes
From an engineering point of view, a more relevant figure-of-merit is
power efficiency fJp(l), defined as the ratio of emitted opticaJ power to the dnv-
ing electrical power. It is given by:
f}p(J) = 'lQ(J) hvf(e V(J))
( 13.2)
where hv is the average energy of the emitted photon, e is the electron charge and
V(l) is the applied voltage at a current density J. For a_ high power efliciency._the
operating voltage (the voltage at which there is suffictent flo":' and hght
emission) should be as low as possible. As seen from the dtagram of F1gure 13-4,
the operating voltage depends on the device energetics as well as the voltage drop
across each organic layer.
13.4.3 Built-in Potential
The built-in potential plays an important role in determining the OLEO
mance. The net voltage across the organic layer is V.,,,,.rV1,;, therefore the blllll-m
potential must be measured and subtmctcd from_ the. applied . bias in to com-
pare the characteristics of two devices. In th1s sunplc p1cture of ng1d bands
(Fig. 13-4), Vl>i is equal to the di fference in work of the tw?
However, phenomena like pinning of the Ferm1 level at mterfacc states, _tom1allon
of a dipole layer or chemical reaction between the metal and the orgamc can oc-
cur and change the value of the buill-in potenti al. I. er al._ [96, 12]
have used electroabsorpti on to measure the Vbi in MEH-PPY dtodes vanous
metal electrodes. This technique is based on the fact that the absorpt1on coeffi-
cient of an onanic layer changes under the application of an electric field .. The
experi ment is .,carried out in OLEO structures,_ in a reflection geometry, wtth a
light beam entering the sample through the semtt ranspa_rcnt and reflected
at the back electrode. The relative change in the opllcal lr".msmtsston (/)t.T/D IS
Figure 13-5. of the clcctroab-
sorption signal at the f undamcntal fre-
quency of the applic.J ac modulation for
fi ve MEJ 1-PPV-ba.=J dic.xlcs. Reproduced
frorn 11121 with permission from ElscvieJ
Scicn.:c.
I 3.4 Clwracteri._ation 431
2.0 .----.----r---,---..,..---....--,.-------,
'""'
w,
"'E
,.........
<
"'s
1.5
._,
c 10' '
<
v;
c
'b
Q)
ooooao -,;:!
.......
1.0
E
10"'
Ooooooooooo I
'-"'
....
1::
o I ;::.--_
::r X
....
u tl'o
-
10"' \
V)
t;AAt;A a
s::
Q)
At>
'"0
0.5 0.0 u.s 1.0 1.5
.....
Vohagc (V)
s::
Q)
t:

u 0.0
0.0 0.5 1.0 1.5
Voltage (V)
Figure 13-6. 1l1.: vultagc k:pcndcm:c uf the .:um:nt densities in the dark (open triunglcs). under illu-
minaJiun (opcrt circles) and chcir dill"crcm:c (lilkd square-') fur all ITO/MEH-I'I'V/Mg OLEO. 1ltc in-
sa shows :.amc data plullcd a.' logarithm nf tl..: .:um:nt (diiTcrcn .. Rcpm<.IUL'I."d with
sion from 197j.
measured a-; a function of applied bias V,,
1
,1'
1
, wi th an addi tional ac modulation at
frequency w superimposed, to allow lock-in dl!tection. The component of llT/T
w is proportional to I V,,,,.rV
1
,;1 and it is nulled the voltage is equal
to built-in potential (Fig. 13-5).
Another way to measure VIIi is by me;ms or photovollaic measurements
[97, 1131. The technique is based on the fact that, at ncar zero applied bias, the
OLEO acts as a photovoltaic cell, where photogencr.ucd carriers drift under the
influence of V
1
,; to produce a current in an external circuit. In a way similar to
electroabsorption, an external bi<L'i is applied in order to compensate the built-in
potential and null the net photocurrcnt (Fig. 13-6). However, it has been shown
that the measurement produces accurate only at low temperatures, where
diffusive transport of charges that arc photogeneratcd at the interfaces is negligi-
ble [97).
432
13 The Chemistry, Physics and Engineering of Organic Ught-Emitting Diodes
13.4.4 Barrier Heights
Energy baniers at the various interfaces play a role_ in the
OLEO performance. Photoemission is a well estabhshed to
organic and organic/organic interfaces and has been used to y1eld
about chemical binding of metal atoms to the organic, doping of the orgamc, and
Metal vacuum Metal OrganiC Vacuum
(a) (b)
2.0
1.5
r-1
t')
I
0
'--'
1. 0
N
......
:;:.......
>-
0
.........,
0.5
0. 0 L-..J'..::::<!t::::...._J_ _ _L. _ __._ _ _.
0.7 0.8 0.9
0.6
Epb[eV]
Figure 13-7. Prim.:iph: of the UPS stud)
of an organic/mclal imcrfacc. (a) Phoux
missiun from lhc metal: (b) phowcnlls
sion fmm an organic layer deposited 011
1hc mclal J{cpnxlut-.xl from
11151 with pcnnission from Elsevier
Science.
Figure: Typical results for inlem::.
phlllocmission measurements on an ITO/
OPPV/Ca diode :st variuus applied
TIJC lines are least-square !ils and their extr:l-
polation yields the barrier height for ap-
plictl vollagc. Inset shows lhc cxpcnmenw
setup. Ro:protluccd wilh pcnni&\ion from
[JI\)1.
13.4 Clwracteri1Jltion 433
electronic band structure r 114-1181. The principle of the llle<ISUremenl is shown
in Figure 13-7. Electrons below the Fem1i level of the metal are photoexcited into
the vacuum by means of deep UV (UPS), X-ray (XPS), or synchrotron mdiation.
The disuibut.ion of their kinetic energy reflects the dc:nsity of occupied states of
the solid. For the case of a bare metal surface, the high ener<6Y onset corresponds
to the emission from the Fcm1i level, while the low energy cut-off corresponds to
the vacuum level. When an organic is deposited on top, the high energy onset
corresponds to the emission from the HOMO of the organic, while the low
cut--otT corresponds to the level at the top of the organic layer.
Optical techniques have also been used to provide information on the device
energetics. Rikken et ul. 11191 and I. Campbell et ul. 1961 have used internal pho-
toemission to measure the barrier height betwcc:n a polymer and metal electrodes.
In this expcrimt!nt, li ght is shone on, or through the semi transparent electrode of
an OLEO and the carriers arc driven into the organic by applying
a proper bias. The resulting photocurrcnt is measured as a function of the photon
energy hv (Fig. 13-H). barrier height rp is obtained by plouing the photocur-
rent quantum yiekl Q. Y. as a function of the photon energy hv:
(13.3)
The experiment is performed at various voltages and the barrier height values are
corrected for the image charge potential by extmpolating to zero voltage.
13.4.5 Charge Transport
O.arge carrier mobilities in organic materials are usually measured with the
photoinduced time-of-flight technique (38). In this experiment, the organic is
_sandwiched between two blocking (i.e. non-injecting) contacts, one of which is
semitransparent. A strongly absorbed pulse or light excites a thin sheet of carriers
inside the sample close to the transparent electrode. Under the influence or an ap-
plied field, this shcr:t or carriers drifts towards the opposite electrode and the re-
sulting photocurrent is measured as a function of time. The mobility is calculated
from the time it takes for the sheet of to arrive at the opposite electrode,
which is manifested by a change in the mtc of the current decay.
The above technique requires organic layers that arc of the order of a few mi-
crons thick, considcmbly thicker than those used in OLEOs. A way to measure
charge carrier mobilities directly on <Ill OLEO geometry is by time-resolved clcc-
troluminescencc metsurements. The technique is based on the fact that for recom-
bination to take place, the most mobile of two needs to transverse the
sample and meet with the less mobile one [120, 121). Therefore, the time onset
for emission corresponds to the transi t Lime of the most mobile carrier. Blom et
a/. [ 1221 have described a high scnsiti vi1y variation of this technique where the
time intcgmted light output is measured as a function of the duration of a voltage
pulse and the tmnsit is cxtmctcJ hy extrapolation to zero light emission
434 13 11re Chemistry, Physics and Engineering of Orgcmic Light-Emitting Diodes
'pulse
L=100 nm
150 200
Figure 13-9. light lliJtpul pulse kugth 011 1l1c line:.
OlfC fits uno thcrr Clllrapnlution yrciJs the time r,,. Inset shows the timing bciWCCil
she application of a voh:tgc pulse uno the ohscrvcd clcctrolumines.:cncc. RcprocJu.:cJ with pcrmissioo
from (122). Copyright IWII hy the
(Fig. 13-9). The si tuation is different in bilayer devices, where the onset of clcc-
trolumincscence corresponds mainly to charge accumulation at the organic/organic
interface [ 123).
Redecker eta/. [124] have recently described anolher technique for lhe mea-
surement of mobilities in OLEO devices, based on the optical detection of !he
charge carrier concentmtion. The technique relies on the fact that charges in or-
ganic materials are in the fom1 of mdical anions/cations with distinctive signatures
in lhe absorption spectrum. Accordingly, !heir concentmtion is derived by measur-
ing lhe change in the optical absorption of the sample during steady-state current
flow and the mobility is calculated in a g.r:_aightforward manner. Recently, Scou et
a/. [125] have time-resolved the spacr.: charge-limited current transients in mono-
polar devices excited by vol tage pulses. The tmnsients show a distincl maximum
!hat corresponds to the arrival of carriers at the opposite electrode and penuit a
very simple and struightforwanl measurement of lhc drift mobility in an OLEO
configumtion. Both of the above techniques arc applicable to monopolar devices,
where one of the electrodes is intentionally chosen to be non-injecting.
13.4.6 Photoluminescence
Absolute photoluminescence cfliciency measurements in thin solid tihns arc quite
difficult, since lighl-lrapping, waveguiding effects and, possibly, distributions in
the emission dipol e moments of imlividual modify the angular dis-
tribution of the De Mello et a/. 11261 have described an improved mcth-
13.5 Dctice Phy!>ks 435
CCO CCO Sc><--=trumCicr
CCO Sc><-ctromctcr
F.xpcrrmcnt (a)
E.xpcnmcuc (bl
EJCik.-ruueuc (c)
13-10. Di:rgmm illustmting rile three cunliguMions of the ,phcrc required foc she cmcicncy
measurement. (a) 1l1e sphen: 1s empty; (b) the :.ample is in plar:c chc la.o;cr beam is oirectecJ :tt the
wall; (c) the laser bc:Jm rs t.lmx:tcd un the sample. ReprucJu.:<.'tl with pcnni:.sion fmm [ t26j.
od for the or the photoluminescence eflicicney in films of OLEO-re-
lated u.smg an integrating sphere anti a ceo spectrometer. Their experi-
ment ol separate. measurements, with the sample positioned in anti
ol the beam (Frg. 13- 1 0), 111 order to account for rclkction of the incident
hght.
13.5 Device Physics
Since. the observation of clcctroluminr.:sccnce in organic materials our undr.:r-
standmg o.l OLEO physics has advanced considerably. From the very begi nnino,
was undr.:rstood to arbe from the recombi nation of
earners, lllJected the electro<.Ies and (at least one of lhem)
lhe bulk ol the orgamc. Understanding, in quantitative detail, the relative
of the processes of charge injection, tmnspon, and rocom-
b.snatcon 111 the ovemll device clliciency has been the goal of inten-
ssve cll'ort 111 both industry and m:adr.:mia ever since. Today, this goal has
to lar<6e extent .tor the case of single-layer devicc.o;, where fully
models are now avaslable. In the section hdow we review the state-
?f-the-as1 m our understanding of the OLEO physics. We do that by tirst examin-
mg. the elemcntasy that underlie OLEO operation anti subscquemly lo-
cusmg 01.1 the physscs ol tll!viccs, where most of the progress has
achscved. For sake of completeness, we will brielly discuss multi -layer
devsccs, elcctrochenucal cells, and microcavity effects.
436 /3 17re Chemistry, Physics a11d t:11gi11cering of Orgwric Liglrt-Emiuing Diodes
13.5.1 The Elementary Processes
In the previous secti on, an energy level diagram that describes the device opera-
tion was shown; where the organic was represented as a fully semicon-
ductor whose bands remain rigid (sec Fig. 13-4). The picture is surely rather sim-
plistic: instead of extended bands, the electronic leveb of organic semiconductors
are best described as a distribution of localized states [ 127]. The absence of long-
range order has profound effects on the elementary processes of charge injection,
transport, and recombination that underlie OLED operation.
The last two processes have been well studied in the past. Liulc doubt exists
that electron and hole recombination in organic materials obeys the Langevin law
[1 28 J, contmry to the case of inorganic crystals, where the recombination r.ue is
an expcrimemall y determined quantity. As for the process of charge tmnsport, it
has been extensively studied in the pa.<il in connection with the application of or-
ganic materials in ele..: tmphotography I 3H 1- Charge transport in these materials
take.<> place vic1 hopping, with each hopping site located in a statistically different
environment due to the lack of long-range order. As a result, there is a di stribu-
tion in both site di stances and energies. Theories (such as the Bassler formalism
a.k.a. Gaussian disorder model I sec Chapter 121) that usc this fact as their staa1ing
point, have been 4ui te successful in describing the charge transport characteristics
of molecularly doped polymers and organic glasses [3HI. although their applicabil-
ity lor the case of conjugated polymers, is still a mauer of debate [129, 130j. The
main consequence of di sorder is that the mobility is electric field dependent and
can frequently be described accordi ng to:
( 13.4)
where 14
1
is the zero field mobi lity and Eo a chamcteristic field. This dependence
(often called Poole-Frenk.el like, although the mechanism is now recognized nol
to be Poole-Frenkel) has been explained recently as arising from energetic disor-
der due to the of each hopping charge with mndomly oriented and ran-
domly located dipoles in the amorphous medium I 131 ]. Because of the long-
range nature of the dipolar field, the energy on neighboring sites is somewhat cor-
related, and it is the nature of this correlation that gives rise to the electric field
dependence. Mobi lities of the form of &J. (13.4) have been mea.o;urcd in molecu-
larly doped polymers, organic glasses, and conjugated polymers 138j.
One result of the field-dependent mobility is that the space charge-li mited cur-
rent (SCLC, the maximum current that can llow in the bulk of the sample) docs
no longer follow a simple \?-tL} scaling [ 1321 on the voltage V and sample thick-
ness L. Murgatroyd (1331 was able 10 show that, for a mobility as in &J. (13.4),
the monopolar SCLC current could be well approxi mated by:
( 13.5)
13.5 Device Physics 437
Charge injection !s the least well understood of the elementary processes. Since
charge_ organic no longer takes place by free propagation in a
IS very tmdi tional semiconductor models to treat injec-
at mterlacc. However, some concepts are tmnsferable. As
se1mconductors, a mctaVorganic contact can either be Ohmic or
InJection lumtlXI I I 341. the fonuer case the contact is capable of providing any
amount of as the space charge-limi ted current Jlowing in the
bulk of orgamc layer. while m the Iauer case charge injection constitutes the
m the now of c_urrent through the sample. It should be emphasized that
there Is no sharp demarcatiOn between these two limits and the behavior of a con-
tact ca_n f:om one limit '<? r_he applied voltage. With very few
all to model lllJCCllon-hnuung comacl:-. in OLEOs have relied
on theo_nes such .as R1ehardson-Dushman thermionic emission 11 35 J and Fowler-
lunneh.ng (1361. which were developed for freely propagating carriers
m crystalhne senuconductors.
Several aucmpts to lake imo accoum hopping trans1xm in the onanic have
r<:cently out Garstdn and Conwdl 1 I 371 have used Carlo
to emission-lim.ited, thcnual injection in an energetically
msuh110r. They found thut disun.ler leads to an increased
lor lllJCcted caniers to return to the metal, reducing the magnitude of
the lllJCCted. Moreover, disorder was found to result in a steeper field de-
pendence ol I.:UITenL Arkhipov et (1/. r 1381 presemed an analytic theo-
ry from _a 10 an organic semiconductor, calculating the
probability ol a locahzcd Ill the tai l of lhe distribUi ion or hopping sites 10
escape _the churge putemial. TI1e injc..:tion current was derived as
a_ ol held, and the width of the disllibution of hop-
pJOg Sites. The mam concluSIOns of the model arc that at high electric fields the
calculated !las the tunneling tonn (although IUJmeling
was not m the .rheor>:) and that disorder enhances the inj ected
current, m disagreement wuh the smmlat ons of Gnrstei n and Conwell (137 j .
et a/. , suggested injected carriers in conjugated polymers
locahz.c m the part of the 1magc charge potemial, creati ng an elecuic di-
pole layer at lhe mterlaee. They calculated the resulting chanrc tmnster mle from
the to _the polymer_ us a of electric tidd and re7t
1
pcrature. A crucial
prcchct_JOn ol ts that f lhc density of ..:onjugatcd segments close to the
mre_rface 1s high, these trapped carriers organize in a bipolaron
laU1ce wh1ch results m an mcrea.o;e of the Schollky barrier. 'Iltcrefore the p . ,
f
1
-
1
. , resencc
o_ llm layers ber_wcen the metal and the polymer should pro-
hlbU the ol a b1polaron tau.ce and enhance injection.
lrea.llng surface as u hopping in the image charge po-
ten_ual, _and Malharas I 1401 have denved a very simple equation that de-
scnbcs the nJe.:ted c_un-clll as a function of electric field, temperature, and mca-
sumble, _ol the organic, namely the c<mstalll, the site densi ty,
the dull n!obllu_y. The cuncm has the usual form of thermi onic emission, but
With an constant that is several orders of magnitude lower
than that m morga1uc scmtconduclors. The of the model arc in agrcemcm
438
/3 The Chemil'lly, tmd Engineering uf Organic Lighr-Emiuing Diodes
with a more rigorous treatment of the drift-diffusion
O'Dwyer (1 41]. The main advantage of this model is that 1t descnbcs the
tion in terms of experimentally obtainable parameters and, therefore, lends 1tself
to experimental test . . .
On the experimental front, the energeucs at metaVorgamc h_ave been
extensively studied wi th photoelectron In combmauon quan-
tum-chemical mo<.leling, information has been obtamcd on both the and
electronic structural infom1ation at the interface. For a review on th1s subject see
the chapter by Logdlund and Salaneck. In general, the mea'iurements confi!m the
presence of an energy barrier that scales to _the ene_rgy levels ol metal
and the oroanic 1115- 1171 in the case where chem1cal mtcracuons arc not too se-
vere r lt 4.t t 81. lmernat photocmission 1961. etcctroabsorption 1961_. an_d photovot-
taic [97, 113) measurements in conjugated polymers corrobomte th1s p1cturc.
13.5.2 Single-Layer J)cvices
13.5.2.1 Analytic Theory
Studies of double canier injection and tmnsport in insulators and semiconductors
(the so called bipolar current problem) date all the way back to the 1950s. A solu-
tion that relates to the operation of OLEOs was provided recently by Scott et a/.
[142), who extended the work of Parmenter and I include _Lange-
vin recombination. In order to obtain an analyt1c soluuon, dll'lus10n was 1gnorcd
and the electron and hole mobilities were taken 10 be electric.: field-independent.
The current-voltage relation was derived and expressed in terms of two indepen-
dent boundary condit ions, the relative electron contributions to the current at the
anode, and at the cathode, _ .
The nature of the analytic solution led to the concept of an ftlclency-currcnt
b.!!Jancc diagmm, which is useful even when the analytic result
do not hold. In Figure 13-11 a, a schematic of the spallaJ of elec-
tron and hole currents inside an OLEO is shown. The m he1ght be
tween the left and right ends of the boundary is the recombination b,
which is equal to
In Figure 13- 11 b, the of the

diagmm is the recombination efficiency, while the abscissa is the be-
tween the electron current injected at the cathode and the hole cun'Cnt lllJected at
the anode nonnali.ted to the total current. Thus = I correspond:. to the
case of devices, - 1 represents hole only, and 0
j ccti on. The lines represent the maximum value of I> given dllrei'Cill.:c Ill In-
jection cuiTenls, when all of the minority (more poorly IIIJCclcd) c<IITiei:S mcom-
bine. The remai nder of the majority carriers pass through the sample Without
combination, conuibuting to the current but not to the emission of light. A senes
of illustrative current proliles is shown for various points on the dwgnun. .
Clearly, the optimal injection condition is for electrons and hoks to be m bal-
ance but thi s docs not m:cessarily guar.mtee that h= I. For example, when both
arc injection limited and the injected charge densities arc small , the prob-
13.5 Device Physics
439
(a)
J.IJ ,[S)l -b
Anu&: x Catlk..Jc
(b)
b(J)

DJ;-..:_ EJu
_..........
.
Electron only
13- 11. (a) A llittram showing the spatiill llislrihution nf lhc r.:J;uivc hulc uno clcclllln <.: uJTcms
m an OLEO. rc.:omhinatiun cllkicu.:y b is Co.j ual 10 1hc ol' the clc..:lron (hole) ..:urrcm 1ha1
docs nu.' nlilkc u lo lhc anullc (calhullc); (h) cllkicncy-..:uiTclll halan..:c Ji .. gr.tm fur OLEOs. Sec 1cx1
Cor t.lctmls.
of I'Ccombination may be negligiblt.! and h remai ns close to zero (point C
m Fg: 13- 11 >: one of the contacts is ohmic, the charge density of the cone-
c-..trrier next to the contact is very large, result ing in strong re-
the minority canier. As a result, the minori ty current at the (oh-
mle) contact 1s ncar zero and the device's opcr..tting poi nt lies on the maximum ef-
line. If tl_lC_ cathode is ohmic. for example, '11= 1 the efficiency is de-
termmed by the IDJCC.:ted hole current J);' 'IJ (point B in Fig. 13- 11 ). When both
arc_ o_hmic, I:Jrge ch<Ut!t.: densities at the contact!> ensure complete recom-
of lllJCCtcd carriers and the device at maximum clliciency (point
A 111 F1g. 13- 11).
13.5.2.2 Numerical Simulations
The analytic theory outlined above provides valuable insight into the factors th:
1
t
1hc . cflicicncy_ <lf lhlWl' Wr. l hl'l'l' l'OlllJlk'ldy analy1ical
soluuon Jlllus1vc tr:mspmt or carriers. lield-dcpcndent mobilities,
and spcc11lc lnJCCllon mechanisms. Therefore, numerical simulations have been
undc11aken in order to provide quanti lative solutions 10 the general case of the bi-
poi:.U: current_ problem typical parmneters of OLEO lll<lterials f 144- 148 1. Em-
phasis was g1vcn to the mlluence of ch:1rge injection anti transport on OLEO per-
formance. I. Campbell et a/. 11 4 71 found that, for Richardson-Oushman thennio-
nic emis:.ion from a banier height lower than 0.4 eV, the cont act is :tble to supply
440
13 77ut Chemislry, Physics and Engineering of Organic liglu-Emittiug Diodes
---
---
-- --.. ... -. ....: :. ___ _
-----
------ .
1011 __
0 20 40 60 l\0 100
Distance from anode (mn)
l<'igu n 13-12. The n:combim111011 profile' fnr ;m OI.ED w11h an uh11111: anode :md. ;m iujL-clion-li milcd
for r.uius uf lhc dcclrun/hulc l{cpruduccd wuh pcnms,tun I rum ( 1451.
the bulk of an OLEO with charge-limited cun-cnt. A somewhat small er val-
ue, equal to 0.3 eV, was found when using an injection law specific to metal/or-
ganic interfaces (1 48). Diffusive transpon of charges was shown to be imponant
only near or below Vuwt= Vb; and under typical operating li45J-
Iy, Murgatroyd' s (Eq. ( 13.5)) was found to hold tor the casc_ol
SCLC as well, with an eflccti ve mobi lity that is a function of both earner mobah-
ties [ 148).
Another issue that can be cl ari fi ed with the aid of numerical simulations is that
of the recombination profile. Malliams and Scott l l 451 have found that recombi-
nation takes place closer to the comact that injects the less mobile carrier, regard-
less of the injection chamctcristics. In Figure 13- 12, the calculated recombi nation
profiles arc shown for an OLEO wit h an ohmic anode and an injection-limited
cathode. When the two carriers have equal mobil ities, despite the fact that the
hole density is substant ially larger than the electron density, elccuons make it all
the way to the anode and the recombi nation profile is unifom1 throughout th
sample.
13.5.2.3 Experimental Studies
There have been numerous studies of the electrical anti emission propct1ics of
conjugated polymer-, small molecule-, and molecularly polymer-based
OLEOs. The cwTent-voltagc and radiance-voltage chamcten sttcs have been mea
surcd as a function of thickness of the organic layer, tcmpemture. different metal
e lectrodes, etc. in an attempt to understand the device physics. A maj or factor in
hibiting progress is puri ty of the organic: impurities that arc incorporated dur-
I 3.5 D(vice Physics
441
ing chemical and processing can severe ly influence electrical properties
and cause artal acts m the OLEO characteri stics. As a result, one has to be crit ical
when d_ata obtained from di fferent materi als, especially in cases where
there as no extensive and systematic chamctcri w tion. In this section we use re-
sults from PPV and its derivatives, which have been avai lable for nearly a decade
and are undoubtedly the most systematically studied materials for OLEOs, to il-
lustrate the progress in understanding OLEO physics.
In a paper in 1994, Parker 1149 J presented a detai led study of device
111 diodes, which helped establish the fuLLy de-
model of Ftgure 13-4. The observation was that, in devices
W_tth vanous MEH-PPV layer thicknesses, the c urrent scaled with the applied elec-
tnc than the indicating that there is no substantial charge ac-
mstdc the devtcc. Th1s conclusion was independently supported by ca-
pac_Hance-voltagc measurements. A second observat ion is that, in devices with
vanous anode/cathode combinaaions, the c un-cnt is contmlled by the smaller of
two bam_crs, but the device e fficiency by the larger. Both cun-cnt anti effi-
Ciency were to scale with the coaTcsponding bm-rier heights according to the
energy between MEH-PPV anti the meta l e lectrodes. indicatinn
.there. IS no subst<m.tia! pinning of the Fermi level of the p<llymer at the inte;
Thts cnncluston 1s 111 <1grccmcnt with results from e lcctmabsorption studies
the Los Alamos group 1961. who found the bui lt-in potenti al in MEH-PPV
dev1ccs to s..:alc wi th the tlilTercnce in the work function of the two metal e le-
ctrodes. comparing th<: magnitudes of the currents in hole-only and e lcctron-
devaces. both Corricrs were found to be mobile. Fi nally, the fact that the elec-
tnc field dependence of the current resembled that of Fowler-Nordheim tunnelino
.to the assumption that device chamctcri stics arc determined by charge
Jectaon. An attempt to quanttly, however, produced a tunneling prefactor that wa.s
several orders of magnitude too low.
This_ conc!usion Wi.ls challenged by Blum ct a/. 111. who studied the electrical
propcn1_cs_ ol _ monopolar devices in a similar PPV derivative. When ITO is used
as the (lllJCCll ng) anode in hole-onl y devices. the observed electric licld and t hick-
ness dependence of th.e current resembles that or a space c haft,;c-Iimited cunent.
conduston W<IS dr.twn that it is not lhc injection, but rather the in-
tnnsac mobility of PPV that tlctennines the electrical char..tcteristics of
hole-only dev1ccs. A (zero hole mobil ity equal to 0.5- 10-fl cm2 y - 1 s- was
Electron-only dcv1ces with Ca electrodes were also studied and their
eleclncal characterist ics were_ found to. be limited by the presence of tr..
1
ps in the
bulk of PPV. Fowlcr-Nortlhcun tunnchng also ruled out by A. Campbell et
[ 1501. who mcasun.:d th<: currclll -volt .. gc, unpedm1c<: <llltl
11'0/PPV I A: I OLEOs. Instead, the datu we1-c modeled using a spucc charge-lim-
Ited theory With an cxponenttal li"<IP di stribution, support ed by the fact that the
current was a power law of the applied volta"e. An
hole mot
11
t
1
ty b ,_
t 10
- (l . 1 O - H ' - 1 I "' C
ween anu .5 10 em- V s was cxtmctcd.
Recently, ct _al: 115 11 have shown ahat fur ahe <111;
1
Jysis of the current-
voltage chara.ctcns_t1cs ol layer OLEOs, it is of fundamental importance to
properly uccount lor the bUllt-m potential. The elt.:ctrical charm:lerist ics of MEH-
442

u
g

>.0
-lt

-s
.....
/3 Tile Chemistry, Physics allCI Engineering of Orgtmic LiJ:III-EmittinR Diodes
(a)
A
"
10"'
...
Ca

AI
0 Au(98 nm)
0
Au (168 nm) .. ..
0
toML--....n.- --'-- --'-- - ..J
0 200 400 600 KOO
((V w " V -..YL)
0
s ((V/cm)o.s)
10'
lcf
10'
1

..

..

(b)
.......

13-13. Currcm-vollagc llala from MEH-PPV-ba.'iCd OLEOs Au and v:uious
ploucd acconling 10 Eq. (13.5); (b) lhc tjUanlurn for the wuh
and Ca cathodes The S(llid line rcprcscrns U1c maximum eJTicicncy of 2%. RepnKluccll wtth pcmus
sion from (151J. Copytighl 1998 by the Amcric:m Physical Society.
PPV-based diodes with Au anodes and various cathodes were measured and ana-
lyzed according to various proposed mechanisms. When the is plotted a
function of the applied bias, it has a form that suggests trap-hmtted conducuon.
However, when the data are rcploucd as a function of the true voltage
Organ
.,c (V. rV ) they have the fonn of a SCLC with a field-dependent mob1hty
"1'1' l>t -6 2 I .-1
of Eq. (13.5) (see Fig. 13- 13). A zero field rnobhty Jto=0.32 1_0 em_ v- s
and a characteristic field
0
=38 kV/cm were extracted. ln devices wllh a Ca
cathode, the electron current is also space charge-limited and the device c_llicicncy
reaches its maximum value. Using a similar analysis in electron-only dev1ces, Bo-
zano et a/. have shown that electrons in MEH-PPV have a field-dependent
mobility which approache!. that of holes under typical_ oper.tting .
From the <tbove theoretical, numeric<tl, and expenmcnlal stud1cs, a consistent
picture of single-layer polymer OLEO operation. h<ts emerg:d. polymer is de
pletcd of carriers at low voltages, with a poss1ble excepuon 111 the case where
chcmic<tl with the electrodes cause doping L41. The device current and
efficiency arc primarily controlled by the small er and the larger_ barrier.
respectively, bot h of which scale according to the dtllercncc
the organic JJOMO/LUMO and the electrode For values of
the barrier heights (less thm1 0.3-{).4 eV), thcmuomc emtsston supphcs the organ
443
ic with SCLC and the clcl:trical characteristics arc limited by the currier mobilities
in the organic. The extent to which carriers (especially electrons) become trapped
is still a mauer of debate. For larger barrier heights, high electric fields and/or
low temperatures, tunneling becomes important.
13.5.3 Multilayer Devices
The presence of internal in multilayer OLEOs greatly complicates the bi-
polar current problem. As charges accumulate at the organidorganic interface,
they cause a redistribution of the electric licld inside the device, which in tum in-
fluences charge injection and transport. Based on chemical kinetics arguments
(1 521 and numerical simulations (153 J, the Mm"burg group has shown the impor-
tance of these internal b<t rricrs in controll inn the device curre111 and eiTiciencv
0 .
Another complication in understanding the multilayer device physics arises from
the fact that it is very dillicuh to correct the experimental data for the built-in po-
tential, si ne!! the elcl:lri<.: licld distribution inside a multilayer dcvke is not known.
This was demonstrated by L Campbell '{ a/. ( 1541. who measured the electric
field distribution in a trilayer OLEO using a spectroscopic version of the eltttro-
ahsorption technique.
On the experimental front, Burrows and Forrest L 155] have measured the elec-
tric ticld and thickness dependence of the <.:urrent and radiance from bilayer de-
vices with various HTL<i and a.'i the EfL. The data were analyzed in tem1s
of tmp-limitcd transport in the Alq
3
l<tyer, with the assumption that the voltage
drop across the HTL is negligible. However, this assumption was challenged by
Vestwcber and Riess ( 1561 and Giebcler eta/. 1157], who demonstrated that HTL
plays an important role in determining the cfliciency of bilayer OLEOs.
13.5.4 Electrochemical Cells
The model of Pei el a/. L I 041 is based on the notion of clcctrochcmical doping of
the conjugated polymer upon application of an eleclric field. As the polymer is
higWy conductive in its doped state, it fonns ohmic contacts with the metal elec-
trodes leading to maximum etliciency. In an alternative, electrodynamic model,
proposed by de Mello et a/. (1051. the application l>f an cltttric lield in an OLEO
doped with mobi le ionic charges (in the context of this model the tcnn electro-
chemical cell is not appropriate) causes ionic charge redistribution throughout the
bulk of the sample, until the local cltttric licld is cancelled. Since the conccntr-
tion of the ions is usually quite lar<Je (in the order of I 0:?
0
<.: m '>. small ionic nm-
tions arc adelJUatl! 10 create large electric liclds. Contrary 10 the elcctruchcmical
mech;mism that results in the creation ()r a heterojun<.:tion in the hulk of the sam-
ple, the ionic mechanism causes the voltage across the sample to
drop at the <.:ontacts, leaving. the cltt1ric licld in the bulk to he ncar zero. As a re-
sult of the large clcctri<.: liclds at the contacts. clc..:troni<.: charge injcdiun is
444
2
c
:I
"0

Oi
E
0
..:..
::-
"iii
c::
..
"0

t
..
(.)
13 7111! Chemi.wy, Pllysic.v am/ ugiul!eriug of Organic Light-Emitting Diude.v
Anode Cathode
r----,r----.--::-n---r- -....,...--.. 1.0 1.0
0.8
0.6
0.4
02
0.20 0.40 0.60 0.80
Normalised distance
0.8
z
0
3
!!!.
._
..
...
0.6 _g

"'a
0.4"-:;-
!!t
0
:I
0.2 "0
g
it
Figure 13-14. Spalial profiles oC
lhc .:arricr dcnsilics and the recom-
bination for of width
100 nm (dolled lines) and 10 IJIU
(solid lines), for e4ual electron and
hole mobi li1ics. Reproduced with
permission from 1105]. Copyright
IW!! by the Physical
Society.
tated (thus the clliciency increases), while in the bulk of the sample the electronic
chaf'Je motion is lliffusive. Numerical si mulations for llcvices with e4ual electron
and hole mobi lities reveal a recombination pmlile with a maximum at the middle
of the sample (contrary to the case of ordi nary OLEOs; see Fig. 13- 12), and a
width that depends on the sample thickness. In Figure 13- 14, recombination is
shown to take place in a thin zone in the middle of the I 00 1-1111 thick sample. 'The
electrodynamic model is very successful in the description of the steady-state and
transient electrical characteristics of the cells, however, the prclliction of a uni-
formly low electric tield in the bulk of the sample is at odds with a previous ex-
perimental observation L 15M 1.
13.5.5 Microcavities
Microcavity effecLc; are based on the fact that the mte of spontaneoul> emission is
proponional to the density of optical final states, therefore the rate can be modified
both spectmlly and spatially in microcavity structures. This phenomenon has been
used by seveml groups to increase the efficiency and control the color of OLEOs
[ 159- 164 1. Tsutsui et at. [ 159 J have demonstrated a decrease in the bandwidth of
the emission spectrum, accompanied by a change in the llirectionality of the emis-
sion towards the forwarll direction in a multilayer small molecule OLEO with a
highly reflective Ag anode. The same effect was observed in single-layer MEH-
PPV structures 1 160) . The Bell Laboratories group fabricated microcavitics by de-
positing small molecule OLEOs on a llielcl:tric stack mirror and demonstrated con-
trol of the emission color I 16 1 J and an enhancement in the cflicicncy [ 162). The
latter was achieved by increasing the net amount of (spectrally and spatially inte-
grated) emitted light and controlling its directionality (sec Fig. 13- 15). Reco.: ntly,
Neyts 1 1651 has outlined a frameworl-. for numerical simulations of microcavity ef-
fet:ts in OLEOs.
Non-Cavily Spectrum (Oj
500 550
Wavelength (nm)
13.6 Degradation
600 650
13.6 Degmdmiou 445
l<lgun: 13-15. Emission spectra
al various angles from the
of a micrucavity
OU:D. The solid line is lhc nonc;lV-
ily al 0" from an
OLEO on 1he same substr.ttc. Re-
pmdtu.:cd with p.:nnission from
11611.
One of the most crit ical issues for the commerciali zation of OLEOs is their opem-
tional and storage stability. Much progress has been made in identifying and at
least pattially eliminating some of the mechanisms of degradation and fai lure.
Runni ng lifetimes arc now regularly repotted in the mngc of tens of thousands of
hours, but further improvements wi ll be required before OLEO displays become a
truly pervasive tet:hnology. In this section we present a summary of the degrada-
tion mechanisms that have been explorell to date. and the means which arc sug-
gested to overcome them. Some modes of failure occur gmdually due to some
chemical 1\!action that reduces either charge injection rates, charge mobility or lu-
minous efficiency. In such cases it is cuswmary to quote the lifetime to half
brightness under some drive conditions. e.g. constant current or constant voltage
ac or de. In other cases, cata-;trophic failure occurs and there is a clearly defined
lifetime.
It Wa'i recognizell very early in the study or PPV anll its derivatives that photo-
oxidation leads to loss or luminescence enicicncy ( 166. 167]. an example of gmd-
ual degntdation. By the use of in-situ infra-red spectroscopy I 168, 1691 it wa..;
shown that the mechanism involves clcavago.: of the conjugated chain at the vinyl-
ene linkage. Fwthennore, singlet oxygen is implicated as the reactive intennediate
[ 1701. It is created by energy transfer to the ground-state singlet from the excited
triplet state of the polymer. electrical cxci tution of the polymer can
triplets directl y and therdorc mllfC rcallily th;m photo-excitation, which involves
intersystem crossing. 011c might uxidation to occur even more readily in an
opemting OLEO llevicc than in an ill uminated fi hn. Ckarly, excitation of the
polymer cannot be avoided, si nce this is the basis of its emission. The only re-
coun.c is the complete elimination of oxygen by suilablc encapsulation of the llc-
This is also a reason that most workers perform llevice anll test-
446 13 71te Chemistry, Physics cmd Engineerillg of Organic Light-Emitting Diodes
ing in the inert atmosphere of a glove-box. However, it has been shown that the
ITO anode itself may act as the source of oxygen for the oxidation of the organic
layer ll68 j. The use of a conducting polymer layer as anode on top of the ITO
greatly reduces the oxidation rate associated with this mechanism (82, 83, 171,
172].
Additional chemical stabili ty can be given to PPVs by substit ution at the vinyl-
ene carbons. Thus, CN-PPV and PPV-DP are more stable than their parent poly-
mers (173]. Caner et at. I 172] showed that a r.mdom copolymer of PPV contain-
ing non-conjugated segments is considerably more stable to phowoxidation than
the fully conjugated polymer. Of course, the electrical and optical properties are
also altered by these substitutions.
Photooxidation is also observed to reduce the photoluminescence of AIClJ
I 174]. However. the details of the chemical pathway is not so thoroughly ex-
plored for this material.
Black-.\pot formation is a phenomenon familiar to virtually everyone who has
studied OLEOs L 175). Black-spots have been most thoroughly studied in Alqr
based devices, and have also been reponed in M EH-PPV [171). In this mode of
failure, circular regions which arc non-emissive in EL (see Fig. 13-16) stan to
grow at random sites over the area of the device. PL excitation, however, shows
that the spots arc s lightly brighter than the unaffected area I 176]. Close inspec-
tion, using optical and e lectron microscopy, frequently reveals a defect at the cen-
ter of the spot consisting of a )A-sized panicle which penetrates the cathode metal
layer to form a pin-hole (seen in optical transmission). Nomarski images show de-
(a) 2 min (b) 10 h (c) 20 h
(d) 30 h (c) 40 h
Figure 13-16. EvoiUiiun of spot fur111a1iun tn air. in :111 ITOITI'O/AI4JMg!Ag tlcvicc. 1lu: si1.e
of the cmis:.ivc area is 2 tnmx 1.6 tntn. Rcpruou.:c<.l Wtlh fmm 1176).
13.6 447
formation of the cathode (bt;.stering) over the non-emissive region. Black-spot
growth is much more mpid in the presence of small amounts of water vapor (1 77,
178j. These observations lead natur.1lly to the following scenario for the loss of
emission I 176). In the fabrication of the device, particulate contamination results
in shadowing during deposition of the cathode layer, providing a pathway for the
penetmtion of a reactive species, which then reacts at Lhc intert'ace between the
electrode and the organic layer, to tom1 a barrier that prevents electron injection.
Over the course of time, more reactant penetrates and diiTuses mdially away from
the pin-hole, reacting to produce the observed circular !-ipols. The bulk of the or-
ganic film is unatTcctcd and continues to photoluminescc - more brightly because
the exci tons cmuwt t-c<tch the quctu.:hing mctul :-.urface.
The chemistry occurring a t the Alq.Jcathcxle imcrface has been explored by a
group at the Univer.;ity of Connecticut 1. They suggest a reaction in which
water releases the hydroxyquinolate liganli, which subsequently polymerizes in
the presence t)f oxygen wit h the release of water. Thus, water is a catalyst for this
reaction and oxygen is consumed. An alternati ve mechanism, involving the elec-
trochemical oxidation of the cathode. has been proposed by Aziz el a/. 1179 j. Ki -
netic stuliies of individual black-spot growth show that their radius in-
creases a:-. the square-root of time. as expected for the r..tdial diffusion of a reac-
tant which is consumed ill the growing circumference of the circle.
Many OLEO devices exhibit a rclutively rapili dl<lllge in emission during the
fir.;t minutes to hours of operation. In a few cases, for exilmple ITO/PEOT-PSS/
PPV/Ca, the brightness may increase ( 1721: a not unfavorable situation which one
might term device bam-in. It was suggested, for this device, that oxidation of the
calcium catholic by residual oxygen in the polymer formed a barrier layer which
results in more balanced charge injection. In the vast majority of cases, however,
the brightness and current (at constant voltage) arc decreased 183(. The full details
of the mechanism involved in this juveuile aging remain to be detennincd, but
there is growing evidence that ion-migr.1tion is involved. Under ac drive condi-
tions devices :-.how significantly slower <tging than under lie drive (I 03. 1 X 1 j.
After aging a diudc (for c"umplc ITO/PV K/ Alq dMg : A g) under de condi tions.
some licgrcc of rccowry is observed on 'resting shorl-l:ircuitctl. or under revcr..e
bias I The time scale (lens of min) anli rhe voltage dependence t)f these
changes is consisted with ion mobilities in orl!anics. The ultimate ellcct of the
mobile ions is not yet known. In the simplest c;se, they will merely produce a bi-
polar layer at the clectrode(s). which opposes the applied electric field and re-
duces the current. They may also act as tr.1ps, whereby positively charged cations
tmp electrons ao; they arc injected from the cathollc, and vice versa. Thus, the
charge mobility near the electrodes is da:reased <llld the injection r.ttc reduced. Fi-
nally there <tre two modes of clcctmcheruistry which may m:cur. r:irst, the ion
nmy retain its dt<trge state while the pol ymer i:-. reJuced at the cat hode or oxi -
dizell ill the anode. This identical to the mec.:hani:-.m which occurs. by design. in
LECs (sec Section 13.3) and results in improved injection propcl'lies. Second. the
ion itscl r may be oxidized or rcJuced. producing perhaps a neutral met<tl <llum
which llcposib on the cathode (sec below) or perhaps a species which
builds up pressure to defmm or delaminate the device (179 J.
448
13 TI
1
e Chemistry, Plrysics wul El1gi11ecriug uf Orgauic Liglu-Eluittiug Dicxles
A frequent and catastrophic failure of OLEOs is electrical shorting, ma7
occur not only in the early opemtion of the device, t? defects m
cation, but also after many hours of stable opcmuon, smplymg a mechams':"
whereby shorts ' grow' to bridge the anode and cathode. The of thss
process is not yet determined; it has been suggested that the nugrats?n of I_n cat-
ions to the cathode, where they arc reduced to neutral In, may result m the
tion of metallic filaments which initiate the short [ 171]. The role of ITO ss sug-
gested by the observation that conducting polymer anodes, even with IT<? under-
neath, are found to be much less prone to shorting, both in polymer {82,
83, 171) and in small molecule OLEOs [ 1831. In some cases, tor ex-
ample on the thickness of the cathode, a short may self-heal by meltsng the sur-
rounding metal to isolate itself electrically (168 J.
Using a stable dopant as the emissive dye has been shown to greatly enhance
the lifetime of small molecule LEOs. Rubrene doped into the Alq_, electron_
port layer II H4l or into the TPO hole tr..tnsport 1_1 HS I extend the
by an order of magnitude. Similarly. sn Alq_, hm. _ a heneh-
cial clftXt {45). The likely mechanism rcsponssbh: lor thss phenomcnl>n ss the
dopant acts as a trap for the exciton and/or the charge. Thus, ol the
host matrix are in their excited (cationic, anionic or cxcitonic) states lor a_ smaller
fraction of the time, ami therefore have lower probability to undergo chemsstry.
Each of the mechanisms described in this section. even though they may not
be full y elucidated, suggest means of extcn_ding_ operational _ li feti me
OLEOs. In addition to the obvious schemes ol dcssgnmg and selecting most
stable materials available and providing completely hcnnetic the
following techni4UCS have been proved to be useful. Mini mization or
contamination during the fabrication of the device not onl y prevents the unmed_s-
ate formation of shorts but it also ensures the deposition of organic and metalhc
layers with the maximum possible integrity [ 184). Thus, arc fewer hvt-lpots
where high current density leads to runaway there arc fewer
pin-holes in the cathode to permit the entry and dsffusson of oxygen _and
water. All materials used should be as pure and free of contanunam_s as
In particular, ionic impurities can (and wi ll ) migrate to the electrodes, changsng
the electrical chamcteristics. Other contaminants may act as tr.1ps, or undergo d cc-
tro- or photochemistry to gcncmtc traps. Lastl7, it is usually helpful to de
vices in the cleanest, driest environment posssblc: a glove-box for the spmnmg of
polymers and a good vacuum system for . the thermal deposition of small _mole-
cules. By combining such attention to detasl s_nany groups now
that it is possible to achieve sevcml tens ol thousands ol hours ol operation a1
useful levels of brightness.
1 J. 7 Application of OLDx iu Flw-Panel 449
13.7 Application of OLEDs in Flat-Panel Displays
'The development of a successful display technology requires several addi tional
considemtions beyond those discussed in the previous sections. The li ght-emitting
clements must be integmtcd with the electronics that interface to the source of the
video signal, and the entire module must be packaged in a way that ensures the
highest possible image quali ty in a fonn-factor that is compatible with other: as-
peelS of the system design and is comfortable for the viewer (186). The engineer-
ing design cri teria that enter these requirements include the contrast ratio of the
display. its accessible color gamut. resolution. the total power consumption includ-
ing both the OLEO aiTiiY and the drive electronics. she weight and thickness tak-
ing into account the encapsulat ion and the electronics. In addition, to all of this
there is one over-riding factor: the manufo.tctur.thility of the display module at a
competitive
In this secsion. we provide a brief introduction to the lield of uisplay engineer-
ing and the human-factors issues whi ch dictate display design. We then assess
how OLEOs measure up to the criteria necessary to achieve a commc::rcially suc-
cessful uisplay technology. But first, we take short detour to lay out the lan-
guage used by display engineers and to provide a means of translating from the
scientilic units th<ll we have used up to now.
13.7.1 Display Engim .. -cring Units and Conversions
In ortler to compare the pcrfonnance of different materials and device structures it
has been most convenient to express the nllliated power in tenns of watts and the
color characteristics in tenns ur the spectral emission. However, the human eye is
not a mdiometric detector and its color sensitivity is not achieved wi th a built-in
spect.umcler. Rather, its response (here we consider the photopic or bright-light
response, as opposed to the scotopic response of the dark-adapted eye) is deter-
mined by three sets of cells in the retina calico rolls. Each set of rods responds to
different wavelengths of li ght in three overlappi ng bands: blue, green, and red
peaking (for the hypothetical iclt'ctl ohscsvcr ddined in 1931 by Lc Commission
Intemationale de I'Edairagc- CIE 11871> at 446, 555, and 599 nm, respectively.
and approximately 60 sun wide (full width at half-maximum). TI1e green rods arc
considerably more sensiti ve than the red and blue and therefore we arc more sen-
sitive 10 lighl in 1he ccmcr nf the optical spectrum.
TI1c conversion of radiated power (P in watts) to luminous flux (F in lumens)
is achieved by consitlering the variation wi th wavekngth of the human eye's
photopic response. Then the spcctml power from the source (P;. in, for example,
W/nm) is convoluted with the relati ve spectral response or the eye ( V.A tabulated
by the CIE) accoruing to:
450 13 The Chemistry, Physics and Ettgineering of Organic Liglu-Emittitlg Diodes
( 13.6)
where Km is a numerical constant approximately equal to 680 lm/W and the range
of integration is from 380 to 780 nm. The luminance of a source (for example, a
pixel of an OLEO panel) is its luminous flux per unit area of emitting surface.
per steradian of solid angle in the direction of observation. One lumen per stem-
dian is one candela. Therefore, luminance has units of candelas per square meter.
The ClE color coordinates are obtained by a similar procedure, repeating the
convolution for each of the tabulated color matching functions that describe the
response of the ideal observer's blue, green, and red cones (bA.. 8A. r;.).
Z = lP;.b;_dJ..
/ .
( 13.7)
then the CIE x, y coordinates arc x = XI(X+)' +Z) andy= )' f(X+ Y+Z). The third co-
ordinate is simply l - x- y and contains no mlditional 111formation. The x and y
coordinates arc conventionall y plotted on the familiar 1931 CIE chromatidty di a-
gram, with green (large y) ncar the top, red (large x) on the right and blue (small
x and y) ncar the origin at the bonom left. It is that. in the conversion
from wavelength-dependent powcr tu a pair of cooruin<tes. c;onsiuerable spectral
information is lost. As a result, it is possihlc for sources with widely dilrering
spectra to have identical color coordinates.
13.7.2 Pixels, Patterning, and Drivers
OLEOs are being considered for the enti re mnge of display appli c;utions, from the
simplest backlights and on/off indicators to the highest resolution screens lor pre-
sentation of computer gmphics. Although OLEOs, in principle, can he applied in
all these arcus, in practice cuch has challenges which must be overcome, not the
least of which are well -suited alternative technologies.
As backlighLs for liquid-crystal displays. OLEOs have the great advantage of
facile deposition over large areas as extremely thin films. However, their perfor-
muncc in tenus of power elTiciency is marginal when compared with the extant
technology of fluorescent tubes. The highest reported OLEO efficiencies are in
the order or 20 lm/W, for a monochromatic green source [188 ], which should be
compared to a typicul white nuorescent tube backlight at about 90 lm/W. In the
Iauer the phosphors arc sclcc;tcd to match the color lifters used in the lilJUid crys-
tal display. Therefore, even taking into account the losses in the diffuser, which
spreads the light from the tube evenly over the area of the screen. the lluoresccnt
tube has a significant power advantage. The applications which would benefit
most from the light weight and thinness of an OLEO backlight, muncly portable
devices such as personal orguni.ters and laptop computas, urc precisely those in
which power cunsumptiun and baucry lifetime an.: at a premium. 1-lenc;c, <1ddi-
/3.7 Application uf OLJ:.Vs in Nat-Pa11el Dilplays 451
tiona( improvements are needed in efficiency to make OLEOs more competiti ve
as backlights.
Indicator lights, fixed paucm, and segmented displays arc applications which
have been suggested for OLEO deployment. Manufacturers of automobile compo-
nents have shown interest in OLEO indicators for the dashboard, where the pri-
mary considerati ons are 1hosc of cost, form factor, b1ightncss, and stability over a
wide r.mge of ambienl condi ti ons. Power consumpt ion is not particularly critical.
The possibility of molding a thin light into a curved dashboard is attractive.
Continuing up the hiemrchy of display complexity, there is a vast market for a-
numeric displays such as arc used in pugcrs, cellular phones, and instrument pa-
nels, and the smull gmphical displays of personal digital assistants (PDAs). This
is being viewed, increasingly, as an area in which OLEOs have an excellent
chance of competi ng with the LCD panels that dominate today. The OLEOs
would be configured as a passive mallix array. The pixels of a passive array arc
deli ncd by the intersections of row and column elec;trodcs (sec Fig. 13- 17). They
arc driven by rupidly ami seliUCiltially enabling one row at a time and writing
dala, l'ht the column drivers. to the desired pixels in that row. If there arc N rows,
each is on for a fruc;lion liN of the time, and must therefore be driven to a mo-
mentary brightness N times greater than the desired average. Because of their
sharp threshold for tum-on [I X61 OLEOs offcr signific<tnlly bclter readability than
rcllcctiv..: LCDs in most indoor lighting nmditiuns and comp:trable power con-
sumption to backlit, transmissive LCOs. Mllst of the portable applications under
consideration are occasional usc' where power consumption is less of an issue.
ln order to succeed at lhe lower end of this market (pagers and cell phones)
OLEOs will need to dcmonstmtc a cost advantage over the competing technolo-
gies. At the upper end (POAs and palm-top computers) resolution, pixel COUll!,
and color arc of prime impo1tance.
It is useful to consider the li miting facLors to the pixel count in a passive array.
Since the peak brightness, and hence the peak current , arc N times greater than
the avcr..Jgc, the OLEO pixels are being driven well past their optimum condition
for power efliciency. Moreover, in order to avoid llicl-er, each row must be au-
dressed at lcust 60 times per second. Titcrdorc the row drivers must switch on
and off in a time less than 1/60 N seconds. The capaci tance and the resistance of
the electrode lines become a significant fuctor. Both depend on lhe length of the
row, i.e. upon the number of columns. Rapid switching and high currents can be
achieved in properly designed drivers, but only at the c;ost of increased power
consumption. lt is possible to divide the screen into four subarmys, !hereby halv-
ing the number of both rows and columns addressed by cuch driver.
Organic layer(s)
Subs trate
13-17. Schcnmlil: nf a snmll
Jl<ll1iun uf Jlassivc malrix pixel mmy.
Ead1 Ju>od <.lclinc<.l by 1hc uvcrlap
uf nne mw ;m<.l uuc cuiUIIIII ckc-
'""lc.
452
13 The Cllemisrry. Physics cmd Engineering uf Orgcmic Ligllr-Emiuing Diucles
An additional limit to the size of a passive array relates to the current which
flows in an OLEO when it is under reverse bias [ 189). When a given pixel is
turned on in the array, there arc many possible parallel paths for the current, each
involving two diodes in reverse bias and one forward. Hence, as the. of
rows and columns increases, there is a higher level of background cm1ss1on lrom
non-selected pixels that limits the contrast ratio of the array. As a result, the con-
trast degr..1dcs as N increases. .
The upper limit for passive matrix OLEOs thus depends on many to-
eluding the reverse current of the _diodes, the curre?t delivery of the row
the roll-off in OLEO power effic1ency, and the bnghmess and contrast rauo re-
quirements of the application. The practical limit is probably less than VGA reso-
lution (480 rows by 640x3 columns, where the factor of 3 reflects the RGB
pixels for color) for power-sensitive portable applications. However, such
emtions are less important where a wall-plug is available and one company m Ja-
pan (ldemitsu Kosan (190 J) has demonstrated full color television using passive
OLEO arrays. . . .
The minimum size of the monochrome pixels (we cons1der color m Sectton
13.7.3) that can be fabricated using OLEOs is dictated primarily by t_he ability to
pattern the electrode which is deposited on top. OLEOs arc not sulfic1ently robust
to withstand the normal processes of photolithography. Among the schemes
which have been suggested for high resolution paueming is one in the
stratc is pre-patterned to provide its own shadow mask l i'J I I. thts means, ptx-
cl sizes down to 300 Jl have been demonstmted, and a lower lumt of about I 00 Jl
is estimated.
Lastly in this section we consider active matrix-driving schemes. Here an elec-
tronic switching circuit is located at each pixel in the array and used lO tum the
OLEO on or off. During each fmmc time, the rows are enabled and the column
data written to open or close each switch and hence the OLEO in
san1e stale throughout the cycle, leading to optimum power effic1ency. Unhke
LCDs, which arc voltage-driven devices and store charge like a OLEOs
are current-driven devices and must be continuously supplied w1th charge. LCDs
can be switched with just one tr.msistor, but OLEOs require at least two (192).
The simplest scheme is shown in Figure 13- 18. One transistor (T I) is used to set
the voltage on the storage capacitor (C), which detennines
transistor (T2), in series wi th the diode, is on or oil'. Some power 1s d1ss1pated m
the switching transistors, as well as in the row and column drivers, but the ovcmll
power consumption is less than for passive driving in _all but atTay.s.
Power consumption can be reduced even further by usmg m
the pixel-switching circuit, but at the cost of added complexity and area
devoted to these non-emissive elements. An additional advantage ol acttve addres-
si ng is that all of the electrode pattcming is done on bcf?rc the
OLEO layers are deposited. The top clcctmde (the cathode m Ftg. 13- 11:!) 1s com-
mon to the whole army and can be deposited through a large shadow mask as a
blanket coati ng without the need for additional pattct.ning. . .
Active matrix drive schemes make OLEOs potenttally compcuttvc over a much
wider range of appljcations. TI1ere is no longer a strict limit on the number of pix-
13.7 Applicmiun uf OLJ::Ds in Flm-Punel Displuys 453
l' igun: 13-U!. of a simple pixel cin:uil for ucl ivc 3tklressing
of an OLEO array. For a CO(()( display of N ruws and M columns, lhis circuit
must be reproduced NxMx3 times.
els in the army. Display resolution up to at least SXGA ( 1024 rows by 1280x3
columns) has been The cost of an active matrix display is dominated
.the electronics. Both single-crystal silicon chips, where an OLEO microdisplay
1s. directly on top of the circuitry 11931. and polycrystalline silicon (p-
SI), lor d1splays above about 5 em diagonal (1941. arc being explored. The form-
er, with pixels each about I 0 in size, is intended for application in personal
head-mounted viewers in which additional optics magni fies the screen image and
it on the retina though it were at normal reading distances. Polycrystal-
hnc S1 opens the of relatively large areu displays for usc in laptop
and llat-pancl televisions. In these applications the advantages of
OLEOs arc their light weight and small thickness, the inherently wide viewing an-
gle, and the fast response. which eliminates smearing of the in rapid action
motion pictures. It remains to be seen whether other considemtions, such as cost,
color gamut, brightness. and ellicicncy, wi ll weigh in favor of OLEOs and against
competing technologies.
We have mentioned extremely small displays which require magnifying optics
to view. Next we consider the issue of maximum screen size. The deposition of
OLEO pttnicularly by evaporation but also perhaps by spr.ty painting
from solutton. IS mherently a lar<JC area process and OLEOs intended for use as
backlights have been malic up to several tens or centimeters across. There is,
however, a cri tical issue to consider, namely that the vast majority of the electrical
power consumed is dissipated as heat. The heat generated is proportional 10 the
areas of the display, amounting to a few walls in a reasonably efficient device
10 em across, at a luminance of 100 cdlm
1
. However, the removal of this heat is
limited by the transfer to the sutnJUnding air and by the convecti ve flow over the
or the display. lt was shown (194llhat 1he center of a 5 em display m:.ty
nse by about 5"C at this luminance, but a 20 em dis ploy heats up by 19 ''C. Some
active mcat1s of cooling would be required for larger displays, but even then one
must consider the eiTecl of nmning a kW room heater while watchinn lane-screcn
N o
13.7.3 Color
TI1e upper end or the dil>play market requires full color capahility, whether the in-
tended usc is fl>r video gmncs, television, computer monitor.. or graphical design.
454 13 111e Cllemiltry, Physics and of Organic ligllt-Emiuing Diodes
OLEOs are obviously able to prc:x:luce light with virtually every color in the CIE
chromaticity diagram but the optimum inexpensive method to manufacture a
pixelated full color display is not yet established. The difficulty lies in pauerning
OLEO materials with standard photolithographic methods. Five schemes to
achieve color have been suggested, as ill ustrated schematically in Figure 13- 19.
The first and most preferable of these is direct patterning of the OLEO itself.
In mult ilayer devices, this may only require patterning the emiuer layer, with
common hole and electron tr.tnsport layers. For vacuum evapor.1tion of the organ-
ic materials, the obvious technique is shadow-masking which may, wi th extreme
care, produce feature sil-es to under 100 1-1 result ing in color triads somewhat less
than 300 For the solution coating of polymers, screen printing and ink-jct print-
ing techniques arc being investigated ] 195, 196 J. One may estimate the minimum
pixel sire, based on comparison with current ink-jet priming technology, at
roughly 50 1-1 but there is clearly room for improvement in manufacturing, as OJr
posed to desktop, printer.
For smaller pixels, alternatives to patterned cmillcrs arc under investigation.
Conceptually, the simplest of these is to design the OLEO pixels to emit white
light and then separately pallcrn fi lters to pass red, green, and blue [ 197]. The
emitting pixels arc now delincd by the pallcrning of the clcctmdc, the OLEO
stack is unilorm across the array ami the additional lithography is done only on
the filter materials, a tcchnolllgy which is well established in the LCD industry.
The primary disadva111age of the color litter approach is that at least 2(3 of
emiued light is absorbed in the ti tters, with the consequent loss in overall power
efficiency.
The fluorescence color converter technique [321 can, in principle, overcom..
much of this power loss by replacing the white light erniuer with a bluc-cmiuint
organic stack, and the absorbing fi lters with green and red lluorcsccnt dyes. Thus
when a green pixel is desired, the OLEO underneat h is turned on and the blu
Patterned emitters
Microcavitles
Color fillers
Fluorescent converters
Stacked
B G R

I
13- 19. SdJclllC.' lu m:lucvc red.
:oml hluc prxclaliun for fu ll culur OLEO dis-
play p:onds.
13.7 Appliattion of OLEOs in J-1m-P<1nel Displuys 455
light is absorbed in thl! converter which emits green; si milarly red. Light from the
'tblue pixels passes directly to the viewer. 111e color conversion approach is not
completely cner<tiY efficient. Apart from the imrinsic energy loss which occurs as
a result of exchanging bl ue photons for green or red ones, 01hcr aspects or the
process are less than perfect. Photoluminescent quantum yields fall short of
100%, especially in dyes ;..md dye combi nations which arc ucsigncd to be highly
absorbing at the primary, blue w;Jvelength [19S ]. The lluorcsccnt emission is om-
nidirectional and some of the light is trappcu by mult iple rellcction inside the dye
layer and the substrate. There is a growing interest in improving the materials
which might be used in lluorcsccnt convCJters. In addition to laser dyes ( 199 J,
which by design have high PL yields and arc available wi th virtually all emission
wavelengths in the visible. conjugated polymers arc being examined [200). The
latter arc extremely absoliling. lluorcsce with high yields anu exhibi t large Stokes
shifts so that self-absl>rption is minimized.
If the spectrum of the emitting material(s) in the OLEO structure has a suffi-
ciently wide banuwiuth, specific wavelength mngcs can be selected and enhanced
by arranging the electrodes to fonn a microcavity stnH.:ture [159- 162]. The RGB
triads in each pixel arc funned by microcavities of differem lengths, adjusted to
emit at the desired wavelengths. This approach is the most complicated in terms
of patterni ng and fabrication. Either or both organic stack and the bottom elec-
trode must be patterned with three different thicknesses. The advantage is in-
creased power efficiency for emission normal to the substr.1te, but off-axis there is
a drop in intensity and a shift in wavelength.
The li fth of the color methods places the three emitting sll1Jctures in a stack
one on top of the other, mthcr than side by side [20 11. Clearly there is a require-
ment here that the two electrodes in the middle of the stnll:ture must be transpar-
ent. The advantages arc that the display can be made much brighter with up to
lhrec times the luminance from each pixel, and the requirement-; for high resolu-
tion patteming arc relaxed by a factor of three. The disadvantages arc that three
limes as many layers must be coated (without defects) over the area of the dis-
play and electrical dri ving circuitry must mal-..e contact with four sets of elec-
trodes. It will be extremely difficult to incorpor.tte a stacked OLEO into a active
matrix array.

H;.
....
13.7.4 Encapsulation

The necessity of eliminating exposure to moisture and oxygen imposes considcr-
restrictions on the materials that can be used for the substrate and packaging
of OLEOs, especially if opemtional lifetimes over 10000 hours and 1>hclf lives of
several years arc to be achieved. Commodity plastics, such as poly (ethylen-
etcrcphrhalate), polycarbonatcs. and polyacrylmcs, arc much too permeable to be
used as substrates or sealants. The most successful p;tckagi ng is done wi rh glass
and metal, eit her directly bonded or glued with an adhesive ti ll ed with inorganic
particles. Composite m;ucrials. n msisting of laminated polymer and glass layers
456 13 Tlte Cltemislly, Physics wul Engineering of Organic Ligllt-Emiuing Diodes
are being investigated for usc as substmtcs and covers, and multiple-barrier cnca
s ulation schemes with geucring or absorbing materials between barriers have been
suggested.
13.7.5 Outlook
Eleven years after the break through publication of Tang and Van Slykc
there is only one commercial product which uses OLEOs in a display, an automo-
bile mdio/navigation aid produced by Pioneer in Japan [78]. However, the level
of industrial imcrcst in this fledgling technology cominues to grow as more in
vestmem is committed to development, and the number of academic groups active
in the field increases steadily. As attested by the citations in this article, this activ-
ity has yielded steady progress in new materials with enhanced tn111sport and
emissive properties and greater slability, in novel device structures that take in:
creasing advantage of these pmpe11ies, in improved understanding of the device
physics and degradation mechani sms, and in better fabrication techniques. '
The performance levels whkh have been reached in terms of luminance,
ciency, operating voltage, color of emission, and stability are already sufficicnttq
permit the description of OLEOs as a 'promising display technology' . But more
improvements arc needed parti...:ularly in the areas of a manufacturable paucming
method for color pixels, integration with driver electronics, heat dissipation,
encapsulation. One may also expect additional incremental improvements in effi.
ciency and stability, particularly at wavelengths which extend the accessible color
gamut. Quantitative numerical models for the dynamic response of multiluyered
devices arc being developed, and will assist in idemifying the bottlenecks aoo
weak spots for the optimum design of device structures.
Technological success is not enough, however; ultimately the market will de
cide whether OLEOs can compete alongside the other contenders in the Oat-panel
display arena. The various advantages of OLEOs will pennit them to address
ious market niches: from the low-end where cost is of pri mary importance, to
moderately complex pot1ablc displays where contmst, color, and efficiency arc re:
quirements, to personal microdisplays where weight and the simple opticul design
of an emissive screen may give OLEOs an advanlage. These arc the areas where
early success, although not guaranteed, is most li kely. 1l1e core sectors of the dis
play market, in lap1op and desktop computers, and in televisions, arc currently
dominated by LCD:; and CRTs, which are both technologies where there is a sig
nitlcant manufacturing base allcr many years of inve:;tment, leading to extremely
low cost-;. To compete here, OLEOs will need to improve and exploit their advan-
wgcs in weight, viewing angle, power consumption, and :;witching speed. Even
then, it is not enough to be better than the other technologies. To displace an en-
trenched technology, the new one musl be much better. How much better? Only
time will tell.
RejN'l!lll"eS 457
AcknowledgeJJJents
The_ prcpam!ion of this review wa:; supported in p<ul by the NSF Center for Poly-
mcne Interfaces and Macromolecular Assemblies (CPlMA) under cooperative
agreement DMR-940035-l.
References
1(-
I. J.l l. BurTuugh<!s, O. O. C. Ur.lllh:y. A.R. Brown, R. N. Mart..s. K. Mackey. R. ll . Friend. P. L
A. G. Nutm-r 1990, .1-17, 53\1.
2. J. Gm.:iner, S. Karg. M. Meier. W. P. Slmhric"l, M. S.:hwucn:r A.-tu Pol)'lll 1""3 44
201. 0 77
3.
' 4.
5.
1'. 6.

7.
8.
9.
M. Ucruld, J. Gmciner. M. S.:hwocn:r. Arta l'olym. 1996 . .J7, 436.
S. Ka'l!. M. Mc1cr, W. J. Ap[l. 1'111'.\'. 19\17, 112. IIJ5 1.
M. M.:ier. S. Ka'l!. W. Ric'' J. Appl. l'lly.. 1997, 82, 1%1.
D. Uraun. A. J. Uec:;.er. Al'l'' l'h.n. 1..<11. 19'}1, 511. I\IN2.
1' . W. M. Blum, M. J. M. de Jl>ng. J. J. M. Yh:gga;1r. Appl. P/1.1'.1. 1..<.11 I!.I'X>, 68, 33Ull.
Y. Ohmori. M. Uchid;1, K. Mum, K. Yu,hino. Solid Stat<' Cmmmm. 1991 . 1>0. 605.
M. 0 . lng;miis. G. Gus1;1fssun, J . M. R. Andcrssun. '1: lljcrtbcrg, 0. wcn-
nerslliilll, Na11m 1994, 372. -144.
10. D. O. ?cblcr. Y. Z. W<mg .. J.W. Blmchfurd, S. W. k\...Cll , L B. Lin, T.L. Guslafson. ILL. Wang.
T.M. A.G. Mac01;1nmd. A.J. Epstein, J. Ap[l/. I 'J\15, 7.'1. 4264.
tt. M. Onod<l. J. Ap[l/. Pll.H. 19')5. 7.'i. 1327.
12. N. C. Grcenham, S.C. Muraui. O.O. C. Ur..ldley. R.ll. Friend. A. U. N<tum 1""3 165
621!.
77

13. ll D. ll;mn:r, H. Naaml;!n. lUI. lliirhuld. l'ltyJ. Ur1: U IWS. 52. 251!7.
14. LS. J. Shinar. Y. W. Ding. T. J. Barton. Swll/r. Mrt. 19'}3, 55- 57, I .
15. Q. Zheng. R. Sun, X. 'lJmng. T. Masuda. T. Kuh;y;L,hi. l[m. J. Appl. l'lry.t. 1997, 36, LJ 5Ull.
16. R. Sun. T. Ma.,uda, T. Kuhaya..;lu. l[m. J. Aptl. P/r.r.1. 11)')6, .15, Ll-13-1: illitl. LIC.73.
17. U. Scherf. K. MUllen. Makrrmwl. Cllrm. Uupid Commrrrr. 1991, 12, 4!19.
18. G. Gn:111. G. Leising. Syntll. Mn 1993, 55-57, 4105.
19. Y. Ohmori. M. Uchidit. K. Mum. K. Yoshino. Jprr. J. Awl. Plr_r.>. 1991. JO. Ll941.
20. M. M. Grell, D. D. C. Bradley. M. lnha.-.c"ar.m, E. P. Woo, Ar/t\ Muur. 19\17, 9, 791!.
21. M. KrcycnM:hmidl, G. Klacm.:r. T. Fuhn:r, J . A.,hcnhurM. S. Ka1-g, W. O. Chen, V. Y. u .'c, J. C.
Scull. R. O. Mi ller. MacmrrHrl. 1991( .1/ . 1()9'J.
22. X. Long. A. D. 1>. C. Ur.tdlcy. M. E. P. Wuu Chtm Pill' < -11 1'"'7
272. (>. LC'
77
23. G. Klamer, M. H. Oavcy, W. O. Chen. J. C. S.:uu. R. D. Miller. Ac/1: Mat<t: IWII. 10. 1)93.
24. M. lnlxl\Ckar.m. W. Wu, E. Wuu, US l'arcnt 57771170. IIJtJK.
25. G. Klacmer. R. O. Miller. Mammw/. IWII . .1/, 2007.
26. E. P. Woo. W.R. Shiang, M. tnbnsckar.UI, G. R. Rnof. US P<tl<'lll570ll 130. 19911.
-27. C. W. Tang. S. A. van Sly"c. Al'l'' Phr.1. l.<' /1. 19117, 5 1. 'JI3.
28. Y. llmnada, /t::1:.' Tmrr.<. HI<'Ctmrr !),., .. I')'J7 . .J.J. 12011.
29. J. Kido, H. Hay<l'iC. K. Hungawa. K. Nagai. K. O"uyanl;J. All'l. 1.<'11. 1994. 65, 2 124.
30. S. Dirr. A. Biihlcr, S. Wie!>c. 11.-li . Jnhanncs. W. Kuw;1bl-y. Jpu .. ( 11[1!1. l'h
1
s. IWII, .17. 1457.
31. C. Husol-awa. II . li>kailin. II . I llg;L,Iu, T. Kusmmnu, tlpp/. l ' lt.n. / .<//. IW3.' fiJ, IJ:!:!.
32. C. Hlt'>ukawa, M. Mmsuura. M. Eida. K. Fukuul-a, N. Nilkamur;l. 1: J. :SII> 1997 5
331. .
33. N. N. Bar.l\hl-uv, D. J . Guerrero. H. J. Ohvus. J. l'. Sy11tlr. M<'l. 1')95, 75. 153.
14. C. Adad1i, T. S. Sailu, A[>[ll. 1'11.\'.r. L<' /1. l 'J'JO, 57. 531.
lS. T. E.- I. Amina";1, Y. Fujitil. J. llam;,d;,, S. Salin, Sylllll. I'J'J3, 55 57. 4157.
458 13 The Chemistry, Physics and Engineering vf Orgunic: Light-Emilling Diodes
36. I. B. Bertmun, Hwulbook of Fluorescence Spectra vf Aromotic Molecules, 2nd cd . ACildemic
Press, New York 1971.
37. M. A. Abkowitz. D. M. Pai. Pili/us. Mag. B 1986,53, 193.
38. P. M. Borsenbcrgcr, D. S. Organic Photurecetnors fur Electroplwtugrtlfl ll)', Marcel Dekker.
New York 1998.
39. C. W. Tang, lnfomaution Di.wlc1_v, Oct. 1996. 16. _ .
40. Y. Shirota, Y. Kuwabar.s, H. lnada, T. Wakirnoto, H. Nalo.ada. Y. Yonenmto, S. Kowmna, K. lmat,
Af'l'l. Phy:r. Leu. 1994, 65. 807. . .
4 1. E. Buchwakl. M. Meier. W. Briiuing. W. Riess. P. Strohricgl, M. Schwoerer 111 hwrgwuc lJiad Or-
ganic /cctmlwuinescence (&Is.: R. H. Mauch, H.-E. Gumlich). W&T Verlag. Berlin 1996, 117.
42. J . Salbcck, ibid. 243.
43. N. Johansson, D.A. dos Santos. S. Guo, J. Comil. M. Fahlman, J. Salbcck, li . Schenck, H. AI
win. J. L. W. R. Salanek, J. C/1e11L Phy.v. 1997, 107, 2542.
44. S. A. van Slykc, P. S. Bryan, C. W. Tang in lnorxwaic uml Orxunic Electmlumincscence (Eds.
lUi. Mauch. 1-1.-E. Gumlich), W&T Verlag. Berlin )996, 1\15.
45. J. Shi, C. W. Tang. Appl. Pllys. l..ell. 1997. 70, 1665.
46. M. I I. Kawalmr.. A. Fujii, Y. Olnmri, K. Yoshino, Jpn. J. Af'l'' Phy.f. 1995 . N. L1237
47. J. Kidn. Bull. Electmdu.-m. 1994, Ill, I.
4R. V. Uulovic, A. Shou:.til.ov. M. A. Baldo, E. Uo:.c. V. G. Ko1.lov, M. E. ThompS<Ml, S. R. forrest,
Clum. ull. I 1198, 455.
49. Y. Satu, H. Kan.u, Mol. Cry.\t. Uq. Crpt. I'J'J.l, 25.1, IU.
50. J. K1do, K. liong:1wa, K. Ol..uyama, K. Nal_!.:li. J. Afl/>1. 1994, 6-1, Kl5.
51. G. E. Juhnson. K.M. l'mc. SI'IE III'J3. /CJ/0, 6.
52. C. C. Wu, J . C. Sturm, R. A. M. E. AJ'I'' 1-<'11. Ill%. M, 3117.
53. H. Su:tuki, H. Meyer, J . Simmcrcr. J. Yang, D. li:1arcr. Atll: Mat<t: 11193, /0, 743.
54. 1.-N. Kang. D.-H. Hwaug, 11.- K. Shim, T. Zyung., J .-J . Kim. Mu.-mmal. Ill%, 2CJ. 165.
55. G. Yu, H. Nishino, A. J . licegcr. T.-1\. Chen, R. D. Ricl..c. :i_v11th. Met. 11195, 72, 249.
56. V. Cimrov;i, D. Neher. M. Remmer.l. I. Kminck. Ac/: Mall'r. J\1?8, 10. 676.
57. S. Ta....:h. E. J. W. Lisl, 0 . Ek:.ll'iim, W. Gr.supn.:r, G. P. Schlichting. U. Y. Gccns,
U. St:herf, K. Mullen, Afi/J/. Phys. u11. 1997. 7/, 281!3.
51!. C. C. Wu, C. I. Wu, J. C. Stunn, A. Kahn. Appl. l'hy.r. l .i'll. 1991, 70, 1341!.
59. M. Ferreira. M. E Rubn.:r. Macmmol. 1995, Zll. 7107.
60. M. Onoda, K. Yoshino, J. AJIIII. 1995, 7X, 4456.
61. J. E. W. Li , W. Ma. L Geng. T. J. M:1rks. G. E. Jabbuur. S. E. Shah.::cn. 13. Kippclen, N.
J>cyghaaubarian, P. Dutla, A. J. Richter, N. R. AnuMrong, P. A. Lee, J . D. Pmc. SPIE
1998. 3281. 148.
62. A. G. Bajo, J. Puloheimo. T. H. SIUbb, Ad1: Mater. 1997. 9, 121.
63. J. GrOner, M. Remmers, D. Neher. Ad1. Matrr. 1997. Y. 964.
64. V. Cimrov:i, M. Rcmmen., D. Neher. G. Wegner. Atlv. Muter. 1996. 9, 146.
65. D. Ad<1m. F. T. Frey. D. Funholf, D. Haarer. H. Ringsdorf, P. SdlUiunachcr. K. Siemens-
meyer. Phys. Rev. uti. 1993. 70. 457.
66. N. Ooden, R. J . Bushhy, J . Clements, U. K. J. Donnvan, T. Krcnu.tis, 1'/rys. Rev. B
11195, 52. 13274-13 2780.
67. 1-1. Tolo.uhiloil, M. Em. T. Af'l'l. Plays. U:11. 19\IM, 72. 2639.
68. I. llamb<:rg. C. G. Gmn4vis1, J. Appl. Phy.r. 1986.60. R 123.
69. M. ROitmml, K.-H. H:ckncr. J. l'hy.s. /) App/. Plly.s. 1995, 2X, 1441!.
70. w. Briitling. M. Meier. M. Hcmld. S. Karg. M. Schwoerer. S_l'llth Met. 1997. 91. 163.
71. M. llcmld, J. Gmciucr. M. S.:hwocrer, A<'la /'<J/ym. 19')(>, 47, 436.
72. J . M. Phillips, R. J . Cava. G. A. Timm<tl>, S. A. Cuncr, J. Kwo, T. SicgriM. J. J. Kr.1jewski, J. H.
Man.hall, W. E l>c.:k. D. H. Rapkinc. Af'f'l. 1'/tys. u 11. 1995, 67, 2246.
73. M. Herold, J. Gmcincr, C. Drummer, M. Schwocn:r. J. Mat. Sci. 19'>7, .12, 5709.
74. S. Tokitu, K. Noda, Y. Tuga. J. D. Af'J'I. PllyJ. 1996, 29, 2750.
75. J. C. Scott, G. G. W. D. Chen. J. C. U\!uch, J. R . .Salem. I'. J. Brock. S. U. Saclls.
C. E. D. Chidsey. ApfJ/. l'/1)'.\. uti. , in Jlre.'s.
76. U. K. Crone, I. H. Camphcll. P.S. D. L. Smilh, Appl. l'bys. ull. 11198. 7.1. 3162.
77. tl. Surul.i, Al'/>1. Pby.,. I A'II. 1\I'X., 6CJ, 1611.
References 459
78. T. Wakimoto, H. Ochi. S. Kawami, H. Oh:tta, K. Nagayama, R. Mur.syama, Y. Okuda, 11. Naka-
da, T. Tohnm, T. Nailu, H. Abilo.o, J. SID 1997, 5, 235.
79. K. Pidder. S. K. Hccks, C. R. Towns, N. T. liarrison, N. R. l-1. Friend, Proc. JDJ<C 1997
F19.
80. J.R. W. Mackie. S. An1., T. Xi.:. Pmc. SP/ )997, J/.m, 21!}.
81. G. Y. Can, G. M. Treacy. F. Klavctt.:r, N. C(llancri, A. J. Hcc .. er, Nature 1992, 357
0
82. S. Karg. J. C. Scolt, J. R. Salem, M. Angclupoulo.\, Symfl. M<t. 1996. 80. 111.
83. S. A. Cart<.'f, M. Angclopuulos, S. P.J. Bmck, J.C. Af'l'l. Plrys. uu. 1997 70
. .
84. Y. Cao, G. Yu, C. Zhanl_!., R. Menon, A. J. 1-lccger. S_mth. Mtt. 19')7, 171.
85. I.H. Camphell . S. Ruhin, T. A. J. D. Kress. R. L Martin. D. L Smith, N. N. B<lf
ashkov, J. P. Fcrr.1ris, J<r., U 11196. 54, K 14321.
86. l.li. Camphdl. J. D. Kress. It L. Martin. 0. L. Smi1h, N. N. B:mshlo.uv. J. P. Ferraris, Appl.
Pb_n . u'/1. 11197, 7/, 352K
1!7. F. Niicsch. L. Si-Ahmed. B. L Zuppmli . Adl: MII/L' T. 1997 Sl. 222.
88. E NucSt:h, K. Kumar:i.,, L Zuppimli. Cllcm. /'11.1:{. l..cu. 1991!. 28.1, 1')4.
89. Y. C:1u, G. Yu. A. J. Hc-cgcr. Atk Matt/: III'JM. 10. 917.
90. LS. Hung. C:. W. Tang, MG. Ma."m llpf>l. 1'/,ys. l..t.u. 1997, 70, 152.
91. EG. Celii. S. J. l ' mr. 17111 mHC l'J'J7. 31-l.
92 E Li. II. 'Jlmg.. J. /\udcl\!1!-l_!.. J . Slnnar. Aflf>l. /'!J1:<. IJ.'/1, 11197. 70. 1:!33.
93. G. E. Jabhuur. B. Kappckn. N. R. N. Pcyghamhari:m. Appl. 1'1
1
.n . l..cu. 19\IM, 7.1.
IIR5.
94. V Uulu\'ic, G. (iu. 1' . E. Bun M. E. Thompson. S. R. Ntllun ('}'}(,, JliO, 2'J.
95. G. P:lrlh<t>:u-alhy. 1'. E. V. Kha lin, V. G. KuJ.Iov, !i. R. llpfJ/. Pin.{. u/1. 19911,
72. 2131!. .
96. l. li. C:unphell, T W. liag.ler, O. L Smith. Phrs. Uc- L('/1. 1119M. 76, 1900.
97. G. G. J. R. Salem. 1'. J. Umcl.. J. C. Scuu. J. Ap,;l. Pity,,. I 119M. '14. 158.1.
98. L Bo1.<uul, S. A. Carter. J. C. S.:un. G. G. Malliam.o;, P. J. Bn>d. llflf'/. l'llyJ. u11. II}C)'}, in prc.o;s.
99. N. C. Grecuh;nn. I. 0 . W. S;uuud, G. R. R. T. Y. A. R.R. S. C. Mur.llti
100.
101.
102.
103.
IOt
105.
106.
107.
108.
109.
110.
Ill.
112.
113.
114.
liS.
116.
117.
118.
119.
A. B. Hulm<. 'l., R. H. Friend, C/lt'm. Pl1y.r. vu. 111')5, U 1. R9. .
S.A. Jcncl..ln;. J. A. 0-.1hcni. s,.;,.,,.,. III'J4, 2fJ5, 765.
D. Anuncnmm. A. Biihlcr. S. Di1T, H. H. Juhann.::s, W. Kowabky, W. Grahn, Pmc. :)1'/f. 1997
3006. 164. .
W Riess, H. Riel, P. F. S.:idlcr, H. VeMw.:her, Ml't. I \19M, 10 pre,._,_
S. A. Villi Slyl.c, C. H. Chen, C. W. Tang, Appl. Phy.r. u11. 1996, f1SI, 2160.
Q. B. Pci, G. Yu. C. Zhang. A. J. Sr i<11ce 11195. 26CJ. 101!6.
J. C. o.lc Mclkl, N. S. C. Gr.dl:1m, R. ll. Fricld. l'lly.v. Ur1. U 199M, 57, 12951.
G. Yu, Q. 1-'ci . A.J. Afpl. /'lly.r. u/1. 1997. 70. 934.
Y. Cao, G. Yu, A. J. 1-kcg.er. C. Y. Yang., Appl. 1'/Jys. i-<'11. 11196, MI. :l21K.
J. G. Gordon, J. H. Kaufnl:lll. R.D. Miller. J. C. Scott. US /'atem5.167,CI24, 19\IH.
G. Yu, Y. Cau. M. J. G:lll, /\. J. llcegcr. Ac/1: Mtl/t'r. I YIIH, 10. 3K5.
M. A. Ualdu. F. O' Bnen. Y. You. A. S. Sihlcy, M. E. Thumpsnn. S. R. ForrcM, Na-
ture 1998, .IY5, 15 1.
N. C. Grccnh:1m, 1'/t. /). '11wsi.r. Cnnhridge 19115.
I. H. C:lmpbcll. P. S. David.'. J . P. fl!rr.1ris, T. W. Hagler, C. M. Heller. A. Saxena, D. L Smith,
S,rnt/1. Mrt. 1996. XO. 1115.
X. Wc1, S. A. Z. V. \)mil. lllt. 11197. 1..! 1.'\.
W. R. Sal;lllc.:lo.. S. Slaf,lriim, J. L. Un.'t.l:as, l'olyma .'iwjitn.. J
11
t,Jfan.r. C:unhndl_!.e
Umvcrsity Press. C':unhri<.ll_!.e 1\IWo.
K. Seki, E. hn. II. bhii \)utll. M,t. 1!.197. VI . 1.17.
R. Schlaf. A. B. l'arlo.iu,.nn. P. A. L<. -c. K. W. N. K. Atpl. l'lly.r. Ldt. III'J8,
73, 11126.
A R<IJagn(XII, C. I. Wu, A Kahn, J. AJifl/. 1'/iy.\. J'J')IS, .'i.l, 164'J.
V.-E. M. G. Ma.<llll. C. W. Tang. Y. Gau, AflfJ/. /c/1. 199M. 72. 26K'J
G. I- J. A. l(ilo.l..,u. D. llr.nm. I'. G. J. S1:uing. R. Dcmamh. Af/'1. l'l1n. l..t.'/1. 1994. (
1
5. 211).
460 /3 Tile Plly.rics uud ugiuetriug of Organic Ligl11-111illiug Diodes
120. H. Vc:.tweber. R. Sander, A. Greiner, W. Heitz. R. F. Malut. H. Biisslu , Syulll. Met. 1994, 64,
141.
121. S. Karg. V. Dy:tkonov, M. Meier, W. Riess. G. Paasch, S}11ffL Met. 1994, 67, 165.
122 P.W. M. Blom, M. C. J. M. VlSSCnbcrg, Pllys. Rt'v. Len 19911,80,3819.
123. J. Pommerchnc, H. Vcstwcbcr, Y. H. T<tk. H. Uas"h:r, S)lfil. Mn 1996, 76, 67.
124. M. Rcdeckcr, H. Biisslcr, H.H. Horhold,J. Pltys. ClleiiL lJ 1997,101, 739!!.
125. J. C. Scou. S. Rmnos. G. G. Malliar.ts, J. lmuJ:. Sci. Teclm. 1999, in pn:ss.
126. J.C. de Mello, H. F. Wiumunn, R. H. Friend, Adv. Mmttr. 1997. 9, 230.
127. H. Phy.f. Status Solidi lJ 1993, 175, 15.
128. P. La11gcvin, A1111. Cllcm. Phys. 1903, 211, 289.
129. D. HC!tcl, U. Scherf. H. Biisslcr, Aclt. Mmer. 199H, 10, 1119.
130. M. Rcdc.:dcr, D. D. C. Br..tdley, M. lnbasckamn, E.P. Woo, Appl. Phys. Leu. l99H. 7.1. 1565.
121. D. H. Dunlap. E. Parris, V.M. Kenkre, Phys. Rev. u/1. 1996, 77, 542.
132. M. A. L<unpen. P. Mark, Curre111 lujrL'Iicm i11 SolicLf, Ac:tdemic Prc.o;s, New York 1970.
133. P. N. Murgutmyd. J. l'hys. 0 : AJ1pl. 1970,3, 1.5 1.
134. M. Abkowitl., J. S. Fac.:i. J. Rchm, J. Appl. Phys. 1998.83, 2670.
135. N. W. A"h.:rol'l. N. D. Mennin. S.Jiid Stutr PhyJic-.1. Holt. Rin.:han. WinMnn, New York 11176,
p. )(13.
136. R. ll . luwlcr. L. Nuruhcim. /'me H. Sm. I '12M. A /IY. 173.
137. Y. N. Gar..tein. E. M. Conwell. C/,..m. /'11.1.1. IYY6, 2.U . '.1.1.
138. V. I. Arkl11pov. E. V. Emclmnova. Y. l I. Tal.. II. 11:1\,h:r. J. tlppl l'h_n . l 9'JII. 8-J, K-Ill.
139. M. N. D. M1chuull. 1.. Zuppiroli . l'hy.1. N...-. 1.1.'11. l9'JH. 8/, ICJ7X.
140. J. C. Scull, G. G. Malliara,, C/um. 1'11,\ .1, l .t /1. 19')'.1. 111 pre".
141. P.R. Eullagc, J. J. O'Dwyer. Plly.f. Rt: Ll'll. 196(1. /6, .'15CI.
142. J.C. Scoll. S. Karg, S. A. Caner. J. ApJI. I'll'-.' 1997. 1'12. 1454.
143. R. H. l'anuenter. W. Ruppd. J. AJ>I>I. l'hy.\ . 1959. 30. 15--IX.
144. Y. Kawabc, G. E. l:lbbour, S. I;. Sh:1heen. 13. Kippclcn, N. t>cygh;unb.tn:m, ApJII. Phys. LctL
1997, 71. 1290.
145. G. G. Mall iam.\, J. C. Scou, J. App/. Ph_v.r. 1998. X3, .5399.
146. B. K. Crone, P. S. I.H. Campbell, D. L Smith. J. AJ1pl. l'hys. 19911, 1'14. 1133.
147. I. H. Campbell, P. S. Davids, O. L. Smith. N. N. B<lt'.J.\hkov. J. P. Fcrr.tris, AJ>pl. Phy.1. utt. tm
72. 11!63.
148. G. G. J.C. Scou. J. AJ>JII. Plty.f. 1999, in
149. I. D. J. AJJpl. Pl1_vs. 1994. 75, 1656.
150. A. J. Cmnpbell, D. D. C. Bradley. O. G. Lillt.ey. J. IIppi. Phys. 1997. X2. 6326.
151. G. G. Malliunllt, J.R. Salcm,I'. J. Brock, J. C. Scull, Phys. Ne1: lJ 19911,58, Rl 3411.
152. H. Y. l-1. Tal., D. V. Khramatchenkov, V. R. Nikit.:nko, Sy11tll. Mtt. 19'J7. 91. 173.
153. D. V. Khnuntchcnkov, H. Biisslcr, V. I. Arkhipov, J. Appl. PflyJ'. 19%, 711. 92!13.
154. 1.11. Campbell, M. D. Joswick. 1. 0 . AJIJII. l'lty.\ . utt. 1995. 67, .'1171.
155. P. E. Burrows. S.R. Forrc.,t, AI'J'I. Phys. l ..t'tl. 1994, 64. 2285.
156. H. Vcstwebcr. W. Met. 1997. YJ. 11!1.
157. C. Gic'bclcr. H. Antoniatlis, D. O. C. Br.ltlh:y. Y. Shirota, J. Ap1l. l'hys. 1999. XS. 601!.
1511. D. J. A. J. I J.:eger. Y. Q. B. Pci, Atlt. Mcutr. 1996. 8. 91!5.
159. N. T:tkada. T. 1\utsui. S. Saito. ApJII. Plt_r.l. ut1. 1993. 63. 2032.
160. H. I-'. Wi11m:mn, J. Gruner, R. H. Frienll, G. W.C. Spencer. S. C. Mli<Jill, A. 13. llnlmc,, Ad1: Mo
ter. 1995. 7, .541.
161. A. Oudabalupur. L..J. Rothberg. T.M. Miller. 1\Jip/. 1'1.1'' uti. 199-l. 65. 2308.
162. R. l l. Junl<m, L. J. Rothberg. A. Duhadalapur. K. E. Slu,hcr. Appl. Phys. I.e://. 19%. 1)1/, 1997.
163. S. Tnkito. K. Nulla, Y. Taga, Appl. Phys. ull. 19%. 611. 2633.
IM. W. Gu.,s, II. VcMwcber, M. HutmJCicr, Y. li. M. Dcu,!>Cn. R. F. M:1h11, Sylllh. Mtt. 1996,
X). 257.
165. K. A. N.:yts. J. Opt. Soc Am. A 19'JH, 15, 962.
166. M. Yan, L.. J. Rothberg, F. l'ap:tllimitrikapoulos, M. E. Galvin. T. M. Miller, P/1)'S. Ucv. l.cll
1994. 71. 744.
167. L. J. Rothberg. M. Yan, F. Pap;.ltlimitr.lkopoulus. M. E. Galvin, E. W. Kwock, T. M. Miller,
Symh. MN. l9'J6. XO. 41.
461
168. J. C. Scoll, J. H. Kaufman, P.J. Bruck, R. DiPietro, J. Salem, J. A. Goiti:i, J. IIppi. Plly.f. 1996,
79, 2745.
169. B. H. Cump.ton, K. F. Jensen. Symll. Ml'l. 1995, 71, 1'>.5.
170. R.D. Scurfuck. B. W.mg. P. R. Ot:ilhy. J. R. She:ll!>. R. L Clough. J. Am. Clum. Sci<. 1995. 117,
10194.
171. J. R. D. U. S,mth. Mtt . l 99H, 115. 79.
172. J. C. C<tner, I. Gri/.zi. S. K. O. J. L.t.:cy. S. G. l..:Jth<ml, P. G. May. O. R. lie P:u10l>. K.
Picl]ler, C. R. Tuwns. II. t-: Willmann. Alfll. l'llys. u tt. 1997, 7/, 34.
173. B. II. Cumpston, K. F. Jensen. J. AJ'f'l. l'olym. Sd. l 91JH, f>Y. 2451.
174. R. Pri.:stky. I. A. D. Walser, C. W. T;mg, R. Dorsinvillc, Symh. Met. 1991, 84, 9 15.
175. P. E. Burrows. V. Bulovi.:. S. lt Forrest, L. S. Sapnt:hak, 0. M. McCarty. M. E. Thompson, Altp/.
Pllys. Lm. 1994. 65, 2922.
176. J. McEl vain. II. Antoniallis. M. R. Hue,chcn. J. N. Miller, 0. M. Roitn1:1n, J. R. Sheats, R. L.
Moon. J. AJif'/. Pl.r.f. l'J%. 8tJ. 6002.
ln. H. Alit.. Z. 1
1
upovi<. S. Xic. A.-M. Hur. N.-X. llu. C. Tripp. G. Xu. AJ>JII. Phys. u11. 199H. 72.
756.
178. F. X.-M. Zhang. D. L ntum-.cn. K. A. Higgin.,un, CIIC'm. Mcuer. 1996. 8,
1:163.
179. H. A/11., '/.. l'upmu:. l'.l'. Tnpp. N.-X. llu. A.-M. llor. G. Xu. Appl. /'/1.1'.1. l.clf. 19911. 72.
:!642.
180. D. Dahle. Scllor11u.us. UC S:uua Cru1. 1997.
181. f. Cac1:tlli. R.ll . Fri,ull. S.C. Mur:oui . A. B. S\'11111. Mtt. 19'J4, 67. 157.
182. D. Zuu. M. Y:thin. T. TsutMii. tlpp/. 1'11,1'.1, Lm. l99H. 72. 24!!-1.
183. H. Antun1<1lli,, M. R Hu.:M:hcn. J. N. Miller, R. L.. Moon. D. U. Ruitm:tn, J. R. She:u.,, Mllt-m-
mol. Symp. 1997. 125. 59.
184. Y. S:ttu. II. K:m:ti, Mol. C1:nt. Utf. Crvst. l>W. 25.1. 14.'1.
185. Y. T. Sam1, K. Shihata. K. Kuroki . Jp11. J. Appl. Pllys. 1995. 3-J. LK24.
186. L E. Tann:1 113.1.). 1-'/at l'cut.-1 J)i.'l'lay.\ cmd CKfs, Van Nustr..mll Reinhold. New y,,rk 19KS.
187. G. W. S. Stiles. Color Scit' lll' <', am/ Mttllm/.f, QIICmlitatil't' Oam tmd
mulcu. Wiley. New Yurk 1967. 1- :!:\'.1.
188. C:unbridgc Di,play Tc'Chnulugy. (li'Cc'-' release 199H.
' 89. D. Br..tun. Mrt. 1997, Y2. 107.
90. C. Hu!>Ok<lwa. M. Matsuur.1. M. Eit!a. K. Fukuuka. N. N:tkamur.J. T. Kusuntoto, J. SID 1997, 5,
331.
191. P.F. li:m, r. E. S. R. Furr.:,t. Af'l'' 1'11)'.1. /.('(/. 1997. 7/,3197.
1
92. M. K. M. Stcw:trt. C. T:mg. J. Bunis, l'mc. SPIE 1997, 3057, 277.
93. FED Curp . pr.:ss rck:t'c 19911.
194. J. C. Sturm. W. Wilsun. M. t,tt.ficc. lEI-: J. Sd Tt'J'il'' {!1111111. Eke. 199H. 4, 75.
'95. T. R. llchner. C. C. Wu. D. M;u-cy. M. H. l.u. J. C. Sturm. AJ'J'I. l'lly.\. L<n. 199H, 72,519.
96. J. Y. Y:mg. Af'l'' Phy.1. u:/1. l')'JH. 7:!.. ::!660.
197. J. Kidu, M. Kimur:t. K. N:.g:ti. Sdt' ll('(' 1995, :M7. 1332.
91!. I::.. G:ttJtio.:r-'ntianch.:. C. S.:nto.:in. A. Lurin. C. 1'. K:.imunll. J.-M. J. Ai'J'I.

19911. XJ. 42.lb.
'99. S. Ta.-.ch. C'. Bmnthtallcr. F. Mq:hll:ltli. G. Lci,iug. G. Froy.:r. L. Athuucl, Mmrr. 1997, II,
33.
200. E 1-hde. M. A. B. J. Sdtw:tn, M. R. Andcrs.'lm, Q. Pci. A.J. Hceger. Sdmn
19%. 27.1, 111.'\.l.
201. 'L Shcn. P. l:. V. Uuluv1c, S. R. M. E. numtpsun. Sl'itm 1997. 276. ::!UOIJ.
14 Physics of Organic Field-Effect Transistors
Gilles Horowitz
14.1 Introduction
The invention of the gennanium tr:msi1>tor in 1947 [I, 21 marked the birth of
modem microelccuunics, a revolution that has profoundly influenced our current
way of life. This early device W<L'i actually a bipolar transistor, a structure that is
mainly used nowadays in amplifiers. However, logical circuit-;, and particularly
microprocessors, prdl:rcmially usc jiel1-e.ffect transistors (FETs), the concept of
which WitS first proposed by Lilicnficld in 1930 131. but was not used as a practi-
cal application umil 1960 14). In a FET, the currcm tlowing between two elec-
lrodes is comrollcd by the voltage appl ied to a third electrode. This operating
mode recalls that of the vacuum triode, which was the building block of earlier
radio and TV sets, and of the li rst electronic computers.
Single-crystalline sil icon is the most widely used mate1ial in microelectronics.
Other inorganic semiconducton; arc employed in applications where very spccilic
properties are required, tor example gall ium an;cnide in high-speed devices. How-
ever, clectronic-grdde silicon is expensive, and is not suitable in domains where
large areas are required, such as active matrix liquid crystal displays (LCDs), in
which each pixel is monitored by one (three in the case of a color display) FE.T.
Here, three families of materials arc in competition: hydrogenated amorphous sili-
con (a-Si: H), polycrystall ine Si, and organic semiconductors.
A field-effect in organic semiconductors was first reported in 1970 [5). How-
ever, it is only more recently t h ~ t organic FET.-; (OFET.-;) have been made with at-
tractive perfommnces. The blossoming of OFE'f.-; apparemly occurred soon after
lie discovery of conducting polymers (CPs), in the late seventies [6). One of the
most exciting properties of CPs is their ability to acqui re a high conductivity
upon doping, and for many years CPs have been mainly investigated in their
doped form as synthetic metals. However, it appeurcd later that under their non-in-
lentionally doped (often called wuloped) form, CPs have semiconducting proper-
ties that could be potentiall y used in electronic devices (for this reason, the acro-
nym CP now stands for either conjugated polymer or cmulucling polymer). The
first polyacetylene OFET was reported in 19lB (7]. but the issue was really
launched just four years Iuter, with a polythiophene-bascd device [8). Almost
simultaneously small molecules 191. and panicularly conjugated oligomers 1101.
'lave also proven to be very promising organic semiconductors. Today, the best
')FETs are made with conjugated oligomers, but polymer-based devices arc still
uwolved.
464 14 Physics of Orga11ic: Fielci-Ejfecl Tra11sistors
14.2 Basic Principles
14.2.1 Junctions
Contacts are the elementary building blocks for all electronic devices. These in-
clude interfaces between semiconductors of different doping type (homojunctions)
or of different composition (hcterojunctions), and junctions between a melill and a
semiconductor, which can be either rectifying (Schouky junction) or ohmic. Be-
cause of their primary importance, the physics of semiconductor junctions is
hu.;ely dealt with in numerous textbooks Ill , 12]. We shall here on
basic aspects of the metal-semiconductor (MS) and, above all, metal-msulator-
scmi conductor (MIS) junctions, which arc involved in the organic ficld-ciTcct tmn-
sistors.
14.2.l.l Metal-Semiconductor (MS) Junction
14.2.1.1.1 Formation of the Junction
The usual way 10 visualize a junction is to draw an energy diagram that shows
the bottom of the conduction band ,. and the top of the valence band Ev as a
function of distance. The so-called band curvature that appears at both sides of
the junction interface reveals a variation in the potential with a distance in the di-
rection perpendicular to the junction surface. The fonnation of an MS barrier is
depicted in Figure 14- 1.
In Figure 14- 1 a, the 11-typc semiconductor and the metal are sepamted from
each other; the Fermi level in the metal is at an energy ,, and the conduction
band edge of the semiconductor at Xs from the vacuum energy. , is the wen
function, and Xs the electron affinity. We assume that the Fermi level 1 of the
metal is below that of the semiconductor. Connecting the metal and the semicon-
ductor (Fig. 14-1 b), result s in the equalization of the Fermi level in both media.
This is obtained by a tnmsfcr of charge from the semiconductor to the metal. As
the energy of electrons outside the surface of the two solids is different, an elec-
tric field grows in the gap between them, together with a negative charge at the
metal surface, exactly balanced by a positive charge in the semiconductor. The
charge at the metal surface conccntmtes within the: Thomas-Fenni screening dis-
tance (0.5 A). Since the free carrier concentmtion in the semiconductor is consid-
embly lower than that in the metal, the charge here extends over a region of sub-
stantial thickness, called the depletion layer. At the same time, an electric field
also develops at the semi conductor surface, which results in an upward bending
of the bands. When the surfaces of the two solids arc put into contact (Fig. 14-
1 c) the voltage diffe rence V; tends to :teru and all the ohmic drop in
the depletion layer, so the barrier height th, is simpl y given by
( 14.1)
(a)
(b)
(c)
J.J.2 Bt1sic Principles 465
l'il(urc 14-1. Fom1;1tiou of a mc-
WI-M:tnicouductor (MS) junction.
In [a) the mcl:tl and the semicon-
doctor arc scpar.tlcd from each
in (h). the twu ntt.-dia ;m:
o.:umll.'\:100 but still rar
frum each 01hcr in (c) the two
!>Oiill., an: in full contact.
Eq. (I is known the Mott-Schouky CtJU<tlion. We note that for a given u-
typc semtconductor. the lxUlicr height increases as the work function of the metal
increases. It is therefore expected that high work function metals will oive a recti-
fying junction, and low work function metals an ohmic contact (it is "'the reverse
for a p-typc semiconductor).
14.2.1.1.2 The Junction at E<1uilibrium (Zero Bioas)
The profile of the electrostatic potential V in un MS junction c:111 be calculated by
solving Poisson's equation
PV p(x)
cJ.r2 = ---;;:-
( 14.2)
Here, c . is the dielectric pennillivity of the semiconductor. The charge density is
given by
p = q(N,t +p - 11)
( 14.3)
where lf is the ah.wlutc electron d la1'6e. N,
1
the density of dopmus, and p and n
the concentmtion of holes and electrons. rL'Spcct ivcly. The usual assumption is
that the quasi-Fcnni level of electrons and holes is constant throughout the deple-
tion layer and coincides with the Fenni level, so that Ll"k! density of electrons and
holes obeys a Boltzmann distri bution. Hence, Eq. (14.3) becomes
[ (
q(V
1
,; + V)) (qV)]
p=q N,1 + p.,. exp - li.T - n
11
exp li.T
( 14.4)
where P . is the density of holes al the semiconductor surfuce, V
1
,; the built-in (or
diffusion) potential that produces the band bending, und u
11
the electron density in
the bulk of the semiconductor; k is the Bolt:l.munn constmll and T the absolute
temperature.
466 14 Physics of Orgu11ic Field-Effect Trunsistors
Although Eqs. (14.2) and (14.4) can be solved analytically (as wi ll be shown
in the next section), here it is sufficient to use the renowned depletion, or Schott-
ky approximation, in which it is assumed that the effective density of charge is
constant and equal to qNtl in the depletion region, and zero outside this region. In
this case, a double integration of Eq. (14.2) directly gives
V(x) = qNu (W- xl
2cs
( 14.5}
where W is the width of the depletion layer. The magnitude of V at the surface
(x=O) is equal to the diffusion potential, giving the following relationship be-
tween w and vbi
W= ( 14.6}
Finally, the total charge per unit area due to the uncompensated donors in the de-
pletion region is given by
( 14.7)
14.2.1.1.3 Current-Voltage Characteristic
The current-voltage protl le of rectifying junctions is strongly asymmetrical. The
reason for this can be explained with the aid of a simple band diagr.tm shown in
Figure 14-2.
Under reverse bias, the band bending and its associated electric field are in-
creased by the applied voltage, and charge tmnsport across the j unction is
blocked. Conversely, under forward bias, the extemal voltage tends to decrease
the band bending, thus facilitati ng charge injection across the interface. Eq. (14.8)
gives the geneml form of the current-voltage curve under forward bias.
(a) (b)
l'lgure 14-2. Energy <.liagmms of a
conductor (MS) rectifying junction under reverse
(a) an<.! forward (b) bias.
14.2 Basic- Principles 467
. . [ qV ]
J = Js cxp- - 1
nkT
(14.8)
where n is the ideal ity factor, which is usually slightly greater than one, and ac-
counts for image force lowering of the barrier ami j_, is the satumtion current den-
sity, whose magnitude depends on the charge transport mechanism at the MS in-
terface (e.g., thermionic emission, diffusion, tunnel ing, etc.). A full description of
the direct currcm in rectifying jw1ctions can be found in several textbooks [ ll-
13]. We arc more interested here in the behavior of the MS comact under reverse
bias. This will be dealt with in Section 14.2.2.2.
14.2.1.2 Mclal-lnsulatur-Scmil"muludor (MIS) .hmltion
Figure 14-3 shows a schematic dmwing of a MIS !. tructure and its cone:;ponding
band diagram at zero bias (here, we deal with a JHypc semiconductor). The small
band bendi ng thut appears <tl the insulmor-scmiconduc.:tor interface comes from the
different work fum:tions of the metal tmd the semi conductor. This difference can
be compensated for by applying the so-called flat-band voltage to the metal, giv-
en by the di fference between the respecti ve work function of the semic.:onductor
and the metal.
l'J,, = x .. + ,. -
1
- C/J, . ( 14.9)
When a positive (negative) bias is applied to the metal. the bands bend down-
wards (upwards), as seen in Figure 14-4.
In the case of negatite bias, the Fermi level moves closer to the valence band
edge. Consequently, the concentration or the maj ority of carriers (holes) at the in-
sulator-semiconductor interface becomes larger than in the bulk. 1l1is corresponds
to the uc:cumulution regime. When a positive bias is applied to the metal, the
Vacuum leve l
Conduction band
14-J. En.:rgy or a mctal-in,ula-
(MIS) jun.:tiun <II .:ttulibnum.
468 14 Physics of Orgu11ic Field-Effecl
(a)
(c)
(b)
(d)
Figure 14-4. MIS junction under negative
and bias; (a) llat-band, (b) accu-
mulation (V<O), (c) depletion (V>O) , and
(d) (V>O, Ep,).
bands bend downwards and, as in the case of lhe MS junction, the region near to
lhe insulator-semiconductor interface is depleted of mobile charges. This is the de-
pletion regime. Finally, when the positive bias is set even larger, the Fenni level
crosses lhe middle of the gap and approaches lhe conduction band edge. Accord-
ingly, lhe concentration of minority caniers (electrons) overpasses that of the ma-
jority canier, and the semiconductor becomes 11-type ncar the insulatOr. This coin-
cides with the inversion regime.
As in the MS j unction, the potential distribution in the semiconductor is calcu-
lated by solving the Poisson-Boltzmann Eqs. ( 14.2) and ( 14.4 ). We first rewrite
Eq. (14.4) as: -
[
+ ( qV) (qV)]
p = q NJ - N;; + p0 exp - kT - nucxp kT
( 14. 10}
14.2 Busic Principles 469
where fF,j and N;, are the densi ties of ionized donors and acceptors, respectively,
and Po and 11
0
the hole and electron concentrations at equilibrium. Electrical neu-
trality in the semiconductor bulk requires:
N J - N;; + Po - lin = 0 -
By inserting (14. 10) and (14. 11) in (14.2) we obtain:
d
2
V = !!..{no [exp(qV) - 1] -p0 [exp(- qV) - 1]}
dx2 Cs kT kT
To solve this difTeremial equation, we imroduce the electric field F:
It is readily seen that:
dV
F= - -
dx
PV dF dF dV
= --= - - -=f -.
dx- dx dV dx dV
(14. 11 )
( 14.12)
( 14. 13)
( 14. 14)
Substituting the far right term of ( 14. 14) into the left hand side of ( 14. 12) yields a
dilferential equation that can be integmted with respect to V, leading to:
F = J2k2)nf(V) (14. 15)
where
[ ] [ ( ] }
1/ 2
qV qV no qV qV
f(V) = { exp(- - ) + --:-:- I +- exp - ) --. - I
kT k7 po kT kT
{14. 16)
In Eq. (14. 16), the sign or the right h<md side equals that of the applied bim;. The
total charge in the semiconductor, Q . is related to the electric field at lhe insula-
tor-semiconductor interface. F., according to Gauss' s law:
( 14. 17)
The variation or the absolute surface chnrge as n function of surface potential (in
linear-log scale) is ::.hown in Figure 14-5.
The 1hrce different regimes or the MIS junclion, nccumulation, depletion and
inversion. are indicated in the figure. Note thnt the charge is posi ti ve in 1he accu-
mulation regime and negative in 1he depletion and inversion regi mes.
470
...
E
:a
s
Q)

"'
.s:;
0
Q)
0
"'
't:
:>
"'
14 Physics of Organic Fic:ld-Ejfect Trunsiswrs
1o
10-l
10.
3
10 ..
10-6
10-6
10.
7
-0.5 0 0.5 1.5
surface voltage (V)
Figure 14-5. Variation of the sw
face charge of u MIS junction as
a function of the surface poten
tial. V, = 2?. to the
UIIM:t Uf the in version n:
gimc.
To obtain a relationship the voltage V..: applied to the metal and the
surface potential V,. we aS!>Ulllc a cominui ty of the electric field at insulator-
semiconductor interface lhal implies
t:, F, = 1:,F, ( 14. 18)
where c, is the pcmlillivity of the insulator, and F, lhc (const;.mt) electric field in
the insulating layer. The voltage drop in the insulator is given by F ,d;. where d; is
the insulator thickness, and the voltage applied to the metal electrode by
(14. 19)
Here, C; = t;f d; is the insulator capacitance per unit area A parameter of interest
is the threshold voltage V" which corresponds to the onset of the inversion re-
gime. Usually, a distinction is made between weak and stmng inversion. Weak in
version starts when the surface potential \1, equals the difference >
11
between the
equilibri um Fermi level and the intrinsic level. The Iauer bei ng located very d ose
to midgap, weak inversion tales pl;.tcc when the Fermi level at the insulator-semi-
conductor imerface crosses the middle of the gap. Smmg inversion <.:orresponds to
V
5
> 2cpb 1131. However, at the ouL-;et of strong inversion, the d wrge in the
inversion layer is still small and the total induced d1arge is close to that of the de-
pletion layer (sec Fig. 14-5). From Eq. ( 14.7), the latter is given by
( 14.20)
This charge induces an electric field given by
I 4.2 Btl sic PrinciJIIes 471
( 14.21)
Using Eq. (1 4.19) we tinally tind
(14.22)
14.2.2 Field-Effect Transistors
11lc bo.t-;ic idea of a field-effect transistor is to modulate the current that flows in a
conducting dw_nncl hetwccn two clccuudcs, the source and drain, by applying a
vol tage to a tlllrd electrode, called the gate. Basically, the device can be viewed
as a capacitor, where one plate constitutes the conducting channel and the other
plate the gate. A FET can be built according to various ;.u-chitectures. We shall
concentrate here o.n three of them, shown in Figure 14-6.
source gate
drain
n-type region
substrate
semiconductor
(a)
(b)
(C)
l,.igurc J.a-6. view uf three
"iud>. uf ficld-ctrco.:t (FI::1.);
( a) Fl:. T
CMISFETJ. (b)
FET !MESFET). (c) tlnn li lm
tur (1Fn.
472 14 Physics of Organic: Fidcl-l:.Jfeu Trcm.1i.wors
The most popular FET is the silicon metal-oxide-semiconductor FET (MOS-
FET), also known as MISFET (metal-insulator-semiconductor FET) or IGFET
(insulated gate FET). In a MISFET, the gate is isolated from the conducting chan-
nel by an insulating layer, and the device opemtcs in the inversion regime. In the
metal-semiconductor FET (MESFET), the gate is isolated from the channel by the
depletion region that forms at the MS interface. Depending on the work function
of the gate electrode, a MESFET can be nom1ally on (the depletion layer only
fonns when a voltage is applied to the gate) or nommlly off (the depletion layer
already exists at zero gate bias). The third structure is the thin-tllm tnmsistor
(TFf). which was first applied to polycrystalline semiconductors [ 14 J, and is now
widely used in hydrogenate<.l amorphous silicon (a-Si: H) devices [ 13]. As indi-
cated by its name, this architecture uses a very thin semiconducting layer. It is an
isolated gate devise, like the MISFET. but unlike the MISFET, it opemtes in the
accwmtlut ion regime.
14.2.2.1 Metai-Insulutor-Semiconductor FET (MISFET)
14.2.2.1.1 Principle ol' Operation
As shown in Figure 14-6a, standard 11-channcl silicon MISFET.o; arc built on a p-
type semiconductor substmlc, on which two 11-typc regions arc grown to form the
source and the drain. The gate electrode is separated from the substmte by a ther-
mally grown silicon oxide layer. A prominent advantage of the MISFET is the
presence of a depletion region that scpamtes the p-type substmte from both the n-
type electrodes and n-channcl, thus providing isolation from any other device fab-
ricated on the same subsrnue. The geometrical parameters of the device are the
channel length L, that is the distance between the two p-11 junctions, lhe channel
width z. and the insulator thickness tl;. By convention, the source contact is con-
nected to ground.
Let us consider that a positive voltage V"' is applied to the gate, so that an in-
version layer grows at the insulator-semiconductor interface (see Fig. 14-7 a). This
means that a negative charge is capacitively induced here, fonning a conducting
channel between source and dmin. If now a small dmin voltage Vd is applied, a
current ld tlows through this channel. In this low voltage regime, the dr.tin current
r-
rg
-Vd=Vg
p-type substrate
- I
(a) (b)
figure 14-7. A in opcr<ttiou. (a) V,, VJ=O; an 11-typc channel of constant thickness
funns at the intcrfucc. (b) V"> V,, V.
1
= the dumncl is pinched on ;Ji lhc
dmin conlm;l. 11te white ar.:a Lhat separate the fHYJlC subslr.llc fnm1 the 11-typc and d101nncl
represents the deplcliun layer.
14.2 Busic Pri11dples
473
is proportional to V.,. As the drain voltage is increased, it eventually reaches a
poult where the channel <.lcpth at the dmin reduces to (Fin 14-7 b) Th' .
known as th f iff - o IS IS
e pmc 1-o (or saLurauon) vohagc V Abo c lh' . 1 h
' h ff' r/. w1 V IS YO tage, ( e
-o poult tl?wards lhe source, and carriers are injected from that
t? the, depktton .rcgt.on the drain. Bcc:tu:.e the number of carriers ar-
at the pmch-oll potnt remams essentially the same, the dr.tin current satu-
rates to a constallt value fd .... ,.
14.2.2.1.2 Current-Voltage Characteristic
the voltage characteristics, we usc Ute grutluul c:l!annel a
1
_
113 J mtroduccd Shockley, which assumes that the
mtluced by the elcctnc hel d pamllel to the channel is much smaller than
that mduccd by the field across the channel i c liJf' jf')l ..--..-- 1 ')F /D 1 h h
. d . . , . . . '' f ,. v . w ere t e
.tn .\, lhc tltrccttons po.trallel mtd perpendicular to the rcspcc-
fhls rcqutrcs I hat the channel length is much . larner than the . llsulator
t tel--ness (L I) 1 1 o
. . . ., '; : n sue 1 _Circumstances. one can ao;sume that the charge in-
duced at .t 0 1Vcn distance .r I rom the source is that of a MIS . h,
1
surface p >t nt'. I V ld be JUnctton w crc tte
. .l ta, .. equal_ IO \1, (.r). The ch:trgc per unit area Q, induced
at the lllsul.tiOr-scn1tl::onductor mtcrlace at a distance x from the source is then:
Qs(x) = -C;[V
11
-
\l,(x)]
( 14.23)
where C; is the insulator Ci!pacitance n.r unit arc t Llcrc v t's tlt n I b tl
1 (& . .
1
J" c a - an po-
tentta I ( 14.9)), whu.:h lor any work function difference bet wee
1
tl
gatc.electrodc and the scnuconductor*). 11te char!'c in the inversion hy r Q
obtatncd by subtracting the charge in the tlcplcti;n hycr rront .lite (().(' lc .' d "'.eds
charge 1121. m Ul:
Q,(x) = Q,(x) - Q,
1
,.,,(x) .
( 14.24)
In lhc strong inversion n:gime, the surface potenti al v ( ) can be
V( )
1
. . ' approximated to
Y'b+ .. x. 1ere V(x} IS the reverse btas :tt point x. Substiluting in (14.24) the to-
tal charge gtven by Eq. (14.23), and th:.tt of the dct>lct ion layer Eq (14 20)
find we
( 14.25)
The drain current 1, is now calculated by estimating the channel conductance .t:
f
z; z
g(x) = L. a(x')dx' = tiQ,(x)l . ( 14.26)
()
) In V1h hcaw.:cn - I V and I V. ,., lhal it <;m he negkctcd in
111
w,
1

474
/4 Physics of Organic Tra11siswrs
Here, a=nqJ.L is the channel conductivity, and J1 the electron mobi li ty, assumed to
be constant all over the channel. The elemental resistance dR of an elemental seg-
ment dx of the channel is given by
dx dx
dR = gL =
( 14.27)
and the voltage drop across this elemental segment by
lddx
(14.28)
The dmin cun-ent is now obtained by substituting (14.25) in (14.28) and integrat-
ing from source (x= O, V= O) to drain (x=L, V= VJ).
z { ( Vd) 2 J2c,qNu 3/2 , )3/2]}
ld = [fC;

V,,-
3
C; [( VJ +2,,)
( 14.29)
(Here, the flat-band potential was neglected.) A typical set of dmin current-volt-
age curves for various gate voltages is shown in Figure 14-8. . .
It is seen that for a given (constant) gate voltage, the dram current first In-
creases linearly with the drain voltage (linear regime), then gradually levels off to
reach a saturmion value (satumtion regime).
In the li near regime (Vd V
11
) Eq. ( 14.29) reduces to
2.5
2
I
1.5
c

:;
0
c
'iii
0
0.5
0
0
. -
. ,
.
-- Vg=2V
- - Vg=4V
Vg=6V
- - Vg=8V
---- - -- --- ---- -- -- ---- --
' . - =-, :t r - .-1 =r T ;- t= - """'i t - -
2 4 6 8
Drain voltage (V)
10
( 14.30)
Figure 14-K. Drain current-voltage
chamch:ristics of a typical MIS.
FET for various gate bia...cs.
14.2 Basic Principles 475
where the threshold voltage V, is given by Eq. ( 14.22). Two useful parameters are
the channel conductance and the transconductance g, which, in the linear re-
gime, are given by Eqs. ( 14.31) and (14.32).
[
()Jd] z
8t1 = DV = L JtC;(V
11
- V,) .
d V
1
= nHISI
( 14.31)
( 14.32)
1be satumtion current 1,
1
.sa
1
is obtained by setting Q,(L) = 0 in Eq. (14.24), which
gives the saturation voltage Vd .. fdl Substituting this value into Eq. (14.29) leads to
( 14.33)
where m is a function olthe doping and approaches 1/2 at low doping levels.
In the satumtion regime, the tmnsconduct;mce is given by
( 14.34)
14.2.2.2 Metal-Semiconductor FET (MESI<' ET)
ln a MESFET, a Schouky gate contact is used to modulate the source-drain cur-
rent. As shown in Figure 14-6b, in an n-channcl MESFET, two n source and
drain regions arc connected to an n-type channel. The width of the depletion
layer, and hence that of the channel, is modulated by the voltage applied to the
Schottky gate. In a nonnally off device (Fig. 14-9a), the channel is totally de-
pleted at :rero gate bias, whereas it is only panially depleted in a normally on de-
vice (Fig. 14-9 b).
To calculate the currem-voltage chamcteristic of a MESFET, we assume that
the conducting channel is at thennal equilibrium, and the space-charge layer com-
pletely depleted. Eq. ( 14.28) becomes
dv
- I R - J,,dx
- tit/ -
lJJIN,1Z(tl,- W(.r)]
(14.35)
where ds is the thickness of the active layer and W(x) the (position-dependent) space
charge layer thid.ness. Thl! Iauer is given by Eq. ( 14.6), which we now rewrite
W(x) =
2c_,[V(x) + Vt.; - V
11
}
qN,,
( 14.36)
476 14 Pltysic:s of Organic Field-Effect Transistors
00
Figun: 14-9. Schematic view of normally on (a) and normally off (b) MESFEfs at zero g.ue voiJage.
Jn (a) a conducting channel alreouly exists, while in (b) the depletion layer extends all over the ch:ln-
nel.
Substituting (14.36) into ( 14.35) and integmting from source (.x:::::O) to drain
(x==L) we finll
( 14.37)
Here,
( 14.38)
is the conductance of the (not depleted) channel, anti
( 14.39]
the channel pi nch-off voltage. that is the voltage at which the depletion. layer ex-
tends all over the channel. When pinch-off occurs (W(L)==d . ). the dr.un current
saturates. This occurs at the saturation voltage
(14.40)
Inserting (1 4.40) into (14.37) leads to the expression of the satumtion current
( 14.41)
14.2.2.3 Thin-Film Transistor (TFT)
TI1e silicon wafers used in conventional microelectronics arc fmgile. relatively ex-
pensive, and their size is limited to that of the singlc-_crystal ingot fru_m which
they arc cut. In applications where large areas arc rcqun-ed, other matenals seem
14.2 Busic Principles 477
more appropriate, namely the polycrystalli nc, amorphous and organic semiconduc-
tors. which are all characterized by a canier mobility much lower than that of lhc
crystalline inorganic semiconductors. For these matt:rials, the FET structures de-
scribed until now arc not appropriate. A thirll geomet ry. the thin film tmnsistor
(TFT). first described by Weimer in 1962 in the case of polycrystallint: cadmium
sulfide 114), is much more attractive. As can he seen in Figure 14-6, the TFT
shares its insulated gate electrode with the MJSFET. However, it di ffers from lhe
MlSFEf in two respects. First, the semiconductor consists of a very thin layer,
even thinner than the insulator. Secondly, the source and drain are ohmic contacts
directly formed on top of the thin semiconductor, so that the conducting channel
is not isolated from the res! of the semiconducting film. However, the low thick-
ness and poor conductivity of the semiconducting film ensure a very low drain
current at zero gate voltage. Accordingly, !he TFf operates in the accumulation
(or enrichment) regime, hy applying a gate vol tage that wi ll induce a majority car-
rier channel at the insulator-semiconductor interface (i .e., a posi ti ve (negative)
voltage for an 1Hypc (p-typc) material. respectivel y). We will see that the TFT
can also opcmte in the depletion regi me, in which case its opemting mo<.le resem-
bles that of the MESFET.
14.2.2.3.1 Accumulation Mode, Linear Regime
Because there is no depletion layer between the substrate and the conducting chan-
nel, the equations of the cuJTCnt-voltage curves are in fact simpler in the TFT than in
the MJSFEf, providel..l the mobili1y can still be assumed constant (which is not ac-
tually the case in most devices, as will be seen below). Under such ci rcumstances.
the charge induced in the channel is given, in the case of an 11-channel, by Eq.
(14.23). In the accumulation regime, the surface potential V...(x) is the sum of two
contributions: (i) the ohmic drop in the accumulation layer, and (ii) a term V(x) that
acrounts lor the drain bias. The first term can be estimated from Eqs. (14. 15),
(14. 16) and (14. 19). In the accumulation regime, and provided Vs>kT/q, the expo-
nential term prevai ls in Eq. (14. 16), so that Eq. (14. 15) reduces to
F ("V.) --exp -- .
e.. 2kT
( 14.42)
Substituting ( 14.42) imo &j. ( 14. 19). we sec that, once more, the linear term V, can
be neglected with respect to the exponential term. In other words, most of the gate-
source ohmic drop occurs in the insulator, so that Eq. ( 14.23) becomes simply
Q(x) = - \.)1,- V(x)] . ( 14.43)
Eq. (14.43) requires accumul ation to extend all along the channel, namely V,
1
<
As the channel is directly in contact wi th the rest of the semiconductor layer, we
have also to account for the bulk conductivity of the semiconducti ng lilm when
intcgmting the drain currem, which leads to an equation of the form
478 / 4 of Organic Fidd-Ejfect Transistors
( 14.44)
Here, Q
0
=-qnc!ls is the bulk charge, where no is the bulk carrier density and ds
the thickness of the semiconductor (recall that q is the absolute electron charge,
and that we are dealing here with an n-type semiconductor). We note that, unlike
the case for the MISFET, the bulk conductivity has the same sign as that of the
channel. In other words, Q(x) and Q
0
are both negative in the case of an n-type
semiconductor. lntegmting Eq. ( 14.44) from source to dr.tin leads to
Here the threshold voltage is given by
qn
0
d .
V, = ---+ Vp,
C;
( 14.45)
( 14.46)
[For a p -type semiconductor, Qu = qpud where p
0
is the bulk hole density. 1l1en
( 14.47)
and JJ and V
11
arc both negati ve in Eq. ( 14.45).]
In the case of an 11-type semiconductor in the accumulation regime, the 1Ff
opemtes at positive gate and dmin biases. We note that the threshold voltage is
negative. In fact, the very notion of threshold is not fully j usti fied in a TFf. In a
conventional MISFEf, the threshold COJTesponds to the onset of the strong inver-
sion regime that follows the depletion and weak inversion modes. The Iauer is of-
ten referred to a.o; the subthreshold regime. In contrast, a dr.1i n current alrC41dy
flows in the TFT at zero gate voltage; it coincides wi th the bulk conducti vi ty of
the semiconductor lilm. As we shall sec in Section 14.6.2.2, a negative ' thresh-
old' voltage is indeed round in some OFET.-;. However. most devices, and particu-
larly amorphous si licon TFfs, present a positive threshold. This must be con-
nected wi th a gate-bias-dependent mobi lity (see Section 14.2.2.3.4). In that case,
the field-elTeet mobili ty abruptly increases above a given (positi ve) gate bias, also
termed threshold voltage.
14.2.2.3.2 Depletion Mode
The principl e of the depletion regime is quite similar to that occuning in MES
FEfs, with the difference that, unl ike the MESFEf, the TFT is an insulated gate
device [ 15 ]. Accordingly, Eq. ( 14.36), which gives the width of the depletion
layer, changes to
W(x) = c . [
C;
14.2 Basic Princ:iples
+ - 1
I
2Cr(Vx - l'f,. - v(x)) l
qNcs
479
( 14.48)
where VJb is the nat-band potential, and N the concentration of dopants (donors or
occepto':' depending on whether the semiconductor is n- or p-type). 1l1e drain
current IS now obtained by integr.1ting Eq. ( 14.35 ), which we now wri te
l"clx = Zqnpjcl, - W(x) )c/V ( 14.49)
where n is the density. (The reason why we introduce a dist inction be-
tween the doping level N and the carrier density ,, will be discussed in Sect ion
14.6.2.2). By diiTcrcntiating &j. ( 14.48) wi th respect tu V and inserting the results
into (14.49) we lind
( 14.50)
which can now be integmtcd from source (x=O, V=O and W=y.> to drain (x =L,
V= V" and W=y2). Here, y , and y
2
arc the depletion layer width at source and
drain, respecti vely.
( 14.51)
Here, C.. = csfds is the dielectric of the semiconducti ng fi lm, and
1
_ ?:_
1
' - L 6t:.,
Eq. ( 14.5 1) can be substantially simplified if we assume that Cs C;, which is in-
the case _when semiconducting fi lm is thinner than the insulating layer. The
dram current 111 the lmear and saturation regimes is then respectively given by
( 14.52)
Z II ,
l,t.nll = 2L'' N - v,,)" . ( 14.53)
Here, V
1
, is the pinch-oiT voltage dclincd in Sect ion 14.2.2.2. It is now given by
( C) qNcl,
= I + 2C + V
11
, :::::: =F -.- + \-'ft
_t., , C,
( 14.54)
480
14 Physics of Organic Ficli.I-Ef[et:l Tmruislors
with a minus sign for an n-type, and a plus sign for a p-typc semiconductor. Note
that in its simplified form the pinch-off voltage is to the voltage
of the accumulation mode, except that the carrier dens1ty no (or Po) IS replaced by
the dopant concentration N.
14.2.233 Accumulation Mode, Saturation Regime
In the accumulation mode, gate and drain biases have the same sign, so that the
drain-gate voltage decreases as the drain voltage Vx. As noted
Eq. (14.45) is no longer valid when VJ > Vg. When thiS t.hc accumulauon
layer ncar the drain changes to a depletio11 as m. F1gure 14- 10.
Saturation turns on when the charge at dram vamshes, that 1s Q(L) = 0.
The saturation current can be estimated by following a method mtroduced by
Brown and coworkers [16) and developt:d further by Horowitz et at. (17_1. We as-
sume that the accumulation layer extends from the source up to a pomt where
V(x) = V..: (sec Fig. 14- 10). beyond it turns to a depktion layer. The drain
current is hence given by the sum ul two mtegrals.
v. z \' .....
l.,,s., = 11C; J ( V..: - V, - V)dV + L JUJIIu J (d., - W)c/V
()
( 14.55)
The second term is integmted up to the saturation voltage V,'"'' where Q(L) =. 0.
As in the previous section, we change the integmtion variable from V to W. wh1ch
is done via Eq. (14.48), and integrate from W(V
11
) = 0 to W(VJ.M) = d, .
z Jv. Z c/n0N !"' ( e.,)
JJ . = - JIC (V - V,- V)t!V + (cis - W) W + C dW
'"' L I g L c., i
0 0
v.v.)+ (1 +J } (14.56)
The result can be simplified by making usc of the above-defined pinch-off volt-
age [Eq. ( 14.54)1 and dielectric of the semiconducting layer .. Further
simplifications result from the assumptions that Cs C, (Eq. ( 14.57)). and that
the dopant and carrier concentrations arc equal (&j. ( 14.58)).
accumulation
gate
depletion
l<' igure 14-ltl. Sdlcm:llic view or Lh.: t:onuucling
t:hillllld ur " TFT in I he al salura-
tiuu.
1-1.3 Clw rg' 7i-ausport in Organic Mllelials 481
z 2
l,t..,, = - j.tC;(V .. - 2V, VII+ v, V,.)
2L '
( 14.57)
( 14.58)
Eq. (14.51:!) is widely usetl to estimate the mobili ty of OFETs. When it is valid,
plotting the square root of the saturation current a!> a function of gate voltage
would give a stmight line, the slope of which is directly rel ated to the motrility.
Furthermore, the point at which the line crosses the voltage axis corresponds to
the threshold voltage. However, it must be kept in mind Lhat the validity of this
equation rests on several underlying assumptions, namely a constant mobility, and
the equali ty between the density of free caiTicrs and that of dopants.
14.2.23.4 Mobility 'fhn.'Shold
In fact, the assumption of a constant mobility is not representative of actual TFf.-;.
To illustrate this, we n:fer to the model of the amorphous silicon TFT developed
by Shur 113. 181. Hydrogenated silicon. a-Si:H, diller.. from crystall ine si licon by
a large density of localit.cd stales in the energy gap. In undopcd a-Si : H, the posi-
tion of the Fermi level is determined by the distribution of localized states. With-
out any gate hias, the transport docs not occur in delocalizcd bands, but
via hopping between the localized levels. Accordingly, the mobility is very low
(sec next secti on). When a gate voltage is applied. the quasi-Fermi level gradually
moves towards the nearest delocalized band edge. Above a given threshold volt-
age, transport in the dclocalizcd band is favored. and the mobility abruptly in-
creases. At very high gate bias. the band mobi lity, around I 0 cm
2
V
1
s- . would
be reached. However, thi s regi me is never attained in pmctice, and the above thresh-
old tield-ciTectmobility in actual devices mnges between 0. 1 and I em:! v-' s-
1
We
note, however, that the very low carrier mobility at zero gate-voltage presents one
advantage: it allows drain cun-cnt on-otT mtios of up to 10
7
. In MJSFETs, thanks
to the deplet ion region that SUITounds the source and drai n contacl'i, the on-off ra-
tio is even higher. Large on-otT ratios arc essential in applications where leakage
currents in the oil stale should be set to a minimum.
14.3 Charge Transport in 01ganic Materials
14.3.1 Localized Versus Dclocalizcd States
The high electrical conductivi ty or metals as well as the high elect ron (and hole)
mobility of inorganic covalently bound semiconductors have both been chtrilicJ
by the band theory II() 1. whid1 swtes that the discrele energy levels of individu;ll
atoms wiJen in the solid into and forbidden bands. The
482 /4 Physics of Orgauic Field-Effect Transiswrs
highest energy occupied allowed band of a metal, or conduction band, is only par-
tially fi lled with electrons. up to the so-called Fermi level. Hence, electrons lo-
cated close to this Fermi energy arc easily excited to the unoccupied level of the
band, where they behave as free electrons. In a semiconductor (like in an insula-
tor), the highest occupied allowed banll is totall y tilled, and called valence band
(VB), whereas the conducti on band (CB) corresponds to the lowest unoccupied al-
lowed band, which is completely empty. The injection of electrons in the CB oc-
curs ei ther thermally (in an intrinsic semiconductor) or through doping (extrinsic
semiconductor). Electrons in the conduction band of metals or semiconductors
move in delocalized states, and their wave function can be approximated to that
of a ti-ee electron, that is. a progressive plane wave
'Pk(r) = expikr.
( 14.59)
In banlls, the charge uansport is limited by the scattering of the car-
riers by lattice vibrations (phonons). Therelore, an increase in the temperature,
which induces an increase in the density of phonons, leads to a dec:n:ase in the
mobi lity.
In disordered materials such as amorphous silicon, the mobi lity is so low that it
would correspond to a mean free path lower than the distance between atomic
sites, which is not physically pertinent. In a classical paper, Anderson [201 has
shown that disorder in a solid may result in a localization of the states, in which
case the one-electron wave function Lakes an exponential fonn
rp(r) = exp(- ,
(14.60)
where a is the size of the localized state. Charge transport in that case occurs via
tunneling between localized states. When states arc localized, the tunneling of car-
riers from one site to the next is assisted by phonons. Hence, the mobility is ther-
mally activated, which means that it when the tempemture increases.
This mechanism is termed piiOilOn-ac:livaled hopping. Interesti ngly, such a mecha
nism is not restricted to llisordercll materials; it c;m also occur in well -ordered
crystals, where strong electron-phonon interaction results in the formation of self-
localized states called polwvns. As pointed out by Bassler {21 ), in real solids, the
activation energy of the mobility is the sum of two terms, one arising from disor-
der, and the second one from the change of molecular confonnation upon addi-
tion of a charge. The essenti al difference between hopping and polaron models is
related to the relative importance of both contributions. In the hopping model, it
is assumed that the coupling between charge and vibmtion modes is weak, and
that most or the temperature dependence mi rrors the energy disorder of the hop-
ping sites, whereas the polaron model considers disorder to be unimportant with
respect to electron-phonon coupling.
14.3 Charge Tmusport in Orxmric Materials 4133
14.3.2 Hopping
14.3.2.1 Rate
A celebrated deriv<ttion of the temperature depcndcnce of the mobility within the
hopping mudd was made by Miller aml Ahrahams 1221. They Iirst evaluated the
hopping r.ne Yij that is the probabili ty that an electron at site i jumps to si te j.
Their evaluation was made in the case of a lightly doped semiconductor at a very
low tempcr..tture. The localized st;.ttes are shallow impurity levels; their energy
stands in a nanow range, so that even ;.tt low tempcrulures, an electron at one site
can easily find a phonon to jump to the nearest site. The hopping rate is given by
(
-) ( '>/{)
)',i = }',/(;) exp - 'kT 1 exp - -,/ ( 14.61)
where f is the Fermi function and y
11
;.t constant that contains an electron-phonon
coupling term and the phonon density of states. ; and E; arc the energy of sites i
and j, respectively, and R;j the distance between them. The fi rst exponential term
on the ri ght hand sille accounts lor the temperature dct>endence of the phonon
density, and the second exponential is the tunneling probability. At low doping
levels, the averuge distance between si tes is large, and the exponential form or the
tunneling probability prevents hopping to sites more distant than the nearest
neighbor. Accordingly, this process is called fixed IWf'f'in,r; . The tempcm-
ture dependence of the mobility is governed by the lirst exponential term of Eq.
(14.61 ). In other words, the mobility is them1ally activated.
Another famous hopping model is Molt's variable range hopping (23], in
which it is assumed that the localized si tes are spread over the entire gap. At low
tempemtures, the probability to find a phonon of sullicient energy to induce a
jump to the nearest neighbor is low. and hops over larger distances may be more
favomble. In thut case, the conductivity is given by
(
T.) 1/ 4
a = ooexp - ; ( 14.62)
More recently, 0. Emin [241 developed an alternative analysis of activated hop-
ping by introducing the concept of coincide11ce. The tunneling of an electron from
one site to the next occurs when the energy state of the second site coincides wi th
that of the first one. Such a coincillcnce is insured hy the thermal deformations of
the lattice. By comparing the liiCtime of such a coincidence and the electron tran-
sit time. one can identify two classes of hopping processes. If the coincidence
time is much larger than the transit time. the jump is adiabatic: the electron has
time to follow the lattice llel'urmati ons. In the reverse case, the jump is non-adia-
batic.
484 14 Physics of Orgauic Field-EJJect Transistors
14.3.2.2 Polarons
A polaron arises from the interaction between a charge canier and the defonna-
tion of the lattice induced by this charge. The concept of polaron was first intro-
duced in the case of ionic crystals [25] (such as transition metal oxides), where
the high polarizability of the ion pairs results in large deformations of the lauicc
under the influence of a point charge. It has been extended later to molecular
crystals [26] and conjugated polymers (27]. A distinction is made between large
[281 and small L26, 29] polarons. In the former, the deformation of the lattice ex-
tends over laq;e distances as compared to the lattice pammeters and vice versa for
small polarons. The ditTercnec between large and small polarons can also be
viewed from the standpoint of energy: for large (small) polarons, the binding en-
ergy
11
is smaller (larger) than the conduction (or valence) bandwidth.
14.3.2.2.1 Polarons in Conjugated Polymers
A polymer is constituted by the repetition, along the chain tlircction, of small
monomeric units. lt can therefore be perceived as a one-dimensional latt ice. Con-
sequently, as in a three-dimensional crystal, the electron energy levels are
distributed in (one-dimensional) bands. A conjugated polymer is characterized by
a regular alternation of single and double carbon-carbon bonds. Double bonds
. give rise to n-clectrons delocalizetl along the polymer chain, resulting in relat ively
wide allowed bands (around I eY). This allows the doping of the polymer
through charge transfer from electron donor or acceptor species. Because of its
low dimensionality, adding a charge to a polymer chain leads to a profound
change in its geometrical structure near this charge. Analogous to ionic and mo-
lecular crystals, the coupling between the charge and the local deformation of the
chemical structure is also called a po/aro11 (27]. The classical picture of a polaron
in a conjugated polymer is shown in Figure 14-11.
The polaron is charactcri:t..etl by the reversal of bond alternation, which, in the
case of polythiophenc, extends over five monomer units [ 30-321, and the appear-
ance of two locali:t..ed states in the band gap*). These states have been indeed ob-
served by UY-VIS absorption of both oligomers and polymers, in solution L33-
40] and in the solid state [41-451.
14.3.2.2.2 Tr<msporl Mechanism of Polarons
Because polarons are localized species, their natural tmnspo11 mechanism is hop-
ping. We shall now brielly describe the small polaron model, as developed by
Holstein and Emin L26, 29, 461.
The medium considered by Holstein is a one-dimensional crystal that containl>
a single excess electron. The l lamiltonian of the system is compose(.! of three
* ) In polymers with a dcgcncr.ucd ground state, ch.u-gccl defects arc tcnncd ;utd g1ve riM: to a
single level in the b;md gap. l>oli.ulm pcnain to IWII dtRt'IIC'ra/ttl ground state which is
the case ror praclicully :111 the cunducting pulynu:rs. except mm. pulyacclylenc.
14.3 Charge TraiiSftOI'I iu Orgcmic Materials 485
Figure t4-11. A pularnn in pulythiophcnc. Tt>p
view j,. a IUUI..-.:ular ,.;heme, the bottom view is
the encrJ y diagram.
tcm1s. First, the lattice component of a sum of N harmonic oscillators
that vibrate at a unique frequency wu-
E _f.. I (II iJ ):! I :! 2
L - L '>M -:- -:---) + -2 Mwuu,
II = I - I ( II,
( 14.63)
Here, u, is the displacement of the nth molecule from its equi librium position and
M the reduced mass of each molecular site. Second, the eltuuvll is described
within the frame of the tight-binding <lpproximation, where it is assumed that the
effect of the potential at a given site or the one-dimensional chain is limited to its
nearest neighbors. In that case, the enCf'JY dispersion of the electron is given by
Ek = Eu - 2J eos(ka) . ( 14.64)
where J is the electron tr,msfer energy, that is a matrix clement of the form
('I';IV;I 'l'j) and a the lattice constant. The conduction bandwidth is 2J. Finally, the
e/ectron-lclflice intt'raction, which is a function of both the clectron coordinates
a00 the lattice displacements, is a-.sumcd to be linearly dependent upon the hitter.
Accordingly, the eleclron-lauice coupling is accountetl lor by a term or the tonn
c, =-Au, ( 14.65)
where A is a constant. In standard one-electron models, this coupling term is
treated as a small perturbation. In the polaron thco1y, the electron-lattice term
must be considered in the order of zero, so that the Holstein's motlel consists of
treating the electml/ic term as a small perturbation.
An important pammeter is the polaron-binding energy L:i,. which is tlefinctl a-;
the energy gain of carriers due to the pl)larizalion anti deformation of the lattice.
In the Holstein's model, =A:! The small polaron limit corresponds to
the limit where the electron bantlwidth '21 is smaller than the polaron-binding en-
ergy
1
, so that the electronic term or the Hami ltonian can be treated as a small
perturbation. The electron mobility is from the hopping time obtained
486 /4 Physics of Orga11ic Ficld-Ejfect Transistors
by solving the time-dependent Schrodinger equation. The high temperature limit
(T >e. where the Oebye temperature e is detined by k8 = Fzw
0
) of the mobility
is given by

ea
2
J
2
- 3/2 ( Eb )
11 -;:::. - - - (kT} exp - - .
li ,fEb 2k.T
( 14.66)
Notice that the term ea
2
fn has the dimension of a mobility, with a magnitude
ranging between 1 and 5 cm
2
v- s- in most molecular crystals.
At very low tcmpemturcs, Holstein predicted that the small polaron would
move in delocali zed levels, the so-called small polaron band. ln that case, mobili-
ty is expected to increase when temperature decreases. The tmnsition between lhe
hopping and band regimes would occur at a critical tempemturc T,-;:::. 0.48. We
note, however, that the polanm bandwidth is predicted to be very narrow
J0-
3
rzw
0
, or cV for a typical phonon frequency of 1000 cm-
1
). It is there.
fore expected that this band transpm1 would be l!asily tli:.turbcd by
crystal defects.
The perturbation theory used by Holstei n in his small-polaron model confires
its validity to an upper limit for J of around ftw
11
, which corresponds to a /lOll-
adiabatic process. The adiabatic process, for which J > liw
0
, has been studied
less extensively. In the high temperature limit, Emin and Holstein [46] arrive at
the result that
3Wo ea
2
[ Eb/2 - J]
jl =--exp - .
4n kT kT
( 14.67)
Emin stresses the point that.. as in the non-adiabatic process. Eq. (14.66) is only
valid for J < Eb/2 to preserve the small polaron chamcter of the charge
14 .. 3.3 Multiple Trapping and Release
An alternative model to account for the low mobility in amorphous materials is that
of multiple tntpping and thermal release (MTR) [47]. In thi s model, a narrow delo-
calized band is associated with a high conccntmtion of localized levels that act as
traps. During their U<msit through the delocalized levels, the charge carrier.; internet
with the localized levels through trapping and thermal release. The following as-
sumptions arc usually made: first, carriers aniving at a trap arc instantaneously cap-
tured with a probability close to one. Second, the release of tmppcd carriers is con-
trolled by a thermally activated process. 1l1c resulting drift mobility Jlo is related to
the mobility Jlu in the dclocali:a:d band by an expression of the form
(
,)
Jlv = JloU cxp - kT .
( 14.68)
14.3 Charge Trwuport i11 Organic Muteritlls 487
In the where there is one single trap level, E, is the energy difference be-
tween thss level and the delocalized band edge, and a the ratio between the effec-
tive density of at_ the dclocalized band edge and the concentration of traps.
If tmps arc energy dsstnbuted, dTective values of N, and a must be estimated.
14.3.4 Field-Dependent Mobility
i!s temperature dependence, hopping tnmsport is also chamctcrizcd by an
elcctnc This dependence becomes mcasumblc at high
field (namely. for a fscld m excess or ca. 10
4
V/cm). Such a behavior was fi rst rc-
in 1970 in (PVK) [48). The phenomenon was ex-
plamcd through a mechanism (49), in which the Coulomb potential
near a charged level is modified by the applied field in such a way that
the tunnel transfer SIIC:. illl"I'CiiSCS. The general dcpcnucnc.:e ur the
mobility is then given by Eq. (14.69)
( 14.69)
where p(O) is the mobi lity at zero ticld, fJ = ,f(if7U; the Poole-Frenkcl factor and
F magnitude the electric field. It has been recognized later by Gill (50), de-
spstc the fact that predicts the conect field dependence. that several objections
can be made ro thss model. The prominent one is that a Imp-controlled charge
transport of carriers, which is not in agreement with
the low mobshty m organsc matClials. The problem has found a satisfactory an-
only recently, Bti.-.sler (21) performed a stati stical Monte-Carlo compu-
tatJon, based on a hoppmg model wi th a Gaussian distribution of localized levels.
In moclel, . Bassler makes a di stinction between diagonal, i.e., energetic, and
off-dwgvnal dssorder, the latter accounts for that in a disordered medium, the in-
tersitc su_bjcct _to local variation. 1l1e cncrgctil.: disorder is depicted by
a Gausssan wsth a standard deviation a and the ofT-diagonal disorder
by a standard devsatson E. 1l1e jump r..tte amono sites was assumed to be of the
MiiiCl'S-Abr..thams type. From a Monte..Carlo Bassler arrives at a uni-
versal law relating the mobi lity to the deurce of both dia"onal and otT-diagonal
disorder: o o
( 14.70)
We a 4}( the :a:su t'Jdd mobi lity as exp[-(7i
1
/T)
2
]. a
behavtor whsch ss mdccd .in real org.wK: semiconductors, and differs
from boLh Millers-Abmhams' fixed r..tnga! <tnd vuriable range hopping mod-
els.
488 14 Physics of Orgu11ic Fie/d-EJJect Transistors
14.4 Fabrication Techniques
Conventional electronic devices are made on silicon wafers. The fabrication of a
silicon MISFET starts with the diffusion (or implantation) of the source and drain,
followed by the growing of the insulating layer, usually thermally grown silicon
oxide, and ends with the deposition of the metal electrodes. In TFfs, the semicon-
ductor is not a bulk material, but a thin film, so that the device presents an in-
verted architecture. It is built on an appropriate substrate and the deposition of the
semiconductor constitutes the last step of the process. TFf structures can be di-
vided into two families (Fig. 14-12). In c:oplu1Ulr devices, all layers are on the
same side of the semiconductor. Conversely, in staggered structures gate and
source-dmin stand on opposing sides of the semiconductor layer.
Most OFETs realized ti II now were constructed according to an inverted copla-
nar geometry built on highly doped silicon wafers covered with a thermally
grown si licon oxide layer (Fig. 14- 12a). The highly doped substrate act-. as the
gate electrode, and the source and dmin arc on the layer by
conventional microlithogruphi\: techni4ues. The mam advantage ol ths approach
is the possibility of using standard technologies or microelectronics, since most of
the device is constituted by silicon. However. ucvices made on the same silicon
wafer cannot be aduresscd individuall y, which constitutes the major drawback of
this technique.
Other techniques that use organic substrates and insulators have been devel-
oped recently, and wi ll be detailed in Section 14.4.2.
14.4.1 Deposition of the Semiconductor
Because most of the OFETs reported umil now were grown on silicon wafers, the
deposition of the semiconductor is the detemlining step of their fabrication. [)e.
semiconduct()(
I
(a)
(C)

I gate I
(b)
-
-
(d)
f' igurc 14-12. Various of (a) Inverted coplan;IJ' on a highly <.loped Si walcr, (b) inverted
coplanar on a ncutml (c) inverted on ll m:utrJI substr.JLc. (d) mvcrtcd staggered
the <.liclc.:tric layer a.' the
i-.
I 4.4 Fabrication Techniques
489
l on nature the semiconducting material. polymer or small molecule,
various deposll10n technrques have been used.
14.4.1.1 Electropolymeriz.ation
polymerization is one of the leadi ng lt!chniques for the synthesis
of and reports on electrochemically grown OFETs date back
ll? the late eighties The main advantage of this technique is the direct synthe-
SIS of the polymer Ill the form of a thin fi lm. However, its dmwbacks are
ous. Firstly, only occurs on conducting substmtes. For this
semJcondu.ctor lilm is first grown on the source and drain electrodes,
the occurring through a latcrul expansion of the depos-
It results . Ill a. h1ghly d1sordered film and a poor quality of the insulator-
mterlacc. Secondly, the CP is obtained in its oxidized (conducting)
so It be rcdUI.:cd (generally electrcxhcmically) to become semicon-
ductmg. Th1s <Ill sourl:c of disordl:r. Today, this tedmique is
no longer used 111 the lahfll:auon of OFETs.
14..1.1.2 Solution-Pmccsscd DcJlosilion
of the most :vays to rcali:l.A! a good quality polymer lilm is spin coat-
mg. the well handled, its allows the proJuction of very homo-
gene.ous a of its thickness over relatively large areas. A
reqUirement lor .this tcchmque Is good solubi lity of the polymer. Unfortunately, a
great_ number . . CPs arc not soluble. l11e problem may be overcome by either
grafting solubhzmg groups to the polymer backbone 151, 521 or the use of a sol-
uble . precursor which is then converted to the CP by an appropriate
phys1cal or treatment 153, 541. Solution-processed deposition has also
a short. mo!ecule. pcntacenc 155/. The main problem with spin
coaimg IS that II resulls m disordered amot]}/wus lilms, which is not favorable tor
the final mobility of the device.
14.4.1.3 Vacuum Evapor.ttion
Spin coating, which require.-; solutions of high viscosity. is usually not applicable
to ones are more appropriately deposited by vacuum eva-
con.sJsts of heating the material under rctluced pressure. (We note
that, m pnnc1ple, th1s techni4ue is not appropriate lor polymers, which tend to de-
c?mpose by at high temperatures). The process is conducted in a very
or. ultra h1gh vacuum chamber. The organic material is put into a metal boat,
wh1ch. 1s heated by Joule elfects, or sometimes wi th an electron gun. The sub-
IS placed a few centimeters above the boat. 11tc advamages of vacuum de-
positiOn the control of the thickness and purity or the lilm, and particu-
l:u-ly the lact that h1ghly lihns can be realized by monitoring the dcposi-
rate and the temperature ol the substrate. Its primary drawback is that it re-
quires a sophistic;ued instrumcmation, which contnt-.ts with the simplicity and
490 14 Physics of Organic Fidd-EJJect Transistors
low cost of spin coating. Vacuum evaporation has been utilized with a great vari-
ety of short molecules, which will be detailed in Section 14.5.
14.4.1.4 Langmuir-Blodgett
An alternative means to realize well-organized thin fi lms of small molecules is the
Langmuir-Blodgett (LB) technique, which allows a fine control of both the struc-
ture and thickness of the film. We note, however, that this technique is in princi-
ple restricted to amphiphilic molecules, composed of a hydrophobic chain and. a
hydrophobic head-group, which is not the case for most molecules used m
OFEf.o;. Nevenheless, LB-grown OFETs have been reported with mixed layers of
quin4uethiophenc (5T) and arachidic acid, which gave well-behaved .156).
However, the necessary mixing of the electrically active compound w1th an mac-
live compound leads to a suhstantial decrease in the mobility, as compared to that
of a vacuum-evaporated film.
14.4.2 All-Organic Devices
OFETs constructed on a silicon wafer do not take advantage of one of the
interest of organic materials, namely the possibility or buikling electronic devices
on plastic substrJtcs. A second important drawback of the silicon-based structure
is tJ1e dilfieulty to individually address the gate of trJnsistors buill on the same
wafer, which would prevent the achievement of integmted circuits.
Several attempts have been made to build OFETs on plastic substrates. One of the
first was reported by our group at TI1iais. First, the device was made on a glass sub-
strate, with a spin-coated organic polymer insulator, and source and dmin deposited
through a nickel shadow mask on top of the semiconducting film (57). In the secooo
step, the glass was changed to a polymeric film (polyimide), thus making the fmt
'nearly-all' organic tr.msistor (the only inorganic materials being the metals
used for the electrodes). It is worth pointing out that these devices presented char-
acteristics comparable to (and sometimes even better than) those made on silicon,
and that no noticeable loss of performance was observed upon bending the llexible
substrate. The improved performance of OFEf.o; made on organic insulators was first
noted by the group at Thiais from a comparati ve study of various insulating materials
deposited on glass 1591. It has recently been confirmed in a repon by a group at IBM
[601. who observed an enhancement of the mobility by a factor of three from poly-
methylmethacrylate (PMMA) to Parylenc-c (see Table 14-1 in Section 14.5. 1 ).
More recently, Gamier and coworkers used a printing tcchni4ue to make
OFETs on polymeric subsuates 161 ). Although printable licld-cllect transistors
based on inorganic: semiconductors have been rcpo11cd as early as 1967 (62), they
did not come to any commercial development. We note, however, that in Gar-
nier's device only the electrodes were actually printed.
A further step has been taken by a group at Bell Ltbs, who built an all printed
device on an ITO-coated polyester substrJte 1631; all the subsequent layers.
14.5 Materials 491
namely polyimide .insulator, poly(3-alkylthiophene), and finall y
the source and made ot a conducting ink, were printed through stainl ess
steel ma'iks. Intcrcstmgly. all the component-; used in that OFET are commercially
available.
More recently, Rogers, Bao and Raju 1641 used an alternati ve microfabrication
in capillaries (MIMICs), which, using lithographic tech-
mques. mvolves makmg an elastomctric micromold into which a solution of con-
ducting. polyaniline is cast onto t1le semiconductor layer, thus defining the source
Jlld A channel length down to 25 could be realized, and the
mobil ity ol t11e all-organic device was 0.01-0.05 em y - s- .
Finally, a group at Philips fabricated an 'all-organic wafer' that consisted of a
polyimide substrJte. a poly(thienylcnevinylcne) (PTV) semiconductor a
poly(vinylphenol) insulator. and doped polyaniline electrodes I65J. All cons,titu-
ent'i arc spin-coated. and the various polymers were chosen so that dissolution of
the underlying layers is avoided at each deposition step. A photoinitiator was
to the polyanilinc to pattern the ek.-ctrodcs, which after exposure to UY-
hght mcreascs the resistance of the conducting polymer by more than ten orders
Finally, vertical interconnections arc simply realized by punching
Wi th pms through the layers. The various circuits made on the 3-inch wafer com-
si ngle with _a canicr mobility of 0.0003 cm
2
y - s- , si mple test
CII'CU! ts, a IS-b1t mechamcally programmable code generator combining 326
transistors. fhe area of this htrge circuit was 27 mm
2
, and fifty of them
could be assembled on a single wafer.
14.5 Materials
The of OFET-; has continuously improved since they were first re-
ported m !8. 9J. The mte of the progress can be visualized in Figure 14-13,
where we p_loued. the field-effect mobility of live prominent organic com-
as a publicati_Jn dale. The data include one polymer, poly-
thiophene and us dcnvat1ves and lour small molecules (three oligothiophenes,
plus pentacene). Note that the highest mobi lity of small molecules was reported
oo single crystals.
We sec that, apa11 from t11c case of quaterthiophene (4T), small molecules have
a higher. .nobili ty than polymers. Another striking point is a general increa<;e in
the .mob.llty . by one or m:gnitude. other yeur (shown by the
stra1ght lme 111 F1g. 14-13). The leld-cllcct mobili ty ol organic semiconductors is
now to their theoretical limit, namely a few tens of a cm
2
y - s- 166). Note
thiS IS also the magnitude Of the time-of-flight mobility of hi ghly pure organ-
IC smgle crystals 1671. OFET-; can now compete with other thin film transistors
such as amorphous silicon devices. The improvement came from several features.
One them w:L'i the of highly onlercd lilms, which is more signifi-
cant lor small mok-culc.., than tor polymers. A second important parameter of a
492
i

:0
0
:::!:
14 Physics of Organic Field-Ej]i!t'l Transistors
101
1()0
0 PT

4T

10
1
.
6T
0 OH6T
1()-2
,.

1()-3

10"4
0
10"5
1o-&
1()-7

1986 1988 1990 1992 1994 1996 1998 2000
Figure 14-13. Evolulioo of !he
ftcld-cffed mobilily of OFE.Ts roc
five organic ma1eri:lls: polylhio-
phenc (PT) and its derivati\ICS,
quatcrthiophcne (4T}, scxithio-
phcnc (6T), c.lihcxyl-SCXIIhiophene
(DH6T). anc.l pclllilCCnc.
FET is the on-off current mtio, which indicates its ability to shut down the cur-
rent, and is pa.1icularly relevant in applications such as active matri x displays and
logical circuits. Bel:ause of the presence of fHt junctions at both the source and
drain electrode, the on-off ratio of MOSFETs is in the 10
9
range [1 2), while that
of a-Si: H TFf is limi ted to I 0
6
[1 3). High mobi lity ensures high on-current and,
hence, also contributes to a high on-off ratio.
14.5.1 Oligothiophenes
The chemical scheme of oligothiophcnes (nT. where n stands for the number of
thiophene units) is shown in Figure 14-14.
Oligothiophenes used in OFETs are either non-substituted or substituted at both
ends by a linear alkyl group. TI1c first rcpon on a 6T-bascd OFET. which was
also one of the first reports of a small conjugated molecule, dates back to 1989
( 10]. The importance of the ordering of the film first appeared when Waragai and
Hotta [68] showed that the dimethyl end-substitution of 3T, 4T, and 5T leads to a
10- to 100-fold increase in the mobi lity. This was confim1ed soon after at 1l1iais
with the dihexyl-substitutcd 6T (DH6T) [69]. X-ray diffmction measurements on
DH6T showed that the improvement was due to the very regular microscopic ar-
mngement of U1e film. DH6T consists of a periodic superposition of parallel
monomolecular layers, in which molecules pack side by side, almost pcrpendicu
lar to the plane of the fi lm. A monoclinic atTangement was suggested and the tilt
angle of the scxithiophene backbone was estimated to be between a 20" and 30
angle to the normal to the film. The hexyl chains present a smaller ti lt angle be-
cause of their larger intcrchain spaci ng. Unfortunately, the number of reflections
obtained from X-ray data was far too low to allow a complete resolution of lhc
DH6T crystal structure. A complete structure of di methyl-substituted quaterthio-
phene was achieved by Houa and coworkers [34[. In that case, U1e uni t cell is
orthorhombic so that the molecular axes in adjacent layers form a zigzag pattern.
R
14.5 Materials 493
.. igure 14-14. Chcmic:ll of unsubstiluled
(R =H) ancl enc.l-subslilulcd uligolhiophene.
1-'-15. l'acking mode of (a)
c.lihcxyl-scxilhio-
phcnc OJ 16T (from l{cf. )69)) anc.l (b)
i nglc...:ryslallinc c.limclhyl t(ualcnhio-
phcnc DMH. vicwcc.l alo11g lhc u axis
(ar1cr Ref. 134)).
The two different packing modes reported in References [341 and [69] are shown
in Figure 14- 15. More recent data on evapomtcd tilms of dihcxyl-quaterthiophene
[70) seem to favor the orthorhombic armngement. It should also be pointed out
that. although their long axes art.! parallel. the thiuphcnl! mukcular planl!..;
do not stack pamllcl to each other. instead, they present a so-called herringbone
arrangement, in which the plane of nearest neighboring molecules present a dihe-
dral angle around 60 (a view of a herringbone packing is given in Fig. 14-16).
Both structures arc maintained over thil:knesscs of up to several micrometers
and confer a two-dimensional chamcter to the medium. Charge transport is fa-
vored in the di rection parallel to the film, that is. perpendicular to the molecular
axis.
More recently, highly ordered fi lms of thl! tmsub.wiwted 6T were also obtained
by heating the substrate and using low deposition mtcs [71 [. Once more, X-my
analysis showed th<lt, like in the case of 0 116T, the packing consists of parallel
layers of molecules nearly perpendicul ar to the substrate. The di fference in this
case is that the thiophene layers are not separated by alkyl layers. whkh could
slightly reduce the two-dimensional character of thl: structure. At the same time,
he field-effect mobi lity uf 6T raised to a magnitude close to (hut half the value
oO that of DH6T. Identical results have bl.-cn reported more recent ly by the Bell
L4lbs group on both 6T 1721 and OH6T [73[. Interestingly, the dl!vices of the Bell
494 14 Physics of Orga11ic Fielti-Ejfect Transistut:r
Labs group were built on silicon wafers. whereas those of the group at Thiais
used a polymeric insulator, polymethylmethacrylate (PMMA). In a more recent re-
port [60j, a group at IBM measured the field-effect mobility of DH6T on various
organic insulators. While with PMMA, Jl extends from 0.04 to 0.08 cnl v-
1
s-
1
,
in good agreement wi th the data of the Thiais group, it increases up to 0.09-
0. 10 cm
2
y - l s-
1
with polyimide, and even 0.095-0. 13 cm
2
y - l s-
1
with Pary-
lene, a commercial polymer of Dupont de Nemours. These data again show the
importance of the insulating substrate on which the organic semiconductor is de-
posited. Its nature must play a role in the ordering of the semiconductor at the
very place where the conducting channel forms.
Another significant feature found recently is that t he effect of the chain length
on the field-eflect mobility is much Jess pronounced than indicated in earlier re-
ports (68, 74}. The increase from 4T to 6T corresponds to about a factor of ten,
while that from 6T to 8T is only two (the low mobi li ty measured for the dihexyl-
substi tuted 8T must be ascribed to the difficul ty in synthesizing and purifying
compound 75 J). Representative data arc gatheretl in Table 14-1. Also note that the
effect of alkyl end substitution is reduced by a factor of two to three (as com-
pared to up to 1000 in earlier reports (681).
The low perfommnce of short chain oligomers repo11ed curlier has been attrib-
uted to high contact resistance, due to poor charge injection. TI1is was confirmed
by introducing a buffer layer of tetmcyanoquinodimethune (TCNQ) between the
4T layer and the gold source and drain [771. which led to an almost three
enhancement of the dmin current. TI1e highest mobil ity for 4T, 6T, and 8T was re-
cently reported by the group at Thiais (781. Unl ike previous reports, their date.
were corrected for contact resistance, which resulted in a substantial increase in
the mobili ty. Moreover, the mobi lity was found to be significantl y gute voltage-
dependent, similar to an issue that has been already mentioned in Section
14.2.2.3.4, and wi ll be more thoroughly dealt with in Section 14.6. 1. 1.
Large 6T single crystals have been grown at TI1iais (791 and used to make
OFET.o; (with a PMMA gate insulator) wi th mobilities of about 0. 1 en? v-
1
s-1
( 15, 801. More recently, the Bell Lab group reported a mobility of 0.05cm
2
v-
1
s-
1
for 4T and up to 0.52 cm
2
v-
1
s-
1
for 6T single crystals [81 ]. These figures are
signiticantly higher than the best results obtained with polycrystall ine fi lms of 6T
(0.05 cm
2
y - l s-
1
) and 0 116T (0. 13 cm
2
Ns), which suggests that. charge transport
in these films is mainly limited by grain Neve11heless, it would be of
primary interest to know whether the mobility of the 6T single crystal is sti ll lim-
Table 14-1. Typical field-cffccl mobility (in cm
2
V
1
s-
1
) of and dialkyl-subslituled oli-
gothiophcncs.
Compound Unsubslilulcd Subslilulcd References
4T
10-4-<> 10-:
1
0.01- 0.02 [70. 76-7111
5T 1.5 10 )
I Til
6T 0.01-{).05 0.04-0. 13 16(1, 69, 72. 7!!1
liT 0.01-{).1 0.01 J75, 76, 7111
, .......

4T/LT 4T/HT
14.5 Materials 495
l' iJ.!urc 14-16. Low tcmpcmlun: (LT} and lugh lcm-
(lil) polymorphs of l.jualerthiophene. Top:
view along lhe /1 axis; boltom: vil:w along lhc
molecular axis (nOie lhc herringbone packing)
(Adaplcd !'rom Rds. I7'JI ;md 11!21).
ited by device imperfections (high contact resistance, poor insulator-semiconduc-
tor interface) or whether it indeed rcprescms the ultimate limit of this material. In
particular, the field-clrect mobility of 6T c1ystals is three times lower than that of
pcntacene (sec below), and still signi licantly lower than the time of flight mobility
reported in anthracene and other molecular crystals [67 1.
An alternative crystal structure has been identified by. the Bell Labs group on
melt-grown 6T crystals [821. Polymorphism in oligothiophenes [711 (and in organ-
ic materials at large) is u well -documented topic. It has been very recently con-
fimlCd in 4T 183-851. Figure 14- 16 shows a view along the unique axis or the
two crystul structures of 4T. The low-tcmpcmturc (LT) form is obtained by depos-
iting the c1ystal at low temperatures. whi le high-temperature (HT) crystals are
achieved at deposi tion temperatures close to the melting point. A view along the
molecular axis is also given to show the herringbone structure of the crystals.
The two fom1s differ by the way they puck, a direct result being the different
tilt angle or their molecular axis (24" and 30" for the low-temperature and high-
temperat ure form, respectively). Another important dill"erence is the fact thai the
inversion center of the molecule coincides with a center of symmetry of the uni t
cell in the HT form, whereas it docs not in the LT form 184j. Direct consequences
of this feature have not yet been identified. It will be of course of great interest to
know what would be its intluence on charge trunspo11 propenies.
14.5.2 Other Small Molecules
14.5.2.1 Phthalocyanincs
Phthalocyanines (Pc's) arc probably the first rclX)I1ed and most studied organic
semiconductors 186). They arc thennally stable up to 4()() 'C, easy 10
rate under vacuum. The Pc molecule (shown in Fig. 14- 17), prcscnLo; the structure
of a molecular cage in which various metals can be introduced.
496
/ 4 Physics of OrgCtnic Field-Effect Transistors
l' igure 14-17. Molecular structure of M= Hz.
metal.
A field-effect was reported on Pc as early as 1970 [5] and OFETs in 1988 [9),
which presumably make it the first OFET built on a small molecule. Their
fect mobility mngcs between 0.0001 and 0.01 cm
2
y - l s- t [87- 89). Phlhalocyanmes
differ from the other small molecules used in OFETs by their two-dimensional struc-
ture, which contmsts with the one-dimensional nature of the other molecules (an-
other exception being the fullercne C(>(). which is three-dimensional). In Pc films,
charge transport is favored in the direction perpendicular to the plane _of the
cule. Accordingly, high mobility requires the molecules to be deposlled standmg
on the edge. This is the way a mobility of 0.01 cm
2
y - l s-
1
has been achieved by
the group at Bell Labs [89]. We also note that, although Pc's have been reported
to behave as both 11- and p-type semiconductors [90}, Pc-based OFETs are all p-
typc. The main problem with Pc's is their extreme sensitivity to oxygen [88].
14.5.2.2 Pcntacene
The pentacene is fonned by five aligned condensed benzene (Fig._ 14-18).
Pentacene belongs to the family of the polyaccnes, the senucom.luctmg_ proper-
ties of which have been extensively studied during the sixties and seventies [91].
Although most of the pentacene-based OFETs of
films, there have been reports on solution-processed devtces [55) usmg a w lubl ..
precursor molecul e. Pentacene films have also been by pulse-laser de-
position [92}, a technique widely used in the field of lugh . superconductors,
and which presents advantages in terms of speed of and
ranges of pressure. Table 14-2 gives typical results obtamed wtth these dttl erem
deposition techniques.
Mobi lities up to 1.5 cm
2
v-
1
s-
1
have been obtained for tilms deposited on
substnttes [94-96). As in the case of oligothiophenes, this has been to a
highly ordered morphology, close to that of a single crystal {941: h1gh
ues are only obtained under very acute deposition parameters (m parttcular an opll
Figure 14-11!. Molt. 'Cular Stru<:turc of pcntaccnc.
14.5 MuteriCtls 497
Table 14-2. Pcrfonnancc of pcntaccoe baMxJ OFETs. Mobility in cm
2
v-' s-'. tempcr.uurc in
"C. RT: room temperature.
Deposition mode Substrate temperature Mobility Rcfcrern:es
V.Jcuum cvapor.uion RT 0.002 (741
Spin-coating 0.001 (55)
RT O.oJ 192)
VJCUum evaporation RT 0.031! (931
V.Jcuum cvapomtion 1\4 0.4 (941
Vacuum cvapomtion 120 0.62 1951
vacuum evapor.llion 60-90 0.3-1.5 (961
mum substrate temperature exists above and below which the high mobility is lost),
which seems to pose problems of reproducibility. The performance of devices grown
under similar conditions presents a large variation [961. It is worth noting that the
mobi lity of a pcntacene single crystal reported by the Bell Lab group [81) is pmcti-
cally identical to that of the best polycrystalline layers 1961. which suggests that the
size of crystal grains in these lilms arc larger than the dimension of the device. The
on-off ratio of pentaccne OFE"Ts was reported to reach lOx J95). We note, however,
that such a ratio was measured by sweeping the gate voltage from - 100 to +100 V, a
r.mge far from that used in microelectronics.
Nevert heless, pentaccnc constitutes one of the most promising materials for
OFETs. This highlights the advantages presented by fused ring molecules, particu-
larly as far as molecular ordering is concerned. Large crystals of polyacencs, up
to the tetr.tcene, have been known for a long time (sec )911 and references there-
in). Although pemacene single crystals do not seem that easy to grow, the ten-
dency of this molecule to form highly ordered cv<tpor.tted films ha:. been reported
since 1991 (97]. We note that the structure of these Jilms strongly resembles that
of oligothiophenes, with mol ecules packed into parallel layers in which they stand
almost perpendicular to the substrate. Moreover, as with oligothiophenes, the crys-
tal structure of pentacenc also shows herringbone packing [981.
The promising achievement obtained with pentaccne has fostered the search for
other fused ring molecules with interesting charge transport properties. Among
them, bcnzodithiophene, formed by two thiophene rings fused at both ends of a
benzene ring (Fig. 14- 19), has been studied by the group at Bell Labs.
The dimer of bcnzodithiophcne was symhesit.ed. and showed a mobility of up
to 0.04 cm
2
y - l s-
1
1991.
More recentl y. OFET.-. were made with a dimcr or auolhcr comlcnscd molecule.
dithienol),2-b : 2' ,3'-dlthiophene 11001. whid1 presents a very similar structure to
that of benzodithiophcne, except tlmt the cent ral benzene ring is changoo to a
l'igurc 14-19. Molecular of bcu.wJillllopllcnc.
498
14 Pl1ysics of Organic Field-Effect Tratlsistors
thiophene ring. Mobility ranging from 0.02 to 0.05 en? v- s- was_ measured. In-
terestingly, this compound crystallizes in a herringbone a very low
dihedral angle, which was interpreted as prone to favor tmnspoct
along the stacking direction. We note, however, that mobaltty h:re
does not constitute a real breakthrough with regard to hterature data on ohgothao-
phene and pentacene.
14.5.2.3 n-Type Semiconductors
All the organic semiconductors investigated so far are p-type when non-intention-
ally doped. Attempts to make them n-type by adding electron donors usually lead
to ambiguous results. mainly due to the low doping levels (i.e., less 10
17
do-
nors per cm
3
) that arc difficult to control in organic materials. One maJOr problem
is that dopants arc not rigidly fixed to the sol!d, so that _they to move under
the high local field that reigns at interfaces an electronac dcvaces: The develop-
ment of organic light-emilling diodes has the concept _ol hole and
tron transporting materials li OI, 1021. whach seems more pca1ment for
semiconductors. This would mean that a given organic material would be mtrms-
c:ully p- or
11
-type, depending on the energy of its HOMO (l lighest_ Occupied Mo-
lecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbatal) _levels, the
molecular equivalent of valence and conduction band edges. Accordang to that
picture, an
11
or p-type material would be char.tcteril.Cd by a high electron affinaty
or low ionization potential, respectively LI03J.
An organic metal-semiconductor (Schouky) diode is made _or a thin fi_lm sand-
wiched between a low work function (e.g., aluminum or calcaum) and hagh woo
function (gold or ITO) metals. Its CUITent-vollage do not
as to whether the semiconductor is u- or p-type. because an both cases the darect
current flows from the anode (high work function metal) to the cathode (low
work function metal). By contr.tst, because the sign of the carriers in the
ing channel in the OFET changes, the accumulati?n set up for
gate biases in an n-type semiconductor and negat1ve baases tor a p-type senucon-
Table 14-3. Pcrfonnanc.:c of OFETs ni<!Jc with rHypc
Compound
TCNQ
Cw
Ct,o+TDAE
c11>
Pel)'lcnc diimide
NTCDA
PTCDA
1.9 10-S
0.002-0.0!!
0.3
0.002
1.5 10 s
0.002
10
4
TCNQ:
TDAE: lclr.Jkis <limclhyktminoclhanc
NTCDA: naphlhalcnc <lianhydridc
PTCDA: jJCI)' Icnc di:mhydndc
References
I 1041
1105, 1061
11051
111171
II 0!!1
11091
IW'JI
14.5 Materials 499
NTCDA PTCDA
Ftgure 14-20. Molecular slt\Jclurc of naphlhalcnc IClrac-.uboxylic dianhydridc (NTCDA) and pcl)'lene
lelrac.:atboxylic dianhydridc (IYfCDA).
ductor. Accordi ngly, the OFET is also a unique and reliable tool for detennining
lhe sign or the majority carriers in an organic semiconductor. Evidence for 11-Lypc
conductivity has been n:purtcd for several materials. a list of which is given in
Table 14-.3.
A bi?_problcm with n-type_ their lmgc in _is
excmphtaed by
the mobt hty ol wluch can be as hagh as 0.08 em v- s

1
m
ultr..a-high V<u:uum, but falls by four or live orders of magnitude upon exposure to
air 11051. This could be due to problcmo,; of comacts. <L'i illustrated by the fact that
modifying the surface of the source and drain electrodes with tetrakisdimethylami-
noethylene (TDAE) leads to a substant ial incre<L'ie in the mobility 11051.
Another interesting feature in the data given in Table 14-3 is the ditTerent mo-
bility reported for NTCDA (naphthalene dianhydride) and PTCDA
(perylene teta-aearboxylic dianhydride). These two compounds present very similar
molecular toqnulac (fig. 14-20), but differ by their crystal packing 11101. While
NTCDA follows the herringbone packing of pcntacene and oligothiophencs, mole-
cules in the PTCDA crystal form stacks of molecules with parallel planes. The
200-fold higher mobility of NTCDA as well as the high mobility of pentacene
and oligolhiophenes would then suggest that a herringbone structure is more fa-
vor.tble for tmnsport than parallel slacki ng.
14.5.3 Polymers
As shown in Figure 14- 13, the field-effect mobility of polymers stands roughly
one order of magnitude below that of the small molecules. This can be under-
stood from the fact that solution-processed materials present a poorer ordering than
evapomtcd small molecules. We note, however. that a mobility of 0.01 cm
2
v- s-
has been reached with a soluble regioregular polythiophenc f 1111. An even higher
mobility (up to 0. 1 cm
2
v- s-
1
) has been claimed recently by a group at Cam-
bridge University [ 11 21. These very promising resulL'i arc most prob;tbly con-
nected to the high chemical order of the polymer used by bl>th groups. The exact
arrangement of the polyma chains in the spin-coated lilms is not known, and its
study wi ll probably aid understanding of the origin ur the improvement.
500

""

:D
0
E
14 Physics of Orgallic Fielcl-ffect Transistors
1o-2
1o-3
lc-4
lo-5
10' 7
1o-9 1o-8 lo-7 10.() 10-5 lc-4 1o-3
conduebVIIY (S/cm)
Figure 14-21. Variation of til\.
field-effect mobility as a functior
of the conductivity of
doped poly(dodc4:yloxy-tcrthienyl'
{PDOT), a polythiophcne deriva
tivc (;IO<tpl<.'\1 from Rd. 11 131).
A group at Philips, Eindhoven, has :-. hown that the mobil ity of
oxy-terthienyl) (PDOT), a soluble polythiophene deri vauve, can be substanltally
increased by doping the polymer (11 3(. l lowcvcr, this enhuncement is accompa-
nied by <10 equivalent increa:-.e in the conductivi ty. Conse4ucntly, the gain in m<;
bi lity is obtained at the expense of the on-off ratio, whid1 reduce:- the technologt-
cal interest of this feature. This behavior was r.ttionalized by using a variable-
range-hopping model, which was fortified b,.>.; the temperature dependence of
conductivity that followed the cxp[- (7
0
/1')
1 4
] 1aw predicted by Mott. The mobtl-
ity-conductivity relationship can be descrilx.'<l by a simple power law, Jt <X J ,
where equals 0.76. Interestingly, on dmwing a log-log plot of their data
with other data from the literature, the Philips group linds a u11ivasa/ curve. vahd
for all disordered organil: semiconductors (which comprises both polymers and
small molecules). The curve is reproduced in Figure 14-21.
Obviously, the data pertaining to ordered small molecules stand thai
curve, as does the mobility measured by the Bell Labs [I ll 1 and Dmbndge
groups on a rcgioregular polyalkyhhiophene. In a subsequent paper ! 16], the
Jips group extended its model to account lor structural ordering. Thts mode l wtU
be presented in Section 14.6. 1.2.
14.6 Models
The development of microelectronics cannot be envisaged without a comprehensive
modeling of the devices. The modeling of OFETs is current ly hampered by several
features. First, charge transport in org<10ic semiconductors is still not completely un-
derstood. 1l1e situation is clear at both ends or the :-calc. In high mobility materials
{JI> 10 c
111
2
y- s- ), tr;msport occurs within dclocalized levels; when temperature
14.6 Models 501
.
decreases, mobility increases accordin& to u power law. On the other hand, transport
in low mobility materials (Jt<O.O I em- v- s- ') is more or less thermally activated,
and corresponds to a hopping mechanism. The mobil ity of organic semiconductors is
in between these two extremes. Here, the polaron model seems more appropriate.
Unfortunately, the polaron model cannot be exactly resolved in the general case.
This sect ion is divided in two parts. In the tirst one, we review the studies on
the transport mechani sm in materials used in OFETs, whereby temperature-depen-
dent measurements are a very powe1ful tool. The study of the gate bias depen-
dence has also been used by researchers. In the second part, we present the few
analytical models of the organic FET.-; that have been developed until now.
14.6.1 Temperature and Gate Bias Dependence
14.6.1.1 Trap-Limited Transport
Since 1991, the Thiais group has developed a charge Lr.tnsport model in OFETs
based on the Multiple Trapping and Release (MTR) model, which is commonly
used in amorphous silicon TFf.;. A prominent feature shared by amorphous sili-
con TFJ:.; and OFE1s i:o. that the tidd-cllect mobi lity is gat' bias-depl'ndut 113,
18]. 1l1is can be understood by recalli ng that a TFT operates in the accumulation
regime, which means that, as the gate bias is increased, the Fermi level graduall y
approaches the nearest dclocalized band edge (see Fig. 14-4b). ln ;unorphous si li-
con [ 13], ncar to these delocalized bands, a substantial density of localized levels
exist.;, which act as traps for charge carriers. At low gate bias, nearly all the in-
duced charge goes to the localized levels, and the mobility is very low. As the
gate voltage increases, the Fermi level approaches the dclocalizcd band and more
and more traps arc ti lled. which eventuall y leads to direct injection of mobile car-
riers in the delocal ized levels, resulting in a drastic rise in the efl'Cctive mobi lity.
We have used this model to rationalize the chamcteristics of 6T- and Dll6T-
bascd OFETs (11 4, 11 5(. llte li rsl point was to demonstmle the gate bias depen-
dence of the mobi lity. The Iauer is usually estimated from the gate voltage depen-
dence of the saturation current. As shown by Eq. ( 14.58). a plot of the square
root of

as a function of V
11
should give a stmight line, the slope of which
would be prop011ional to the mobi lity, and which would extr.tpolate to zero cur-
rent at the threshold voltage V,. A typical plot is shown in Figure 14-22. It was
obtained by the author on a lightly doped DJ-l6T-based device.
The departure of the experimental data from the vr;;:, versus Vx straight line
at low gate biases is generall y anributcd to a subthreshold regime (like in conven-
tional MISFETs). We note, however, that such an interpretation is at variance with
Eq. ( 14.47), which predicts a positive value lor V,. As noted above, another origin
of this departure would be a decrease in the mobility at low gate voltages. a.; in
amorphous silicon TFT.; 113. I R (.
An allcmaLive method to estimate the mobility consists or usi ng the
in the linear regime. given hy Eq. ( 14.32). We no1e thal the
502
/4 Physics of Organic Field-Effect Trcmsistors
0.003
0.0025

0.002
)
0.0015
?'
0.001
0.0005
0
0 10 20 30 40 50
gate voltage (V)
Figure 1422. Varimion of the root of the satur:uion current as a function of the gate vol101ge
for a typical lightly ..loped DH6T OFEc
threshold voltage does not appear in this equation. Accordingly, the mobility is
simply obtained by differentiating the drain current low dr.tin as _a
function of the gate voltage. Typical results obtained from the same devtce a<; m
Figure 14-22 are shown in Figure 14-23. In that case. we do observe a decrease
in J.l at low gate biases. . .
A crucial element in MTR is the profile of the locahzed slate density as a func-
tion of energy, the so-called density of states (DOS). Unfortunately, a direct deri-
vation of the DOS from the variation of the mobility is not straightforward. In
two papers published in 1972 and 1976 [116, 117), Spear and
oped a method based on a simplified description of the layer,
was assumed to behave like a depletion (Schottky) layer, wtth a constant densaty
of carrier up to a given thickness A. This method has been more recently
by Powell [ 1181, who concluded that is was only able to_ give a rough of
the DOS. Ncvettheless, we have used this method to eslt mate the DOS tn 6T aoo
DH6T [ 11 5) and found an exponential distribution of the form
N10 ( Ec- - E)
N,() = - exp --- .
kTo kTo
(14.71 J
Here, N
10
is the total density of traps and To is a characteristic temper.tture that ac-
counts for the slope of the distribution. Results arc gathered in Table 14-4. It
both materials, a comparable characteristic temperature was found, while the total
density of traps was ten times higher in 6T than in DH6T. . . .
At the same time, we determined the ' tr.tp-frce' mobility, that ts, the mobthty
corresponding to a high gate bias, at which all traps ti_lled. as
shown in Table 14-4, we found a similar trap-free mobthty tn 6T and DH6f, de-
0.0001
-10 0 10 20
gate voltage (V)
30
/4.6 Models 503
l'igurc 14-23. Variation of the
mobility, as deduced
by differentiating the drain current
at V,1= - 1 V. as a function of the
40 g;1te voltage, for the same device
in Figure 14-22.
Table 14-4. of the density of state (DOS) in 6T ami DH6T. as detcnnmcd from li.:kl-encct
dal:l (from Ref. 11151).
Molcwlar tcm '>
Microscopic mobility V
1
s-
1
)
Density of tmps (.:m-
3
)
Oiaracteristic tempcmture ( K)
Doping level (cm-J)
6T

0.03
3-10!1
1
455
4-1017
Dli6T
1.3-1021
0.04
4.510
1
'
1
495
3-10
11
spite the fact that the effel:ti ve mobility of the former is ten times lower than that
of the Iauer.
However, although it allowed a correct descriplion of the char-
acteristics, this model presents several inconsistencies. The main one concerns the
mechanism of trap-free transpm1. As noted by Wu and Conwell (1 19), the MTR
model assumes a tr.tnsport in dclocalizcd levels. which is at variance with the low
trap-free mobility found in 6T and Dli6T (0.04 em:! y - t s-
1
). Next, the estimated
concentrations of traps arc rather high as compared to the total densi ty of mole-
cules in the materials (see Table 14-4). Finally, recent measurements on single
crystals 115, 80, 81] show that the trap-free 1110bility of 6T could be at least ten
times higher than that given in Table 14-4.
In a more recent paper, we showed that, to obtain the actual mobility, the cur-
rent-voltage data should be corrected lor the conlact series resistance (78 ). Cor-
rected results for 6T and shown in Figure 14-24.
Note that, in contr.Jst with Figure 14-23, the con-ccted mobility does not satu-
rate at high gate voltages. The trap-free li mit would be, therefore, beyond the
voltage range and hence mul:h higher than that given in our earlier report; this
may conciliate our model with the mohilily found in si ngle crystals.
504
14 Physics of OrgCinic Field-Effec:r Trcmsiswrs
0.07
0.06
0.05
0.04
0.03
0.02
0.01 L_._........L.......... ...J...o......... J...........J. ........ ...J...o.......... J................L......... ..L...J
0 10 20 30 40 50 60 70 80
gate voltage (V)
Figure 14-24. Variation of the mo-
bility as a function of gatetl voltage
of vacuum-cvaporatetl 6T and 8T.
Data were for the contacl
resisrancc (from Ref. (7!1)).
We finally note that the MTR model is u priori more appropriate to disordered
materials. It is not expected to give good results with single crystal OFET, espe-
cially when the mobility becomes temperature-independent (see Section 14.6. 1.2).
However, it has recently been invoked in the case of polythiophene [ 112], the mo-
bility of which is also thermally activated.
14.6.1.2 Polaron and Hopping Models
The variation of the transconductance at low drain voltages was al so used by the
group at Philips [161 to estimate the mobi lit y of pentacene and poly(thienylene- vi-
nylene) (PTV). The mobility, measured down to around 100 K, wa.-. thermally acti-
vated. Moreover, a gate bias dependence of both the mobility and its activation en-
ergy was found. A distinction is made by these authors between highly doped and
lightly doped materials. The former includes doped polymers and the Iauer undoped
polymers and pentacene. The data were interpreted in the fr.1me of variable range
hopping for doped PTV and PDOT [ 1131. Variable mnge hopping is revealed by a
power law relationship between mobility and conductivity (sec Section 14.5.3 and
Fig. 14-21). The variation of the activation energy with gate voltage is attributed
to a density of localized levels, which dynamically change upon introduction of
charges, either by doping or by field-effect. These disorder levels are localized deep
in the gap, and are the li rst to be occupied at a low gate bias. Increasing the gate bias
moves the Fermi level towards the polaronic levels, so that, at high (absolute) gate
bias, the acti vation energy saturates at a value that COITesponds to the polaron-bind-
ing energy. (We note that, according to the Holstein model (Eq. (14.66)) thi s would
rather coincide with half the binding energy). For pentacene, this limit is around
0.1 eV (which would give a polaron-binding energy or 0.2 eV).
More recently, a comprehensive model has been developed by Vissenberg and
Mauers [ 1201to account for these data. The model is based on a variable range-hop-
ping system with an exponenti al distribution of localiLcd states (&j. ( 14.7 1 )). The
14.6 Models 505
following expression is obtained for the temper.lture- and gate voltage-dependent
mobility
J-l - Uo [ n(To/T)3 l Tu/ T [(C;V,l]To/T-t
- q (2a)
3
B,.r(J - T/To) r(J + T/7'o) 2k1'ut:s
( 14.72)
Here, a is an effective overlap parameter that characterizes the tunneling of
charges from one site to the other (it has the same meaning as a in Eq. (14.60)).
To is the characteristic temperature of the exponemial distribution and u
0
and B._.
arc adjustable pammcters connected to the percolation theory. 8,. is the critical
number of bonds reached at percolation onset. For a three-dimensional amorphous
system, 8,. 2.8. Note that the model predicts a power law dependence of the
mobi lity with gate voltage.
The polaron model was also used by Waragai and Houa [ 1211 to analyze tem-
perature-dependent data on methyl-substituted oligothiophenes. While their data
did not cover a sufficient temperature mnge to discern a clear temperature depen-
dence of the mobi lity, they noticed that11 represented a drai11 voltage dependence,
which they auributed to the F
1
a dependence given by Eq. ( 14.69). Accordingly,
the temperature-dependent mobility could be filled to a thermally activated law of
the form JL = Jlu exp( - ,"
1
/ kT), where
1
,
1
=
11
/2 - y.JF, y being a tempera-
ture-dependent constant. By extrapolating ,,, to zero electric field, they found po-
laron-binding encrgic.-; of 0.24, 0. 18. and 0. 16 eV for ST. and 6T. respectively.
We note that these values arc not very different rrom those reported by the Philips
group on pcntacene. However, the drain voltage-dependent mobility reported by
Hotta and Waragai could alternatively be auributcd to the phenomenon of channel
shortening, which will be dealt wi th in Set.:tion 14.6.2. 1.
The Bell Labs group has reported on a significantly different behavior of 6T
[122). We note that, in this work, the mobility was from the saturation
current (Eq. (14.58)), a method that does not give access to a possible gate volt-
age dependence. When the tempcr..1ture is lowered, a dec.rease in the mobility is
detected as well. These authors find a polaron-bi nding energy of ca. 0. 1 eV, twice
as small as previous reports. The remarkable point is that, at tempcmtures lower
than ca. 50 K, they observe a dramatic rise in the mobility, which then stabiliz.es
to a value close to that measured at room tempcmturc. The sharp Lmnsition was
interpreted within the Hohaein's polaron model. It would mark the passing from
the hopping regime to the polaron band regime. This interpretation has been con-
firmed from a more theoretical point of view by Wu and Conwell [ 119!. Unfortu-
nately, it appeared later that this transition was in fact due to an experimental arte-
fact, which was the presence of oxygen in the semiconducting lilm [123 j. In the
data presented in Ref. 1123 J, the transi tion appears to be sample dependent. Re-
markably, in some devices, the tr;msition is very weak and the mobility is practi-
cally independent of the temperature, particularly at low temperatures.
More rcccmly, the Thiais group reported on temperature-dependent mobility of 6T
and down to 10 K [ 124). In this case, the mobility was estimated from the linear
regime und corrected ltlr the contact resistance. Data for shown in Figure 14-25.
506 14 Physics of Orgu11ic Field-Effect Tramistors
-o--20V
0.1 -
-o--40V
-o---60V
---Q---8QV
0.0001
0 20 40 60 80
1000ff(K
1
)
J:<' igure 14-25. Arrhenius plot of
the temperature-dependent mobili-
ty of 8T evapor . .lled film. Data
were recorded at various gale vol-
tages and corrected for the con
t.acl series resistance (taken from
Ref. [1241).
The prominent features of these data arc the following. The temperature depen-
dence shows three domains. At high temperature, down to around I 00 K, the mo-
bility is thermally activated with an activation energy of 0.1 eV for 6T and
0.08 eV for 8T, which compares well to the data reported by Brown [16] anc.'
Waragai f 121 ). Then, there is an intermediate regime, where the activation energy
is much lower (4 meV for both 6T and 8T), and, finally, a low temperature do-
main, below 25 K, where the mobility becomes tempemture independent. Finally
the mobility is gate voltage-dependent, and this dependence is more pronounced
at low temperatures.
A most remarkable set of data was repolled by Nelson and coworkers [961 on
pentacene. Three devices, made within the same run, were presented. The data an
shown in Figure 14-26.
,.,
~
0.1
0.01
:g 0.001 ~
E
0.0001
-o-(a)
-o-(b)
-o--(c)
0.00001 . . . . _ . ~ . . _ . . . ~ ~ I !........_._._)_
0 10 20 30 40 50 60 70
1000ff(K
1
)
Jo'igure 14-26. Tcmpcmlure de-
pendence of lhe mobility of pen
aacenc-evapur.ued film. Data are
shown fur three devices grown
under similar conditions (data
taken from Ref. [961).
14.6 Models 507
In device (a), the mobility is thermally activated and rapidly falls down below the
detection limit. Device (c) presents a practically temperature-independent mobility.
Note that there is a mobility increase at the high tempemture (!ell hand) side of
the curve. Noticeably, the magnitude of the mobility practil:ally equals that reported
for pentacene single crystals [81 ]. It is thus probable that, in this particular device,
the size of the crystal gmins is larger than the dimension of the channel, so that the
transistor behaves like a single-crystal OFET. In device (a) charge transport is pre-
sumably limited by grain boundaries. It could be described by either the trap limited
or hopping model, which both lead to a thermally activated regime. Device (b)
would correspond to an intermediate situation between devices (a) and (b).
14.6.2 Current-Voltage Characteristics
Attempts to model the l:UtTent-voltage characteristics of OFETs are still scarce. A
preliminary model has hecn developed by the group at Thiais, based on the above
treated MTR model (114]. The model is based on two crude assumptions: first, a
single trap level close to the valence band edge (recall that oligothiophenes are p-
type materials) and, second, a constant microscopic (trap-free) mobility. The main
result was that, depending on the gate voltage. the drain current shows two re-
gimes, namely a trap-limited current at low gate bias (which resembles the sub-
threshold regime of amorphous silicon TFT.o;) and a trap-free regime at high gate
bias. The transition is m<trkcd by a change in the slope of the square root of the
saturmion drain current versus gate voltage plot. Accordingly, we defined a pS(!u-
do threshold voltage at this transition, which explained the high negative value of
the threshold voltage reported on many OFET.-;.
14.6.2.1 Short-Channel Effects
A ditferent model has been reported by the Bell Labs group [ 125], who assumed
constant mobility and trap-free materials, but also other improvements were
added. First of all, they took the contact resistance of the source and drain elec-
rodes into account, and the leakage through the insulating layer. More interest-
ingly, they also introduced two short channel eftects. The first one is the so-called
channel shortening that occurs when the channel length is comparable to the
source and dr.tin depletion layer width, in which case the gradual channel approx-
imation is no longer valid. The channel is then divided into a conducting part of
length L
1
= L - M in series with an insulating region of length M, with M=O
when Vd < Vd,_..,, and M ex Vd""" - Vd when Vd > Vd.uu Here, Vd,.,.,1 is the drain
satumtion voltage. Channel shortening induces a slow increase in the dr..tin cur-
rent in the saturation regime, a femure that could account for the behavior re-
ported by Hotta and War..tgai [ 1211 (a slowly increasing satumtion cutTent with in-
creasing drain voltage) on dimethyl-oligothiophenes.
The second short-channel effect is a drain field-dependent mobility, whil:h oc-
curs for source-drain fields above 10
5
Y/cm, in agreement with similar phcnom-
508 14 Physks of Orgunic Field-Effect Transistors
ena observed in other organic materials (see Section 14.3.4). Note, however, that
these authors adopted an empirical dependence of the mobility as a function of
the drain field, rather than the conventional law given by Eq. (14.69). Neverthe-
less, this effect could be advantageously used to improve the performance of
OFEf by reducing its dimensions.
14.6.2.2 On-Off Current Ratio
Models have also lx:en developed to determine and optimize the parameters that
control the on-off ratio of OFETs. For instance, the Thiais group has shown that
the accumulation mode was not the only one to account for [ 126]. One has also
to consider the depletion mode, which appears when the sign of the gate voltuge
is reversed (sec Section 14.2.2. 3.2). Evidence for a depletion regime, which lx. '-
comes important when the semiconductor shows a significunt doping level, can be
seen in Figure 14-27. . . . .
Curves in Figure 14-27 pertain to a DII6T-based dcv1ce. The d11lcrcnce w1th
Figure 14-22 is that at zero gate voltage, a signific.snt dmin cunem already
This is the sign of u higher conductivity, the magnitude of whi ch can be esti-
mated by measuring the slope of the curve at zero gate ;md drain voltages. From
the geometrical dimensions of the device (L=50 !llll. Z=5 m.m and d., =.45 nm),
we obtain a =O.OOI S/cm. If we now draw the square root ot the saturatton cur-
rent at = as a of gate vollac
then the siOJX:

of the stratght lme gtvt:s us a mobthty Jt=0.056 em Y s .
Note that, as expected by Eq. ( 14.47), we tind a positive threshold voltage
V,=5.9 V. From Eq. ( 14.47) and the magnitude of the ins':Jlator capacitance
(C;= 10 nF/cm
2
); this gives us a carrier density p
0
=8 10
16
cm-
3
. Combined with
the mobility, this corresponds to a conductivity of 0.0007 S/cm, in fair agreement
with that deduced from the l ,r V,
1
curve at zero gate voltage. N01e that this con-
ductivity is significantly higher than that reported for unsubstituted 6T ll 0, 127).
-25
-20
1
-15
c

:::>
0
c
"!!
"0
-5
0
0
--o-V:e20V
9
- 10V
-o-- ov
- -10V
---a- - 20V
-5 -10 -15 20
drain voltage (V)
-25 -30
Figure 14-27. 0.-ain
char.1c1eristics of a doped
DH6T OFET showing tluth accu
mutation ( < 0) depletion
<Vx>O) regimes.
0.006

0.005
Sl
0.004

:;
0.003
0
c
.Q

0.002
:::>
ii
.!!!.
0.001
0
10 5
0 5 -10 -15 -20 -25 -30
gate vollage (V)
14.6 Mo1<'/s 509
Figure 14-28. Plot of the square
root of the saturaJion current
(taken al Vol = V
11
) against the gate
of the same device a.' in
Figure 14-27.
As all measurcmenb were perl(mned in air, il is must probably due to oxygen
dopi ng. <1 IC<tture that has been already not iced in oligothiophenc II 01 <tnd poly-
thiophene 112H I OFETs.
In such p-type-dnpcd the drai n current can he strongly reduced hy ap-
plying a positive gate bias, to make the operating mode change to /epletion. in
which case the current voltage curves arc described by Eqs. ( 14.52), ( 14.53) and
(14.54). By comparing the threshold voltage, obtained from the uccumulation
mode, and the pinch-olf voltage of the depletion mode, we lind that the currier
concentration is not the same in the depletion and accumulation regimes. To ex-
plain this disagreement, we allribute a different meaning to, (11
0
in Eq. (14.46))
and N (Eq. (14.54)1). The former represents the free carrier density and the taller
the total concentmtion of doping centers. The diftercnce can now be ascri bed to
traps induced by disorder. Interestingly, we find that 11/N r.tnges between 10-
3
and
10-
2
in 6T, whereas it is close to unity in Dll6T [15 j. Once more, this could mir-
ror the much beuer ordering of the Iauer compound. In addition, improving the
on-off ratio can be obtained by reducing the pinch-off vollage, which results in
loweri ng the off-current. We see from Eq. ( 14.54) that this can be done by lower-
ing the thickness of the semiconducting lilm and its doping level at the same
time.
The difference between '' and N has also been noted by the group at Philips
[16). They auributed it to a distribution of localized states below the Fermi level.
The ratio n/N is found to vary from 0.01 in di sordered PDOT (a derivative of
polythiophene), to 0.25 in ordered pentaccne. These authors attempt to predict the
on-off ratio of their OFETs. The on-current was taken at V
8
= Va and the off-cur-
rent detined as tl1e saturarion cunent at zero gate bias (note that this on-off ratio
docs not take advantage of the depletion mode). The off-current is calculated by
accounting for the depletion region that devclups at the drain electrode (sec
Ftg. 14- 1 0), and between the source and the drain. The on-off rat io is estimated
for two limiting cases depending on the dopi ng kvcl of the semiconductor. In all
510 / 4 Physic's of Organic Field-1:.1fect Transistors
cases, it is found to depend on the dmin voltage (equal to the gate voltage). At
high doping level, the on-off ratio is given by
At low doping level it becomes
1
11
, J1 C'fVJ
1
11
g qNd}
( 14.73)
(14.74)
Eq. (14.74) was simplified by assumi ng Cs Cj. Clearly, the on-off ratio is not
solely dependent on the mobility to conductivity ratio 11/a = l fqn. ll can also be
enhanced by using insulator with high capacitance per unit area and above all by
lowering the thickness and doping level of the semiconductor layer. We fi nally
note that Eqs. (14.73) and (14.74) do not account for the possibility of oper.tting
the device in lhe depletion mode (V
11
negative for an n-type, positi ve for a p-type
material, respectively) to enhance the on-oil mtio. Such a feature would be partic-
ularly interesti ng in the case of highly dopctJ semiconductors.
14.7 Concluding Remarks
The performance of OFETs has shown real breakthroughs over the past ten years.
These devices now compete with the inorganic TfTs in terms of tield-effect mo-
bility, and their on-off current ratio is approaching that of the inorganic TfTs. To
conclude this chapter, we would like to stress two crucial needs for the develop-
ment of organic FETs. First, because these devices arc hampered by inherently
limited performance, they will only compete if they can be fabricated with simple
and low cost technologies, such as spin-coating and printing techniques. So from
this standpoint, polymers present advantages over small molecules. Secondly, inte-
grated circuits based on OFETs will not develop before reliable models are avail-
able. Conventional models developed for inorganic semiconductors have proven
to be inadequate for organic materi als. Hence, considerable effo11s need to be in-
vested to understand the charge tr.tnsport mechanisms in oP.;anic semiconductors.
Such an effort should be directed both to theoretical works and to obtaining
highl y pure model materials. From this second viewpoint, small molecules arc
probably more interesting than polymers.
Referellces 51 1
References
I. J. 13ad4.-cn. W. ll. Ur:.tllain. Pl11s. Rl't: 1941l. 74. 230.
2. W. Shockley. /Jell Syst. J. 1949, 2<'( 435.
3. J. E. Lilienrield. U.S. Patent 1745175, 1930.
4. D. Kahn. M. M. Alalia. IRE Soliti-Stute Dcic<' Cuufenmce, Carnegie lnslilule of Tech-
nology, Pinsburgh, Pa. 1%0.
5. D. F. Barbe. C.R. Weslgale, J. J'hys. Cllem. Solids 1970. 31. 2679.
6. H. Shirakawa, E. J. Loui"- A. G. MacDiarn1id, C. K. Chiang, A. Hecger, J. CheuL Soc. Cllem.
ClJIIU/11111. 1977, 578.
1. F. Ebisawa, T. Kurokawa, S. Nar.t. J. Appl. Phys. 1983, 54, 3255.
8. 1-1. Kucwka, A. T'umu1-a. T. Ando, Syntll. ML't. 191!1, IH, 699; A. H. Koezuka, T.
Arxlo. Symll. Mtl. 1988, 25. I I.
9. C. Clarisse, M. l : Riuu. M. Gmmcau, M. Lc Cmudle.:, l::ltctlllfl. u/1. 191l8, 24. 674.
Ill. G. Horowil:t., D. fichuu. X. Z. &>eng. Z.G. Xu. F. Gamier. ::iolitl Stt/11' Cm111111111. l91l9. 72. Jil l.
II. E. H. Rodherk:k. R. ll . Metui-Sl'lllicmuluuor Cmuucts, Oxfonl Unaverslly New
YOI'k 191l8.
12. S. M. St.c. Plly.\iO of Smtinnuluctur Otlin.f. John Wiley. New York I
13. M. Shur. l'llysic.Y t!{ Jtminmductor tftticl'.>. Prcnlio:e-l lall. Eng.lcwuuJ Cliffs I \190.
14. P. K. Weimer. Pnw. IN/:..' 1%2. 50, 1462.
15. G. HomwiLL. R. E Kouki . /:.'111: Plly.>. J. AJIJI/. l'lly.<. 1991l. 1. Jul.
16. A. R. Brown, C. P. Jarn:n. D. M. de U.-cuw. M. Maners, Smth. M<'l. 1997, XII. 37.
17. G. Homwil7, R. Hajlauu1. H. Bouchrilm, R. Boul'._.:uiga. M. Hajlaoui . Atlt: Muter. 1998. 10. 923.
18. M. Shur. M. Hao.:k. J. G. Shaw, J. AJ>JJI. Pllys. 191l9, 66, 3371.
19. C. Kincl, lntmJuctiu11 It> &1liJ SICII<' Pllysics. John Wiley. New York 1976.
20. P. W. Pllys. Ret: 1951l, IOV. 1492.
21. I I. Bassler, Plly.>. Slllt. Sol. (b) 1993. 175, 15.
22. A Miller. E. Plly.>. Rttd%0, 120, 145.
23. N. F. Mon. E. A. Davis, Electrrllllt' 11rcx:es.>es in lltlllcr_y.rw/lille mmeriull. Clarendon Press. Ox-
fOI'd 1971.
24. D. Emin. i.fsttl'.< of dtttrmttc /rtllllJ'"rl in in.mlt/1111[: fHI/\'IIt<'f.f, in NtttttiiNHJk of Cmttlmtittg
(&I.: T. A. Skotho:i m) Mat'\:cl Dckk.:r. New Yurk 191!5.
25. J. Yanmshil:!, T. 1. Pllys. Clt<m. So/it/.v 19511. 5. 34.
26. T. Hulsleiu. /\u/1. l'l11.\. 1\159. 8. J:!5.
1:1. K. Fc.-.scr. A. R. Uisl;nll. D. K. Cuuphcll. l'lty.>. Rtt: II 191lJ. 27. 4!104.
28. H. Friilk:h, Atlv. Pl11.r. 1954. 3, .1:!5.
29. T. Hoblein. A1111. Pllrl. 1\159. S. 3-tJ.
30. J. u>mil. J . L. Ureilit. ... Atlt: Mute: 1995. 7. :!95: J . Cumil. D. Ucljntme, J. L. nn.:.Ja.,. J. Clum.
Pity.<. 1995, IW. !W2.
31. C. Ehrcndorfcr. A. Karpfcn. J. 1'/tys. Cltcm. 1\194. VH. 74\12.
32. AJ. W. Tol , Clttm. Pin.\. 1\1%, 20H. 7J.
33. D. Fi.:hou, G. Hnwwilz. F. Gamier. Synlh. Mel. 19'Jtl, .Ill. 125: D. Fichou. G. Horowil,, B. Xu.
E Gamier. Sytttll. ML't. 1\190, 39. 24.l
34. S. Holla. K. Warugat. J. Matrr. Cltcm. 1991. /. !!35.
35. J. A. Oi:u. 1{. L. Wu, J. M. ' li1ur, L. H. Oao. Mt11a 1992, .J. 254; J . Guay,
A. Dmt .. R. L. Wu. J . M. Tour. L. H. Oao. Cll<'m. Mttlt'r. 19\12 . .J. 1097.
36. J. V. Caspur, V. Rmnmnurthy, D. R. Curhin. J. Am. C/11'111. Sm. 1991, 113, 600.
37. C. H. Evans. J. C. Scaimtn. J. Attt. Clt<m. St><. 1990. 112. 2c.<..,t
38. V. Winlgens, P. F. Gamier. J. l'ily.v. Clttm. 98, 221!.
39. B. Zinger, K. R. Mann. M.G. Hill, L L. Miller, Cltrllt Mutt!r. 1\192, 4. 111 3.
40. D. M. Deleeuw, S.mrll. M<t. 1993. 57 . '5'>1.
41. Y. C:to. D. Gun. M. Pang. R. Qiau. Smtlt. Mrt. 19117, IX. 11!9.
42. K. Tanaka. Y. Y. O..hima, T. Y;nuabc. S. llulla, Syutlt. Mtt. 199-t. M. 295.
512 14 Physics of Orga11ic Field-Effect Trunsistors
43. M. G. Harrison, R. H. Friend, F. Garnier, A. Vassar, MoL Cry5J. Liq. Crys1. Sci. Tecllllulugy S
l ion A-Mvl. Cryst. uq. Cryst. 1994, 252, 165.
44. P. A. Lane, X. Wei, Z. V. Vardeny, J. Poplaw:.l.i, E. Ehrcnfreund, M. lbr.Jhim, A. J. Fmnk, S}nlh.
Met. 1996, 76, 57.
45. E. J. M. P. Crcuscn, MC't. 19'J6, 76, 233.
46. D. Emin, T. llolstein, A1111. Phys. 1%9, 53, 439.
47. P. G. Lc Comber, W. E. Spear, Phys. Rei( Leu. 1970, 25, 509.
48. D. M. Pai, J. C/Jem. Phys. 1970, 52, 2285.
49. J. Frenkel, Phys. He1( 1931!, 54, 647.
50. W. O. Gill, J. Appl. P/Jy.t. 1972,43, 5033.
51. Z. Xie, M. S. A. Abdou. X. Lu, M. J. !A-en. S. Jlokk:roO, Ctm. J. Phys. 1\1\12, 70, 11 7 1.
52. M. Willandcr. A. C. Svensson. Synth. Mel. 1993, 57, 4099.
53. J. H. Burroughes, C. A. Jones. R. H. Friend, Nalllre 1988,335, 137.
54. H. Fuchig;uni, A. Tsumur.t, H. Koczuka, Appl. P/ay.s. U!u. 1993, 63, 1372.
55. A. R. Brown, A. Pomp. C. M. Halt, D. M. Deleeuw, Scienu 1995, 270, 97:!; A.R. Brown, A
Pomp. D.M. de lccuw, D. B.M. Klaa.'i...en, E.E. l lavinga. P. Herwig, K. Mullen. J. Apfl. P/Jys.
19%. 79,2136.
56. J. Palohcimo, P. Kuivalaiucn, H. Stubb, E. P. Vli -Lahti, Appl. Play.v. Leu. 1990, 56,
1157.
57. X.Z. Pcng, G. D. fil.:huu. F. Ganncr. 1\ppl. Plly.. u!ll. 1990 . .57, 201J.
58. F. Gamier, G. llorowitt. X. Z. Pcng. D. Fichnu. 1\tlv. Mmtt: 1990. 2, 592.
59. G. Horowitz, X. Z. Peng, D. Fi<:hou, E Gamier. Spath. Mtt. 19')2. 51. 419.
00. C. D. Dmutr;tkopuulus, B. K. Fum1;m, T. Grah;un, .S. l legde, S. Purushothamun. Symh. Met. 19911,
92. 47.
61. F. Garnier. R. llajlaoui, A. Vassar, P. Srivaswva. Sdt'll<'<' 1994. 265. 16!!4.
62. V. T. Sihvoncn, S. G. Parker, D. R. Boyd, J. l::/ectrrxltt'm. Sot. I %7, /14, %.
63. Z.N. Bao, V. Fcng. A. Dodabalapur, V. R. Raju. A. J. Lovinger. C/JI'm. Mlll<'r. 1997,9, 1299.
64. J. A. Z. N. 13ao, V. R. Raju. Appl. Phys. Leu. 1998, 72. 27 16.
65. C. J. Drury, C. M. J. MuLo;acrs, C.M. Halt, M. D. M. Jc Lceuw, App/. Pltys. uu. 1998,
73. /08.
66. S. J-1. Glarum, J. Plays. Chem. Solids 1%3,24, 1577.
67. N. Karl, J. Marklanncr, R. Stehle, W. W.llta, Symll. Met. 1991, 42, 2473.
68. H. Al..imichi, K. S. Holla, H. Kanu, II. Sakati, Appl. Pll_v:r. Leu. 1991. 58, 1500.
69. F. Garnier, A. R. Hujlaoui, G. Horowilt. F. DeloiTrc. B. Servct, S. Rics, P. Alnul, J. ANL
Cllem. Soc. 19Y3. //5, 8716.
70. F. Garnier. H. 1-ltilaoui , A. El Kassmi, G. Horowil't., L Laigrc, W. PorLio, M. Annanini, F. Prova-
soli, Clacm. Mut. 1991!. in press.
71. B. Scrvet, G. llurowi tt, S. Ries, 0 . L.tgorssc. P. Alnot. A. F. DcloiTrc. P. Srivastav;J, R.
Hajluoui, P. L:mg, F. Gamier, Chent. Muter. 1994. 6, 1809.
72. A. Dodabalapur, L Torsi, H. E. Science 1995. 268, 27(); L Torsi, A. Dodabalapur, A. J. Lo-
vinger, H. E. Katz. R. Rucl, D. O. Davis. K. W. Baldwin, CltC'm. Miller. 1995, 7, 2247.
73. H. E. Kau. A. Dodabalapur. L Torsi, D. EIJcr. Client. Mutl!r. 1995, 7, 2231!.
74. G. HorowitL. X. Z. Peng, D. Fichou, F. Garnier, J. Mol. 1t'L'I ron. 1991, 7. 1!5.
75. R. Hajlaoui. D. Fichou, G. Horowitz, B. M. Conswm. F. Garnier, Adv. Muter. 1997, 9
557.
76. H. E. Katt. L Torsi. A. Clll!m. Muter. 1995, 7, 2235.
77. R. Hajlaoui, G. Horowitz, F. Garnier, A. An:c-Brouchct, L L..aigrc, A. El F. Ocnumzc, F.
Kouki, Ada: Mater. 1997, 9, 389.
78. G. Humwatz, R. liajlaoui, D. Fichou, A. El J. AJpl. Pl1ys . in
79. G. Hurowitl. B. Bache!, A. P. Lang, F. Dcmanze. J. L Favc, F. Gamier, Cllem. Muter.
19115. 7, 1337.
!SO. G. F. Garnier. A. Vassar, R. F. Kouki, Ad1. Muta. 19%, <'I. 52.
81. C. Kloc. H. Schoen, R. A. Laudisc, D. V. Lang. B. 001tlogg, /Si98 Marcia Me<ting uf th< 1\uwricWI
SodC'ty. Los Angeles, March 16-20. 1991!.
82. T. Sicgrbt, R. M. Fleming. R. C. H:II.!Jun, R. A. uudi..c, A. J. Lovinger, li.E. Katz. P. Briden-
baugh. D. O. J. Muter. Ns. IY95. 10, 2 170.
l<efere11ces 513
83. W. Portio, S. Destri. M. Maseherpa, S. Bruckner, Acta Polym. 1\193, 44, 266.
84. L Antolini, G. Horowitz.. F. Kouki, F. Garnier, Adl( Mmer. 1998, 10. 3!S2.
85. T. Siegrist, C. Kluc. R. A. U!U<Iisc. H. E. Katz. R.C. Hac.klon, Atf. Mater. 1991!, 10, 371.J.
86. D. O. Eley, Nature 194&. 162. 819; D. O. Eley, G. O. Parrill. M. J. Perry. D. H. Taysum. Tmns.
Famtluy 1953. -lSI. 71.J.
87. R. Madru. G. Guillaud. M. AI Soxloun, M. Maitrnl. J.J. Audn!, J. Simon, R. Even, Client. Pl11s.
uu. 1988. 1-15, :WJ.
88. C. Clarisse, M. T. Riou. J. Appl. Pltys. 1991, 6SI, 3324.
89. Z. N. 13;KI, A. J. Lovinger. A. DuJahalapur. Atlfll. u 'll. 1996. 69, 3066; Z. N. Bao. A. J.
Luviuger. A. Dodalxtlapur. Mmu 1997, Sl. 42.
90. 0 . F. O;.uh..:. C. R. J. Chern. I'&Lys. l'J7U. 52. 4<l4h.
91. M. Pope. C. c. Swcuberg, El<ctnmic i n Orllauic O ystal.f, OxlorJ University
New YO(k 191!2.
92. A. J. Salih, J. M. J. M. Maud, l'hil. L.u. 1997, 75, 169.
93. C. D. Oimitral.upuulus .. A.R. Bmwn, A. l'ump, J. Appl. Phys. Ill%. XO. 2501.
94. J. G. L;,quindanun. H. E. Katz, A. J. Lovinger, A. Oo<labalapur, Clum. Matr. 1996. ,'1, 2542.
95. D. J. GunJlach, V. V. Lin. T.N. JackloOO. S. F. Nchnu, D. G. Schlom, / EEE I:Je,trvu. Ocicc Leu.
1997. IN, K7.
96. S. F. Neb<lll, V. V. Lin. O. J. GunJiach. T. N. Appl. Phys. Leu. 1991!. 72, 1854.
Y7. T. Mi ual.ata. I. Na!;uya, M. 01'.:.tki , J. Aflfll. Pl1y.v. 1991, I>SI, 7354.
9!!. R. l3. C'alllphcll. J. Muuu:ath Ruberhun. J. Tnlller. Ada Crnl. 1%1, /-1, 705.
99. J. G. L.tquind:mum. H. E. Kat/., A. J. Lovinger. A. Oodahal;tpur, A<lv. Mat<r. 1997, 9, 36.
100. H. R. H. friend. X. C. l.i, S. C. Mur.uti. A. 0 . Holmes. N. Fe<.xlcl-. Appl. Phys. Ll'll.
IYY7. 71, 3K71; X. C. Li. H. SirTinghaus. E i\. 13. S.C. Muraui, N. FCC<ler, W.
Clegg. S. J. R. ll . friend. J. Am<'r. C'lrtm. Sm. 199M, 120. 2206.
101. C. Ad;tehi, S. Tol..ito, T. T.,uL,ui. S. Sailu. Jup. J. Awl. Phy.v. I<JHH. 27, L71J; C. Adachi, S. To-
kilo, T. S . .Saito. Jap. J. AJpl. Phy.t. IYtil!. 27. L261.J.
102. C. W. l:mg .S. A. van Slyl..c, C. H. Chen. J. 1\ftl. Pllys. l 9H9, 65, 3610.
103. D. A. SaniO!>, C. Quaumcchi. R. H. Friend. J. L. J. Clwm. P/t_y.v. 1994, / 00,3301.
104. A. R. Brown, D. M. Deleeuw, E. J. Loo . E. E. l lavinga, Symlt. Met. 1994, 66.257.
105. R. C. Haddon. A. S. Pcrcl, R. C. Murri.,, T. T. M. A. F. Hcl=J, R. M. Ae ming. AJpl.
Plly.f. Leu. 19'J5, 67. 121.
106. C. P. Jam:u, K. Pichler, R. NewhouiJ. R. ll . f neud, Synth. Met. 19'Xt, 77. 35.
107. R.C. 1-laJJon. J. Am. Cltcm. Soc. 1996. /!.'! , ] ()41.
108. G. l!l)mwitL F. Kuul..i, P. Spcanmur. 0 . Fichou, C. Nogucs, X. Pan, F. Gamier, Ad1. Mala
1996. 8, 242.
109. J. G. Luquiud;mum, H. E. Katz, A. DoJahalapu.-, A. J. Lovinger, J. Am. C/wm. Soc 1996, 1/R,
1133 I.
110. S. R. ro.n:.,t. Clum. Ntt: I Y\17, Sl7, 17'>3.
Ill. Z. N. B01o, A. Dodabalapur, A. J. Lovinger. ApJI. Jlllys. L.u. 19%,611, 41()!S.
112. H. Sirringh<tus, N. T .. -s.,lcr. R. 1-1. Fnend, S<'i<'ll<'t IYY8. 21ilJ. 1741.
113. A. R. Brown, D. M. Deleeuw. E. E. H01vinga. A. Pomp. Sylllh. Ml'l. 1994, 6S, 65.
114. G. Horowill., P. DclalliK>y, J. Apfl. Plays. 199 1, 70. 469.
li S. G. llorowitt, R. Hajlaoui, P. Dclannoy. J. Pfl1x. Ill f 'rcmce 1995, 5, 355.
116. W. E. Spear, P. G. Lc Comber. J. NmrCryst. Solitll 1972, H- /0, 727.
117. A. Madan, P. G. Lc Cumber. W.E. Spear. J. Nwt -Crylt. 1976, 20, 239.
118. M. J. Pvwcll, Phil. M11g. 8 1981, -IJ, 93.
119. M. W. Wu, E. M. Conwell. CIJem. Pin-s. L.u. 1997. 266. 363.
120. M. C. J. M. Vissenbc.I' J , M. Hea. lJ 1998, 57. 12964.
121. K. H. Akimichi, S. Hnua, 1-1. K01no. II. PIJy.f. R<': lJ 1995, 52, 17K6.
12:!. L. Tmsi. A. L.J. Rnthhe rg. A. W. l'. Fung. H. E. Ka11., Sci<'ll<'<' 1996, 272, 1462.
123. L Tursi. A. DuJabal01pur, L.J. l{uthbcrg. A. W. l'. Fung, H. E. Katt.. 1'1/ys. Hel'. lJ 1991!, 57.
2271.
124. G. 1-lorowitl., R. Hajlauui. R. B<lua:;uil!" M. I-IO!Jiauui , /ntnl<llimwl Con}a<'ll<'<' 1111 Sl'itme 111111
1(dl/lala,l(,\' of Symlrctic M<'l<l/s, Muntpdhcr, Fr.mce, July 12- 18, 19<JIS. Symh. ML'l. 1999. 101.
401.
514 14 Physics of Orgw1ic Field-E.ffeLt Trcmsiswrs
125. L Torsi, A. Dodabalapur, H.E. Katz., J. Appl. Plays. 1995, 78, 1088.
126. G. Borowiu.. Adv. Mater. 19%, 8, 177.
127. G. Horowilz, X.Z. Pcng, D. Fichou, E Gamier, J. Appl. Plays. 1990, 67, 528.
128. D.M. Taylor. B.L. Gomes, A.E. Underhill, S. Edge, P. l. Ch:mcnson, J. Phys.-1>-AwL Phys.
1991, 24, 2032.
15 Conjugated Polymer-Based
Plastic Solar Cells
Christoph J. Brabec, and N. Serdar Sariciftci
15.1 Introduction
:
A tremendous rescarl:h ellort was devoted to the development of photovoltaic
cells duri ng the late seventies and early eighties. During this time interest was
also devoted to the development of organic semiconductors, because they offer
the advantages of low cost and facile processing. Organic materials for use in
photovoltaic devices require a good chemical stability and large optical absorption
in the visible mnge. For this purpose the llrst studied compounds were merocya-
nines [I J and phthalocyanines l2], which can readily be deposited as a thin film
on various even llexible substrates by vacuum evaporation. Power conversion effi-
ciencies of such devices are about I% for small size photovoltaic clements.
It is indeed intriguing and economically advamagoous to think of large area
photovoltaic element'i based on thin plastic lilms, cut from rolls and deployed on
permanent strul:turcs and surfaces. In order to fulfil these low cost and large area
requirements, cheap production technologies for large scale coating must be used
together with low cost material. Polymer photovoltaic cells hold the potential for
such low cost cells. The tlexibility of chemical tailoring of desired properties, as
well as the cheap technology already well developed for all kinds of plastic thin
film applications, meet exactly the above mentioned demands for cheap photovol-
taic device production. The mechanical llexibility of plastic materials is useful for
all photovohaic applications onto curved surfaces for indoor as well as outdoor
applications.
Ellicicncies of the lirst polymeric solar cell s. based on hole conducting conju-
gated polymers (mainly polyacetylene) were mther discouraging l3J. However, the
breakthrough to higher efficienci es was achieved by switching to different classes
of electron-donor type-conjugated polymers (polythiophenes (PT), poly(para-
phenylene vinylene)s (PPV) and their deri vatives) and by mixing them with suit-
able electron acceptors l4). Prototypes of photovohaic devices based on a poly-
meric donor/acceptor networks showed solar energy conversion efficiencies of
around I% [5]. In particular, the photovollak properties and the photophysics of
conjugated polymer/fullerene solid composites have been well investigated over
Lhe l<l<;t few years [6].
Besides the necessity for improvement in efficiency, stability is another prob-
lem for all the appli cations of conjugated pol ymers. First experiences on conju-
516 15 Co11jugated Polymer Bused Plastic Solar Cells
gated polymer LEOs showed that a shelf lifetime of several years as well as an
operational lifetime of tens of thousands of hours are requested for all dumble ap-
plications. For photovoltaic devices the economically important connection be-
tween operational lifetime and efficiency will determine the exact numbers, but it
is evident that the life.time of solar cells has to be similar or even higher than for
LEOs. Protection from air and humidity is absolutely necessary to achieve such
lifetimes. Recent reports from LED research indicate that this problem has been
sufficiently overcome for enteri ng the large-scale application, which in return is 3
good sign for plastic solar cells.
Compared to the research efforts, devoted to small molecule organic solar cells,
a relatively new approach of exploiting solar energy of organic materials using is
to use organic polymeric solar cell s (and here especially the internal donor/accep-
tor 'plastic solar cells' ). Due to the progress of polymer synthesis, conjugated
polymers are now available with a purity compardble to the small organic mole-
cules. The most considerable dill'crencc between these two classes of molecular
semiconductors, however, is the degree of order and the subsequent macroscopi...
migr.nion process. In small molecules the mobility of photogener.lled charges is
limited by the relatively small n overlap and therefore electron hopping from mol-
ecule to molecule is dominant. In conjugated polymers the imrinsic mobility on 3
polymer chain is detem1incd by strong covalem intrachain interactions. Impurities
in these systems may now completely dominate the mobility through trapping
processes.
The aim of this chapter is to give a state-of-the-art report on the plastic solar
cells based on conjugated polymers. Results from other organic solar cells like
pristine fullercne cells 17, 8), dye-sensitized liquid electrolyte )9), or solid slate
polymer electrol yte cells [I 0 ), pure dye cells )II, 12 ), or small molecule cells
r 13], mostly based on heterojunctions between phthaocyanines and perylenes )14],
will not be discussed. Extensive litemture exists on the fabrication of solar cells
based on small molecular dyes with donor-acceptor systems (see for example (2,
3] and references therein).
The chapter is organized as follows: the second section will discuss the photo-
physics of conjugated polymer/fullerene composites as a standard model for a
charge-genemting layer in plastic solar cells. Pristine polymer devices will be dis-
cussed in the third section while bilayer and interpenetrating network devices are
presented in Scetions 4 and 5. Section 6 contains some remarks on large area
plastic solar cells and Section 7 concl usions.
15.2 Conjugated Polymers as Photoexcited Donors
Several auempts to use organic polymeric semiconductors as the active compo-
nent in photovoltaic devices have been reported during the last two decades. Inter-
est in the photovoltaic properties of conjugated polymers like polyacctylene, var-
ious derivatives of polythiophenes and poly(para-phenylcne vinylcne)s arose from
15.2 ConjugCited Polymers us Plwtoexcited Donors 517
the discovery of mobile photoinduced charged states in this class of organic semi-
conductors. The idea of using this property in conjunction with a molecular elec-
tron acceptor to achieve long-living charge separation was based on the stability
of the photoinduced non-linear excitations (such as polaron) on the conjugated
polymer backbone. Independently, the Santa Barbara- and Osaka group reported
studies on the photophysics of mixtures and bilayers of conjugated polymers wi th
fullerenes 15. 6, 15- 23]. The experiments clearly gave evidence of an ultrafast
(subpicosecond), reversible, metastable photoinduced electron tmnsfer from conju-
gated polymers onto the in solid films (see Fig. 15- 1 ). Once the photoexcited
electron is lmnsferred to an acceptor unit, the resulting cation radical (positive po-
huon) species on the conjugated polymer backbone is known to be highly delocal-
izcd and stable as shown in electrochemil:UI and/or chemical oxidati ve doping
studies. The long lifetime of the charge transferred state and the high quantum ef-
ficiency of this process ( 100%) in conjugated polymer/fullcrene composites,
compared to pristine conjugated polymer films, the development of photo-
cell s.
The first photovohaic devices hascd on this photoinduced electron transiCr
were diodes consisting of hilayers from conjugated polymers and fullerencs. Rec-
tification ratios in 1he order of I 0"
1
were demonstrated, but photo voltaic power
conversion eiTicieneies of these devices were low due to the small charge-gener.at-
ing interface. The superior solubility of functi onali zed fullerenes compared to Cw
enabled the of highly fullerene-loaded composite films. Significant im-
provement in the relatively low collection efficiency of the 0/A bilayer has been
achieved by control of the morphology of the donor/:aeceptor components in a
composite f1lm to obtain <Ul intcrpcnclmting network. The power conversion effi-
on
Figure 15-1. Schcmalic illusll'a-
liun of lhc photoinduced clcclmn
tmnsfcr from conjugated, scmi-
.. mducting polymers onto Buck-
min, lcrfullcn:nc, C
00
(l'cpnxluccd
by pcnnision of John Wiley
(rum Ref. 16().
518 15 Conjugated Polymer Plu.st1c Solar Cells
P3AT (A .. alkyl)

1.1<0 II
MDMO-PPV

0

H H H H H
I I I I I

I I I I
H H H H
PA
Fagure 15-2. Abbreviation and structure of common conjugated polymers as well as fullecenes or
other acceptono for conjugated polymers.
ciency of solar cells made from MEH-PPV /fullerene composites was subsequently
increased by two orders of magnitude. The central photophysical results of this ul-
trafast photoinduced electron transfer will be discussed by reviewing experiments
from two well-characterized conjugated polymers, an alkoxy PPV (MEH-PPV or
MDMO-PPV) and P30T. The chemical structures of these polymers a.-; well as of
the most frequently used fullercnes arc given in Figure 15-2.
15.2.1 Optical Properties
15.2.1.1 Linear Optical Properties
Figure 15-3 shows the optical absorption spectrum of a MEH-PPV/C6C> film with
different Cffl content compared to the optical absorption spectrum of the compo-
nents alone. The peak at 2.5 cV is identified as the n-n* absorption of MEH-PPY
and is clearly observed along with the first dipole-allowed tr:.msition in Cc.o (at
3.75 eV). The spectrum is a simple superposition uf the two components. Further-

9
NC""'CN
1
4
Figure 15-2. (Continued)
0
I 5.2 Conjugated Polymers us Plwtvext:ited Duuors 519
0
5 6
more, the positions of the absorption maxima of the single components in the
composite arc not shifted compared to the pristine materials. There is no indica-
tion of states below the n-n-* gup of the conjugated polymer that might arise
from ground slate inter.tctions such as doping.
Figure 15-4 shows the intensity of the photoluminescence as a function of the
fullercnc concentration in MOMO-PPV/PCBM composites. The strong quenching
520
1.0

!!
0.8
1:
:>
.f
0.6
..
._,
.,
u
c:
..
Jl
.. 0.4
0
"' Jl
<
0.2
0.01
1.0
,.....
!::
0.8
c:
:>
-e
0.6
.!!.
.,
u
c
..
-e 0.4
0
....
Jl
<
0.2
15 Conjugated Polymer Based Plastic Solur Cells
(a)
2
(b)
3 4
Energy (eV)
3 4
Energy (eV)
.s
Figure 15-3. la) Optical absoqJUoD
spectra of MEH-PI'V and C60- (b)
Optical absorption spcctm of MEH-
PPV!C....., films with diO'crcnt conc:CP-
u-.ttions of Coo (rcprudiJCC<l by per
mission of the American Physical
Society from Ref. (381).
of the luminescence was also reported by Morita et a/. [20) for another conju-
gated polymer P30T and is consistent with ellicient electron
fer. Poly(alkylthiophenes) do not exhibit ground state dopmg s1mtlar to the subSlJ-
tuted PPVs. Luminescence quenching already happens at very low fullerene con-
centr..ltions (below 1 mol% fullerenes). Percolation of the fullerunc to a
path (at approximately 17 vol%) is not n_ecessary for luminescence quenching.
The inset in Figure 15-4 shows the lummescence spectrum of M_EH-PPV /Cc;o
composites compared to MEH-PPV alone. The strong photolummescence ?f
MEH-PPV is quenched by a factor in excess of I O:l but no signific_ant m
the shape of the spectrum arc observed. The lumincsccnc_e 1s
from Tu=550 ps to Trmt 60 ps (the instrumental resolution) llld1catmg the CXIS
tence of a mpid quenching process; e.g. subpicosccond electron tr.msrcr.
15.2 Crmjugated Polymers as Photoexc:ited Donors 521

; 0
1.0 1.0
i 0.1 0.1
.s 0.6 . :. 0.6 i
g i'.
0.4 0.4
i 0. 2 -;
....) 00 o.o ..J
1.0 . , 2.0
fn<'IY (<V)

- ... .,..
0,1 10 100
Concentration of PCBM Jmol%1
Figure 15-4. Jntcn.,i ty of the a function of the J>CBM concenu-.11ion in MEH-
PPVIPCBM The inset shows lhc Jumilll. -sccnce of pristine MEH-PPV (solid lri<mglcs, Jefl-
hruld axis) and a MEH-I'PV/Cw oomposilc (cirdcs, righl-hand adapted from Ref. 14)).
15.2.1.2 Photoinduced Absorption
Quenching of Ute Intersystem Crossing to U1e Triplet State
The occurrence of luminescence quenching can be explained by various mecha-
nisms. The excited singlet state can relax to the ground state also by non-radiative
processes (them1al heating), and energy transfer or elcctron transfer processes.
Since the absorption and luminescence studies demonstrate that the excited states
of the conjugated polymers strongly interact with Cw. a comparative spectro-
scopic study of thi s excited state is ncce..<;sary. The tirst results of the excitcu state
spectroscopy of these composites originate from ncar-steady-state photoinduced
absorption (PIA) studies. To clearly distinguish the spin multiplicity of the
induced absorption (PIA) peaks, photoinduced absorption-detected magnetic reso-
nance experiments were performed f 19). The full spectral range photoinduced ab-
sorption spectra are displayed in Figure 15-5. Results show that the PIA bands
centered around 0.3 eV and 1.1 cV arc significant only in the composite material.
Pure MEH-PPV shows the single PIA band from the triplcH1iplet absorption, as
assigned earli er [24]. The PIA of Cc
111
is neglected in this comparison because the
magnitude of the signal is l<f times smaller when photoexcited with 2.5 eV as a
result of the very low optical density of c(l(l in this rugion.
ln absorption-detected magnetic resonance studies, the PIA band at 1.35 eV in
the pure MEH-PPV shows a strong response at the (forbidden) half-field reso-
nance of spin= I (D.m =2). triplet character for this PIA band and domi-
nance of the neutral photoexcitations in MEH-PPV (sec Fig. 15-6). A small resid-
ual spin= 112 response within the pure MEH-PPV shows the presence of photoin-
duced mdicals. Upon adding C('l(l> the triplet signal lor the 1.35 eV PIA band is
completely quenched. Instead a strong spin= 1/2 signal dominates, indicating
charged polarons as photocxcitati nns on the polymer. This shows that the photoin-
522
15 Conjugated Polymer Based Plastic Solar Cells
\ .5
T
(a) MEH-PPV
\ .0
0.5
(b}
E" 0.5
.....
:!
MEHPPVC60
..0.5
PHOTON ENERGY (eV)
1.0 0.1 (c)
0.5
0.0 OL_._-O.l.. .1.-.___0...L. .2-..__0::-L.-:3 _.._-::0.-:- 4_._-:0.5
pHOTON ENERGY {eV)
Figure 15-5. Photoinduced absorplion
and photolununcsccncc (PL) spec1ro1 li
MEH-PPV at 1!0 K; (b, c) photoinduced
ab!)OfJltio n of MEH-PPV/4,o al
4 K with argon ion laser at nrn
modul:ttcd at 200 H. 111C abbrevrauons
T, LE. HE. EA stand for uiplct:triplct ab-
sorption. low-energy b;_nd. hrgh-eocrgy
band. and electroilbsorptron features,
spcctivcly. IRAV !>lands for infrared_
vatcd (reproduced by pcmuSSIOO
of the American Physical from
Ref. j i'JI).
1 ffi ently fast 10 quench the inter-
duced electron tr.msfer occurs on a ttme-sca c su tct
system crossing to the triplet state.
Photoinduced IRAV Studies .
1
1
.
d nu ated polymers the quasi-onc-duncnstona c ectromc
In scmtcon ucltng, co J g ' . A . . 11,
..
1
gly coupled 10 the chemical (gcomctncal) structure. s a
structure ts s ron ) . dressed wtth
the non-linear excitations (solitons, polarons, and pmrs a;e.b.dd --n
local structural distortions creating states at cnergtcs _wtthtn .t . :n
>a 'New' vibmtional infmrcd absoq')tion bands_ w_llh . .
g ) .1 . I by .1
0
p-ttll' and/or photocxcuattun. Sohtons. pola10ns are
moues arc muur.;eu u o . k R
charged ' defects' whit.:h break the local symmetry and therefore m .t c aman
0
<: _,
....
-IS
.:... -2
..
-3
0
_,
! -2
-3
HF
0
15.2 Conjugmed Polymers as Plwroexcited Donors 523
MEH PPV
(a)
FF FF
$ =112
$ = 1/2
I
500 1000 1500
H(Gauss\
l'igurc 15-6. (a) Phowiuduccd absorp-
tiun-&:ICCtctl magnetic resonance
(AOMR) spectrum o f MEH-PPV. IIF
and FF represents the hair Jicld and
run li cit! powder pauem for the triple!
(S = I) rc.\onancc, respectively. lb)
ADMR !>.pcctrurn o f
composite lilm. Both spectra were
:U probe energy 1.35 cV,
T=4 K :Uld 3 GHt resonant mi.:m-
wavc (rctjucnc y (repro<.lu.:cd by p.!r-
rnissiun of the American So-
c iety (rum Ref. l19j).
modes infrared active. Recent IRAV doping studies of P30T [::!5, 26j showed sig-
nificant dillcrenccs in the IRAV bands depending on the doping mcchm1ism (i.e.
chemical, electrochemi cal, phototloping). In the theoretical fr-.unework of the mod-
el presented by Zcrbi <' I a/. (27(, the IRAV band!. 10 lolally symmetric
Raman active vibrational modes, which couple 10 the n-clectron system along
a so-<:allcd 'ellecti ve conjugati on coordinate' . The distribution in the
fomled polaronic or bi polaronic state causes high dipole moment changes during
vibration, thereby breakiny the symmetry. In general, in the frequency range be-
tween 1600 and HOO em- . four modes exist in for polythiophene,
which, in unsubstituted polythiophcnes, rise to a pattem of three strong
bands in the photoinduced absorpt ion Sp<X:Irum (28( and in the doping-induced
absorption spectrum [291. as well as three main Raman bands. Very recently Eh-
renfreund and Vardeny 1301 established a link between the doping-induced elec-
tronic slate within the semiconducting n--n* energy gap the lRAV bands of
doping-induced infrared spectrum, which was on a linear response theory
by Girlando, Painclli and Soos [31(.
Linear IR absorption studies proved thai there is no interaction between the
conjugated- polymer bad.bonc ;and lhc

molecule in the stale. as al -
524
1:::
....
<I
"
20
15
10
s
0
0.0
Energy(eV)
Figure IS-7. (a) Pholoinduccd IR absorption
speclrn of P30T and P30T/4o (5%) at 80 K
obtained by pumping with an Argon ion laser
at 2.41 eV (reproduced by pennission of the
American Physical Society fi'Om Ref. 132)).
ready found by UV-Vis absorption measurement:-. The infmrcd spectrum, which is
dominated by the vibrational of the conjugated polymer backbone,
shows no change upon addition of 5% Cc.u Upon photocxcitation of the compo-
site, however, the photoinduced electron transfer creates long-lived charges in the
conjugated polymer/C(
141
composites. The high and the longer life-
time of the photoinjected charges on the polymer backbone strongly
IRAV modes. In Figure 15-7a the PIA spectrum of a P30T composite with Coo is
compared to a spectrum of a pristine P30T tilm. Addition of a few weight per
cent of 4.t
1
strongly enhances the intensity of the IRAY bands and the lower po-
laron peak of the polymer L321. Addi tionally, two electronic absorption bands, lo-
cated at 1.15 and 1.25 eY, arc detected. These bands arc associated with the for-
mation of the c-
60
anion and the onset o( the second polaron absorption band is
observed. The quenching of the triplet peak around 1.45 eV can not be seen in
this figure.
Time-Resolvt.>d Photoinduced Studies
It is still not clearly understood why the forward electron transfer is happening so
fast while the back transfer is several orders of magnitude slower. Theoretical
models for the photoinduced charge transfer in conjugated polymcr/Cc.o compo-
sites have been developed to estimate the time constant of the tr.msfer. A model
based on the assumption that the charge tmnstcr is a pair process of purely elec-
tronic origin proposes a transfer l':.lle in the ps regime (33(. Models Laking imo ac-
count electron-phonon interactions for coupled Su-Schricffcr-Heeger [34] models
but neglecting electron-electron interactions find that photoinduced electron trans-
fer takes place between 200 t:-; and 300 fs 135).
Sub-picosecond photoinduced absorption studies were employed to demonstrate
the speed of the photoinduced ek:ctron tr.msfer. Upon addition of C,,o to P30T,
the PIA spectrum, decay kinetics, intensity dependence all change dramati-
cally (361. Already at I ps after photocxcitation by a 100 fs pump pulse at

0.6 ..
,

t:
0.4
<t
0.2
0.0
15.2 Conjugated Polymers til' Plwwexcited Donors
1.0
..
0.8
..
"
..
- 0.6
..
..
!
\
..
..
..
..
""'l. ...
.... ..
..
..
0.8 1.0 L2 1.4 1.6 1.8 2.0 2.2
Energy (eV)
0.4
0.2
0.0
;)
!!
1-.
j::
<t
525
.
lo' igure 15.7(11) of the photoinduc(X] absorption speclr.t for ncar steady state (mi llise(:ond)
and ullmfast (picosecond) time for PJOT/Cr>O composi lc lilnll>. The picosecond photoinduced
sp.:etra arc taken al 300 K :ll Jch1y times alter a 2.0 I eV tOO fs pump pulse for PJOT :md
P30f/C,., (repl\lduccd by of World Scicntitk from Ref. [171).
2.01 eY, charge transfer is observed for P30T/Cllu (1%) (see Fig. 15-7b). Similar
results were found lor

composites. Femtosecond pump probe mea-
surements on MEH-PPY/4
1
systems allowed estimation of the excitation din"u-
sion range on the polymer prior to charge tmnsfer wi th 5-10 nm (37).
15.2.1.3 Sensitization of Photoconductivity
Figure 15-8 shows, on a semilog plot, the spectral response [38) of the cw-PC of
MEH-PPV alone and MEH-PPY/C
1141
composite for diiTcrent conccntr.J.tions of
ew. These room tenper.J.ture data arc nonnalizcd to the constant incident photon
nux of about 7 .51 0
1
photons/cm
2
s. The admixture of I% of C
60
results in an in-
crease in the initial photocUJrent by one order of magnitude. Studies on the photo-
conductive spcctr.J.I response of MEH-PPY may give valuable information on the
acceptor properties of MEH-PPV shows a sharp photocurrent onset at about
2 eV that coincides with the optic;al absorption c;dge across the energy gap.
Although the efkt:t of thl..' on thl..' 111ohility of 11lc carril!r should be considcrl..'d
(the mobility will probably decrease as a result of tlu: deep trap sites associatcu
with Cc!(J clusters), the significant effect of Cc
111
on the generation ct:.
ficiency is evident from the observation lhat even I % C"'
1
in the polymer matrix
enhances the cw-PC by more than an order of magnitude. This observation is in
full agreement with the photoinduced electron tmnsfer phenomenon which leaves
metastable positive polarons on the polymer backbone after the electron transfer,
i.e. 'plrotodopin g'.
526
-
Cl)
-OJ
(,)

"' ti
::::1
"0

0
(.)
g
0
.t::
p..
OJ
cu
- Cl)
>-.
"0
"'
Cl)
I 5 Cunjugmed Polymer Bused Plustic Sowr Cells
10-ll
10-14
10.1$

.r.8
a
I
0
10-16
F

2 3
,.,. ... _ .......... .

o 50 % ln MEH-PPV
A 5 % MEH-PPV
o 1 MEH-PPV
MEH-PPV
Energy (eV)

s
Figure 15-8. Spectral response of the sreoldy s1;11e pho1oconductivity of MEH-PPV alone and Mai
PPV/Cc,.;
1
for sever.tl concentrolliOliS a1 300 K and a biasing field of l<f V/cm (reproduced by pcnnis-
sion of Elsevier Science from Ref. ( 18)).
15.2.2 Magnetic Properties
15.2.2.1 Light-Induced Electron Spin Resonance (LESR)
A very powerful method to investigate photoinduced charge tr.msfer systems is
the light-induced electron spin resonance studies (LESR). Dclinitive evidence of
charge separation is obtained from these experiment-;. Figure 15-9a shows the
ESR upon illuminating the MOMO-PPV/PCBM composites with light of
h1=En- n where En--n is the energy gap of the conjugated polymer (donor). Two
photoinduced ESR signals can be resolved; one al g =2.0026 and the other at
g = 1.9997. The hi gher g-value line is assigned to the conjugated polymer cati on
(polaron) and the lower li ne to the CC..
1
anion. The assignment of the low-
er g-value line to C("
1
is unambiguous, as this atypically low g-value is character-
istic of fullcrene anions [391; the higher g-value is typical of conjugated polymers.
At 200 K, the LESR signals have nearly vanished. demonstrati ng the reversibility
::;
.i
Cii
c
Cl
;;;
a:
Cl)
w
..J
3360
3360
(a)
3370
Magneric Field [GJ
(b)
3370
Magnetic Field [G)
15.2 Conjugated Polymers as Phutoexl.'ited Douors
527
3380
3380
Figure 15-9. (a) Lighl -induL'Cd cleelron spin rcso-
nam:c of MOMO-PPVIPCBM upon suc-
illuminalion with 2.4 1 cV :ugon ion laser.
(b) lmegratcd LESR intensity IESR (illuminatcxi)-
ESR (tlark)J of MDMO-PPVIPCBM (reproduced
after Ref. 140)).
of of radicals. Subsc.!quent LESR measurement cycles
heatmo to K. _to I?<J K. illuminalion with light, switching
hght _off and up agarn yu::ld denllcal results. More information on Lhe re-
behav1or t_hc radicals is gained from the integrated
SignaL ot the 11lummated ESR signal of Figure 15-9a is shown
tn Ftgure The stgnal shows two peaks with comparable areas, manifesting
that both _radtcals have equal amounL-; of spin. Lately 1401 the saturation behavior
lt_ne shape o_r the of conjugated polymcr/CM, systems have
_siUdled. Analysts conlmns the llmling that the two dilTercnt peaks bclon. tu
hght-mduccd radicals. g
528 15 Conjuguted Polymer Bused Plustic Solar Cells
15.3 Pure Conjugated Polymer Photovoltaic Devices
15.3.1 Definitions
We define the following:
Calculation of the power conversion efficiency 1]11! was performed using the re-
lation
( 15. 1)
where V,>< /,.,., FF. P;, arc the open circuit potential, short circuit current, filling
factor and incident power, respectively. The filling factor was b,t
calculation of the maxunum power rectangular area under the 1/V curve m the 4
quadrant. The filling factor FF was C<IIculated from:
FF = 1
1
,/(V,,.. 1.\C' ) ( 15.2)
where V
1
, and /
1
, represent the intersection of the IN curve with the maximum
power rectangle. The spectrally resolved (IPCE) or the 'incident photon to con-
verted electron' efficiency 'lc is defined as follows:
2 ")
1],.[%] = 1240 ]/ A[nm]/[W / m-J. (15.3)
15.3.2 Basic Transport Properties
Initial efforts on photovoltaic devices using conjugated polymen; were pertom1ed
with polyacetylene [3] and some polythiophenes [ 41, 42]. From the conjugated
polymers of the first generation, PPV (poly(para-phenylene vinylene) was the
most successful candidate for single layer polymer photovoltaic devices [43]. Un-
substituted PPV is generally produced from a soluble precursor polymer with sub-
sequent heat conversion. The radiative recombination channels of the injected
electrons and holes withi n PPV and its derivatives, which resulted in light emit-
ting diodes (LED 144-47] ), opened thi s class of easily processable materials with
high electroluminescence quantum efficiencies for photovohaie devices. Interest-
ingly, it was found that the same devices, under reverse bias, exhibit excellent
sensi ti vity like photodiodes (48}. ln forward bias, tunneling injection diodes ex-
hibit relatively high efficiency electroluminescence, which is promissing for flat
panel and/or flexible, large area display applications. In reverse bias, on the other
hand, the devices exhibit a strong photoresponse with a quantum yield >20% (elf
ph at - 10 V reverse bias) 148]. Devices based on derivatives of polythiophene ex-
hibit even better photoresponses (HO% elfph at - 15 V), competitive with UV-sensi-
tized Si photo<liodcs 14H). A photovoltaic response was observed under zero bias
15.3 Pure Cunjugtttccl Polymer Plwtovo/Uiic Devices 529
conditions. The integration of three functions, elcctroluminescencc, photodetector.
and photovohaic response in the same devices otTers special opportunities. The
triple function capability offers promise especially for novel, input-output displays
powered by organic photovoltaic.
Betore investigating the photovoltaic properties of single-polymer-layer diodes,
it is important to have a model that accurately describes the device operation in
the dark. In recent studies Philips group modeled the IN behavior of single-layer
MDMO-PPV diodes (49-51 ]. They found that, at higher voltages the electron and
hole currents in PPV-based devices with low contact barriers are determined. by
the bulk conduction properties of the polymer and not by the injection properties
of the contacts. The conduction of the holes is govemed by space-charge etTects
and a field-dependent mobility, while the electron transport is limited by traps.
The following set of equations are given:
t:ot:r oE(x)
- = p(x) - n(x) - 11
1
(x)
e vx
J = 1
1
, + 1, = eJt
1
,[E(x)]p(x)E(x) + CJl
11
[(x)]n(x)E(x)
( )
(
N, ) (c -,.)
n, x = - exp --
kT, kT,
I o1, I D1
1
,
--= - --= Bp(x)n(x)
e Dx e Dx
( 15.4)
Here JP and 111 are the hol e and electron current densi ties respectively with their
hole and electron mobilities 11
11
and Jt,, and the density of the mobile holes and
t!lectrons p (x) 11 (x). The density of the trapped electrons is denoted with
11,(x). B, the bimolecular recombination constant, is the only fi t pammeter in thi s
model. The field-dependent mobility was originally derived by Pai et a/. L52] to
describe mobility of photoinduced holes in PVK. Here ll denotes an activation en-
ergy and y is a coefficient compar.1ble to the field dependence in the Poole-Fren-
kel [53] effect. The model tor electron tr:.tps assumes quasi equilibrium between
the trc1ppcd and the free elecuons l54) whereby n,(t:) represents the trap density of
st:ues at energy c., ,. the energy of the conduction band, N the total density of
traps. and J..T, an energy characteri1.ing the trap distribution. The photovoltaic re-
sponse of these devices is mosl important between zero vol tage and the open cir-
cuit voltage. The expansion of thi s model to low voltages for hole-domimttcd- or
electron-dominated devices showed good agreement with experiments.
530 15 Conjugated Polymer Based Plastic Solar Cells
CB
VB
lihoft circuit
conditions
-
ITO
CB
VB
tlat band under
open circtJil
c--
Al
ITO
cu
VB
forward bias
electron injection
AI
Figure 15-10. Schematic band diagrams for single-layer conjugated polymer dcvi.:es at vmious values
of forward bias. Forward bias is deli ned wilh respect 10 lTO.
The simplest and most widely used model to explain the response of organic
photovoltaic devices under illumination is a metal -insulator-metal (MIM) tunnel
diode [55) with asymmetrical work-function metal electrodes (sec Fig. 15- 10). In
forward bias, holes from the high work-function metal and electrons from the low
work-function metal are injected into the organic semiconductor thin film. Be-
cause of the asymmetry of the work-functions for the two different metals, for-
ward bias currents arc orders of magnitude larger than reverse bias currents at low
voltages. The expansion of the current transport model described above to a car-
rier generation term was not taken into account until now.
Parker [55] studied the IN properties of MEH-PPV sandwiched between var-
ious low-and high work-function materials. He proposed a model for such photo-
diodes, where the charge carriers are tnmsponed in a rigid band model. Electrons
and holes can tunnel into or leave the polymer when the applied field tilts the
polymer bands so that the tunnel bmTicrs can be overcome. It must be noted that
a rigid band model is only appropriate for very low intrinsic carrier concentmtions
in MEH-PPY. Capacitance-voltage measurements for these devices indicated an
upper limit for the dark carrier concentmtion of 10
14
cm-
3
. Further measurements
of the built in fields of MEH-PPV sandwiched between metal electrodes are in
agreement with the results found by Parker. Electro absorption measurements [56,
57] showed that various metals did not introduce interface states in the single-par-
ticle gap of the polymer that pins the Schottky contact. Of course this does not
imply that the metal and the polymer llo not intemct [58, 59] but these interac-
tions do not pin the Schottky barrier.
The photovoltaic properties of PPV and PPV based soluble polymers have been
quantitatively confirmed also for polythiophcnes. The IN characteristics of ITO/
P30T/Au [60] and of ITO/P3HT/Au [61] diodes showed excellent rectification
behavior and a high photosensitivity under reversed bias.
15.3 Pure Conjugated Plwtovoltaic Devicel
531
15.3.3 Metal/Conjugated Polymer Contacts
Friend al. the influence of electrodes with different work-functions on
the of_ PPV photodiodcs [431. For 11D/PPV/Mg devices the fully sa-
tur..lled open voltage W<ts 1.2 V and 1.7 V for an ITO/PPV/Ca device.
These values l_or the V, ..... arc almost equal to the difference in the work-function of
and Ca wuh respect to ITO. The open circuit voltage of the ITO/PPV/AI de-
VICe at 1.2 Y, however, is considerably higher than the difference of the
w?rk-function between and AI. The Cambridge group references its ppy
With a very dark carrier concentmtion and consequently the formation of
. at _the is not expected. The mobility of the
holes was mcaliured at 10 em Y s [621 and that for the electrons is expected .
fo be clearly lower.
A similarly high V,,. lor lTO/PPY/AI photovoltaic devices also wa.<; observed
otlu.:r er a/. [63, 641 report the observation of a quantum cffi-
IPCE ot m ITO/PPV/Al photodiodes and of a power conversion effi-
Ciency of 0. 1% under low light intensities of 1 mW/cm
2
. The t i-
fi_lm of their ?cvices v<tricd between 100 to 600 nm. The ::n
C1rcu1t voltage ot these dev1ccs, as delmed with respect to the ITO electrode was
measured <ts 1.2 V: The high open circuit voltage was explained by the fom;ation
of a Sch?llky at AI/PPV interface. The predicted band bending due the
was verified hy XPS measurements [65. 661.
The lonnallon ol a Schottky barrier at the AI!PPV interface was also observed
by The prcp;trcd by the Bayreuth group appeared
to_ be, cons1derably more conducung 16?1 "!he properties of the devices studied by
lhls group be modeled by cons1denng a Schouky junction at the cathode.
_observation of a depletion _!aye! at the AI interface and its dependence on the
voltage allowed the est1ma11on of the intrinsic hole concentration a-; bcino
h1gh ao;. 10
17

[681. Schwoerer era/. [69] reported the photovoltaic
m PPV_ d1odcs w1th a power conversion efficiency between 0.1 to 1%
wuh th1ck_ncsscs varying between 100 and 500 nm at very low li<>ht
mtensu1es. _The V,,. . of these lTO/PPV I AI devices varied between 0. 7 and J.3 v.
The low hll factor (0.22) indicated the formation of a backdiodc interface be-
tween the and_ one of the metal electrodes. Detailed infom-.ation about the
of the d_cv1ces can be obtained by frequency-dependent impedance mea-
suements (sec F1g. _15-11 ). observation of two semicircles in the impedance
proves ot d1fTercnt RC circuits, representing the bulk and the
The htgh resistance of the junction dominates at low bias while with in-
creasmg b!as the junction resistance dccrc<Lo;es, whereas the bulk resis-
tance rcmams practically unafti::ctcd.
. Although the ob_scrv_ations_ for PPV photodiodcs of different groups arc quite
there arc s_tlll drscuss1<ms on the nature of the polymer-met;
1
1 contacts and
the tormat1on space layers on the AI_ interface. According
to Ngu_ycn tt a/. [70, 71 I band bcndmg Ill mcwi/PPV tnterfaces is either caused
by surface sl<ltes or by chemical reactions between the polymer and the metal and
532
c

' .......
N
Oo.J
E
I
1.2
0.9
0.6
0.3
0.0
15 Conjugated Polymer Bused Pwstic Solar Cells
T 295K
0
2
Re(Z) / kO
4
Figure 15-11. Impedance phJis of a AVPPVI!"f? diode under var!ous forward biases. The lhickness of
lhe device il, -350 nm (reproduced by pcmUSl>IOfl of Elsevet from Ref. !691).
is not directly related to AI deposition but may be also found for other metal/PPV
interfaces. Traces of oxygen were found at the metal interface in, however, most
of the XPS studies. According to Konstadinis et al. (72} oxygen on the surface of
the polymer depletes the near surface region of vinylene groups, thereby leaving
the phenylene groups available for attack by_ Other models
that photochemical oxidation of PPV results m SCISSIOn ol the polymer cham [731
or a possible reaction of the surface layer of AI with PPV to bonds
[74], thereby generating an insulating barrier. An excellent rev1ew on conJugated
polymer surfaces and interfaces was rccenlly published [ 109}.
15.3.4 Spectral Response
While the nature of the rectifying interface in ITO/PPV/AI photovohaic devices is
still unclear, the consequences of this interface on the W characteristic_s
been observed by all groups. Moreover, consensus is found for the relattonsh1p
between the optical absorption and the spectr.11ly resolved photocmrent. _Gener-
all y, this relationshi p may be classified into two categories: a good be-
tween the spectra so that the maximal photocurrcnt for at the
peak of the absorption spectrum is said to be symba_t1c. If the of the
photocurrent occurs for photon energies where the 1s vel""! weak
(filter effect), then the correlation is said to be anubat1c.
reported for lTO/PPV/AI photovoltaic devices, independent of the di-
rection as long as the li ght intensities were low and the PPV th1ck
(see Fig. 15-12). The antibatic behavior of the thin PPV cells IS explruned by
the different mobility of the holes and the electrons m PPV and thl.! fact that the
photoactive region is restricted to a thin layer adjaCI.!nl to the PPY/AI lhc
ITO/PPV interface is only contributing weakly to the photovolla1c propcrt1cs [69].
/
15.3 Pure Conjugated Polymer Plzotovoltuic Devices 533
1 .2
PPV
c
1.0
_ - _
/

0.8 :;
.....
u
0
0 0.6
.c
Q..
"0
0. 4
Q)

0.2 (ij
E
-1.0V. OV
0
0.0
z
LOV
-0.2
2.0 2.5 3.0 3. 5
Energy (eV)
l<"igurc 15-12. Spt.-clmlly resolved phutocurrcnl of a ITO/PPV/Mg pholodicxlc at diiTcrcnt bias after
com:c1ion for dark current. littlll and monochromalur rc'ponsc. and nonnaliwlion to 1he same
value. The broken line i' 1hc spcclrum of PPV (reproduced by pcnnission
of the lnstilulc of Physics from Ref. !431).
First, the ohmic interface at thl.! ITO side is supposl.!d to be rather inctTective in
the charge carril.!r separation. Second, the low mobility electrons, photogenerated
at the ITO side. have 10 pass the PPV bulk to reach the AI interface. Both limita-
tions do not occur on thl.! PPV/AI interface. Due to the higher mobility of the
holes compared to the ell.!ctrons the positive caniers can reach the ITO electrode
the electrons are din..--ctly collected the AI ekctrode. The exact peak
lion of lhl.! pttotocutTent for antibatic conditions depends strongly on the thickness
of the lihn. For a reduction in the polymer layer, both the more pronounced con-
tribution of high energy photons as well as the increased internal electric field
will intlucnce the maximum of the spectral photocu1Tent. Higher efficiencies for
such photovollaic devices are usually gained by illumination of the device
through a semitransparent AI interface 175 J.
Recently systematic studies on the dependence of the de and ac photocurrent of
MEH-PPV photodiodes on the tilm thickness as well as applied voltage have
been presented [76}. Genl.!rally the same features as for PPV diodes were ob-
served in the case of MEH-PPV.
forward bias the photocurrl.!nt follows more the absorption spectrum
response) as under rcvl.!rsc bias (antibatic response). With increasing (k-
VICC th1ckness the symbatic and antibatic behavior becomes more pronouncl.!d
(Fi g.s. 15- 13 a and b). Several theoretical models developed to rclatl.! the speclfal
photocurrent to the absorption were considcmd, i.e. the modd of Gosh eta/. [77],
Tang and Albrecht 178j, De Yore 179] . Gosh and Feng [HOI. and Desormeaux
[81 ]. first _two models [77, I only consider photoinduced charge carrier
genl.!rallon w1th111 a narrow region close to one of the electrodes, while the other
three models solvl.!_ the dilfusion equation to specifi c boundary conditions.
However, the snnuhttcd action spectra calculated by these models arc all very si m-
534 15 Conjuguted Polymer Based Plastic Solar Cells

3.5
!!
c
--Rovers. bias (-1 2v) )>
"
..
3.0
0"
--.forwiwd bo>ls (8v) .
"'
-e
. 0
.!:!.
1.0
Absp\lon. Q
"
:
2.5
.g
c
.. g
0

"

2.0
n ,.
0

,
0 ...
u : ,
1.5
n 0
:i
3
0
0 0.5
)
ii"
.c:
t .O

Q.
'0
_!/\

"' 0. 5 w
.. 0
E
0
0.0 0.0

0
z
1.6 t .8 2.0 2.2 2.4 2.6 2.8
(a)
Energy (eV)
3.5
--Revuse btu ( Zv) )>
----FOtWard boas ( ZI .... .. ..
3.0
0"
"' 0
2.5

c;
l .0 . .. AI>S<><plton, a
"'
"
2.0
n
0
t.S

3
r;
;;;
t.O
.%
0.5

0.5 .....
0
0
0.0

1.6 1.8 2.0 2.2 2.4 2.6 2.8
(b)
Enes-gy ( eV)
Fagure 15-13. (a) Photocurrent action spcctr.1 ::u room temperature for a thick photooicxle (ITQnllO nm
MEH-PPVIAI) under illumination through the ITO electrOde. under forwarll bias (dash dot) and rc-
ver.;c bias (solid li ne), with the room tempcr.llurc abwrption .sp.:ctrum line) shown for com-
parison. (b) Photocurrcnt action spectra at room Lempcr.llurc for a thin photodiude (IT0/120 nm MEH-
PPV/AI) unocr illumination through the rro electrode. wN.Icr forward bias (dash dol lim:) Wid reverse
bias (solid line). with the room tcmpcr.sturc absorption (dashed line) shown lor compa1ison
(rcpro<luc(.-d by pcmi:.sion of the American Society from Ref. 1761).
ilar and, in addition, the simulations arc in mther poor agreement wilh the experi-
mental data [76] and Jhe symbatic and anti batic response of the devices could
only be reproduced qualitatively.
There is experimental consensus on the most important parameters of single-
layer polymer photovoltuic devices, 1he short circui t current Is,., the open circuit
voltage V,"., and lhe ti lling factor FF. From these parameters lhe efficiencies of
PPV based devices were typically calculated to be around 0 .. 1% under monochro-
matic low light intensities. Eflons to extend the classical semiconductor picture of
lp
I
-
metal!
.... +
high workfuncliun
metal
I 5.3 Pure Conjugated Polymer P/wtovoltaic Devices
vacuum level
)
Xs
)
CB
...__.
w
E

Vll
_)
.
conJugated polymer
vacuum level
YO

'
onj ugalcd polymer

n1Clal2
p
(a)
low workrwJCtion
metal
(b)
535
.. (a) Energy diagram of a metal 1/scmiL'Onductor/mctal 2 Sdtottky banier under open cir-
CUli whereby the metals have di!Terent worl..-functions (t/J wort..-runclion, x . electron allini-
ty; IP u>nz.allon putent1al; gap, W depletion width). (b) Ch:ll);e gener;uiun process in si ngle
layer conjugated polymer dev1.:e under shon circuit conditions in the MtM model. VJJ valence band
CJJ (.'Onductinu band. hand gap. p. P' pusitive and neg:llive
536 I 5 Conjugated Polymer JJased Plastic Solar Cells
MIM or SIM [82-84] diodes to the PPV/Al interface provides a good qualitative
understanding of the device opemtion in terms of Schottky diodes for high impur-
ity densities (typically 10
17
cm-
3
) and rigid band diodes for low impurity densi-
ties (typically<I0
17
cm-
3
). Figure 15- 14a and b schematically show the two mod-
els for the different impurity concentmtions. However, these models do not allow
a quantitative description of the open circuit or the spcctntl reS<?Ived
photocurrent spectrum. The transpon of smglc-layer d1odcs
with asymmetric metal electrodes arc well descnbed by the double-earner current
flow equation (Eq. ( 15.4)) where the holes show a field dependent mobility and
the electrons of the holes show a temperature-dependent tr.tp distribution.
15.4 Conjugated Polymer Bilayer Devices
The analysis of the pure conjugated polymer single-layer device characteristics
above points out that the charge genemtion process in these monocompound
layers is mther ineflicient. The devices showed l PCE around I % while the power
conversion efficiency was usually around 0. 1 %. h is useful to take the processes
of the single-layer devices into account in the photodetcction mode, i.e. under re-
verse bias. If the potential difference between the electrodes is high enough to
overcome the Coulomb aumction barrier of the photogener.tted excitations, effi-
cient charge generation takes place, typically with quantum yields of 20% or
more at - I 0 V ( 48]. Without the high reverse voltages the absorbed photons will
mainly create excitations which decay geminately (either with
minescence or non-radiatively). Thus, the photocurrent efftc1ency of such dev1ccs
will be limited. In the photovoltaic mode, where no external voltage is applied
and shon circuit conditions exist, the only potential difference available is the
work-function difference of the electrodes. In the MIM picture rhis potential
difference will generate a constant field over the whole device. In contmst, in the
Schottky picture thi s potential is mainly expected to build up at the electrode in-
terfaces.
To overcome this limitation of the photoinduced charge carrier genemtion, a
dual molecule donor-acceptor approach has been successfully veritied for conju-
gated polymers (85]. For example, in such devices, consisting thin
film with conjugated polymer/fullerene mixture, the photogenerat1on efhc1ency of
charges close to the D/A interface is almost 100%. In such a single-layer photoac-
tive mixture lilm a 'bulk heterojunction' is formed between the electron donors
and acceptors. Among the many acceptor molecules that show photoinduced
charge transfer with conjugated polymers, fullerenes gave the most promising re-
sults. Also it was shown that functionalized, soluble C(\(, derivatives perform al -
most identical photophysical functions to pristine C
60
L86]. For a systematic inves-
tigation of the acceptor side in conjugated polymer composites, two series of
homologous acceptors were chosen, based on tetmcyanoquinodimethane (TCNQ)
and quinone derivatives As donors, two different conjugated polymers,
15.4 Co11jugated Polymer IJiluycr Devices
537
and P3MBET, were used. As a measure of the efficiency of the photo-
mduced charge transfer, the degree of luminescence quenching and the ratio of
the charged photoexcitation bands to the neutral photoexcitation bands were
taken. These two numbers are plotted in Figure 15-15 versus the electrochemical
reduction potential. A maximum in the photoinduced elet:tron transfer was deter-
mined for c(\()o
Considering_ the energy band diagmm in Figure 15-16, the heterojunction
the mterface between e.g. a conjugated polymer and a C
60
should have
a rccll!)'mg current-voltage char.tcteristic even using the same metal contact on
both Stdes (analogous to a p-n junction). One bias direction of such a device
(electron injection on the semiconducting polymer side and electron removal on
c(\(,) is unfavomble. This polarity of the devke results in very low
current dens111es. On the orhcr hand electron injection 01110 C6<
1
and electron re-
from _the serniconducring polymer is energetically favorable, creating con-
ductmg on both sides. This polarity of the device results in relatively high
dens1t1es .. 1l1us, dev1ces of organic semiconductors using two layers wi th
electronic structures, as illustmted in Figure 15- 16, exhibi t rectify-
mg dtode charactensucs. Analogous arguments for molecular diodes were first
proposed by Aviram and Rattner years ago for Langmuir-131odgeu D-A structures
(95].
>'

vi
>
.......
. g
"'
...
u
u
a
u
"'
u
j
0.30
O.l.S
0.20
O.I.S
0.10
o.o.s
0.00
r-.,---.---r----..---r---.----,-----...---. 3.o
.s 4.C60
3.
so
,-
-o
1.0

00 0.2
112
(V) vs. SCE
Fagurc .tSlS. luminescence (open marl\cn;) wilh MEH-PPV of
films of Wllh c .. , "series ofTCNQ likc ucccplors 1- 6 (sec Fig. 152 fur ab-
brcvallons) a.' a funcllun ul lhcr rcJuclum pulcnliah al W K. Righl h;mJ allis shows lhc of lhc
inlcnsi.ly of I he hand' Ul 134 ;mu 1.22 cV (!.<>lid marl.cr.;) hy
penmssu>n ol I he Amcn.:an lnshlUh: of frum Ref. 11!7 J).
538 15 Conjuguted Polymer Brued Plustic Solur Cells
n MEH-PPV
2.8cV
(a)
4.1 eV LUMOC
60
E
I
4.JcV
4.7cV -------------------
4.9cV nMEH-PPV
AI
ITO
6.4cV
HOMOC
60
---------------------------
n MEI H' I'V
(b)
LUMOC
60
E

------
ITO nMEH-I'I'V AI
--------
---------
HOMO C
60
Figure 15-16. Schematic flat band dmgmrn of a MDMO-PPV!C,., syslcm (a) and under short circuit
comlilioru; (b).
The usc of organic bilayers with photoinduced electron transfer at the interface
has been widely investi gated over the last couple of decades (for a summary of
the early repons see for example [2, 88J). Tang demonstrated photovoltaic activity
in small molecular bilayers that were vacuum evaporated [ 14]. In this pioneering
work Tang used a vacuum-evapomted coppcr-phthalocyanine (250 A) and a pery-
lene derivative (450 A) system sandwiched between an ln
2
0.1 and silver elec-
trodes, rcsJX-'<=ti vely. 1l1is bilayer device, shown in Figure 15-17, del ivered remark-
able current-voltage chamcteristics with a high rectification, high tilling factor,
and a photo voltaic power conversion efficiency of around I%. Until recently the
Tang cell was the most efficient organic solid state photovollaic cell. In the fol-
lowi ng section we will di scuss the realization of u Tang cell-like structure based
on a conjugated system.
539
Liqhr
.S.
T
CuPc
PV
15-17. Conligur.1tion of a ITOICul'c(250Al/PVC450A)/Ag \:ell (rcprodoccd by pcnuis.,ion of
the Amcri\:an h.-titutc uf Phy,ic, from (14().
15.4.1 Conjugated Polymcr/C
60
Heterojunction Photodiodes
The first realization of a conj ugated polymer/fullerene diode L89] was achieved
only recently after the detection of the ultr..tfast photoinduced electron tr.msfer for
an ITO/MEH-PPV/C
61
,1Au system. 1l1e device is shown in Figure 15- 18. Figure
15-19 shows the current-voltage chamctcristics of such a bi layer in the dark at
CO?m devices discussed in the following section typically had a
of 100 tor the MEH-PPV as well as the fu llerene layer. Posi tive bias
ts defined as postttve voltage applied to the lTO contact. The exponential current
tum-on at 0.5 Y in forw<trd biils is observable. The rectification r .ll io at
2 V is approximatdy
Illumination by visible light changes the cunent-voltage behavior dr..tmatically.
15-20 shows current-voltage data. with the ITO/MEH-PPV/C
61
,1Au dc-
v_rce 111 the dark and w1th the device ill uminated by 5 14.5 nm light with an inten-
SI(y (P;,) of I mW/cm
2
The open circuit voltage (V,,..) was 0.44 V and saturated
around 0.53 Y stronger ill umination. The short circuit current density (/ ... )
":'us 2.08 Alene Assuming a lilling factor of 0.48, a power conversion cfli-
Ciency of _was calculated. An open circui t voltage of about 0.5 V appears
to be char..tctensuc for the MEH-PPV/C
1111
imcrtace. Simi lar values were oblaincd
with ITO/MEH-PPY/Ct11/Al devices and with AUMEH-PPV/C(l(,IITO devices.
540 15 Colljuguted Polymer Bused Plusric StJiur Cells
Probe to ITO
Conducting Polymer
10"
3
c-
E
(.)
10"
5

Cii
c
10"
7 Q)
...
0
...
Figure 15-18. Schel1llll.ic cross-section of a bilayer device fair
rkatcd from MEH-PPV and Coo.

c ...
Q)

10-
9
::J
(.)
1 o_,,
-2 - 1
2
c

0
3

-2
Ql
0
c:
-4
"'

0
-6
-8
-2

0
Bias(V)
l"
A
A
A
A
A').
A
1 0
Bias (V)
2
Joigurc 15-19. Dark current ven<us vuk-
age charJCteristics of lhe ITO/MEH-PPV/
C
1
./Au device a1 room temperature (re
produced by permission of the Amcrk.-an
lnsl itulc of Physics frum Ref. [89)).
Figure 15-20. Current versus
charncteristics uf the ITO/MEH-PPV/Ctof
Au device in the dark (diamonds) and
upon illumination wilh the 514.5 nm line
of argon-ion laser of I mWicm
2
(trian-
gles) (repro<lucetl by pcnnission of the
American Institute of Physics Ref.
[1191).

15.4 Colljuguted Pc1lymer Bilayer Devices 541
oc:P
00
0 ,
0 8
0
0

J:iigure 15-21. Sh0r1 circuit current
circles) and photocurrent aJ
- 1 V bias (open as a func-
tiun or light intensity fur the ITO/
MEII-PPV/C,./Au <lcvice (repro-
duc.:c<l by pcnnissioo of the Ameri-
can Institute of Physics from Ref.
(KCJI)
Figure 15-21 shows the Jependence of the shon circuit current and the photo-
current at - 1 V (reverse) bias as a function of the illumination intensity
(514.5 nm); the data show no indication of saturation at light intensitjes up to ca .
1 W/cm
2

The spectral dependence of the photoresponse of these bilayer heterojunction
devices, ill u111inated from the ITO side, is displayed in Figure 15-22. The onset of
photocurrcnt at hv= 1.7 eV follows the absorption of the fullercne, indicating a
symmetric hole transfer from the excited fullerene to the MEH-PPV. The mini -
mum in the photocurrent at hv=2.5 eV corresponds to the photon energy of maxi-
mum absorption of MEH-PPY. 1l1e MEH-PPV layer, therefore, acts as a filler,
which reduces the number or photons reaching the MEH-PPV/Ct.o interface.
Thus, the thickness of the MEH-PPV layer determines the antibatic spectral be-
1.6
1.4
;;
1.2
.!i

"'
t.O c
8.
"'
0. 8

0
0 0.6
c
IL
0.4
0.2
0.0
1.5
r.

,. .
......

,

. ' ....
\,.,

2 2.5 3 3.5
Energy (eV)
4
Figure JS-22. Spcc.:tr.ll respunsc uf the
photocurrcnl in ITOIMEH-PPV/C.,.,IAu
photo..lioo.: at (reverse) - 1 V (repru-
uu.:c<l by of lhe American lnl>ti -
tulc uf lrum (119().
havior of these devices, similar to the pristine single layer devices discussed
above. The generation of photoexcitations, which result in separated charge car-
riers, again occurs only at the heterojunction interface.
Yoshino and co-workers also reponed the optical response of a heterojunction
device comprising a P30T and C
60
bilayer [90}. The photorcsponse of these de-
vices shows a broad excitation profile mnging from 750 nm into the UV.
Comparison of the spectml response and of the power efficiency of these first
conjugated polymer/fullerene bi layer devices. with single layer pure conjugated
polymer devices showed that the large potential of the photoinduced charge trans-
fer of a donor-acceptor system was not fully exploited in the bilayers. The de-
vices still suffer from antibatic behavior as well as from a low power conversion
efficiency. However, the diode behavior, i.e. the rectification of these devices, was
excellent.
ll was suggested later [91) that the low efficiencies of these photodiodes might
be attributed to interdifrusion of the sublimed C
1
>1
1
into the relatively soft MEH-
PPV. However, studies on bilayers formed between fullcrcncs and polymers with
strongly differing glass tempemtures (91, 921 proved this hypothesis to be incor-
rect. Recently, two groups [9 1, 921 made usc of the fact that the C
00
layer is
weakly absorbing in the visible part of the spel:trum, and can be used as a spacer
layer between the absorbing conjugatc<.l polymer layer and the back aluminum
electrode. The thickness of the layer was selected 10 give constructi ve interference
from the back-reflected beam with the incident beam. Friend et a/. prepared het-
erojunction cell s by spin-casting PPV precursor onto ITO glass. Afler the heat.
conversion, C()(, was evapomted on top or the PPV and finally AI contacts were
evaporated. ITO/PPV/CoofAI devices were studied wi th a difi"erent thickness of
the single organic layers. The highest IPCE efficiency of 9% wa.o; reponed for a
device with 65 nm PPV and 40 nm C<.cl 1l1e V,,.. approached 0.8 V under full illu-
mination. Similar high IPCE efficiencies of 6% were reached when C<>1
1
was re-
placed by bis-(phenethylimido)perylene [93]. The difference of 0.25 V compared
to the Vue for MEH-PPV/C
60
photodiodes is explained by the larger bandgap of
PPV compared to MEH-PPV. The spectral dependence of the l>hor1 circui t photo-
current did not completely follow the absorption spectrum, symbatic response was
observed. The optimization of the thickness of the single layers in bilayer devices
strongly enhances the efficiency. However, it must be mentioned that these bilayer
structures are limitctl in efliciency by the restricted dilfusion r.snge of the photoex-
citations, in comparison 10 the optical absorption depth.
Considering that the most polymers have a photoexcitation diffusion length in
the order of I 0 nm, Iganlis et a/. [92j argued that it is not necessary to have thick-
er polymer layers. Their photodiodes were based on heterojunctions between
poly(3-(4'-(1",4",7"-trioxaoctyl)phenyl)thiophene) (PEOPT) and C
611
An AI elec-
trode was used as electron collector and a PEDOT-PSS (poly(3.4-ethylenedioxy-
thiophene)-poly(styrenesulfonate))/1TO electrode served as a hol e collector. In or-
der to maximize the energy of the exciting optical electric field at the polymcc/
C
00
interface, it is necessary to know the electric tield (square) distribution inside
the device. Figure 15-23 shows thi s distribution versus the thickness of the fuller-
enc layer for two dilferent thicknesses of the PEOPT layer. At this interface 11
2
1.2
oro M;orr coo .,
Q)
0 1.0

"t:
2
c:: 0.8
0
"'
0
j::: 0.6
0.
0
w
0. 0.4
(U
"!.,_
w 0.2
1.0
!!! OS
0
0
o 50 100 150 200 250 300
350
Oostance from GlassllTO inlerface (rvn)
20 40 60 80 100 120 140 160 180 200 220 240
c60 thickness (nm)
543
15-23. C:okuhllcJ value ur lhc M(uarc uf lho.: nunnaliled clcclricill fidJ j
2
1 ill the C(l(/I'EOPT
interface for PI::OPT of JO oun (so litl line) and 40 mn line) lhicknesl> of the
Cw IOJyer :ol :o w-.1vclength of 4<0 11111. ' l11c im;c:l shows the cakulilt<."t.l distribution of the :.<juan: of the
upoical field llll>id.: an ITO (1 20 nmlfPEOOT-I'SS ( 110 nmi(PE0PT(J0mn)/C("'
(32 nm) device al tho.: same wavcl.:ugth (reproduced by p.:rmissmn of Wilcy-VCH from Rd. 19211-
shows a periodic variation with the thil:kness of the Cbo layer, having a global
maximum at about 32 nm for the C<.o layer, independent of the thickness of the
conjugated polymer layer.
The spectr.sl response of two devices with different thin PEOPT layers is
shown in Figure 15-24. The IPCE for the 30 nm PEOPT device is as high as
23% at the maximum and still 17% for the thicker device. Also of imponance is
the similarity between the action spectrum and the absorption spectrum of the
conjugated polymer. Both curves arc very similar with the absorption spectrum
slightly red-shifted. The enef'JY conversion efficiency of the most optimized de-
vice was calculated to be 1.7'1' at low light (15 ).1W/cm
2
) under monn-
chrumatic illumination.
In general, these results suggest that the cniciency of these bilayer devices is
sh-ongly connected to the device geometry rather than to the quantity of absorbctl
light. Highest etlicicncics are reached when the maximum of the square of the in-
cidem electric tidd is placed at the charge-generating interface. This strategy is
dictated by the l<tthcr small photocxcitation di Jrusion mnge of I 0 nm or the most
conjugated polymers.
An approach for improving the response of conjugated polymcr/fullerene bi-
layer devices, which is based on an additional excitonic middle layer inserted into
the D-A interface, was suggested by Yoshino t 'l at. (941. In lhe middle layer li ght
absorption dcctron-holc pairs, which migrat e towards the <tnd
544 15 Conjugated Polymer Based Plustic So/ur Cells
25
20

0
w 15
(..)
n.
10
_/'_.:"
5
_9. _i
:' II
., ..
.:'"
300 350 400 450 500 550 600
A.(nm)
)>
o-
C/1
0
...
o-
1))
::J
0
(1)
-
I))
650
Figure 15-24. Spcctr..tl rcspon.'e of made with o.lllfcrcnl Pt.::OM' pnlymcr thid,nc>.'>cs: Al.fCw
(35 nm)/PEOPT (30 nm)IPEOOT-I'SS C liU mnJ/lTO C 120 (>oOlid cm:h:s) ;mtl: Al.fCw
(35 nm)/PJ::OPT (40 nm)!Pt.::OOT-PSS ( 110 nm)/ITO t 120 11111)/glass Cupcn The
spectrum of the PEOPT polymer plolllxl fur compamon (snlid hn.: ) (rcpmducco.l by pcrmi .,ion of
Wi ley-VCil from Ref. [921J.
dissociate efficiently, creating electrons in the acceptor and holes in the donor.
Additional , both interfaces, the donor-middle layer as well as the middle layer-ac-
ceptor interface are charge-genemting interfaces. The device and the electronic
structure of the single components are shown in Figure 15-25. The results of irra-
diation from both sides have shown that both interfacial regions contri bute to the
charge generation by photoexcitation dissociation. 1ne photocun-cnt was enhanced
considembly and the spcctr..tl response was broadened in these three layer cells
compared to cells without the middle layer. As the fi lm thickness of the si ngle
layers was around 110 nm, the total etliciency of these devices was clearly lower
compared to the optimized bilayer devices. l lowevcr. it is worth noting that the
insertion of a middle layer wi th a large photocxcitation difl'usion length may over-
come the 10 nm limitation of the conjugated polymers.
Although the quantum efficiency for photoinduced charge separation is close to
unity for a 0/A pair, the conversion efliciency in a bi layer heterojunction device
is limited:
(i) due to the molecular nature of the charge scpar.11ion process, eflicicnt charge
sepamtion occurs only within a small region at the 0/A interface; thus, photo-
excitations created far from the 0/A junction recombine prior to dillusing to
the heterojunction;
(ii) even if charges are scpanued at the 0/A interface, the photovoltaic conversion
efficiency is li mi ted by the carrier collection efticiency; i.e. the separated
charges must be collected with minimum losses.
I 5.5 Cvujugutcd Polymer Bulk Heterojunction Diodes
545
OEP
OOPPV
o----------, ll h v PJ

E OuatU Substrate t-
(a)

3.lleV- - S.-
T
-3.3eV
Ito -4.2oV
2.3eV I --.
UoV V///////hl
I
ITO 5.3eV
{b)
OOPPV So I
OEP 1.8oV
!-6.8oV
c.."'
15-25. (a) of poly(2.5..Jioctyloxy-tHmt phcnylcue vinylcnc) (OOJ>PV)
OClacthylJlOil'hlne (0El') :md the Mructurc of the lhn:c layer photocell. (b) Schcmatie energy band
of th.: three layer plwtocdl (rcpmdut"Cd by pcnnissiou of the Japanese Physical Society froon
Ref. [94J).
However, it is impo11ant to note that, si nce the seminal publication of Avir..tm and
195 J, there allempts to demonstr..tte that a sui tably designed or-
gantc molecul_c dcposllell 111 a layer between two electrodes would give current-
behavtor analogous to the behavior of a p-n junction even when Schouky
barncr of the metal electrodes are not imponant. Continuing from the
work of_ Geddes et_ al. 196, 971 electrically rectifying properties have been re-
ported tor LangmUJr-Biodgeu ti lms of zwiuerionic molecule, C H -yQ3CNQ
[98 _the of asymmetric conduction is not

that the
rectJhcauon Js solely a process 1991. onl y the introduction of passive
layers between the acuve molecule and the electrodes provided conclusive
that rectifier-like arc to molecular pro-
ce:-ses [_100}. molecular rccllli C<IIlon m polymer ltlms was also reached by
onentatton ol polar push-pull molecules contained in a polymer mattix [ 10 1
102]. ,
15.5 Conjugated Polymer Bulk Heterojunct.ion Diodes
IS.S.l Conjugated Polymer/C
60
Bulk Heteroj unction Photodiodcs
cells made with pure conjugated polymers, energy conversion ef-
IJcJencJcs were typically 10-
3
-:- 10-
1
%, too low to be used in pr.1ctical applications
(48, 63, 67 j . Thus, photomduced charge tr.tnsfcr across a donor/acceptor
546
(0/A) interface provides an effecti ve method to overcome early time canicr re
combination in organic systems and thus to enhance their optoelectronic response.
For photovoltaic cells made with bilayers of conjugated polymer and the electron
withdrawing fullcrene C
60
, monochromatic energy efficiencies as high as I% and
IPCE efficiencies as high as 15% were measured [92, 93). Although the quantum
efficiency for photoinduced charge separation is ncar unity for donor-acceptor
pairs, the conversion efficiency is limited to some small regions around the inter-
face.
Consequently, interpcnetmti ng phase-separated 0/A network composites, i.e.
'bulk hcterojunction', would appear to be ideal photovoltaic materials [5}. By con-
trolling the morphology of the phase separation into an interpenetrating network,
one can achieve a high interfacial area within a bulk material. Since any point in
the composite is withi n a few nanometers of a 0/A interface, such a composite is
a 'bulk 0/A material. If the network in a device is bicontinuous,
a-; shown in Figure 15-26, the collection efiiciency can be equally efficient.
Creating the 'bulk D!A heterojunction' is obviously an important progression
towards creating enicient nanostructurcd p-11 junctions in organic materials. It was
shown that the short circuit current of bulk hcterojunctions devices is directly re-
lated to the amount of fullerenes in the mixture [48, 103), which was also calcu-
lated by Monte-Carlo simulations f I 041. Highest efficiencies were found for cells
with ca. 80 wt.% fullerenes. Tile limited solubility of pure c(l(l in organic solvents
and its tendency to crystallize during film formation limits its usc in high concen-
trcltion blends. To overcome these problems, a series of soluble derivatives,
mostly mcthano-fullcrencs [ 105 J. were developed. With these soluble derivatives
it is possible to make more than 80 wt% fullerene-loaded PPV tilms. For a Cal
MEH-PPV: [6,61PCBM (I :4)/ITO device l5J, the photosensitivity was found to
be slightly sublinear with light intensity (1'
94
) and the efficiencies were as high
as IPCE=29% and tJ.,=2.9% (monochromatic) under 20 mW/cm
2
Under mono-
chromatic lower light intensities the efficiencies even increased to an IPCE=45%
and IJ.,=3.2%. Still, this device works as an efficient photodetector with a photo-
sensitivity of "'200 mA/W at - 2 V and 17.-> 60% el/ph at monochromatic ill umina-
tion at 20 mW/cnl. Figure 15-27 shows the /IV curve of a Ca/MEH-PPV:PCBMI
ITO device. One can observe clearly that the open ci rcuit voltage of the pristine
MEH-PPV device of - 1.5 V is reduced down to V for the MEH-
PPV: PCBM device, in accordance wi th the energy loss due to the tmnsfer of
electrons from the MEll-PPV LUMO down to the Cc141 LUMO niveau. As shown
Wire to ITO

(wilhlwithOOt C60)
Wire to
Front Bectrode
;.,___
\__Glass
Figure 15-26. Schematic illustralion of a device
fru111 a si ngle luycr nf an intcq>cnctmt-
ing donor-a.:ccptor (wnjug;.stcd pulymcr/C.,u) net-
wort.
15.5 Conjugated Polymer Bulk Heterojunc:timr Diodes 547
.......................
'/
oo -e--o.-o .o-----e-o ..
10"'' L,_..._J._..._J._...__.!.,_..._J._...._J._..__L__o.....,JL-....._j
-2 - 1 0
Bias (V)
2
Figure 15-27.
of a Ca!MEH-
PPV: (6,6JPCBM/ITO device in
the (open circles) and under
20 mWkm
2
illumination m
430 nm (solid circles) (reproduced
by pconission of the Americ;m
Association for the Advmu:cmcnt
of Scien<X from Rd. I :I J).
above, the short circuit current. /,.., reaches 0.5 mA/cm
2
under 20 mW/cnl ill umi -
nation, corresponding to a collection etliciency of ,,,.=7.4% electrons per incident
photon. This value is approximately two orders of lll<tgnitude higher than that of
pure MEH-PPV tunnel diodes as well as of the non-optimized MEH-PPV/Cb4.
1
het-
erojunction device as dc.-;cribcd in the previous section. ll1e
quantum elliciency of this blend device was I ()
1
- 1 0
4
times less than in pure
MEH-PPV devices, consistent with the ultntfast charge separation,
which quenches the emission of the donor. The clftcicncies are nearly indepen-
dent of the incident ill umi nation intensity as shown in Figure 15-28. Fut1hennore,
the intemal t:lliciencies arc even lliglter when corrected for the small thickness of
the til m, which absorbs only 60% of the incident photons.
Ideally, the work-function of the cathode metal should be close to the accep-
tor's LUMO whi le the work-function of the anode should be close to the donor's
HOMO level. An 'ohmic' contact would then be formed selectively at both metal/
organic semiconductor interfaces, being ohmic for the holes as well a') for the
electrons. TI1e observation of a V,, of 820 mY for the Ca/MEH-PPV:PCBM/lTO
device [481 and of 720 mY for a AJIMOMO-PPV: PCBM/ITO device f 103, 1061
can not be explained. The open circui t voltage for merul -insulator-mctal (MIM)
tunnel diodes is generally accepted to arise from the work-function di fference of
the two electrodes 1551, which would yield a V,,.. of 0.4 V (AI 4.3 eV; ITO
4.7 eV) or lower for these hulk hete.-ojunction devices 1107, 108J. Consistent wiU1
the MIM diode picture, the V,.,. for single layer MEH-PPV devices sandwiched be-
tween ITO and C<1 was f(>und to follow the diflcrem:e in the electrode work-func-
tions l48). Using an AI electrode instead of Ca. the V,,.. decreased slightly but re-
mained much higher than the difference between AI and ITO 1481. In donor-ac-
ceptor bi layer photocells the V,.,. has a different physical origin. Studies on bilayer
devices of JT0/MEH-PPV-C1>!/Au showed 1891 that, under imense ill umination,
the MEH-PPV-Cw interface yidds an open drcuit voltage around 0.53 V. This
value of the V,,.. seems to be indicati ve for the MEH-PPV-C"'
1
interface with non-
rectifying metal contacts.
548 15 C()lljUJ;tlled Polymer Based Plastic Solar Cells
...

101
(a)
..!! l ---
- 10. --- - .... -- - -+- ..
10. 2 ................... L................ .u.u-11.-.................. "--._._,'-LWII
106 lOS 10 4 10.) 10-1 10-t
Light Intensity ('W/cm
2
)

. ..
(b)
---
--- - ..- -- - -+- ..
10-1 L-. .................. "--' ................. .......... "--................. "--..................
10-6 10-s 10-4 10-l 10-1 10-t
Light Intensity ('W/cm
2
)
Figure 15-28. (a) Carrier cnUectioo efficiency, 11.- and (b) energy conversion effi.:i_ency, 11,. of devices:
Ca/MEH-PPV: [6,6)PCBM (1 : 4)/ITO (solid squares). Ca/MEH-PPV: [6,6)PCBM(l : I)IITO (open
squares), AVMEH-PPV: [6,6IPCDM (I : I )liTO (upcn diamonds). Ca/MEH-PPV: [5.6[PCDM (I : I)/
ITO (open circles). Ca/MEH-PPV:

(3 : I )/ITO (open rriangles) and Ca!MEH-PPV/ITO (solid cir
des) (repnxlucc<.l by of the American for the Advancement of St:iCrt<.'C fruro
Ref. [5[).
In two-component charge transfer systems, such as in the bulk-heterojunction
solar cells presemed here, devimions of 1he Vm.. from the results of pristine single
layer or bilayer devices are expected for two reasons: first, some pan of the avail-
able difference in electrochemical energy is used imernally by the charge tr .msfer
to a lower energetic po)>ition on the electron acceptor; second, the relative posi-
15.5 Conjugated Polymer JJulk Hctcmjtmcticm Diodes 549
Lion of the lowest unoccupied molecular orbital (LUMO) of the electron acceptor
may be below the low work-function of the cathode.
Compared to pristine MEH-PPV photodiodes, addition of C
60
lowers the aver-
age built-in potential by 0.6 V, in accordance with the position of the C6o LUMO
level relati ve to the MEH-PPV upper polaron level. Therefore, an open circuit
voltage as high as 0.72 V is not consistent with thi s picture. Variations of the ITO
work-function due to different production technologies, as well as the unknown
oxygen content in the different devices, may contribute to these deviations in
open circuit potential in different devices. The fonnation of charge space layers at
the electrode/polymer interface [I 09 J may lead to local potentials intluencing the
open circui t potential. In inorganic solar cells, Fenni level pinning of a metal elec-
trode to surface states of a semiconductor is a frequently observed phenomena
(82, H4]. Obviously, Fermi level pinning of the low work-function electrode to the
CC.o niveau might explain the experimental observations. Also, it is well known
that oxygen fonus rectifying junctions in small organic molecule photovoltaic de-
vices based on phthalocyunines [2). Systematic studies on the open circuit poten-
tial in these devices prove to be difficult and the semiconductor physics of these
devices is still not fully understood.
Recently, uniform films wi th high concentrations of Cc.r
1
were cast from 1,2-di-
chlorobenzene solutions containing up to I :4 weight ratio MEH-PPV: C
60
[I JO) .
For devices made from these high concentration blends, charge collection efficien-
cies around IJ,.=26% (electron/incident photon) and power conversion efficiencies
around IJ,. = 2.5% (electrical power out/incident light power) have been realized.
Qualitative similar behavior was found lor bulk heterojum:tion diodes based on
a soluble polythiophenes [107. Jill instead of poly(para-phenylene vinylene)s.
Seveml reasons can be given. why polythiophenes are potentially interesting mate-
rials for photovoltaic. First, the solubility of these polymers allows the fonnation
of complex morphologies due to phase separ.ttion and supmmolecular reorganiza-
tion [ 112). Second, via simple substitutions on the main chain, the bandgap of
polythiophenes was shown to be modified at least in the mnge between 1.7 to
3 eV [ 113, 114 ). This can not easily be obtained tor PPVs. Third, the enhanced
photochemical stability of the polythiophcnes makes them even more attractive
for photoconversion ( 115}. Highly efficient photovoltaic devices (IPCE "'15% at
15 W/m
2
) were constructed on ITO glass using different polythiophenes or blends
of polythiophenes II 07] with C
60
. The photo voltaic behavior was found to be
strongly dependent on the morphology of the blends. where c()() seemed to func-
tion as a kind of compatibilizer lor the diffcrelll polythiophenes [107).
15.5.2 Conjugated Polymer/Conj ugated Polymer Bulk
Heterojunction Photodiodcs
In the previous section, devices with fullerenes as photoinduced electron ac-
ceptors in blends with conjugated polymers were discussed. Clearly one of their
disadvanl<tges is thai only one of the two components is photoactive in the charge
550 I 5 Conjugated Polymer Based Plastic Solar Cells
IT() I If
PI:.UUT.,..Au
AlurCa
Figure 15-29. Chemical structures of the COO
jugated polymer.> used in the device ou1d the
device structure of the laminated solar cell. For
the top h;llf of the c:lcvice, AI or Ca was evapo-
rated on subs1r.u.cs, and the acceptor ma-
terial MEH-CN- PPV (mtd a small amount of
POPT, usually 5%) was cmttec:J. The half
with the POPT (anc:J a small amount of MEH-
CN-J>PV, usually 5%) spin co:tlcc:l on ITO
and hcatcc:l lu 200" C under vacuum
bclure lhc c:lcvicc laminatcc:l tugcthcr by
a light pre.'ISure.
separation process due to the low absorption of C
60
in the visible range. More-
over, it is very intriguing to suppose that the charge transport properties for the
two different charges arc unbalanced. For example, whi le holes wi ll undergo a
combined diffusion proceliS along the polymer chai n with addi tional hopping be-
tween the chains, electrons are transported by an excl usive hopping pro-
cess between small molecules. The use of polymers as both donor and acceptor
components offer d ear advamages to this problem. Since there is almost no entro-
py of mixing for macromolecules, phase separation is expected in polymer
blends, leading to microstructured donor-acceptor j unctions. Moreover, by using
donor and acceptor polymers wi th different bandgaps, one can design the sensitiv-
ity of the cell to photon energies out of the whole visible r.mgc.
Two different groups reported simultaneously on the construction of photovoltaic
bulk heterojunction fonned between two different conjugaK-d polymers 1116, 117).
Both approaches used the MEH-PPV as donor conj ugated polymer in composite
with cyano-substituted MEH-PPV type polymer. The lower LUMO of the high elec-
tron aflinity material, on the one hand, eases the electron injection from a slightly
higher work-function metal such as aluminum and, on the other, im:reases the trans-
pot1 of electrons due to the electron withdrawing substitutional cyano groups. Both
effects are also posi tive for the photovoltaic applications and thus the blending of the
two polymers (cyano substituted and MEH-PPV) led to high efficiency devices.
Gang Yu reported power conversion ell iciencies around I% and IPCE around 6%
at low light intensities 111 6]. The fonnation of a bicontinuous network of the two
polymers is of great imponance. The best results for photovohaic devices were
gai ned with ca. 5 wt% CN-PPV in the composite. Recent reports on polymer/poly-
mer devices, wi th up to monochromatic power conversion efliciencies and an
IPCE of 29% at the absorption wavelengths, led to consider.1ble improvement in the
general efficiencies of these types of photovoltaic t:ells 1118 ). In their report. Gr . .m-
I 5.6 Flexible, Large Anti, Plastic Solar CelL\ 551
strom et a/. usc a wel l known tcchni4ue from polymer processing which faci litates
the melt-blending of two different polymer layers under applied pressure, i.e. lami-
nation. The necessary requirement or melt processable materials is met by using a
poly(3-phenyloclylt hiophcne) us donor polymer o.111d a cyano-substituted MEH-
' PV as acceptor moiety. Two glass substrates were coated with low- and high
work-function metals as well as with acceptor-rich ( 19: I) and donor-rich ( I : 19)
polymer composite layers, respectively (sec Fig. 15-29). This different stoichiome-
try of the two layers creates a for hole conducting and electron conducti ng
components in the bulk hcterojunction. The two glass slides were lhen pressed. while
heating and the two polymer fi lms were blended by lamination. This method clearly
demonstrates the large potenti al of polymer technology uti lized in photovoltaic de-
vices using conjugated polymers.
15.6 Large Area, Plastic Solar Cells
The clear advantage of plastic solar cell s compared to other inorganic and organic
photovoltaic devices is due to the potential of producing large area devices with
simple plastic processing technologies. To fully utilize the potential of the conju-
gated polymers ao; plastic photoactive materials as well as to investigate the de-
vice technology problems of upscaling large area photovoltaic clements on flex-
ible ITO-coated plastic (PET) substmtcs. 6x6 em large area device$ were n:ecntly
demonstmtcd II 06, 11 9 j. Using the same coating technique (blade coating from
solution), the active area of the cells has been expanded up to lOx 15 em. De-
vices wi th an open ci rcui t potential of ;::;0.72 V, a short circuit current of
1.5 mA/cm
2
, a fill ing factor and a total current of -30 rnA under
an illumination uf I 0 mWh:m
2
at 4HH nm, can be routinely fabricated.
Figure 15-30 shows a comparison between the two photovoltaic cells: the small
area on glass and large area on pla.o;tie substrates, respecti vely. Both cells show
comparable open circuit potential, V,,.. ( and short cin:uit current densi-
ties, / ,. .. The ohmic contribution to the phoHx:utTent is larger for the glass cell.
The overall conversion efticiency, IJ,., of the llexible plastic solar cell presented
here is calculated at ca. 1.2% under monochromatic il lumination (488 nm) at
10 mW/cnl and a filling factor FF,... 0.35. Typical values for 11., are between 1%
and 1.5%. These variations in the elliciencies arc explained by the observation of
different open circuit voltages for the standard ITO/MDMO-PPV: PCBM/AI de-
vices, as explainetl above I 1061. These data clearly show that upsculing to llcxible
substr.ttes docs not negati vely influence the d licicncy of the cells based on conju-
gated polymcr/fullerenc composites. Figure 15-31 shows the characteristics of the
flexi ble cell in comp:uison to a polycrystalli ne Si cell in a linear plot, where the
IN characteristics in the 4'
1
' 4uadram c.u1 be seen more precisely for the determi-
nation of the FF. Although the polycrystall inc Si cell is referenced with 13.3%
power efficiency under AM 1.5, it is clear that under such specific illumination
552
/5 Conjugated Polymer Based Pla.wic Solar Cells
10)
10
2
NE
u
10'
,,

..
..
c
.,
t:
:>
10
u
to
10-l
- I
' o I
... , ,
'
' . '
' ' --flexible, ilL
'.
"
"
" u
- - - - flcxibcl, dark
glass, ill.
glass, dark
0
Voltagc fVl
Figure 15-30. IN charactcristiCl; of small area
glass cell ( e dark - illumin;uoo with
41!8 nm, I 0 mW/cm
2
) and a ncxihlc large area
polyc:.tcr cell (---- dark - - illuminated
with 41!K nm, 10 mWt.:m
2
).
.
.
""' .
1'10 /
..
....
5 0
..
...
;:I
u
-ax 10"
- 1,0 -4,5
Flexible Plastic Solar Cell
-Reference Si Cdl
0,0 0,5 1,0 I,S
Voltage IV)
Fis!ure 15-31. IN characteristics of a large area pl:.stic :;olar cell < illuminated with 41!8.nm. !0 mV{_I
cm"2). Ff for the ITO plastic cell is 0.35. As rclerencc a photocurrcm or a polycrystulhnc S cell IS
ploncd ( e ), 10 limes reduced.
conditions ( 10 mW/cm
2
, 488 nm) the elliciency breaks down, while the plastic so-
lar cells still work at its optimum. Due to their low optical density, the plastic so-
lar cells can reach the maximal efiiciency even at low light intensities.
15.6 Flexible, Large Area, Plastic Solar Cells 553
15.6.1 Stability of Plastic Solar Cells
The stability of such devices under ambient conditions wi thout any protection is
extremely poor. It is irnpemti ve that the plastic photovoiLaic elements have to be
protected. Comparisons of liiCtimes of such a large area photovoltaic cell (fabri -
cared in air and under arbitmry condi tions i.e. not taking into account any dust-
free and/or oxygen-free condi tions), unprotected or protected wi th a special coat-
ing, d early show that protection against oxygen increases the lifet ime consjdcr-
ably (see Fig. 15-32). Further systematic studies showed that, upon addition of the
fullercnes to the conj ugated polymer matrix, the slability of the matrix is in-
creased [ 120, 1211. Figure 15-33 clearly shows the enhancement of lhe stabili ty
of the conj ugated polymer/fullerene composite compared to the conj ugated poly-
mer component alone. Since the studies arc directly related to specific infrared ab-
sorption of the conjugated polymer itself, it is concluded that the stabil ity of the
conj ugated polymer component itself is increased upon addi tion of c6U This is
propm.ed to originate from the photostubilizing ctfccl of the fullerenes because of
the ultrafast photoinuuced electron tr.tnsfer. Since the electrochemical potential of
the exci ted state of conj ugated polymer (one electron exci ted to the LUMO level)
is very high, it might immediately lead to di rect electrochemical interactions with
the ambient air humidity etc. The ulltufast electron trJnsfer from this LUMO level
of the conjugated polymer onto the LUMO of C(>(J immediately empties the ex-
ci ted state of the polymer and lowers the electrochemical energy of the excited
electron bringing it down to more stable potent ials. In addition, the intersystem
crossi ng of the polymer produces triplet excited states and these may in return re-
0.95
0.9
0.85
"'
0.8
"'
1d 0.75
Cll
0.

0.7
0.65
0.6
0.55
0.5
0 2 3 4
Ar -e-
glass protected, 92 -.&-
plastic protected, 0
2
-v--

5 6 7 8 9
hme (h)
IS-32. Tim.: dcpcndcm:c of tlw ur nne sped lie ahM.>I'}llinn band ( 1506 em
1
) u(
MDMO-PPV under oxygen, al);llll, oltygcn prul.:c:tcd with loil. oltygcn Jlrol.:c:tcd with
nh1c.
554
1.05
0.95
0.9
<0
"'
0.85
iii
0.8

8. 0.75
"!'
0.7
0.65
0.6
0.55
0.5
J 5 Conjugcued Polymer Based Plastic Sowr Cells
0
2
MDMO-PPV 1500 em
1
---T--
MDMO-PPVIC60 1:3 1506 em '
3 4 5 6 7 8
1ime (h)
9
Fit,;ure 1533. lime depcnJCJM:C of ham.b. ML>MO-PJ>V (1506 \Jownwanl
full triangles). 1: 3 mixture of MDMO I'l'V/Cw al lhc MDMO-I'I'V bauJ :11 1506 em (Jownward
open triangles).
act by energy transfer creating singlet oxygen I 122). This hihly reactive form of
oxygen is expected to react with the polymer backbone creaung carbonyl de-
fects eliminating the conjugation of the polymer. By the ultrafast photomdured
electron tnmsfer the inter-system crossing to the triplet state is also completely
quenched by the ultr.tfast photoi nduced electron transfer, as shown above.
15.6.2 The Guest-Host Approach:
Blending with Conventional Polymers
The impo11ance of melt processing properties for conjugaK'CI in . device
construction was demonstmted recently 1118]. However, most ol the cOnJugated
polymers show no or only side-chain glass tmnsitiuns. The of the
photoactive conjugated polymcr-fullercne blends int_o a polymer ma-
trix (guest-host approach), presented in recent stud1es II 06. 1231. 1s a _sound and
promising method towards this direction and to improve the photoacuve sample
quality for the following reasons: . . .
1) the conjugated polymer di luted by a proper host matnx shows less mterch:un
interaction compared to pure films;
2) macroscopic ordering of the conjugated polymer can be performed by me-
chanical stretching of the host polymer. .
3) the slability of the conjugated polymcr-fullerenc devices embedded mto a:>n
venti onal polymers (guest-host is hi gher due to encapsulauon
against environmental inlluences;
1x10
E 1x10
1

.s
c

a 1x10-3
1x10 ..
--O%PVK
0,0 o.s 1,0 1,5
Voltage IVJ
15.7 Outlook and Strategies 555
io' igurc 15-34. W curves of AUPVK-
MDMO-I'PV-PCBMIITO photocells. The
com:cnlmlion of the convcntionul polymer
I'VK in lhc blend is dcnuled in lhc ligurc.
The were illuminated through the
ITO ill.: by 4() mW/.:111! at 41!!1 11111.
4) by selecting a_ suitable host matrix, the charge tr.msfer between conjugated
polymer and may be advantageously tuned, either by changing the
tntermolccular distances due to morphology control or by the overall dielec-
tric constant of the system.
Also: the rheologic<JI wi ll become rclevmu for J;uge-scal e production of
plac;uc solar cells. For th1s purpose and for the reasons listed above, the behavior
of highly cllicicnt conjugated polymer/methanofullcrene cells (ITO/MDMO-
PPV: blended into a conventional polymer matrix were studied [106.
1231. F1gure 15-34 shows the IN charJcteristics or such blended cell s with vary-
ing contem of _conventional (polyvinylcarbazole, PVK). Jntroducing
small amou_ms ol (10 wt%) dtd not change the efficiency of the cells signifi-
cantly. By mcreasmg the PVK conccntmtion a strong decrease of the Is, resulted.
The pcrcolati?n for interpenetrating network of the conjugated poly-
rner/methanolullerenc 1111xture m the host matrix detemti ncd the onset of a
strongly enhanced photovoltaic response. The intensity dependence or the spec-
photocurrem of_ the circuit current indicated that at higher
hght tntenstues enhanced anmhtlauon ol mobile charge catTiers occurs. A suitable
of the host matctial may favombly tunc the donor-ucceptor network proper-
lies.
15.7 Outlook and Strategies
The excellem photosensitivity and relatively high energy conversion eflicicncics
obtained fmm the bulk heterojunction materials are promising. The monochro-
matic power cflicicncics for conjugated polymer photovuhaic an around
556 15 Polymer Bused Plustic: Solar Cells
1.5% for devices with air-stable AI electrodes and ca. 4.8% for devices with Ca
electrodes. Further optimization of device performance can be achieved by optimi-
zation of the device physics:
(i) optimize the choice and the quality of metallic electrodes to achieve good
contacts on both sides for collection of the oppositely charged photocarriers;
(ii) optimize the choice of the D/A pair (the energetics determine the open cir-
cuit potential). In addition, the band gap of the semiconducting polymer
should be fitted to solar emission spectrum for efficient harvesting;
(iii) optimize the network morphology of the phase separated composite material.
lbereby the mobility of the charge carriers within the different components
of the bulk hcterojunction has to be maximized.
In organic photovoltaic elements genemlly two different tasks arc to be clearly dis-
tinguished: the photuinduced charge generation (electron tmnsfcr etricicncy) and the
transport of created charges to the electrodes (charge carrier mobility). These two
different tasks are ol\en confused and arc expected to be fulfilled by one and the
same material simultaneously. By optimi:ting the photoinduced charge generation,
the optimisation of the charge carriers is not automatically achieved. As we have
clearly shown above, the photoinduced charge genemtion in the conjugated poly-
mer/fullerene bulk heterojunctions is nearly I 00% (subpicosecond electron transfer
rate, approximately 1000 times faster than any competing photophysical relaxation
channel). However, the sweep out of the created charges is only possible in a very
thin sample due to the limited charge catTier mobilities. A clear strategy is to separate
the two tasks by increasing the components in a device upon adding other charge
transport components (or evaporating additional layers) to the charge generation
components. Such a stmtegy has been successfully demonstrated recently [ 124) by
building a multilayer organic solar cell consisting of a charge generation layer
(Zn-phthalocyanine mixed with C
60
) sandwiched in between a hole transport layer
(Zn-phthalocyanine pure) and an electron transport layer (perylene derivative).
Such devices showed a 1.05% AM. a 1.5 power conversion elliciency, and had en-
hanced perfomtance compared to the simple Zn-phthalocyanine-perylene devices
made using the same group. This strJtegy should be adopted to the optimi:te of plas-
tic solar cells based on conjugated polymers.
Acknowledgemetrts
The author gratefully acknowledges the co-workers at the University of Linz, Franz
Padinger, Thomas Fromherz, Helmut Neugebauer, Markus Scharber, Desta Gebeye-
hu, Antonio Cmvino, Gebhard Matt, the collaboration J.C. Hummelen and
Rene A.J . Janssen (both li01n The Netherlands), Nawrio Martin (Spain), Olle lnga-
nas (Sweden), Mats Andersson (Sweden). Michele Maggini (Italy), Maurizio Prato
(Italy). David Faiman (Israel}, Erhard Glotzl (Austria). We would like to thank Diet-
er Meis..soer for stimulating discussions, which were essential. Financial supports of
the Europeam. Comit'fission (DGXII. JOULE Ill), Quantum Solar Energy Linz
GemwH Chril(lian Doppler Foundation, Austrian Foundation for Scientif-
kc E{csearch (FWF P- 126i!t1(:HE) as well as the Netherlands Agency for Energy and
(NOV EM) arc all gratefully acknowktlgcd.
References 557
References
I. G. A. Oum1bcrlain. Solur Cells I YIU, 8, 47.
2. J. Simon. J.-J. Andre. Mol<'cular Semimll<luctur.r. Berlin JYIIS.
3. J. Kanicki. in T. A Skuthcim (Ed.) flmu/book uf Cmulurtiug Polymers, Vol. I, Marcel Dc.kker,
New Yod I YSS.
4. N. S. Sarici flci. L. Smilowitz. A. J. Hccgcr. F. Wudl. Sdc11ce. 1992. 258. 1474.
5. G. Yu. J. Gao. J. C. Hunuuelen, F. Wudl. A. J. Hecger. S<:icnct' 19YS, 270, 171!9.
6. N". S. Sariciflci, A. J. Hccgcr in Hwulbuok af Vrguuic Conductive Molecules a till Polymers. \\>1.
I. 1-I.S. Nalwa (Ed.). John Wiley & Sons. New York 11197.
7. C. H. Lee. G. Yu. D. Moses. A.J. Hccgcr. V. I. Snlannv.llflfll. Plt1.r. Ll'tt., 1!1194. 65.664.
I!. M. Kullun. D. Faim.an. S. Gurcn. E. A. Kat/ .. E. KunuiT. A. Sha;lk."l'. S. Shlutina. B. Uwn. S(1/ar
Elwrgy Matrrialx ""'I Solar C<'ll.r l 'JW1. 44, 4K5.
9. B. oRegan. M. Gratzd. Nutun JY'JI . 353. 737.
10. U. D. L.upo. P. Comic. J. E. Moser. F. Wcb.,oncl, J. S:tlbcck. II. Sprcit:t.er. M. GriiiL.el. Na
turr 19YH, JY.'i. 51!3.
II . V. Y. MciTil . J/JM J. /i(.. l>t(lop. 1978. 22. 35:\.
12. D. L. Murcl. A. K. T. t'cng. E. L. Swgryn, P. E. l
1
urwin. R. E Shaw, C. Fishman. fllllll.
Pity.. Lm. 1978. 32. 4'>5.
13. A. PiL-chuwski. G. R. Giro.!. D. L. Murcl, :. L. Stugryn. J. Jllty.. CIJtm. 1 YH4. &i. 923.
14. C. W. Tatlg.llppt. Pltn. Lm. 1986. -IX. IK3.
15. L. Smilowitz. N.S. S;uicitki. R. Wu. C. Gcuingcr. A.J. l-lccgcr. F. Wuo.ll. Jll11.v. 1J IWJ. 47.
IJK35. .
16. B. Kr..llthcl. J. C. llununclcn. D. Vat:ar. D. Muses. N. S. S:lficifid, A. J. Hccgcr, F. Wudl, J. Ctre11L
19%, 104. 4267.
17. N. S. Saridlki. A. J. Hccgcr, l11t. J. Mml. Plt_1.r. 1J JW4, X. 237.
liS. N.S. Quaut. 1:.1ectr. IIIIlS. 19. 131.
19. X. Wd. Z. V. V:tnlcny. N.S. Sariciflo.:i. A. J. H.:cgcr. l'ltv.r. Hi!t>. 1J 1!.1%. 53. 211!7.
20. S. Morir:t. A.A. Zakhidov. K. Yo,hinu, Sulid Stat<' Cm;llttrm. IW2. X2. 249.
21. K. Yos hmo, X. H. Ym. S. Morita, T. Kawai. A. A. Zaklmlov. Salitl St<lt<' Cm111111111. JW3, 85. &5.
22. S. Morita. A. A. Zakhio.lov. K. Yushino. lp11. J. IIppi. Pflyl. t'JYJ . 12. LK?:l.
23. K. Yoshino. T. Akashi. K. Yo:.hilll<>lu. S. Morita, R. Sugimuru. A. A. Zakhio.lov. Solid Swte Cum-
11/UII. lYY-l. YO, 41.
24. L. Smilowitz. A.J. Hccgcr. Splitt. Mc-t. 1Y92. 41!.
25. I I. Juhannson. C.J. Bmlx.-c. H. Neugebauer, J. C. Hunundcn. R. A. J. N.S. Saricifici.
S)Yitlr. Mn. ICSM 91!. in print
26. K. Lee. E.K. Miller. N. S. Saricifld, J. C. llummclcn. F. Wuo.JI . A. J. Hccgcr. Plrv.r. Rev. 8 JY%.

27. G. 7..crhi. M. .c. Ca\liglioni. in J. L. R. Silhcy. (&!.\.). CmrjttJ:ated Pulymcrs.
Kluwcr Acad.:nuc Donlrct:hl. lltc Ncthcrlano.ls IYIJJ. 435; G. Zerbi. C. Castiglioni.
M: Del Zoppo. Ill K. Mullen. G. Wegner (l.:.h.). Elc-ctnmic Matcriul.<, 77re Oligomer llpprCiltdr.
Wrlcy VCH IWI!. 345.
28. Z. Vank.-ny, E. Ehrcnfrcund. 0. Brafruan. A. J. Ht.-cgcr. F. Wudl. Syutlt. Met. 1981, 18. 11!3.
29. H. Ncugcb:mcr. A. Ncckcl. N. in H. M. Mehring. S. Ruth (&Is.).
l:J(:ctmuic 1
1
mptrtits of Polymc-rx mul Hdutttl Cmtrpow,/.r (Springer Scri.:s in Sulio.l Slalc
Sprint:cr. Berlin Hci<klhcrll- IY85. (J.I . 227.
30. E. Ehrcufrcuno.J. Z. V. Vardcny. J. lui. Opt. t"ttgimuiiiJ.: (SP/1:.") IY97. 3145. ]24.
31. A. Girlandu. A. l'ainclli. Z.G. Suos. J. Ctum. Jlf11.r. IY'J3. Yc'i. 74W.
32. K.H. Lee. R.A.J. J:m>.-.cn. N. S. Sari.:ilki. A.J. iccgcr. l'lty.r. Rl!t: tJ 1994 .JY, 57KI.
33. M. J. l{tcc, Y. N. Gancnstcin. Pln.v Uct: IJ t'JY7. 5.1, 107M.
34. A. J. Hccgcr, S. Kicvcbon. J. R .. Schriclrcr. W. P. Su. Mod. Pit\'.' 111118. 60. 7!!1.
35. J. Br'tlcnin!l.. B. Friedman. J. Ctwm. Pltys. IW7. 106, %34.
36. U. Kra:thcl. 0 . 1\kUr.lllch. N . .S. SariL' IIki. D. Mo>es, A. J. Hc,gcr. l'lt.rs. Net: IJ 1994. 50. IIi.
558 15 Polymer Based Plastic Solar Cells
37. D. Vacar, E.S. Maniloff, D. W. McBr.mch, A. J . Heeger, Plays. Rev. B 1991, 56, 4573; E.S. Manil
off. V. Kl imov, D. McBraoch, Playl. Rev. B. 1997, 56, 1876.
38. C. H. Lee, G. Yu. N. S. Sariciftci, D. Moses, K. P.olkb<tz, C. Zhang, A.J. Hecger, F. Wudl, Pllys.
Rev. B 1993, 48, 15425.
39. P.M. Allemand, G. Srdanov, A. Koch, K. Khemani, F. Wudl, Y. Rubm, F.N. Di.:dcril:h, M. M.
Alvarez, S. J. Anz, R. L Whcucn. J . Am. Chem. Soc., 1991, 113, 2780.
40. V. Dyakooov, M. C. Scharbcr, C. J. Br.tbcc, J. C. Hununelen, N. S. Sariciflci, Plays. Hev. B . in
print 1999.
41. G. Horovilz, Muter. 1989, 2, 287.
42. S. Glcnis, G. Touri lkm. F. Gamier, Titilt Solid Films 191!6, 139, 221.
43. R.N. J. J. M. Halls. D. D. C. Brn<.lley, R. ll. Friend. A. B. Holmes, J. Phys. Co11tlens. MetTer.
1994, 6, 1379.
44. J . H. Burroughcs, D. D. C. Bradley, A.R. Drown. R. N. Mruks, K. Mackay, R. H. Friend, P.L
Bum, A. B. Holmes. Nuwre 1990, 347, 539.
45. D. Braun, A. J . lle..-gcr, API'/. Pltys. Le/1. 1991, 191J2, 58.
46. D. Braun, A.J. llcegcr, II. Krocmer, J. /t'ctnm. Muter. 19111. 20, 945.
47. N. C. Gn:enham, S. C. Momui . D. D. C. IJr,l(lley, R. H. Friend, A.B. Holmes, Nuture 1993, 365,
621!.
4H. G. Yu, C. Zhung, A.J. He.:gcr, AJ'pl. l'lly.f. Lt/1. 1994, 64. 1540.
49. P. w. M. Blum. M. J. M. de Joug, M. G. v:m Muuslcr, Plays. Hev. lJ 1991,55, Mo.
50. P. W. M. Ilium. M. J . M. de Jong, J . J. M. Vlcggaar, Apfll. 1-!!11. 1'>'X. 6/i, :nOll.
51. P. W. M. 13lom. M. J . M. de Jung. S. Breedijk, Appl. Pity.,. Lt11. 1991,71,930.
52. D. M. Pai, J. Clwm. Plt)s. 1970, 52, 22!15.
53. J. Frenkel. He. i9311. 54, 647.
54. M. A. Lamperi., P. Murk. Currentllljutitm in Soliels, Acudemic Pres..., New York 1970.
55. I. D. Parker, J. Al'l'l. Plly.v. 1994. 75, 1<56.
56. L.H. Cunpbcll, T. W. Hagler, D. L. Smilh, J. P. Fcrmris, Pltys. Net. uu. 199<. 76, 1900.
57. C. M. Heller, 1. H. Campbell. D. L. Smilh, N. N. Oarashkov, J. P. Ferr-.lfis, J. A11pl. Pllys. 1991, 81,
3217.
58. M. Fahhnan, 0 . Beljonnc. M. Loglund, R. H. Friend. A. B. HollllL'l>, J. L Breuas, W. R. Salancck,
Clrem. Phys. Le11. 11193. 2/4, 327.
59. P. Dannet un, M. Fahlman, C. FuulJUCt , K. Kaerijama, A. Sonoda, R. Laa.arona, J . L. Or&las.
W. R. Salaneck, S)71tla. Met. 1994, 67, 133.
60. G. Yu, K. A. J. Hccger, Appl. Plrys. Le11. 1994, 64, 3422.
61. G. Guslafsson. M. Sumlberg, 0 . Ing;mas, C. Sven.'ISon, J. Mol. /ectroll. 1990, 6, 105.
62. T. Takigochi, H. D. Park. II. Ucno. K. Yoshino, R. Sugimolo, S)1llfL Met. 1981, 17, 657.
63. H. Anloniadis. B. R. Hsieh, M. A. Abkowilz, M. Slolka, S. A. Jcnekhc, Polymer Pre[lriuts 1993,
34.490.
64. H. Anloniudis, B. R. l bich. M. A. Abkowirz, S. A. Jcnckhc. M. Slolka., S)lUir. Mn 1994.62.265.
65. Y. Gao, K. T. Purk, B. R. llsieh, J. Cl1em. Phys. 1992, Y7, 69'Jl.
66. Y. Gao, K. T. Pad. B. R. llsieh. J. Appl. Plays. 11193, 73, 7!!94.
67. S. K;ug, W. Ric...s. V. Dyakonov, M. Schwoerer, Symh. Met. 1993, 54, 421.
68. S. Karg, W. Riess, M. Meier, M. Schwocr.:r. Mol. Cryst. LicJ. Cryst. 1993, 71J, 236.
69. W. Riess, S. Karg. V. Dyakonov, M. Meier, M. Schwoerer, J. of Lumillescellce 1994, 906, 60.
70. T. P. Nguyen, V. V. l l. Tr.tn, A. Guyot, Symlt. Met. 11193, 235. 55.
71 . T. P. Nguyen. S. Lcfmnt, S. de Vus. Y. Gao, Met., lCSM 96, 1997, 659.
72. K. Kon:.ladinidis, F. M. Galvin, R. L. Opi la. J. Appl. Plryx. 1995, 77. 2645.
73. F. PaJl<tlimilmkopoulos, M. Yan, L. J. Rothhcrg, H. E. Katz, E. A. Chan.Jrus.o;, M. E. Galvin, Mol.
Cry.w. Liq. Cryst. 1994, 256, 669. . .
74. P. Dm1ne1un, M. UigdiUilll, M. Fahhnan, M. Ooman, S. W. R. Sitlancck, R.
C. Frcdriksson. J. L. OrCdus. S. Graham, R. ll . Friend, A. 0. Holmes, R. Z.mtboni, C. T:1lilllli,
s,,tiL Met. 11193, 2/2, 55.
75. A. C. Arias, M. K. Pelrilsch. R. l-1. Friend, Symlr. Met .. lCSM 91!, in print
76. M. G. Harrison, J. Grilncr. G. C. W. Spencer, Plrys. Nev. IJ. 199(. 55, 7831.
77. A. K. GO!>h et al., J. Ap[>l. 1'/r_ys. 1974, 45. 230.
7H. C. W. Tang. A. C. Albrecht, J. C/leuL Plry.s. 1'J75. 62, 2139.
Rejere11Ces 559
79. H. B. DeVore, Phys. Re1. B. 1956, / 02, 1!6.
80. A. K. Gosh, T. Fcng. J. AI'JII. Plrys. 19111, 49, 591!2.
81. A. Dcsonncaux, J . J. Max, R. M. Leblanc, J. Plt_ys. Clrtm. 1993, 97, 6670.
1!2. S. M. S:te, Plry.rics of S.mimuductor Veic-<.'.1 (2nd cdn.). Wiley, New York 19111.
1!3. R. H. Ouhe. Pmp<'J1it.r of Seminmullc/tln. , Cambri.Jge University Pres,., Cum-
bridge 1992.
!14. P. Wiir1cl, Plrysik tier SolurJII<II, Spcklrum, Al.adcmbcltcr Ver1:tg, llo.:idclbcrg 1995.
85. J. J. M. Ha lls, K. Pichler, R.H. Friend, S. C. Moraui. A. B. Appl. Phys. ull. 19%. 68.
3120.
86. R. A.J. D. Mu.-.o. N. S. Saricilki. J. Ch<'m. Pity.\. 1994. 102.
87. R. A. J. J:.ul.'i.\Cn, M. P. T. Ouisliaan ... C. Hare. N. Martin, N. S. Sanciflci, A. J. Hccger, F. \Yudl,
J. Cl11:111. Pltys. 19%, IIJ.I, 4267.
Ill!. H. Meier, OTJ:(CIIic &mimml11m1T.s, Ver1ag Chemic, Weinhcim 1974.
!19. N. S. Saricilki. D. Braun, C. Zhang. V. I. Srdanuv, A. J. Hccgcr, G. Slucky, F. Wudi,App/. Plrys.
u11. 1993, 62, 5H.'i.
90. S. Morila, A.A. 7..akhidov. K. Yoshino. J1m. J. Appl. Phy.f. 199.' . 32, 873.
91. J . J. M. llalls. K. l'idller. R ll. Friend, S. C. Mumni, A.D. llohucs, Appl. Pltys. Leu. 1996. fXi.
3 120.
92. L. S. Ruman. W. Mmnruu, L. A. A. M. R. U. At/1. Mattr. 11198,
10. 774.
93. J. J . M. Hal b . R. H Friend. Swllr. Met. 1997, X5, 1307.
tJ4. A. Fujii. A. A Zakhi.Jov. V. V. Llorol.ov, Y. Olunuri . K. Yoshino. )Jill . .1. AJIII/. Plt)W., 19%. 35,
14]1!.
95. A. Aviram, M. A. Ritlner. CIICm. L.11. 1974, 21J, 277.
'X>. N. J. Geddes. J. R. Smubles. D. J. Jarvis, W. G. l'arker. O. J . Sandman, J. A1wl. Pltys. L.11. 199(1.
5fl,l '>l b
97. N. J. J.. Sambh:s, O.J. Jarvis. W.G. l'arkc r. D. J. Sandman, J. Appl. Pln.r. 1992. 71,
756.
tJI!. G. J . '[7riu Soli.ll-'ilnLv 199tl, /.'ill, 155.
99. R.M. Mcll.ger. C./\. Panctra, New J. Cll<'m. 1991, 15, 2()<}
100. A.S. Martin. J. R. G. J . l'flrs. Nct: /.<//. I'J'H. 70. 2 11!.
10 1. C. Scntein, C. t'iurini. A. Lorin, J .-M. Atfl: 1997. V. 1!09.
102. C. Scntcin. C. Fiorini. A. Lorin. L. Sicul, J.-M. Nunt.i, Op1. Mcllcr. 19911. 1), 3 16.
103. C.J. Br.sbcl:, F. Padinger. V. Dyakonov. J .C. Hummelcn. R. A. J . Jansscu, N. S. Saridflci, in Mer
leculur Nurwstruclllrl!'s, PIV<eetliiiMS uf tile llltenwtimutl '"' /ectrom'e Pmperties
of Nmel Materials, Kin:hbcrg 1998.
104. O. E.. Sidorcnko, M.R. Shar.:afuldinuv, A. A. Zal.hidov, K. SI'JIIII. Ml!'t. 1YY7, X5, 11 37.
105. J. C. Hummclen, B. W. Knighl, F. Lcpet:. F. Wudl, J. 01');. Cltcm. IW5, 60. 532.
106. C. J. Bmbcc, F. Pa.Jingcr, J . C. llununclcn, N.S. Sariciflci . J. Allfll. Pll)'.f. , in prilll 1999.
107. LS. Roman, M. R. And..:r.oson, T. YohilllllC.'>, 0 . lnganas, Ad1: Mc1tcr. 11191. IJ, 1164.
lOll. K. Yoshino. K. Tada, M. H. Kajii. Y. Hiruoaka. N. T:llla, Y. Kancuchi, M. Yoshida,
A. Fijii, M. Hamaguchi. H. Ar.ski, T. Kawai. M. OLitkr . Y. Olunon. M. Onoda, A.A. Zakhidov,
S)'llllr. Mtt. 1997, 84, 477.
109. W. R. Salaneck, S. J.-L Breda.,, CcmjiiKCJtcd Pol_l'lll<'r Surfaces umllnteifaces, Cam-
bridge Umvcrsily Cambridge Ill%.
110. J. Gao. F. Hide. H. Wang. Symlr. Mtl. 1997. X.J. 979.
Ill. K. T<I<Ja, R. Hidayal, M. Hirohala, T. Kawai, S. IJ. Lee, l.U. Bakhal.liruv, A. A. Zukhidov, K.
Yushino. Syntlr. Mtt. 1991, 85, 1349.
112. M. Gn111slrOm, M. Berggren. 0. lnganas. M.R. T. Hjcnbcrg, 0 . Wenncn.lroan, Afl/ll.
Lt-11. 1994, 65, 962.
113. M. R. M. Berggren, 0. lngunii>, G. Guslul'sson, J. C. Guslafsl>onCarlbcrg, D. Sclse,
T. Hje11berg. 0 . Wennerslrom, 1995. 28. 1525.
114. M. Berggren. G. 0 . lnganiis. M. R. An.Jcrsson, T. llJcnbcrg, 0 . Wenncn.lrom, Appl.
Plry.r. Lm. 1994,65, 141!9.
II S. M. S. A. Abdou. S. Hol<krufl, Clrcm. Mater. 11194, (), %2.
11 6. G. Yu, A. J . llccgcr. J. Al'l'l. Plr.1'1. 1'J95, 7.'i, 4510.
117.
11 1!.
119.
120.
121.
122.
123.
124.
J. J. M. Halls, C. A. Walsh. N. C. Grcc.nham, E.A. Marscglia. R. H. Friend, S.C. Moratti, A.B.
I Iohnes, Nature 1995, 376, 498. . .
M. Gr.mstrOm, K. Pctritsch, A.C. Arias, A. Lux, M. R. Andersson, R. H. rncnd, Nature 1991!,
395, 257. . r . ,. I M lCSM
C. J. Br.
1
bec, F. Padmger. J.C. Hummclcn, R. A. J. Jans.-;cn, N.S. Sanc11C1, ->)11t l . et.,
98, in print . .
H. Neugebauer, C. J. Brabec. N. S. Sariciflci, Syutll. Met., lCSM 98, 111 pnnl. . . .
H. Neugebauer, C. J. Brabec, J. C. Jlummclen. N. S. Sariciflci, Suwr 11ergy Mutenuls a11J Sowr
Cells, ECOS 1998, in pnnl.
G. D. Hale, S. J. Oldenburg, N. J. Halas, Phy!.. Rev. 8 1997, 55, . . . , .
C. J. Br.Jbcc, 1-1. Jolmnsson, F. Padingcr, J. C. Hummclc.n, N. S. Sanc1IIC1, Solar &tergy
11l.f 1111<1 Solar Cell.r, ECOS 1998, in print . .
J. Rostalski, 0 . Meissner, Solar &1ergy Materials a11d Solar Cells, ECOS 9!!, m pnnl.
16
16.1
A Model Oligomer Approach
to Semiconducting Polymers
Paul F. van Hutten and Georges Hadziioannou
Introduction
16.1.1 Background
The currcm rescan.: h on semiwnducting polymers is locused on luminescent de-
vices (light-emitt ing diodes, lasers) and strongly directed towards enhancing the
efficiency of the quantum conversion. A lower tum-on voltage, a lower current,
and a more balanced charge uansp011 are key factors in meeting this obj ective.
Such improvements will at the same Lime enhance the stability and dumbility of
the devices. The desired char..tcteristics are achieved by changing the device archi-
tecture and/or modifying the chemical structure of the polymer. The Iauer chemi-
cal option usually involves changes in the size, and arrangement of the
substituents on the conjugated backbone.
Poly(para-phenylene vinylene) (PPV) is one of U1e most extensively studied n-
conjugated organic materials for the fabrication of polymeric light-emitting diodes
(LEOs) Ll , 2). The introduction of alkyl or alkoxy side-chain substituents or the
intetTuption of n-conjugation along the polymer backbone by means of copoly-
meriwtion provides soluble and therefore processable materials and allows tuning
of the emission properties 13- 5). The attachment of electron-withdmwing cyano
groups onto the vinylene segments was found to result in red-light-emitti ng poly-
mers with increased electron affinity, which dr..IStically improved the quantum
yields of luminescence in multilayer LEOs [6, 7). The chemical approaches not
only modify the characteristics of inu-achain and their migration behav-
ior, but also the interchain phenomena. Charge transpo1t (polaron hopping) and
the occunence of such proposed species as excimers and bound polaron pairs [7,
8] will be affected. The objective of much of the current scientific effort is to pin-
point and control the important factors in U1e competition between radiative and
non-radiative decay.
Optical and electrical properties of conjug:ucd mate1ials are known to be
strongly dependent on the coplanarity of the conjugated n-system and on the in-
lel'Chain distance of conjugated segmcms. Knowledge of the inll uence of substitu-
ents on these structural features is an essential pan of the understanding of struc-
tu-c-property relationships in conjugated polymer materials. 1l1c aim of the
562
16 A Model Oligomer Approach to Semicomluctiug Polymers
described in this chapter is to explore such substituent effects and to relate struc-
tural aspects of the solid state, such as molecular conformation and pac:king, with
the physical properties of the solid. in pruticular its behavaor.
Although the structural organization in solid PPV-based matenals
fore of fundamental interest, little effort has been made to chamctenze the sohd
state of PPV and its derivatives in tenns of molecular conformation and packing.
Pristine PPV [9, 10] and several substituted PPVs have been subjected to a study
of crystal size, perfection, and mosaic spread in oriented sample.-; <;;ee e.g. [II J),
but the molecular confonnation in the unit cell has not been detenmned. Unfortu-
nately, polymers arc quite inaccessible with regard to solid-state structure; this is
particularly true for amorphous polymers, which are prefeaTed _because of
optical darity. The study of weii-Oefincd conjugated therefore
increased attention since it has already proven to be valuable an the case of oh-
gothiophcncs, notably scxithiophene, where single crystals suitable for
graphic analysis (12, 131 and wcll-oaicntcd thin films 114,. 15) be obtatncd.
Motivated by these considemtions, our research group m Gronangen
investigating model compounds that are analogous to the d tmmophorcs m h_ght-
emitting polymers, in particular the copolymers that have recently been descnbed
[ 16].
16.1.2 The Copolymer Approach to Controlled Light Emission
in Polymers
In aromatic organic molecules, photoluminescence represents the mdiative deca7
of mobile n-n* singlet excitations (in the text of this chapter, the term photoluaru-
nescence will be used to mean exclusively) L 17]. The HOMO-
LUMO energy gap is dete1mined by the chemical nature of the molecular struc-
ture and to a significant degree by the extent of delocaliwtion of the n-clectrons,
the so-called effective conjugation length. In blue-light-emitting materials, the n-
delocaliwtion is small and the realization of blue emission in polymers therefore
demands a high degree or control over the conjugation length. It has to be
than the effective conjugation length of most fully conjugated polymers, whach ts
determined principally by random conformational or chemical defects in the poly-
mer backbone and is dilficult to adjust. Control of the conjugation length or en-
ergy gap can be gained by preparing p<utially conjugated polymers._ l11ese can. be
of two types: (I) polymers with a non-conjugated backbone the acttve
chmmophores as side-groups L 18-201 or (2) (co)polymers contatnmg
conjugated sequences in the main chain [5, 21-271 .. 1l1cse app_roaches to am-
proved luminescence arc based on the idea of transfcrnng the lununcsccnce pmp-
erties of small organic molecules to polymer:->.
We have studied two types of polymers that both belong to the second case:
those in which luminescent chmmophores (typically n-conjugatcd oligomers) arc
separ..ttcd by higher-energy-gap blocks (see Fig. 16-1 a) and those in _which the
chromophorcs arc linked to each other in a non-coplanar way (sec Fag. 16-1 b).
/6. I Introduction 563
a
,.
B
,.
B
,.
b
A A
,.
A A
Figure )(,. J. Schematic repn:scntatiun uf cupulymcn; with wdl-(!cfincd conjugation length: A is a
conjugaiL-..1 dtrumophure. B i.s an interruptiuu uuit: (a) altcmuting L"t1puly1m:r; (b) polymer wilh stereo-
chemically dclincc.l non--coplan;IC
l11c luminescence can be rather precisely controlled (c:ulur tw1i11g) through the na-
ture and size of the active (A) block. Moreover, as the excitation is confined with-
in the low-energy-gap block A, its diffusion along the chain is prevented. Since
this would reduce the chance of migmtion to non-radiative traps (quenching
sites), the block structure is expcclcd to enhance the luminescence efficiency, at
least in systems in which there arc few interchain contacts. l11e B block is a
spacer, prd!!rably sdu:tcd so as to improve proccssability (such a polymer is not
a block copolymer accon.ling to the definition in polymer science: A and B often
cannot be described in terms of a repeating unit. We will usc block to mean fimc-
tiolltli unit).
Several examples of alt!!rnating conjugated copolymers have been described, in-
cluding systems based on oligothiophene blocks linked through oligosilylene units
[21, 22], oligo(para-phenylt!ne vinylene)s connected through aliphatic spacers
(23- 251 and naphthylelhylene moieties assembled with aromatic esters (261. Ex-
amples of the stereochemical approach are regioregular polythiophenes L27] and
copolymers of pam-phenylcne vinylcne and para-phenylcne l5 j .
From the point of view of one-dimensional electron delocalization, the pres-
ence of blocks of one or more silicon atoms between aromatic units in a chain in-
vaaiably strongly interrupts the conjugation, eiTccti vcly turning the chain into a
string of individual aromatic units 121, 22, 28, 29]. l11e latter property, in con-
junction with the synthetic versatility of sii:Jnes, ha.'i been exploited by the Gro-
ningen group to define the luminescent moiety in light-emitting polymers; a sub-
stituted silylene group has lx.-cn used as the intc1rupting unit in copolymers of the
type presented in Figure 16- 1 a. l11e sp
1
-bonding configuration on silylene renders
the copolymer molecule very lkxible even when the conjugated blocks arc rigid
rods; this rcsull'i in a dramatic enham:emenl in the solubility. Note that the use of
disilanylene or longer interrupting blocks is not preferred since that would intro-
duce labile. light-sensitive Si-Si bonds in the pulymer dwin.
16.1.3 Oligomers as Model Compounds for Structure-Property Studies
Ever since PPV was founll to have promisi ng light-emission charat.: teristics Ill. ef-
forts in the synthesis and study of rdated oligo(phcnylcne vinylene)s (OPVs)
have intensilied. l11e research group in Groningen has focused on OPVs that cor-
respond to the conjugated building blocks of the copolymer.; prepared in our labo-
564
16 A Model Oligomer Approach to Semicuuducting Polymers
mtory {1 6]. Since in both types of compounds, i.e. model oligomers_ and copoly-
mers, the chromophores are chemically unifonn and well-defined, thas enables us
to verify the proposed spatial confinement of the excitat_ion in copolymers.
Several of these model compounds have been obt:uned as smgle crystals, of
which the structure has been deteamined by means of X-my crystallogmphy [30-
32j. The availability of accurate information about the and packing
of molecules in the single crystal allows one to propose more det:uled less
speculative explanations for optical and electrical associated_ wath the
polymeric solid state. Some of the cuaTent issues, for mstance, concern
cular excitations: Do they actually occur? Are they related to aggregatiOn phe-
nomena? How do they depend on intennolecular distance and orientation? In_ an
electrically driven light-emitting device, the transport of minority charge earners
should be facilitated. Charge carrier tmnsport is obviously strongly dependent on
the type of molccul:u packing, and on intermoleculaa: sepamtion in geneml. It will
be instructive to sec how the packing of molecules m the crystal depends on the
substitution pattern of the molecule. In the work by Gamier ct a/. 1331 on
gothiophcnes, it was shown that a. g.ive _rise to _rackmg
modes entirely different from those ol oligomcrs !?roper -r:''e
approach through model compounds h;t'i been suu:csslul lor th.: case ol
phene. Optical :u1d properties have been rel ated to the
tion :111d packing mode in single crystals or than hlms of scxa-
thiophene (33- 351. 1l1is molecular cmnpound has been lound to have useful prop-
erties for applications l36-38J. The of an oligomer crystal docs_ probab_ly
not, by itself, have :uty predictive value for the: structure a related hght-effilt-
ting polymer solid, but the insights obtained w1ll be applicable to
will help one select reasonabl e models for their solid state on the basas of optacal
properties. . . . . . . .
These model compounds can also be used m dev1ce fabncataon, sance thtn
films of appropriate thickness can be obtained by sublimation de
position onto a substrate in vacuum. Electrical as well as optacal propeataes of
such devices have tumed out to be strongly dependent on both the molecular
pucking within the crystallites :111d the _morphology. Understanding
and control of this aspect is one of the current scenuhc challenges.
16.2 Synthesis and Solution Properties of OPVs
16.2.1 Synthesis
16.2.1.1 Introduction
Oligo(l,4-phenylene vinylene)s are in principle accessible via a large of
methods [39]. However, out of this large number of methods, the usc ol only _a
small number has actually been reported. The must extensively used method IS
16.2 Synthesis und Solutiorr PrUJJenies of OPVs 565
the Wittig reaction, the coupli ng of suitably substituted aldehydes with triphenyl-
benzylphosphonium salts t40-t4]. The yields achieved by this method are gener-
ally moderate to high. A major drawback of this method is. however, the simulta-
neous production of cis- and trcms-isomers. 1l1e fornter can be transformed into
the mms-isomer by boiling in a solvent containing iodine. lltis can be circum-
vented by using a modification of this reaction which employs phosphonatcs in-
stead of the phosphonium salts, namely the Wittig-Horner reaction [45].
Instead of building the oletinic double bond in the synthetic step, it c:111 be pre-
fanned :u1d incorpomted in the forn1 of styrene-type molecules using the Heek re-
action 146). 1l1is reaction is a palladium-catalyzed vinylation of organic hal ides
[47J, which leads to lhe formation of carbon-carbon double bonds in pure trans
configur.1tion with very few side-reactions, and it has the further advantage of
being compatible wi th a number uf substitucnts. llms, onhogonal approaches to
the synthesis of a whole series of oligomers arc fca.-.ible, employing alternating
Wiuig-Homer and Heck for the fast synthesis of long OPVs [481. Yet
another, somewhat similar approach is the combination of Wittig-Horner and
McMurry re;tctions l4lJJ. llte usc of metathesis 1501 or the Siegrist reaction [51]
has also hccn rcpoatcd. 1ltcse reactions, used a.-. polycondensations, have the
dmwb<lck of yielding mixtures of oligomcrs mther than the monodisperse oligo-
mers that can be obtained with the stepwise syntheses mentioned above. For cya-
no-substituted OPVs, the Knucvenagel reaction ha.-. hecn employed [6, 31, 52].
16.2.1.2 General Stn1tcgy
As motivated in Section 16. 1.3, our study of model oligomers is a spin-off from
U1e work on copolymers. It is therefore useful to consider the latter in more detail
at thi s point. The structures of the copolymers synthesiLed are summarized in Fig-
ure 16-2. Two different types of backbones c:u1 be distinguished. In structure I,
which con-esponds to the first approach (see Fig. 16- 1 a), PPV-type units arc
linked through a ncxible dimethylsilylene unit (x= I or x:::: 2). In structure II, the
desired control of the conjugation length is achieved through stcaic interactions
between the side-chai ns :111d the rings within the terphcnyl parts of the copolymer
rt
compound A K
R
Ooc:t-SIPPV3 o-c,H., 1
Qbu.SIPPVJ (>-(;.He
oc:t-SiPPV3 CaHn
Ooc:tSIPPVS 0 -C. H, 2
R
compound A
Ooc:t4 PPPV3 0-CaH,
II
Obu4PPPVJ 0-C;io
Oci4-PPPV3 c.H.,
R n
Figun: 16-2. Clu:miGtt .arudun- numcth.:tatun: uf cunj ut,t;tlcJ .:upulynt.:r' I and II.
566 16 A Model Oligomer Approach 10 Semiconducting Polymers
--
l(x= 1)
R
--l(x=2)
R R

R R
--
II
Figure 16-3. Synthesis of conjugilled copolymers I and II; R::alkyl or alkoxy; X::halogen (Br or 1).
[5], which force the rings to be non-coplanar. Effectively then, PPY-typc blocks
arc linked but not conjugated through a phenyl ring. 1l1is corresponds to the sec-
ond concept (see Fig. 16-1 b). The presence of side-chains on the polymer back-
bones is also intended to provide solubility. We have considered different types
(alkyl CnH
21
,+
1
or alkoxy O-C,.H
21
,+
1
) and lengths (C.t and C
8
) of the side-chains
in order to study their influence on the properties of the copolymers.
The synthetic strategy towards the copolymers is shown in Figure 16-3. The
use of bifunctional monomers in a Heck reaction allows the synthesis of poly-
mers, and the great potential of this approach has been demonstmted previously
[53-55]. The syntheses have been described in detail by Hilberer et a/. ll6j.
16.2.1.3 Synthesis of Model Compounds
16.2.1.3.1 Three-ring OVPs
By using some of the monomers and intermediate compounds in a Heck reaction,
the series of model molecules shown in Figure 16-4 was synthesized. Coupling of
a disubstituted dihalogenated benzene with divinylbenzene, under the same condi
tions as the copolymers [ 16], afforded the fully conjugated polymer Ooct-PPV.
For the model compounds, acetonitrile wa.<; used as a sol vent in order to avoid the
high-boiling DMF. Reaction of the dihalogenatcd benzene with styrene gave the
distyrylbcnzene derivatives Ooct-OPV3 and oct-OPV3, corresponding to the con-
jugated part of copolymers I (x= I). By using disubstitutcd monobrominated ben
zene we obtained Ooct4-0PV3 and oct4-0PV3, which correspond to the PPY-
type block of copolymers II. All the model compounds were obtained in good
yields, with the double bonds all in the trans configuration, as indicated by NMR
spectroscopy.
We have also synthesized a number of similar copolymers and model compounds
bearing cyano groups on the vinylene linkages (Section 16.2.1.3.4). The nomencla-
ture of the m()dels referred to later in this chapter is given in Figure 16-5.

R
-
+
16.2 Syml!csis cmd Solmion Pmpetlics of
R
Ooct..OPV3
oct-OPV3
R Ooct4-0PV3
oct4..0PV3
567
Figure 16-1. Syrllhcsis or mu<.lcl corresponding to the chrmnophorcs in the copolymers I
and II. R::alkyl or alkoxy: X:: halogcn (Br or 1).
--(A_CA'_
0oc&-OPV3-c;-
l'igurc l<>-5. Chemical stru.:turc and numcndaturc li.lr the uligo(pamphcnylcnc vinyknc)s.
16-2.1.3.2 Synthesis of
Unsubstitutcd OPV5 (u-OPV5) was synthesized in a Wittig-Horncr reaction from
4-st yry lbenzaldehyde and tctracthyl-11 ,4-phcn y lcne-bis( mel hy lcne) 1-biphosphonate
in DMFffHF (sec Fig. 16-6). The yellow crystall ine solid obtained appeared to be
insoluble in common solvents. It was characterized by mass spectrometry:
M+=4g6.64.
568 I 6 A Model Oli8mner Apprvucll w Semic{)luluc:till8 Polymers
16.2.1.3.3 Synthesis of oct-OPVS and Ooct-OPVS
Rcad.ion scheme for
lhe synthesis of u-OPVS.
Oct-OPV5 and Ooct-OPY5 were prepared following a procedure U1at was used to
prepare ten-butyl-end-substituted oligo(phenylene vinylenes) (43]. Benzyltriphen-
ylphosphonium bromide was lengthened by a styryl unit via a Wittig reaction
with 4-methylbcnzaldehyde. The methyl group of the stilbene was functionaliz.ed
by bromination with N-bromosuccinimide (NBS). The phosphonium suit of the
stilbene was obtained by a subsequent reaction with triphenylphosphine in tol-
uene.
The target molecules oct-OPY5 and Ooct-OPV5 were prepared in a final bis-
Wiuig reaction from 4-styrylbenzyltriphenylphosphonium bromide with 2,5-di -11-
octylterephthaldialdehyde or 2,5-di-n-octyloxyterephthaldialdehyde (see Fig. 16-7)
in modemte yields [56).
1
H-NMR spectroscopy of the mw product indicated the
fonnation of both cis and trans double bonds. The pure all-trans fi ve-ri ng oligo-
mers were obtained by heating with a catalytic amount of iodine in xylene [57).
16.2.1.3.4 Synthesis of Cyano-Substitutcd OPV3s and OPVSs
The cyano-substituted five-ring oligorners were formed in good yields in a Knoe-
venagel condensation between an aldehyde and a cyanornethyl-substituted com-
pound. according to a procedure previously reported by Greenhan1 el a/. [6). lllC
Knocvenagel condensation needs careful control of reaction conditions in order to
Figure U>-7. Reaction scheme
for lhc synthesis of oct-OPVS
(R=II-oclyl) and Oocl-OPVS
(R =11-<><.:lytoxy).
16.2 aud Solulicm Pmperties of OPVs
PII(OAc)z/ P(c>IOI))
+
ElaN

SU.NOH
THF/t-auOH
A
Figure 16-8. Reaction schclllc for lhe synlhesis of Ouct-OPVS-CN' (R=u-octyloxy).
569
avoid possible side-reactions such as Michael addition of nucleophiles to the new-
ly formed vinylenc linkage or direct attack on the cyano group.
Ooct-OPY3-CN' was synthesized from (4-cyanomcthyl-2,5-bis(II-OCtyloxy)phcn-
yl)acetonitrile and benzaldehyde. Ooct-OPY5-CN' was synthesized as depicted in
Figure 16-8 from (4-cyanomethyl-2,5-bis(ll-octyloxy)phenyl)acetonitrile and 4-styr-
ylbcnzaldehyde.
TI1e analogous oligomcrs with the cyano-substituenL'i at the outer positions of the
vinylene groups adjacent 10 the centr.ll ring were accessible via Knocvcnagel con-
densation of 2,5-di-n-octyloxyterephthaldialdehyde and phenylacetonittile (0oct-
OPY3-CN"), or 4-styrylphenylacetonillile (0oct-OPV5-CN"). The 4-styrylbenzal-
dehyde and 4-styrylphenylacetonitrile were prepared in a Heck coupli ng of styrene
with 4-bromobenzaldehydc and 4-bromophcnylacctonitrile, respectively [56J.
16.2.2 Optical Properties in Solution
16.2.2.1 Comparison of Copolymcn; and Related Oligomcn;
16.2.2.1.1 Three-Ring Chromophores
In dilute tetrahydrofuran solution, the polymers and the models show a strong ab-
sorption band in the ncar UV and/or the blue part of the visible spectrum (Ta-
ble 16-1 ). They arc all highly lluorcseent, showing an emission band in the blue-
green range. For the copolymers, the optical properties in solution are indepen-
dent of the length of the side-chain. TI1is result is expected since these properties
are related to the n-conjugated system, which is hardly influenced by the length
of the side-chains. It also justifies that we have only considered one length of
side-chains (C
11
) for the model compounds.
510 16 A Model Oligomer Approacla to Semic:vuductiug Pvlymcrs
Table 16-1. Absorption and emission data for copolymers and OPV3s in THF solution.
0
)
Compound Absorption Photoluminescence Shin
</JI'l. h)
(cV)
).1\b .. """' m.u. c APL. mml 1'Lnu

(nm) (eV) (L mol ' (0111) (eV)
cm-
1
)
Ooct-PPV 435 2.K5 3 1500 ill. 520 2. 50, 2.38 0.40 0.35, 0.47
Ooct-SiPPV3 400 3. 10 45300 ill. 475 2.74, 2.61 0.68 0.36. 0.49
Obu-SiPPV3 400 3. 10 44900 452,475 2.74, 2.61 0.57 0.36, 0.49
oct-SiPPV3 360 3.44 28600 412,438 3.01, 2.83 0.6 1 0.43, 0.61
Ooct-SiPPV5 425 2.92 79300 490, 515 2.53. 2.4 1 0.40 0.39, 0.5 1
Ooct4-PPPV3 415 2.99 69800 463,490 2.68. 2.53 0.53 QJ!. 0.46
Obu4- PPPV3 410 3.02 461, 41!5 2.69. 2.56 0.70 0.33, 0.46
oct4-PPPV3c) 361! 3.37 51()()() ill.448 2.94, 2.77 0.1!0 0.43, 0.60
Ooct-OPV3 390 3. 18 42100 440,460 2.1!2, 2.70 O.t!7 0.36. 0.48
oct-OPV3 35 1 3.53 47 100 3. 10, 2.93 0.80 0.43, 0.60
Ooct4-0PV3 380 3.26 41!000 426,450 2.91, 2.76 0.81! 0.35. 0.50
oct4-0PV3 355 3.49 52600 401. 423 3.09, 2.93 0.78 0.40. 0.56
) lAb..., nw is the wavelength ab:.orptmn maximum. /:.'""' ""'' the corresponding energy. and
c the extinction <:ocflicicnt; l
11
_ "''" represent:. the photoluminescence maxima, t::,.,,. """' the corre-
sponding energies. and </J
1
,L the photoluminescence <IUilntUIIl yield; shifts arc as t::"'" ,...,.-
Pt... .,., . UndcriinL'tl vlucs denote the tlbsolutc maxima. UV-vis abS(llpt iun spcctm wen: on
an SLM Aminco 3000 Am1y spcctruphotumctcr. 1-'hotoluminc...ccm:c sfX."CII'il were rccordl.'tl on an SLM
Aminco SPF-500 spcct rolluoromctcr. 111C cxo:itation wavelength 10 11111 below the absorpllllll max-
imum.
b) Photolumincsccocc <juantum yiekls were rcltltivc to <juinine sulfate (</1 =0.55) in sulfuric
acid (58, 59(. 'The experimental inaccumcics lead to an ovcroll l error of about 10-15% in the vdl-
ucs of quantum yickls.
'')This polymer was denoted TOP-PPV in 151 and 160).
For copolymers of structure I, for both types of side-chains, there is a striking
similarity with the optical properties of the corresponding models; the absorption
and photoluminescence maxima of the polymers arc only 0.08-0.09 eV red-
shifted relative to those of the models. as shown in Figure 16-9 (left) for the
octyloxy-substituted compounds. 1l1e small shift can be readily explained by the
fact that in the copolymers the chromophorcs arc actually substituted by silylcne
units, which have a weakly electron-donating character. The shifts between ab-
sorption and luminescence maxima are exactly the same for polymers and models
and the width of the emission bands is almost identical. 1llc quantum yields are
only s lightly reduced in the polymers. 1l1csc results confinn that the active chro-
mophores are the PPV-type blocks and that the silylenc unit is an efficient n-con-
jugation inteiTupter.
For copolymers II compared to the tetrasubstituted OPV3s, we find rather small
differences in the optical properties (0. 12- 0. 16 cV shift in maxima) when the side-
chains are alkyl (oct4-PPPV3 and oct4-0PV3). For alkoxy side-chains (0oct4-
PPPV3 and Ooct4-0PV3) the diiTerence is lartier (0.23-0.27 eV), as shown in Fig-
ure 16-9 (right). This can be explained by the stetic intemctions in the tet]>henyl part
4.5
Q)
0
c:
Ill
e
0
"'
.D
<( ..,;.
16.2 Synthesis cmd Scdlllitm Properties of OPVs
Energy (eV)
4.0 3.5 3.0 2.5 2.0
300 400 500 600
Wavelength (nm)

'iii
c:
Q)

...J
a..
4.5
Q)
0
c
Ill
.D
0
"'
.D
<(
Energy (eV)
4.0 3.5 3.0 2.5 2.0
300 400 500 600
Wavelength (nm)
571

'iii
c:
2
.s
...J
a..
Figure 16-Y. Normalilcd a!JS(>rption (thin lines) and photolumi nescence (heavy lines) spcctm in THF
solut ion. Left: Ooct-SiPPV3 (- -) and model Ouct-OPV3 (- - - ); right: polymer Ooct4-
PPI'VJ (-- ) am.l model Ooct.J.-OPVJ (- - - ).
of the copoly111ers. It is known that. even in non-suhstitulcd oligophenylcncs, two
adjacent phenyl rings are nol coplanar [61, 62]. Steric hindrance between protons
induces a twist between the phenyl rings. Our nmlecular modeling calculations
(AM I semi-empirical quantum-chemical method as implemented in MOPAC6
[63]) indicate that this twist angle is about 40' . which still pem1its some overlap
of the n orbitals. In the cakulations on substituted terphenylenes, either methoxy
or ethyl groups have been taken as substituents, which are long enough to represent
the static interactions for alkoxy or alkyl tails of :my length. In order to obtain po-
tential energy curves, the central ring was rotated stepwise by tixing interannular
dihedrals at (/J and -({J; all other bonds and angles were fully optimized within the
constraint of inversion symmetry. In Figure 16- 10, the curves were made to coin-
cide at 90". Substitution with methoxy groups is found to increase the barrier at
0; the minimum ener<6Y sti ll occurs at approximately the same angle: (/Jm;
11
= 40.2u
for R=H and (/1
1111
,=42.6" for R=OCH,. Since the methoxy substitution has in-
creased the energy difference between 0" and 90", however, an actual population
of methoxy-substitutcd rotamers would exhibit a somewhat larger erfecti ve dihedral
angle than 42.6". Alkyl (ethyl) substitution has a more pronounceo clfcct. 1l1e
energy minimum shifts to 56.7" and is found only to be 2.5 kJ mol-
1
(':::::.Nkn below
the energy at 90''. Since the potential energy curve is signilicantly flatter around 90"
than in the previous cases, the ethyl-substituted rotamers will be distributed more
broadly with an etlective dihedral that is shifted towards 90. Our findings suggest
that overlap of n orbitals is signilicantly diminished in the case of alkoxy substitu-
tion and ellectively absent for alkyl substilucnts. This means that in copolymer struc-
ture II, the conjugation is interrupted rather effectively when alkyl chains arc pre-
sent, but less so in the case of all,oxy suhstitution.
For all compounds, I he nature of the side-t: hain hus. a strong effect on the ab-
sorption and emission fcaturc.'i. The change from alkyl to alkoxy is accompanico
by a 0.25 to 0.35 eV red-shift in the absot]>tion and emission maxima. 1l1is result
572 16 A Model Oligomer Apptvacll 10 Semiconducting Polymers

0
30
....,
c
e> 20
"' c
"' 10
]l
0
0
a.
R R

R R
-10
0 30 60 90
Dihedral angle q> (degrees)
lo' igure 1(.-UI. Potential energy (per phenyl-
phenyl bond) for rotation in the terphcnyl
molecule shown ( : R=H, +: R=OCH
3
,
e: R=C
2
Hs). The centr.sl ring was rotated
uml subsequently the geometry was fully op-
timized while retaining inversion
for the molecule.
is mainly due to the increase in the electron density in the chromophorc when the
n-electron-donating oxygen atoms of the alkoxy side-chains are attached. TI1is
phenomenon can be exploited as a way to tunc the optical propetties, in particuhu
the color of the light emitted by lumincsccncc, for our copolymers. Another way
of color tuning is increasing the length of the chrornophorc, which means an in-
crease in the conjugation length. TI1is also results in a red-shift for the absorption
and emission, as demonstrated by the polymers Ooct-SiPPV3 and Ooct-SiPPY5,
for which the chromophorc size incrcuscs from 3 to 5 rings. Five-ring model com-
pounds will be the main topic of the subsequent sections.
TI1e solution photoluminescence quantum yields of the copolymers are high
(0.4-0.8) and indicate a great potential in light emission applications [60, 64-69).
16.2.2.1.2 Five-Ring Chromophores
A comparison of the absorption and emission spectra of Ooct-OPV5 with those of
the full y conjugated, similarly substituted polymer Ooct-PPV shows that the ab-
sorption and luminescence maxima of the five-ring model compound are only
slightly blue-shifted relative to those of the polymer (see Fig. 16-11). Hence, the
Q)
()
c:
<U
-e
0
Ul
.0

4.0
300
Energy (eV)
3 .5 3 .0 2 .5 2.0
400 500 600
Wavelength (nm)

Ul
c:
Q)
c
_J
a...
a.igure 1611. Nommlizcd ;absorption (thin
line.') an<! phutolumincsccucc (heavy line.')
spc.:tm in of Ooct-SiPPV5 (---),
(),and Ool:tPPV (- - - ).
16.2 SymheJis a/Ill Solutioll Properties of OPVs 573
optical properties of these oligomers have nearly converged to those of the poly-
mer at the five-ring level. The luminescence quantum yields of oct-OPV5 and
Ooct-OPV5 in solution are nearly 90%, more than twice that of the polymers .
By the same token, the optical properties of copolymer Ooct-SiPPVS are very
close to those of the fully conjugated polymer; the absorption and emission spec-
tm of Ooct-SiPPV5 are only slightly blue-shifted relative to Ooct-PPV (see
Fig. 16-11 ). For Ooct-PPV, the emission spectra are broader at the blue tail than
for Ooct-SiPPV5, indicating that the conjugation length is more precisely defined
in the Ooct-SiPPV5 copolymer than in the fully conjugated polymer, where it is
determined by the polymer backbone conformation. Moreover, Ooct-SiPPV5 has
other attractive properties, for example a much better solubility.
16.2.2.2 Substitution Effects in OPVSs
lne influence of substitution on the optical properties of the OPV 5s in dilute so-
lution is demonstrated in the absorption (sec Fig. 16-12, left) and photolumines-
cence spectra (sec Fig. 16- 12, right). l11e absorpt ion maximum of the alkoxy-sub-
stitutcd oligomer Om.:t-OPV5 (422 nm) is red-shifted by 0.20 eV relative to the al-
kyl-substituted oligomer lX.:I-OPV5 (395 nm). as a result of the elcctron-donaling
effect of the alkoxy substitucnts. In emission, the red shift is only slightly smaller,
0. 16 eV. It has lx.:cn demonstrated thill cyano substi tution onto the vinylenc lin-
kages of PPV results in a lowering of both the HOMO and LUMO levels (61.
Since the LUMO level is stabilized more than the HOMO level. the absorption is
red-shifted. Indeed. for the alkoxy-cyano-substituted oligomer Ooct-OPV5-CN", a
red shift in absorption (0.20 eV) and emission (0.25 eV) relative to Ooct-OPY5 is
observed. However, the absorption of Ooct-OPV5-CN' is blue-shifted, with a
maximum at 360 nm and a shoulder at around 400 nm. A band at 360 nm is also
found for Ooct-OPV5 and Ooct-OPV5-CN" and is assigned to a local excitation.
These findings seem to support the results of our quantum-chemical modeling,
Energy (eV)
4.5 4.0 3.5 3.0 2.5
c a b d
300 400 500 600
Wavelength (nm)
:::
"(ii
c:
Q)
E
_J
a...
3.5
Energy (eV)
3.0 2.5 2.0
a b c d
400 500 600 700
Wavelength (nm)
Figure )6-12. absmvtinn (ldl) <tllll llhotolulllinc,.;cncc (right) spcctm of OI'V5s in chloro-
form solution: (a) IK:tOI'V5. (h) Ouct -0l'V5, (.:) 0odOI'V5-CN'. (tl) Ooct-OPV5-CN".
574 16 A Model Approach to Semic:owlucting Polymers
which predicts a reduced planarity of the molecular n-system in Ooct-OPV5-CN'
as a consequence of cyano substitution on the inner vinylene carbon. A larger
twist angle at the centr.1l ring would favor a local excitation, and this may be
further promoted by the conj ugation of the cyano groups to the penultimate rings.
The luminescence of Ooct-OPV5-CN' is much less blue-shifted relative to
Ooct-OPV5-CN" than the absorption and is even slightly red-shifted relative to
Ooct-OPV5. However, whereas the luminescence spectra of oct-OPV5, Ooct-
OPV5, and Ooct-OPV5-CN" are very similar in shape with a sharp maximum and
clear vibronie details, the luminescence spectrum of Ooct-OPV5-CN' is feature-
less and also broader than those of the other oligomers.
There are also stri king differences in the quantum yield of photoluminescence
(Table 16-2). The SiPPV copolymer and several fi ve-ri ng OPVs (oct-OPV5, Ooct-
0 PV5, and Ooct-OPV5-CN") have high photoluminescence quantum yields be-
tween 0.4 aml 0.9. The PL decay curves arc single-exponential and com!spond to
lilctimes around I ns. value!) are simil:tr to those reported for other substi-
tuted 5-ling PPV oligomcrs 1701. However, in thc casc o f Ooct-OPV5-CN', the
photolumi nescence quantum yiclJ is extrcnacly low. 0.04. PL lifctimc measure-
ments yield a fast douhlc-expuncalt ial PL tb::ay of XO ps, of :u1 efficient
non-radiati ve decay channel (sec l;ig. I 6- IJ ).
Stmt ing from the assumption that the gcom..:try relaxation after exdtation is of
primary impo1tance with respect to the lumi nescence rcsponse, we decided to em-
ploy a solid polymer matrix to suppress confonnational changes of the oligomers.
For the measurements, dilute blends with polysulfone as the tr.msparent host ma-
trix were prepared. ln Figure 16-13, the PL decay curves for the two cyano com-
pounds in both chloroform and polysulfone are presented, as are the PL spcctm of
Ooct-OPV5-CN' in chloroform and polysulfone [69].
From the identical shape and position of the absorption spectr.1 (not shown) in
chloroform and polysulfone we conclude that the distribution of gcomellies of the
Ooct-OPV5-CN' molecules is the same in both situations. In polysulfone, the
non-radiative decay channel is effecti vely inhibited and a normal
Table 16-2. Ab,.'Orption and emission for ropolymcn; <Uld OI' VSs in o.:h lorufom1 solulion.
Compound ).1\t.. . ..... )
""""""'
;. ..... " .... , , .... .......
Shirt b) <P, . ") r,,._ ,
11
)r,'L. 2
(nm) (eV) (0111) (eV) (eV) (n')
Oucs-PPV 435 2.1!5 495. S20 2. 50. 2.31! 0. 35, 0.47 0.4
Ooct-SiPPVS 425 2.92 4\IU, SIS UJ, 2.41 0.39. O.SI 0.4
o.:I.QPVS 3\IS 3. 14 455, 4114 2.73, 2.S6 0.41, 0.51! 0.9
Ooct.QPVS 422 2.94 41!3, Sl 3 2.57. 2.42 o .. n. o.52 0.9 1.2
Ooct-OPVS-CN' 360,400 3.44. 3. 10 502 2.47 O.lJ7. 0.63 H.04 O.Oil 1.3
Ot>et-OJ>V5CN" 453 2.74 536, S61l U J. 2. 11! 0.42, O.S6 0.7 1.4
") Un<.lcrlincd values denote the absolute maxima.
b) Snal'l is delincd here as lhe diiTcrcncc bclwccn
11
.,, , ,,,... an<.l 1'1. """''
c) Ph01uluminc....:cncc <luantum yields were mcasurc..t in 1'1-IF solutiun an..t relative ttl 4uinim: sulfate
(<IJ =O.SS) in )Uifurie at:id.
11
) I'L wen: al the of the I'L maximum.

'iii
c
0.1
.!:
...I
0..
2

t, = 1.7ns
t. = 1.71\S
4
/6.2 Syutltesis cmd Solutiou PtVperties of OPVs 575
6 8 10
Time (ns)
1(>- 13. PL decay O.:I ITV\.0:. uf OPV,.; ( I ) syslent response; (2) Ooct-OPV5-CN'
in CIICI,: (3) Ouc OPVS-CN" in CHCI, : (4) Ouo.:I-OPVS..CN" in poly,.ulfonc; (S) Oo.:t-OPVS-CN' in
puly,.ullune. ln,.el : l't. " I>CCi r.l uf <">...:1-0I'VS-CN' 111 o.:hluruli.>rm (--) an..t p<.>lysnlfone t ).
ti:al decay with a time of 1.7 ns is oh:;crvcll. Clearly, the cllkicnt non-ra-
diative tkcay channel observed for Ooct-OPV5-CN' in chloroform is connected
with the extent of conformational freedom it possesses in the surrounding medi-
um. Restriction of the molecular motion severely reduces the efficiency of the
non-radiative decay pathway. For Ooct-OPV5-CN", the decay curves in solution
and the solid polysulfonc matrix do not differ much (r= 1.4 and 1.7 ns, respec-
tively). These results indicate that the confom1ational freedom is somehow ac;so-
ciatcd with the position of the cyano substituents on the oligomer backbone.
Neve1thckss, the slight in the PL lifetime or Ooct-OPV5-CN" may also
be attributed to the same effect, which is probably general for all PPV-type com-
pounds. Apparently, due to the specific substitution pattern of Ooct-OPV5-CN' ,
the excitation energy is lost to a large extent through intramolecular modes (711.
The relaxation processes for Ooct-OPV5-CN' may be visualized with the help
of Figure 16- 14. which shows the potential energy surfaces of the ground and ex-
cited state associated with tl1c c:is-tmm i:mmeriu tion of stil bene [721. The actual
coordinate for OPV5 (for stil bene: the twist angle) is not it could well be
multidimensional. After optical excitation, the molecule moves from the Frank-
Condon region of the S, surface to a twisted geometry along the potential sur-
face, with either a small barrier or none at all. In the twisted region, non-mdiative
relaxation to the ground-state is very r..tpid. For the situation where the molecules
arc dispersed into a solid matrix, the ground and excited state potential surfaces
look different tiom the ones displayed in Figure 16-14. The constraint on the
twisting motion in this case will favor a normal radiative relaxation process.
Although the r:tdiati vc lifetime has incrc:sscd to normal values upon changing
the matrix from chloroform to polysulfone, the emission speclrum (i nset sec
Fig. 16- 13) for Ooct-OPV5-CN' is unchanged; it is still broad and featureless.
1l1is points to inhomogeneous bmadening, a result of the fact that emission
comes from a distribution of wi th varying non-planar geometries, which
576 16 A Model Oligomer Approach to Semiconclucti11g Polymers
500
1 ps
;--;;.
5
::::- 400
4
0
. >
....,
300
3

::'!. >.
>.
1.7 ns
200
2
Cll
Cll
c
c w
w
100
0 0
0 w 00 120
angle (degrees) b
trariS tis
l<igure 16-14. Onc.<Jimcnsional n:prc.-.cntation of the ground and cxcitcd-st;Jtc for
l rWIS and ds"stilbcnc 1121.
Figure 16- t S. Structure of a cyw10-substitutcd co-
(Xllymcr of type II (sec Fig. 16-2).
are highly constrained in the matrix. The broadening of the spectrum in chloro-
form may have the same origin. Our results suggest that a conto rmationally re-
laxed excited stale is not reached upon photoexcitation. This issue might be clari-
fied by measuring time-resolved spectra.
The copolymer with the structure shown in Figure 16-15 displays a behavior sim-
ilar to that of0oct-OPV5-CN'. In solution. one tinds a fast double-exponential decay,
while in a polysulfone matrix single-exponential decay with a time constant of 1.7 ns
is observed. We attribute this behavior to the same confom1ational phenomena.
16.2.2.3 About the Geometry of the Excited State
The results presented above show that there arc striking differences in the lumi-
nescence properties of the cyano-substituled compounds. For the solution photolu-
minescence, these differences must originate from basic properties of the individu-
al molecules. Clearly, the position of the cyano substituent on the vinylene link-
age is a crucial factor. It has been reported that the cyano group docs not have a
strong effect on the ground-stale electronic structure of PPV-typc molecules 173].
Apparently, however, the excited-state properties are strongly dependent on 1hc
position of this substituent. The rcsulL'i obtained in the polysulfone matrix are
very informative and suggest that the compounds beari ng the cyano group at the
inner vinylcne carbon atoms rcarmnge strongly after excitation. The bond-length
changes that occur upon excitation may lead to changes in the stcric interaction
between the ring substituents and the cyano groups.
16.3 OPVs in the Cmulensecl State
577
The influence of bond-order changes that result from exci tation on the molecu-
lar is an that has not received attention so far. It is generally
accepted that Ill lhe case of polythiophene, n-n* excitation will lead to an in-
creased planarity of the molecule; since the LUMO makes a contribution to U1e
wave function of the molecule in the excited state, U1e intcmnnular bonds assume
double-bond character and force the rings to become coplanar [74, 75). In this re-
spect. and its derivatives and related molecules may differ considerably from
polyth1ophene. In polythiophcne there is only one bond between the rings, in
PPV there arc three (the vinylcne linkage). It is the rotation barrier of the middle
the double bond, that imposes a rigid-rod character upon PPV. Upon cxcita-
bond order of this bond decreases and one Can expect signiticant rota-
honal around this bond, i.e., a much more fl exible molecule (U1c mecha-
underlying _cis-trans isomelization). We suggest that this floppy
11
ess plays a
role Ill the competition between radiative and non-radiative decay.
Hence, 11 would be worthwhile to investigate, at a sufficiently accumtc level of
theory or computation, differences in steric interacti on and in bond order asso-
wi th a different position or the cyano group at the vinylene linkage, for the
cxc1lcd slate.
16.3 OPVs in the Condensed State
16.3.1 Single Crystals
Several OPVs have been synthesized and electrically and optically characterized
142, 45, 76-79], but only very few crystall ographic studies have been carried out
to date 142, Our group recently reported the single-crystal X-ray data for
Ooct-OPV5 Ooct-OPV5-CN' 131], and Ooct-OPV5-CN" !32). Although all
synthesized have been obtained as crystalline solids, only the octyloxy-
substllutcd ones have been obtained, U1rough crystallization from solution as sin-
gle crystal s that were suitable for X-my crystallogmphic analysis. The crystallo-
graphic data arc compiled in Table 16-3.
of data on the organization in the solid stale has been pointed
out m l 6. 1.3. from their value in establishing structure-property
crystallographiC data on the molecular geometry should be the sl<trt -
mg pouu .1r quamum-chemical compul alions on oligomcrs and polymers 1 H3,
84). A coplanar <trrangcmcnt of phcnylcne and vinylene segments has sometimes
assumed lor (phenylene vinylenc)s I H4, H5 1 although the importance or the
dthCllral angles between these segments has been pointed out before 173).
578
.,;
>
0..
0
M
>
0..
9
16 A Model Oligomer Approach to Semicvnducting Polymers
-!:
ff 1ii: Iii:
z z
y y
g 8 8 g
0 . .
-a
s
N
I
II
<> 0.
.... ;:J
a.e
Vl ""
\0

\ti
I I
0 c'i
-i -i

C'i
-I
8 0
DO
"' ;:J
;:
0
z
"'
c:
0
16.1 OPVs in the Cv11dt:t1J"ed State
16.3.1.2 Crystal Structures of FiveRing OPVs
16.3.1.2.1 Ooct-OPVS
579
Ooct-OPV5 crystallizes into yellow needle-shaped crystals when crystall ized from
a THF/mcthanol mixture. The unit cell is monoclinic, space group nta, and con-
tains eight discrete molecules separated by nonm1l van dcr Waals distances (30J.
Figure 16- 16 shows that the conjugated backbones lie parallel to each other and
are li ned up into strings along the a-axis and separated along the c-axis by a layer
accommodati ng the aliphatic octyloxy side-chains. The molecules are contained in
layers pamllel to the (010) plane (intcrlayer distance bn=3.71 A); the molecules
are not n-stacked, where typically, molecules are at a distance of 3.3-3.4 A (861.
The octyloxy side-chains are not fully stretched in an all-trans configur.1tion, but
curved towards the periphery of the conjugated backbone. Strong disorder is
0 . b
Figure 16 16. Mulccular packing of Ooct-OPVS in the crystal latuce. Len: oblitjuc view of the unit
cell of Ooct-OPV5; right : projection of the unit L"CII on a plan.: perpendicular to the (l axis .
-
, ... _ .. <\-1
"J ';
;.,
l
Figure 16-17. Lcll : lrJiblllis,ion cl.:ctrun micrograph of mall single cry,tal s nf Ouct-OI'V5; scale
bw-: 5 111C arrows indicate the /l axis dir"<-'t:tiun. Right: electron di lrractiun path:m of the s.unc sin-
gle ery.tals. TIIC arrow indicate, the 613 :.pol (cry"al dimen.,ions :::::.Sx40
Philips
STEM CM 12 upcr.llcd at 120 1.. V, ln:.titut C1arlcs Sadrun, Stmshourg).
580 16 A Model Oligomer Approach to Semico11ducti11g Polymers
found in one of the two octyloxy tails, which prevents the exact localization of
the outermost carbon atoms of this tail.
Small needle-shaped single crystals were examined by transmission electron
microscopy (TEM) and electron diffraction (ED) (see Fig. 16- 17). The results
show that the crystals are elongated along the b-axis, which is the direction of
weak intermolecular TC- TC interactions, and have a well-developed (ab) top surlal:e.
It corresponds to the surface of aliphatic tails (direction of weak intermolecular in-
temctions). There are indications of displacement of successive (ttb)-layers along
the a-axis, in line with the other signs of disorder in the aliphatic layer.
16.3.1.2.2 Ooct-OPVS-CN'
Omnge plate-shaped crystals were obtained by crystallization from a chloroform/
11-hexane solvent mixture. The unit cell is triclinic, space group PT, containing
one discrete molecule, which has a crystallogmphically imposed center of inver-
sion [311. The molecule has a remarkable, wave-like shape (Sl-'C Fig. 16- 18). Such
distortions indicate the presence of considemblc packing forces. The dense pack-
ing (the crystal density of 1.210 g cm-
3
is I 0% higher than that of Ooct-OPV5)
may be driven both by side-chain armngcmcnt and by electrostatic intcmctions be-
tween the polar groups. Although the shortest interatomic distance between nl!ar-
est (a-axis) neighbors is ca. 3.5 A, one does not expect TC- TC interaction to occur
for these molecules, since the TC-systems are both laterally and axially disploced in
A
Figure 16-18. A: molecular packing of Ooct-
OPVS-CN' in the crystal I:Uticc (view al a
slight angle with l"eSJ'C'=I 10 lhc long molecular
axis). B: lop-view (lop) and side-view (bonum)
of lwo nearest-neighbor Ooct-OPVS-CN' mole-
cules in the crystal, 1-.:latcd by a translation
along the u-axis. Atom colors: light and dark
gray: carbon a10ms of the front and rear mole-
cule respectively; white: oxygen :noms; black:
nitrogen ahllllS. Atom decreases
with incrca!>ing dist;utce (rum (lOIOI O( obsava-
lion.
16.1 OPVs in the Coudeusecl State 58l
a view perpendicular to the plane of the central ring. l11e aromatic systems face
the octyloxy substituents of Lhe neighbor molecules. The conformation around the
double bond that bears the t;yano group is different from that found in other OPV
crystals studied so far. The introdut;tion of the cyano group has caused an almost
180'' rotation around the single bond to the central ring and results in the molecu-
lar backbone and octyloxy tail being in close proximity.
16.3.1.2.3 Ooct-OPVS-CN"
Omnge-red crystals of Ooct-OPV5-CN" were obtained from a chloroform/n-hex-
ane mixture. l11is compound, which has its c1ano substituents at the outer posi-
tion of the central vinylcne linkages, has a PI crystal packing which is very dif-
ferl!nt from that of Ooct-OPV5-CN' J32J. As Figure 16- 19 ill ustn.ttes, nearest-
neighbor (a-axis related) molecules exhibi t only an axial <.lisplaccmcnt of approxi-
mately half a phcnylcnc vinylcnc unit. In a view perpendicular to the centrJI ring,
the aromatic systems overlap to a large extent. Since the dis1ance between the
conjugated backbones is approximatdy 3.5 A. significant TC-TC interactions be-
tween neighboring molecules arc to be expected (TC-stacking). The configumtion
of the vinylenc linkages is such that the molecule assumes an S-type shape in the
plane of the aromatic backbone. The octyloxy chains are extended in this plane,
nearly pcrpcndkular to the molecular axis. Overall then, the whole molecule
looks rat her plat. tr.
A
B
..... T!lf'\ Hll q lJ' ""- " '
: l5A
\"'r4UJ I , 1 ',>1r 1 \o \ ..... ... 1
16-19. A: n-stackcd arr.1ngcmcn1 of
OoctOPVS-CN" molecules in the lat-
llcc (view at a slight >Jnglc with lu
the lung nmlccular axis). 13: lop-view (lup)
anti sitlc-vicw (bunom) uf two ncmest-ncigh-
bur OuciOPVS-CN" molecules in the
tal . related by a translation the -axis.
The distaucc of 3.5 A to thc
shoneM diManu: between lwu on dif-
ferent mokculcs (s..-c 1-'ig. 16- l ll for detaib) .
582 16 A Model Oligomer Approach to Semiconducting Polymers
16.3.1.3 Crystal Structures of Three-Ring OPVs
16.3.1.3.1 Ooct-OPV3
The structure of Ooct-OPV3 (see Fig. 16-20) is much simpler than lhat of Ooct-
OPV5. Each cell contains one centrosymmelric molecule. The backbones are very
planar, with dihednlls of less than 2, which makes the n-system of this molecule
the most planar among the OPVs studied so far. The backbones are shifted along
lheir long axis such that vinyl groups are above phenyl groups and vice versa;
there is also a slight lateml shift. 1l1e separation between the aromatic planes is
large, however, with a shortest C-C distance of 7.3 A, and the space between
these planes is tilled by the aliphatic tails of neighbor molecules. One docs there-
fore not expect any n-interactions.
16.3.1.3.2 Omc-OPV3
This cell is very di fferent from that of Ooct-OPV3 and contains lour symmetry-re-
lated molecules. Due to the shorter substituents, the density is much higher. De-
spite this, there is no n-slacki ng (sec Fig. 16-21 ). The successive n-systems within
one, non-centrosymmetric molecule are arranged in a helical fashion because the
dihedral angles all have the same sign.
powder data, Yang et ul. [421 arrive at a similar but less dense (1.218 g
em- ) cell for this compound.
Figure 16-20. Molecular p-.u:king of Oo.:t-OPVJ . Four arc shown, view<.-d nearly along the
long molecular (lcfl) and perpendicular lo thai OIXis (righl).
g:

.L. 2;t
Figure 16-21. Molc.:.:ular packing nf Omc-OPVJ. Till! four molecules thai make up one unil cell arc
shown, viewed al a angle wllh rcspccl 10 the long molc.:ular (lcll) aml perpendicular to the
pl:mc of the ccnlr:tl ring (right).
/6.3 OPVs in the Cunclensecl State 583
16.3.1.3.3 Ooct-OPV3-CN'
The two molecules in this cell are symmetry-related and centrosymmetric, and
have a very non-planar confom1ation because the dihedml angle between the cen-
tml ring and the cyano-carrying vinylencs is aJmost 40". Of lhe octyloxy-cyano
compounds considered, this cell has the lowest density. The nearest-neighbor dis-
tances are large and space in between backbones is filled by the tai ls. There are
no n-stacks (sec Fig. 16-22). The molecular armngement is entirely different from
lhat in the cell of the five-ring homologue, Ooct-OPY5-CN'.
16.3.1.3.4 Ooct-OPV3-CN"
In the cell, this molecule is much more planar than Ooct-OPV3-CN'; the tilt angle
between lhe rings is 8. The packing in the triclinic unit cell (see Fig. 16-23)
closely resembles that of the related live-ring compound (Sec-
tion 16.3. 1.2.3). The alkoxy chains extend out as far as possible, and the n-conju-
gatcd hackbones arc stacked on top of each olhcr a.<> densely as is compatible
with this. Phenyl rings o}' one molecule face vi nyl moieties of neighbors, at <l dis-
tance just below 3.35 A, implying considemble n-intcmction. 1l1c stacking is
l' igurc: t 6-22. Mok-.:ular packing of Ooci-
OI'VJ-CN' . The octyloxy
r.tlc the non-planar n-syslems.
Figure 16-23. n-Stac.:king uf a-axis neigh-
bors in lhc crystal lallicc or Ooci-01'V3-
CN'".
584 16 A Model Oligomer Approach to SemicondtiCiing Polymers
tighter than in the analogous OPV, which is reflected in an almost equal
value of the cell density (1.17 g em- ), in spite of a lower aromatic content Re-
markably, the cyano group is virtually in the plane of the central ring; packing
forces have overcome the forces of steric hindrance between cyano group and
ring hydrogen.
16.3.1.3.5 Oct-OPV3
The asymmetric unit in the triclinic cell consists of two half molecules. The aro-
matic systems of the two molecules in one cell are almost to each
other (see Fig. 16-24). Because of the small value of a, 4.8 A, the two molecules
of neighboring cells that are related by this translation are quite close lO each
other. A view perpendicular to the rings shows, however, that the n-systems do
not have overlap in projection. Each molecule shows dihedral angles of ca. 12";
these have opposite sign on both sides of the vinykne linkages, resulting in paral-
lel phenyl(cnc) rings within a molecule. The first C-C bond in the alkyl tail is in
a plane perpendicular to the central ring.
16.3.1.3.6 Oct-OPV3-CN"
As explained in Section 16.2.2.1.1, the steric requirements of an octyl substituent
are more stringent than those of the octyloxy group. We succeeded in synthesiz-
ing the octyl compound with cyano groups at the outer positions on the vinylene
linkages, but not the one with the cyano groups on the inner positions (oct-
OPV3-CN').
For oct-OPV3-CN", the single crystals obtained were rather defective and the
structure has been relatively poorly resolved. The asymmetric unit is one and a
half molecules. By the symmetry of the space group, P2
1
/a, this gives 6 mole-
cules per cell, of which two have a center of inversion. Table 16-3 shows that the
pattern of dihedml angles is irregular. The molecules are arr.:mged in two groups
of stacks with almost perpendicular orientation of the long axes. Within each
stack, phenyl rings are above vinyl units and the interatomic distances arc below
3.5 A at some places, in spite of the rather non-planar backbone (see Fig. 16-25).
Figure 16-24. Molecular packing of
oc1-0PVJ. Tite 1wo molecules 1ha1
make Ul> one unil cell have nearly pc,...
pcmlicular
16.1 OPVs 111 the Condensed State 585
Figure 16-25. Molecular packing of oci-
OPV3-CN". Tile six molecules shown rc-
J>rcscnl lhc con1en1s of one unil .:ell.
16.3.1.4 Optical Propc1tics of Single Crystals
For the three octyloxy-substilutcd five-ring oligomer.;, the normalized photolumi-
nescence spectra of the single crystals are depicted in Figure 16-26. Due to the
large absorption coetlicienl (more than 10
5
em- at the maximum) we were not
able to measure the absorption spectra of the relatively thick (20-30 pm) single
crystals (see Table 16-5 in Section 16.3.3.3.1).
For Ooct-OPV5 and Ooct-OPV5-CN' , the PL spectra show vibmtional structure
characteristic of single-molecule luminescence. In addition, the PL lifetimes for
the single crystals, 1.0 and 2.2 ns respectively, arc typical values for small organic
dyes. For both oligomers, no significant n-n interactions were expected on the ba-
sis of the molecular packing in the crystal structure. The observation of lumines-
cence originating from an intramolecular excitation agrees with these conclusions.
For Ooct-OPV5-CN", the molecular organization in the single crystal lattice is
such that n-n interactions between neighboring molecules are likely to occur (sec
Fig. 16-19). This is in line with the emission properties of the Ooct-OPV5-CN" sin-
gle crystals, which ditlcr significantly from those of the other two oligomers. The
luminescence spectrum is featureless and red-shifted in comparison to that of its iso-
mer Ooct-OPV5-CN'. Moreover, the PL lifetime (:::::8 ns) is significantly longer.
This behavior is similar to that reported for cyano-PPY films, which was attributed
to excimer luminescence originating from interchain excitations [7]. An excimer is a
pair of identical planar molecules in a cofacial arrangement, formed as a result or
auracti ve intemctions arising upon excitation of one of the molecules, which have
a repulsive (dosed-shell) interaction in the ground state. Typically, excimcr l(mna-
lion occurs when the aromatic planes or the molecules arc separated by 3-4 A pn,
In the excimer, there is n-orbital overlap between the molecules and a single
wave function describes the electronic state of the pair. The absence of vibronic fea-
tures is one of the characteristics of cxcimcr luminescence. Another is the long ra-
586
2.5
500
/6 A MO<Iel Oligomer Approuc:ll to Semic:mu/uctiug Polymers
1 2
Energy (eV)
2.0
3
1.5
to 20 30 40
Tme(ns)
600 700 800 900 1000
Wavelength (nm)
Figure 16-26. Normalil.Cll photoluminc:.cencc spcctr.t of ( I) Ooct-OPV5. (2) Ouct-OPV5-CN', and (3)
Ooct-OPV5-CN" single crystals. Inset: concsponding PL<.k=y curvt:s (semi log plot).
diative lifetime, caused by the symmetry-forbidden nature of the tmnsition. l n the
case of conjugated polymers, the excimer is thought to be formed by planar chain
segments of two or more polymer chains which are parallel to each other and scpa-
mted by a distance smaller than 4 A to allow n-orbital interaction.
16.3.2 Thermal Properties: Liquid-Crystalline Phases
The DSC them10gr..un of oct-OPV5 displays two endothermic peaks (fable 16-4).
The first peak, with a maximum at 167"C, corresponds to an enthalpy of forma-
tion of H6 kJ mol-
1
This peak represents a tmnsition from a crystalline to a liq-
uid-crystalline phase. The second peak is found at 194' C and correspom.ls to an
energy of fonuation of only 2. 1 kJ mor
1
, indicating the transition from the meso-
phase to the isotropic melt. Liquid-crystalline properties have also been observed
for side-chain-substituted PPV-homopolymcrs and have been attributed to the ri -
gid rod of the trcms-phcnylene-vinylenc backbone, which can act as a mesogenic
unit lg9j. l11e dialkoxy-substitutcd oligomers Ooct-OPV5 (sec Fig. 16-27, lcli)
and Ooct-OPV5-CN" show u similar thermal behavior. No liquid-crystalline be-
havior could be detected with DSC fur Ooct-OPV5-CN', but a cry still-to-crystal
phase transition occurs at 136 "C (sec Fig. 16-27, right), which is accompankd by
a change in the luminescence color from orange to yellow.
Under an optical microscope wi th crossed polarizcrs, the LC-fonning OPV5s
show isolatL-d llroplets and extended domains having the typical Schlieren texture
16.3 in the Cmuleusetl State
Table 164. DSC data for five-ring
Compound T,,) T, MI., l:J.Hc
("C) ("C) (kJ 100t
1
) (kJ mor')
u.:t-OPV5 t67. t94 t50. t92 !16.0. 2. t -64.6. -1.9
Ooct-OPV5 t!l3. 204 tn. 202 17.0. 0.98 - 55.3. -O.Il
Ooct-OPV5-CN' 136. 154 114 31.2. 60.5 -75.9
Ooct-OPV5-CN"b) 200.230 t86. 207 79.5. l.l9 -67.2, -0.9t
"> Fir..t heating
"> Firsa cnoothcnn at 118 C (28. I J.J mol- '). auribull'tl to sjtJc-c;h;Un niChing.
160 220 100 120 140 160
T (OC)
J.' igurc 16-27. DSC thennugram., uf Ooct-Of>V5 (left) and Ooct -OPV5-CN' (right). n.:cordcd on a Per-
kill Elmer 7 scrio thctmat aJkltysis system at heating and cooling rate.\ of tO C min"
1
.
f
s
0 10 20 30
2 0 (c:klgrees)
l'igurc 16-2H. Oll\:t-OPV5 111 it. pha-.: <II IIJ() C. Left : tpllcal m..:mgr.ph
(scale 511 lllll; phutnmi.;m,..,npc). Right : X-ray ( fl-2 (1 in u;msJlli'-
skm mode. CuKu ratliatinn. /. = 1.5-ttX A).
588 I 6 A Model Oligomer ApJirom:ll to Semiconducting Polymers
and a chamcteristic shear opalescence a nematic phase (see Fig. 16-28.
left) (90). An X-ray diffraction pauem from Ooct-OPY5, recorded at I90C, con-
finns that the observed mesophase is nematic (see Fig. 16-28. right). The X-my
profile shows a broad peak at low angle and a broad halo at wide angle. The peri-
odicity related to the low-angle peak is 16.8 A.
16.3.3 Thin Films
Thin fil ms of conjugated oligomers with well-defined chain length have recently
become of considerable interest for the preparation of, for example, field-effect
transistors 136-31:l j and light-emitting diodes (see Section 16.4). Fil ms prepared by
vacuum sublimation/deposition are generally highly crystal line due to their low
molecular weight and high purity. By controlling the processing conditions, such
as deposition rate and substrate temperature, the thin-fi lm morphology can be var-
ied and controlled. For exmnple. by raisi ng the substrate temperature to tempem-
tures just below the melting point of vacuum-deposited u-sexithiophene films. the
orientation of crystallites could be drastically enhanced, leading to improved tmns-
port prope11ies [9 1 ). In pri nciple, the order may result solely from self-organiza-
tion in the film as a result of h1vorable intermoll!cular intemctions in the case of
an inert substrate, or may be at least partially induced by intemctions wi th the
substrate surface in the case of an intemctive substmte 114, 33, 921.
Optical properties of thin fil ms of conjugated organics have also been found to
be strongly dependent on structuml features such as the coplanarity of the conju-
gated n-system. interchain distance of conjugated segments, and the macroscopic
orientation of conjugated segments [93]. Thin films of conjugated oligomers, for
which single-crystal structuml information is available, have the particular adv<m-
tage that this structuml information can be used for the interpretation of diffrac-
tion data of those films, thereby facilitating the determination of thin-fi lm struc-
ture and/or orientation.
In a recent paper, we have demonstrated that highly oriented thin films of oct-
OPV5 can be prepared by deposition onto highly preoriented polytetrafiuoroethyl-
ene (PTfE) substmtes [94). Annealing of the fi lms on PTfE for. 2 min at 120C
(below the crystal-liquid crystal phase tmnsition) results in a connected mosaic of
needle-like crystals in which the conjugated backbone of oct-OPY5 is aligned par-
allel to the chain axis of PTFE. The results are a clear demonslmtion of the epi-
taxial growth of the oligomer onto oriented PTFE. The alignment of the back-
bones gives rise to a strong dichroism in absorption, and to polarized light emis-
sion with a ratio of intensities of light polarized parallel and perpendicular of up
to 16. Similar results have been obtained for Ooct-OPV5 156).
In this section, the thin-fil m formation of OPVs is investigated with optical mi-
croscopy and X-ray diffr.tction (XRD). In the case of Ooct-OPY5. this has been
supplemented with surface imaging by means of atomic force microscopy. It is
demonstrated how an annealing treatment of the li lms after deposition innuences
/6.1 OPVs in tlte Condensed State 589
the polycry!>talline morphology and the orientation of the molecules. The intlu-
ence of di fferent substitution patterns on absorption and photoluminescence spec-
1m is discussed and differences between thin-ti lm spectra and dilute-sol ution spec-
1m arc discussed in tenns of molecular conformation anti packing. The application
of these films as a luminescent l<tycr in devices will be discussed in Section 16.4.
with particular <tllcntion to the influence of thin-film morphology on LED perfor-
mance and on stimul ated emission phenomena.
16.3.3.2 Thin-Film Structure
16.3.3.2.1 Ooct-OPVS
Optical Microscopy
fi lms on glass substrates were prepared by evaporation from a molybdenum boat
at 10 ...
6
mbar and at a just above the melti ng point of the oligomer.
The ti lm was dc1x>si ted at a rate of 2-4 A s-
1
. 1l1e as-ueposited layer showed a
fine-gmincd polycryswll ine structure when observed in the optical microscope.
Heating the films resulted in a morphological change. which was not reversible
upon cooling. This morphological change occuncd below the first melt ing point
of the oligomer and manifested itself in an increase in the crystall ine domai n size.
ln the case of Ooct-OPV5. annealing the film at 120"C caused an abrupt recrys-
talliZ<ttion resulting in an increase in the domain size from ca. 4 to 20 J.lm (see
Fig. 16<!9A.B). Crystalli zatiun of the film from the isotropic melt at 210 "C re-
sulted in the formation of domains wi th dimensions up to several mi ll imeters (see
Fig. 16-29C). One observes, after nucleation. a very rapid crystal growth in small
bundles running parallel to the substrate.
X-Ray Diffraction (XRD)
The XRD pattern of an annealed ti lm of Ooct-OPV5, recorded in retlection scom-
etry, shows a progression of peaks corresponding to a lallicc spaci ng of 16.05 A (see
Fig. 16-30. right). Based on the single-crystal data t30J (Section 16.3. 1.2. 1) and pre-
ferred growth along the b-axis, the pattern is assigned to a series of (002n) reflections
fup to (0018)). implying deposition with tl1e (ab)-plane onto the substrate. The XRD
Spl.'Cirum of the as-deposited tilm reveals only a few, broader reflections (see
f ig. 16-30. left). The XRD-pallems thus clearly indicate enhanced molecular orien-
tation a.-; a result of annealing. The narrowing of the diffmction peaks !Or the an-
nealed film as compared to the as-deposited film demonstrates the increase in crys-
tal domain size. in accordance with the morphological observation. The lauicc per-
iod changes upon annealing and is in each case smaller than that of the single crystal
(f6.34 A): fi lm as-deposited 14.9 A. annealed film 16.05 A. The existence of var-
ious ctystalline fo nns can be explained by the compressibi lity or the aliphatic layer
between the conjugated backbones. resulting in dcfonnabili ty of the uni t cell. The
molecular depicted in Figure 16-3 1 is proposed for the highly oriented
annealed film of Ooct-OPV5 on gl;l!)s.
590 16 A Model Oligomer Approach to Semi,ouclucting Polymas
Atomic Force Microscopy (AFM)
Figure 16-2!.1. l'\ll<uit.ctl-liglu
uf :1 thin ( :!00 nm) lihn
uf Uuct-OI'VS v:Kttttln ocpusih.:u
ulllu a /\: as-<l.:pos
itcll: U: lur S min at
1211 C; C: :e lkr enol
in!_! from th.: i'-4llmp11; 111ch at
2 111 C. Sc:Jic h;er; l(l() 11111.
Whereas XRD pauems of the thin crystalline fil ms provide information on the ori-
emmion and lauice distances perpendicul ar to the substmte, AFM proven to
be a powerful technique for obtaining structuml information of thin-li lm surfaces
of conjugated materials 1951. AFM imaging of the surface of a thi n ( 10 nm) ;m-
nc.tlcd film of Ooct-OJ>V5 conli mlcd the domain structure of the annealed Ooct-
1x10'
;:;.
u;
c
Ql
16.1 OPVs in the Condell.H'cl Sww
2x10'
;:;.
u;
c
Q)
591

--.--1 1_1--.-' ----i
0 20 40 60 0 20 40
20 (degrees) 21l (degrees)
Figure 16-.30 .XRI) uf a thin 1200 111111 lilm ur Otx:t-OI'VS. v:ecuunH.Icpositcu nn glass. Left:
right : annc:.kll li>r S 111in :at 120 C (1/-20 in rcllcdinn mutlc una
t..u hnrimntal thlrrJchmctcr. with Ni montx:hmm:Jtit.ctl CuKu radiation li.= I.S41X A); Rig:tku
RU:!OOB rutatiug:Jihldc at -10 t.. V. 40 m/\) .

I
E
I;
..
16-31. Schcll&<lllc
tiun 11f unc unit cell uf Ooct-OPVS
ull U g_la:ot..'
Figure t6-32. /\I'M tn-
txgaph (unlihcrctl image) uf a thin (Ill nm)
tiltn of Oax:t-()t>V5. ill I :w C li>r S
min (l':ort.. Sdcntili.: 1\FM.
10 11111 tulle anti triangut:u mi<.: mt:b-
ic:nctl Si .::mlll.:vcrs with iutq:r:atctl Ill>'>
t/..: IIKipm. k =O.J.l Nm
1
antlw,:. 71 t..ll.r.);
arnl>icnt cnvimnnk.'nl).
592 16 A Model Oligomer Approach to Semicmulucting Polymers
OPV5 layer. At the surface of the crystall ites, terraces with step heights of
151 A were observed, which is consistent with the interlayer spacing determined
from XRD patterns. At higher magnification, the surface displays striations (see
Fig. 16-32). The periodicity of the pattern is 181 A, which corresponds to the
periodici ty of aliphatic chain ends (or: of tcrn1inal phenyl rings) along the a-axis
of the monoclinic unit cell and is thus consistent with deposition of the microcrys-
tals with the (ab)-plane in contact with the surface. The surface structure obtained
with AFM supports the thin-film structure (sec Fig. 16-3 1) proposed on the basis
of X-my data for film and single crystal. The molecular spacing along the b-axis,
3.77 A. could not be resolved with AFM.
16.3.3.2.2 Ooct-OPVS-CN'
1l1e XRD paucrn of an as-deposited fi lm of Ooct-OPV5-CN' indicates a poorly
crystall ine film; it shows a si ngle rel1ection peak of low intensity (sec Fig. 16-33).
Anneal ing of this film for I 0 min at I IU' C incrca.'i(!s the cryst<tllinity, as is dem-
onstmted by optical microscopy. n,e XRD pauern shows reflections at 4.7H'',
9.5H
0
, 14.40, 19.25". and 29.02. These rellcctions are assigned to be a progres-
sion of (00n) rcnections Jup to (006), wi th the absence of (005)1, corresponding
to a lattice periodicity of 18.4 A. The results thus indicate that upon annealing a
large degree of orientation is obtained, with a grem majority of crystals having
the (ab)-face par..t llel to the substrate, the Iauicc spaci ng being dose to the c-uxis
of the single-crystal structure (c= 18.426 A) 13 1 J. The low degree of crystall inity
in as-deposited fi lms of Ooct-OPV5-CN' compared to Ooct-OPV5 is likely to be
due to the large steric interaction barriers that have to be overcome in going from
the vapor phase to the ordered solid state.
16.3.3.2.3 Ooct-OPVS-CN"
For this compound, the diffracti on pattern (sec Fig. 16-34) indicates that the as-de-
posited film is considerably more crystalli ne than that of Ooct-OPV5-CN'. An-
nealing carried out at I60C for 5 mi n results in a polycrystallinc fi lm with im-
5x1o'
>-

c
Q)
c
0
3x10'.-------------,
10 20 30 10 20 30 40
20 (degrees) 26 (degrees)
Figur e t 6-33. XRO (11-2(} of a lhin (200 IIIII) film uf Ouo:t-OPV5-CN' on
Len: annealed a1 l wc fur Ill min.
3x10'
;::.
"iii
c
Q)

0 10 20 30
26 (degrees)
16.3 OPVs in the Contlellsetl Swte 593
I
j
10 20 30 ' 40
26 (degrees)
foigurc 16-34. XRD ({}-20 scan) of a thin (300 11111) li lm of Ooct-OPV5..CN" vacuum-deposited on
L.:lt: a).OCpositL"tt ; nght: ;mncalctl at Hill c for 5 min.
proved orOer. The li r.;t renection appears at 3.94. which corresponds to a
periodicity of 22.4 A. This value, however, is larger than any of the imerplanar
in the uni t cell of the single-crystal structure that was found earlier
(Secti on 16.3. 1.2.3 ). Apparentl y, unother polymorph of this compound has been
lo nncd.
16.3.3.2.4 Ood -OPV3
The as-deposi ted li lm is with domain size:, in the I 0 J.l lll mnge. In
such lilms, much larger domains can sometimes be found in a mi nor amount.
Electron diffraction has shown that these large gmins have a crystal structure that
corresponds to that of the si ngle crystal, whi le the small domains have a ditTercnt
structure. Annealing of the film leads to growth of the large domai ns; their size
may reach several mm (annealing carried out at T.u was found to be 107C
from DSC). Polarized optical microscopy shows that these domains arc actually
crystal aggregates, rather similar to spherulites (see Fig. 16-35). In agreement with
the above, XRD of an annealed ti hn produces strong reflecti ons that agree with
the si ngle-crystal data.
16.3.3.3 Optical Properties
16.3.3.3.1 Five-Ring OPVs
Figure 16-36 shows the absorption spectra of U1in films of four differently substi-
tuted five-ring OPVs. In contrast 10 the solution spectra, which show structureless
low-energy absorption bands, the absorption bands of the fil ms arc structured. ln
the solid slate, the molecules arc spatially constrai ned, whereas in solution diiTcrcnt
confonners exist, resulting in a distribution of accessible levels. As a consequence,
some details appear in the absorption spectrum of the li lms which can be attributed
to vibronic coupli ng, while. in di lute solution, the spectrum is a broud featureless
band. For oct-OPV5 and Ooct-OPV5 films. the absmvtion maxima arc red-shifted
over approximately 0. 1 c V rdati vc tu the solution (see Fig. 16- 12). 1l1e low-enci'JY
ubsorption band of a thin lilm of Ooct-OPV5-CN" displays an larger
594 16 A Model Oligomer Approach to Semicuucluctillg Polymers
l'ii!,UI"C 16-35. Polario\l!d-lighl npli<:al
mk:rogrnph., of lilnL' of O...:l-OPV3.
Ttl!l: hllllllHI:
fur 30 min al 70 C. &ak lxlr: 100

red-shift. It is expected that the increased steric interaction caused by the introduc-
tion of the cyano substituent will lead to a non-planar confomtation in dilute solu-
tion, wherl!aS X-ray data have shown that this molecule is very planar in
In gener.tl, the spectra of films to varying degrees, on the morphology
of the fi lms, and hence they change wi th annealing. The values in Table 16-5
should therefore be considered as approximate. The rather detailed absorption
spectrum of a li lm of Ooci-OPV5-CN' given in Figure 16-36 is an example: it
h<l'> been found to be of composi te! nature in which the low-enefgy pan origi nates
from the crystalline phase and the pa11 (above 3.0 cV) is ascribed 10
a disordered phase! (this pan resembles solution spectrum). 1l1e absorption
spectm confirm the low degree of crystallinity of as-deposited lilms of Ooct-
OPY5-CN' indicated by XRD, whereas films are highly cryswlline.
Shifts between the film photoluminescence S(X. 'Clra of the various oli gomers fol-
low the same trend as found for the solution spectra, but the lilm spectrum is
strongly red-shifted rel ative to the solution spccttu m in each case (Tables I 6-2
and 16-5 ). The photoluminescence spcclm arc strongly influenced by intermolecu-
16.3 OPVs in the Cuudeuse1 State 595
Table 16-5. Solid-slale abwrplion and emission dala for OPV5s.
Compound Sample n.._,
Ab,o.. " ""' '
}.l-t .. .. ,._, b)
l'L "''" ")
lyp.:" (IIIII) t.:V) (11111 ) (cV)
M: -'l 5.N. :iC!J
1.::!0
a.'
+t:! :!.1\1 ::!.34
:Ul 44:! :!.XI 5.W :!.311
M:
_ .. ,
560 :!.:!I
CN'
Out:l-OI'V5-
_ .. ,
6311 I.'J7
CN'" -161\ :!.65 (l(l'l :!.0-1
an -175 ::! .61 6 15
' l ..:: inj!lc .:r Y lal : :L': lilm :L'-.k:P"ilctl: :111: .uu..:akd li lm.
" 1 llnJcrlrnt:tl valu.:' tknntc lhc :rh,.>lulc m:.>.irna.
'l Shell b tlcli ll<-.1 1"-rc :L' lhc hdwccn /:""'" "'" ami /:,., . .,..,..
"1 1'1. tlclay were niCa,un,l .rl lh.: w:evd.:n!!lh >f the 1'1.
Shin c) </11"- rl'l.
1
.,) ri'L !
(cV) (liS) (ns)
- 0.5 1.()
O..t6 0.5 1.1
0.5() 0.7 1.7
(),4 2.2
().5 11 .0
ll.b I (),.j I.-I 7.0
0.5'J 0.6 3.-1 1\.11
, Nn .lh""llllllll ' (lC<tr:r ,nultt h.: IIICa.,un:\1 l<r lilt: ' "'l.!k .:rylal llC.:au,...- lhc nple.::e l dt:ll>lty lou
high.
300 400 500 600 700
Wavelength (nm)
Figure 16-36. absorption spcclr.t of
thin li hns of (a) ocl-OPV5, (b) Oot:l-OPV5.
(c) anJ (tl) 0.lCl-OPV5-CN".
Jar interactions that arc a consequence of the condensed slate of the material. We
will consider Ooct-OPV5-CN" in more detail.
The ab:.orption and emission s pel:lra anJ PL decay of Ooct-OPV5-CN'' in (AJ
solution, (B) as-deposi ted film, (C) annealed lilm, and (0) single crystal arc
shown in Figure 16-37. along wilh oplical micrographs of the a.-;-deposi tcJ and
mmcalcd Annealing an as-tkposited film at 160 C for 5 min results in the
formation of small cryst;LIIitcs, suggesting an enhanced molecular ori-
entation and an increase in 1he crystall ine fraction upon annealing, in agreement
with lhe XRD (sec Fig. 16-3-l).
In the absorption spectra of the thin lilms. the low-energy shoulder is rc.:o-
shifted and slighlly mo11! pronounce&.! for the annealed film. 1111.: emission spcclr.t
596 16 A Model Oligomer Approach 10 Semiconducting Polymers
Energy(eV) Energy(eV)
4.0 3.5 ao 2.5 2.0 2.4 2.2 2.0 1.8 u
A BCD
.,

u .. ..
c c c
..

..
-e
.6
0
.!:
.. .J .J
)
Q. Q.
<
300
-
500 600 700 500 800 100 800 0 10 20 30 40
Wavelength (nm) Wavelenglh (om) Tome(ns)
IC>-37. Tua> nonu;oli/.ct.l ;ohsurplinn (lcfll aml (middle) an<l 1'1.-<lccay curves
(right) ur O<x:lOI'V5..CN .. in (A) sululiuu, (U) as..Jcpuo.ilell lilm, (C) annealed li hu ( lh() C. 5 min),
ami (D) single cryslal. Bonom: polarizcdlight onicrosmphs of the two lhinfilm morphologies; s.:ale
bar: 100
of the films are intermediate between the single-molecule luminescence in solu-
tion and the excimer luminescence associated with the crystal lattice (Sec-
tion 16.3. 1.4). Apparently, for the as-deposited and annealed films there are contri-
butions from both a disordered and an ordered (crystalline) morphology. The PL
spectrum of the as-deposited film (B) shows vibrational features, common for sin-
gle-molecule luminescence, indicating that the contribution from the disordered
fraction is dominant. For the annealed film (C), a broad and featureless composite
spectrum is observed, due to a larger contribution from the crystalline fraction.
The disorder-to-order transition is also clearly reflected in the time-resolved PL
decay curves. For Ooct-OPVS-CN" in solution and the single crystal, single-ex-
ponential decay curves are observed coJTesponding to PL lifetimes of 1.4 and
8 ns, respectively. They are representing the two extremes: single-molecule and
excimer luminescence. The PL decay curves for the a-;-deposited and annealed
films show double-exponential dependencies with lifetimes of 1.4n.o ns (r
1
1T
2
)
and 3.4/8.0 ns, respectively. The contribution of the decay associated with sin-
gle-molecule decreases upon annealing, which is in agreement with
the observed increase in the crystalline fraction.
16.3 OPVs in rile Condensed Stare 591
For one of our cyano-substituted copolymers (see Fig. 16-15), we have found
similar behavior as displayed by the Ooct-OPV5-CN" films: an appreciable red-
shift of the absorption (0. 13 eV) and luminescence (0.20 eV) spectra of the solid
state relative to the solution, a broad and featureless luminescence spectrum, and
a relatively long PL lifetime (2.6 ns) in comparison to related copolymers investi-
gated. This lifetime is still short in comparison to 5.6 ns reported for cyano-PPV
(7]. Possible reasons for the difference in PL lifetime could be the intermolecular
distance or displacement (the axial register is likely to have a strong influence in
the case of the copolymer), which together determine the magnitude of 1r-9rbital
overlap, or the degree of symmetry of the ensemble of interacting chain segments,
which also affects the emission probability. For instance, the symmetry will be
lower if the chain segments are not par..tllel to each other but slightly inclined. In
spite of this difference, we suggest that, also in the caSe of the copolymer, the mo-
lecular packing gives rise to luminescent interchain excitations.
1().3.3.3.2 Ooct-0l'V3
In the case of Ooct-OPVJ. an annealing leads to a blue shift in ahsmv-
tion (very broad spectra. Fig. a:- well as in photoluminescence (from 4R I
to 460 mn, 0.12 e V. al'tcr 30 min <II 70 C). These spectm will he of a composite
nature. :-.ince optical micmscopy indicated that there arc two types of domains in
the a.s-dcpositcd rilm. that anne;1ling favors the growth of the type whid1 has
the structure or the single t:ryswl. Since there is no 7l-:o.I<Kking in the
:-.truclurl!. although moln:ul;ar n-syskm is planar Fig. 16-:20. Tallie 16-3).
the spectral :-.hift :-.ugg,c:-.ls thai n- n overlap may he significant in the smaller
lallites of the <ls-dcp,lsiiLd lilm. ThL 1'1 . decay in ;umcakd films nnTL'sjhlnds to
that of the single crystal, which is in line with the previous results, and has a ra-
diative lifetime of 1.7 ns, while this is 0.8 ns for the as-deposited film.
Q)
u
c
<ll
..0
0
(j)
..0
4:
4.0
300
Energy (eV)
3.5 3.0 2.5
-.... _ ....
-.
400 500
Wavelength (nm)
600
J<igure IC>-31!. Nurmali:t.cd ;obsurJlliuu (lhiu
lines) and phuluhuuiolC....:cucc (heavy lines)
spcclr;o oi OociOPVJ film,
(--) ;uoll ;umcalcll (-- - ).
598 16 A Model Oligomer Approach to Semiconducting Polymerx
16.4 Light Emission Applications of OPVs
16.4.1 Introduction
Electroluminescence (EL) and stimulated emission have been extensively investi-
gated for PPV and its derivatives (for a recent review sec [96, 97J). A whole r.mge
of polymeric LEOs, emitting over the whole visible spectrum from blue to red, has
been reported 198- 101]. LED performance was greatly improved by the addition of
charge-tmnsport layers, which effectively balance the injection and transport of op-
posite charges and move the electron-hole recombination zone away from the metal
cathode [ 102]. For commercial viability, the long-tem1 device stability still needs to
be improved, especially for polymers emiuing in the blue.
The amplification of light and spectral narrowing under pulsed optical excita-
tion, using conjugated polymers as active medium, has been demonstrated in solu-
tion L60. 103], dilute blends 1104], and neat thin lilms [64, 105-1081. TI1e two
proposed photophysical processes responsible for the observed laser-like phenom-
enon in photopumped neat films without external feedback system are Amplitied
Spontaneous Emission (ASE) (64, 1091 and supertluorescence (SF) [ 107, II OJ.
The observation of stimulated emission from photopumpcd neat lilms shows that
singlet inlrachain cxcitons can be generated with high yields in the condensed
phase. Since it is well-established that clcctroluminesccncc from polymer LEOs
originates from excited states identical to those created by photocxcitation. this
suggests the possibility of an electrically pumped polymer laser. An imp011ant
question to be answered is whether or not it is possible to obtain electrically in-
duced net gain. Based on the lasing threshold under optical excitation, it is esti-
mated LI051that current densities in excess of 10.1 A cm-
2
are needed to establish
net gain in devices, which is substantially higher than currently achieved in
polymer LEOs. The low current in polymer c.-;pccially for elec-
tron transport, arc the of the low charge can-ier mobilities, high trap densi-
ties, and poor charge injection in conjugated polymers. However, clectrolumines-
cencc of a 3 nm thick PPV film by tunneling injection from a scanning tunneling
microscope tip, with cunent densities of the order of 10
4
A cm-
2
, has been re-
cently reported ( Ill ).
Ordered conjugated organic materials exhibit low trap densities and high
charge canier mobilities, for both electrons and holes. As an example, in single
crystals of anthracene {87], the hole and electron mobilities are approximately
I cm
2
v-
1
s-
1
and the crystal photoluminescence quantum yield at room tempem-
ture is almost unity. Both [87] and stimulated emission ( 1121
have been demonstrated in anthracene single Hence, single crystals of
OPVs are potentially interesting for electrically driven devices. For practical appli-
cations in devices, however, single crystals are not convenient. As an ahemativc,
thin films having the desired geometry can be prepared by vacuum deposition
from the vapor phase 178, 113- 1161. The Jrawback is that the optical quality of
polycryswllinc lilms may be rather poor due to SCiiHCring from gmin boundaries,
16.-1 Light Emission of OPVs 599
which particularly lor laser [117]. Additionally,
grain boundaries also have a negative impact on the electrical properties of such
films.
This describes the usc of oligomer films as active media and demon-
the imp011ancc of the film morphology to both the electrical and the opti-
cal properties. This a factor which has hardly received <Illy auention until now.
but one which certainly deserves for polymers as well. The crucial
importance of the microstructure is equally demonstrated by studies of the photo-
voltaic effect [ 1181; this topic will not be dealt with here.
16.4.2 Light-Emitting Diodes
lll.4.2.1 Single-Layer Devices
Light-cmiuing diodes were realized in a standard conliguration ITO/OPYS/AI. Thin
films of0PV5 were deposited onto an ITO (indium-tin oxide) electrode on glass, by
vacuum sublimation from a molybdenum boat at a deposition rate of 2-4 A s-
1
. The
ITO-covered glass slides had been cleaned using a procedure based on rinsing in de-
ionized water and ultrasonic rinsing in polar. and non-polar organic solvent-;. The
thin layers showed similar lll01])hologics in the optical microscope as layers depos-
ited onto glass suhstmtcs. The cathode consisted or a I 00 nm aluminum layer depos-
ited direclly onto the organic layer al a pressure of 2-10-e> mbar. The cathode wa.o;
deRQsitcd through a shadow mask to produce diodes with active areas of 7 I o-
2
cm
1
. Clear light emission could be visually observed over the whole activt: area
of the device.
The electrical properties and efficiencies of the single-layer devices arc summa-
rized in Table 16-6. The cflicicncy values arc significantly higher than lllOSC or
single-layer LEOs prepared from suhsliluled olignthiophcncs and arc comparable
to LED cllicicncics for PPY-hascd polymers. The minimum thickness or 1he ac-
tive layer must he amund 150 nm or more to ohlain repnK.Iuciblc dilxle ch;tr;ll;tcr-
istics. Thinner devices all sullercd from sh011 circuits anti non-unitonn light emis-
over the active area of the diodes. 1l1e current-voltage characteristics tor a
single-layer configuration arc shown in Figure 16-39. The arrows indicate the
electric lield strength at which light emission became detectable. All ITO/OPY5/
AI diodes showed rectifying behavior and we were not able to observe electrolu-
minescence in reverse bias li.lr any of these devices.
Electrical measurements on devices with different layer thickne.-;s have shown
that the diode curTcnl depends on the applied field rather than the drive voltage.
This is similar to what has been observed with our altcrn;lling PPV copolymers
[6gl - II indicates thai field-driven injection detcnnines the electrical char.tctcris-
tics. From Figure 16-39 it is evident that u-OPVS has the lowest onset for both
current and emission. By ml!ans of Fowkr-Nordheim analysis of the /-V-charac-
tcristics and optical absorption measurements, we estimated the injection barrier
fix holes

and the HOMO-LUMO gap, respectively [ 1191. 1l1c results of

this arc given in 16-7. The diiTcrcnl' C between the onsets or cu1Ten1
600 /6 A Model Oligomer Approach to Semiconducting Polymers
Table 16-6. properties and efficiencies of single-layer and double-layer OPV5-LEDs with
ITO hole-injecting contacts in operation.
Compound Film Cat.htxlc Film v ............ <) 11UU ....JR External
lh ickness ') (V) (10" V m
1
) eOiciency
(nm) oo-
2
%J
u-OPV5 :IS AI 380 18. 1 0.5 1.1
Ooct.QPV5 as AI 193 24.4 1.3 0. 1
an AI 20.4 1.1 1.2
:IS Ca 183 11.8 0.6 10.0
Ooct.OPV5-CN" as AI 150 20 1.3 1.5
Ooct-OPV5/ as AI 150145 8.7 0.5 3 1
Ooct-OPV5-CN"
Q) a.: as-dei)()Si tcd; an: annealed.
b Film thicknes. measured with" 3 130 surface (lf'olllcr.
c) Tum-oo is defined here as the point at which the cnussion is dctcctahlc. Current-volt:tgc (/- V) and
luminance-voltage CL- V) nlCasurcmcnts wen: pcrfot1ncd in a nitmgen atmosphere glove box 10 avoid
exposure to ambient oxygen itnd water. / -V of the wa.' pcrfom1CU with a
Keithley 236 SMU operating in pulsed mude Ill ntinimiL.C heating uf the device. L-V characteristics
and cxtcmat tjUalllum cllicicncics (phomn/clcctrun) were measured with the device moumed on an in-
tcgr.tling sphere. Light were with :1 c:tlibrat<.xl photudiude. using the Keithley
236 SMU and a Stanford Research SR 400 phutun-counJing device.
10

1
E
0 8
<
...
1
I
0
::::.s

1 (ij
c
1
G) 4
"0
1
c:
2
J
:::l
11
()

0.0 0.5 1.0 1.5 2.0 2.5 3.0
Field (10
8
V m-
1
)
Figure 16-39. Electrical characteristics of the ITOIOPV5/AI devices: u-OPV5 (.&.), Ooct-OPV5 (Q ),
and Ooct-OPV5-CN"' <> The arrows indicate the onset of light emission.
and light for u-OPV5 and Ooct-OPV5 is significant and contradicts the energy
otfsets in Table 16-7. The /- V-<:haracteristics are determined by the majority car-
riers in these devices, which are holes. On the basis of the similar hole-injection
barrier for both OPVs, one would expect approximately the same electrical char-
acteristics. However, the onset for light emission for u-OPV5 appears at half the
16.4 Light Emi.Hicm A[1p/icaticms of OPVs 601
Table 16-7. Estimated HOMO-LUMO gaps and hole injection barriers.
Compound
u.QJ>V5
Ooct-OPV5
Ooct-OPV5-CN"
") Optical <lbsorption mcasurcmcnL,.
") Fowler-Nordheim
HOMO-LUMO gap'')
(cV)
2.7
2.4
2. 1
0.2
0.2
0.4
electric lield strength found for Ooct-OPV5. Moreover, the barrier for electron in-
j l!ction is approximately 0.3 eV higher for u-OPV5. An explanation for this dis-
crepancy may be that the charge carrier (holes and electrons) mobilities are much
higher in the case of u-OPV5, resulting in a higher injection rate of charge car-
riers 11201. The higher mobility might be anticipated because of the absence of
side-chains on this molecule, and the resulting closer packing of the n-systems in
the solid. (Recent crystal duta 11211 reveal a herringbone-type arrangement.)
When the clcctricul characteristics of Ooct-OPV5 ami Ooct-OPV5-CN" are
compared, it is found that the onset of current appears at higher dri ve field in the
case of Ooct-OPV5-CN". This is consistent wi th the value found for the hole in-
jection barrier, which is 0.2 eV J,uger. However, the onset of emission appears at
the same field as for Ooct-OPV5, which rctlects the lowering of the LUMO level
due to the presence of cyano groups (LUMO of Ooct-OPV5-CN" li es approxi-
mately 0.5 eV below that of Ooct-OPV5). This results in a better balance between
electron and hole currents and hence a more efficient luminescence for the Ooct-
OPV5-CN" device.
To optimize the performance of single-layer Ooct-OPV5 devices, Ca instead of
AI was used as the cathode, which lowers the injection barrier for electrons with
approximately 1.3 eV. The change of cathode resulted in a more than twofold re-
2.5
Energy (eV)
2.0
..
.
.
.
.
.
.
.
.
.
.
'
'-
500 600 700
Wavelength (nm)
1.5
--
BOO
1(,441. Nnrmali:t.c.J clc.:trolumincsccnce
'pcclt';o of the JTOIOI'V5/AI Jcvices: u-OJ>V5
(- ), Oot:t-OPV5 ( ), and Oot:t-OJ>V5-
CN" (- - - J.
602 /6 A Model Oligomer Appro(ICh ro Semiconducring Polymers
duction of the drive field at tum-on (610
7
V m-
1
) and two orders of magnitude
enhancement in EL efficiency (0.1 %), due to improved electron injection.
The electroluminescence spectra of the single-layer devices are depicted in Fig-
ure 16-40. For all these OPVSs, EL spectra coincided with the solid-state photolu-
minescence spectra. indicating that the same excited states are involved in both
PL and EL. The broad luminescence spectrum for Ooct-OPVS-CN" is attributed
to excimer emission (Section 16.3.1.4).
16.4.2.2 Influence of Morphology on Device Performance
The influence of the thin-film morphology on the device perfommnce was investi-
gated for Ooct-OPVS by means of annealing (as described in Section 16.3.3.2.1).
For Ooct-OPVS, annealing leads to an increase in the single-crystal domain size
and an enhanced molecular orientation. The external efficiency of an annealed
LED 1.2 10-
2
% one order of magn_itude higher
that of a pnstme LED (0.1 10 -%) (msct F1g. 16-41 ). Anncahng ol Ooct-OPVS him
was found to resull in a 20% increase in the photoluminescence quantum yield as
measured under laser illumination in an integrating sphere. This 20% rise in PL ef-
ficiency alone cannot an:ount for the increase in EL cflicicncy. Figure 16-41 shows
that the cell current hardly changes UfX>n annealing. Since the majority charge car-
riers in these devices arc holes, we conclude that the hole current is the same for
both morphologies. Fowler-Nordheim analysis of the /- \.'-characteristics revealed
that the barrier lor hole injection is the same for both morphologies, and from the
similar absorption spectra for both we can conclude that the HOMO-LUMO gap
does not change upon annealing.
The electron current in such devices is much smaller than, and fully masked
by, the current of the majority carriers. For this rea. .. on, AI/Ooct-OPVS/Ca devices

txto' txto
Field (V m-')
I<'IJ;UI'C 16-4L Ek-clricat char.scleristi<:s fur siogle-layer IT0/0tx:J-(>I'V5/AI devices with ao as-t.lcpos-
ilctl (0) or ;mncaled (120 .. C, 5 min; e> active layer. lnM:I: luminance as a funclioo vf cdl current fur
built thin-lihn
/6.4 Lighr Emission Applicarious of OPVs 603
were prepared, which can be considered as electron-only devices. In annealed
electron-only devices, the current was approximately one order of magnitude high-
er. Hence, the increase in efticiency upon annealing is attributed to an increase in
electron mobility. 1l1e improvement of molecular orientation and the reduction of
the density of grain boundaries upon annealing may be considered as possible ex-
planations for the electron mobility. Other groups have reported that
amorphous films display higher EL efliciency than crystalline films [78, 79]. Our
system is different. however. as we compare two crystalline morphologies having
different molecular orientation and crystal size. An increase in crystallite size is
accompanied by an increase in EL efficiency. The influence of the oligomer-metal
interface on the electron-drift mobility could be important as well.
16.4.2.3 Double-Layer Dcvic<.'S
So far, we did not in using Ooct-OPV5-CN' as the active luminescent
layer. Nevet1heless, the compound can be used to enhance the performance of
LEOs. For a multilayer device (IT0/0oct-OPV5 (I SO nm)/Ooct-OPVS-CN'
(ISO nm)IAI). efliciencics of up to 0. 1% have been auained, a IS-fold increase
with respect to an as-prepared Ooct-OPV5 devi..;c. The operating currents <Ire an
order of magnitude lower lor such a multilayer indicating that the Ooct-
OPVS-CN' layer results in a more balanced charge mmsport, similar to what has
been found lor multilayer devices prepared with cyano-substituted PPVs 161.
..-.. 10-3
'l'
E
0

1o
(/)
c
Q)
-o
c
105
L..
:::J
0
Field (10
8
V m-
1
)
0.3 0.6 0.9
"'-
..
.. 1
- c
" ..
---
Energy(eV)
2.0
1.2
r/
- -'
-r
r.: 1 w
500 000 700 1)00
10
1
..-..
N
I
10 E
-o

Q)
101 g
ct!
c
E
102 ..3
Wavelenglh (nm)

0 5 10 15 20 25
Bias (V)
Figure 16-12. Scmilog plm of current dcn,ily <e> and lumin111c:c (0) of ao ITO/OoctOPV5
(150 nm)f0uci-OPV5-CN" (45 om){ AI double-layer device a func1ioo of bias voltage. Inset: dou
ble-laycr clectrolumines.:encc spc..,:tnnn.
604 16 A Model Oligomer Approach to Semiconducting Polymers
It was expected that further improvement of the EL quantum efficiency could
be achieved by the fabrication of multi layer devices in the configuration metal/
Ooct-OPV5/0oct-OPV5-CN"/metal, since Ooct-OPV5-CN" has a higher photolu-
minescence efficiency than Ooct-OPV5-CN' (Section 16.3.3.3. 1 ). In such double-
layer devices, Ooct-OPV5 is the hole-transport layer and Ooct-OPV5-CN"
tions as the electron-transport/emissive layer to balance charge tmnsport and InJec-
tion. The characteristics of the devices prepared are summarized in Table 16-6
and depicted in Figure 16-42. The voltal}e at EL was was also
significantly reduced to 8.7 Volt (4.510 V m ). External effic1enc1es of up 10
0.3 1% were attained in an ITO/Ooct-OPV5 (150 nm)/Ooct-OPV5-CN" (45 nm)l
AI device, which corresponds to an internal effiCiency of 1.5%, a more than
one order of magnitude enhancement of the efficiency in comparison to single-
layer Ooct-OPV5-CN" devices. Despite the high EL efficiency only low current
levels were read1cd before critkal device failure, which resullcd in a maximum
brightness of only 30 cd m-
2
Orange-red emission was observed above tum-on
in the double-layer device, indicating thai Ooct-OPV5-CN" is the emissive spe-
cies in the device. However, the elcclroluminescencc spedrum (inscl Fig. 16-42)
revealed that there is a small contrihution of EL emission originating from Ooct-
OPV5 (see an-ow in the inset).
16.4.3 Stimulatl'<l Emission
16.4.3.1 Single Crystals
We have measured, in an intcgmting sphere, light emission spectra from single
crystals and thin films of our oligomers under intense optical excitation with the
third harmonic of a nanosecond Nd:YAG laser (A.=355 nm) [117). Emission spec-
tra of single crystals of Ooct-OPV3 and Ooct-OPV5 (thickness 30 Jlm), at low
and high excitation energies, are shown in Figure 16-43.
At low excitation energy, only the ordinary broad photoluminescence spectrum
is observed. Above a well-defined excitation energy threshold, which depends on
the size of the illumination spot, a sharp emission peak centered near the photolu-
minescence maximum and surrounded by broad luminescence tails appears. This
behavior can be auributed to li ght-induced net gain due to stimulated emission.
The higher the exci tation energy the more dominant the spcctmll y naJTOW emis-
sion becomes, with a relati ve suppression of the broad luminescence backgmund
(for Ooct-OPV5, /
54111111
//
1
.L. !iW ""' >100, peak width (FWHM) nm at
E.," =0.5 m]). The intense emission mainly emerges from the edge faces of the
crystal. The observed behavior is known for organic single crystals with high PL
quantum yield and was already rep011cd a long time ago for anthracene 11121.
There is a strong resemblance between Amplified Spontaneous Emission (ASE)
and true lasing and it is therefore sometimes difficult to distinguish one from the
other. In the cases described here, the observed spectral evolution could be as-
signed to ASE, but also to lasing with a positive feedback provided by light re-
flected from the crystal boundaries. The Iauer might suggest the presence of spec-
2.8
440
2.7
Energy (eV)
2 .6 2.5
460 480 !iOO
Wavelength (nm)
/6.4 Light Emission AJJp/ic(ltivns of OPVs 605
Energy (eV)
2.4
520 540 560 5lKl 600
Wavelength (nm)
Figure 16-43. Left emission spcclrd uf a or Oocl-OPV3. Excilalion energy: (a) 27 111.
(b) 0. 1 K mJ, (c) 1.0 mJ. Righi: cmissiun spcdra uf :1 single uf Oocl.()PV5. Excitaliun energy:
(a) 0.2 mJ o111d (h) 0.5 mJ.
tral modes within the nan-ow peak. However, mode structure was not observed in
any of our measurements. Since both ASE and ltL-; ing are based on stimulated
emission, the dilferencc is not very important in the context of the electrically
pumped organic laser. Moreover, because the distinction is not a key issue here.
we consider the gain phenomena observed in systems without external feedback
to be mirmr/ess lasing.
16.4.3.2 Vacuum-Dcpositw Films
For this study, thin films were deposited onto glass substrates. The as-deposited
films showed no spectral narrowing at any pump energy up to the damage thresh-
old. Stimulated emission was observed only in annealed films. The spot-to-spot
reproducibility of the measured was good, and we could measure
with excitation energies of up to 4 mJ ( 1.8 mm beam diameter) without visual
damage of the illuminated spot.
In Figures 16-44 aJld 16-45, the emission spectr.t of annealed thin films of
Ooct-OPV3 and Ooct-OPV5, respectivel y, are shown as a function of excitation
energy. For Ooct-OPV5, Figure 16-46 gives the integrated intensity and spectml
linewidth as a function of excitat ion energy. Above an energy threshold of ap-
proximately 1.6 mJ. a sharp emission peak appears with a bandwidth of nm
centered around 548 nm (0- 1 transi tion). The amplitude of the peak intensity
scales supcrlinearly with excitation energy. TI1is, together with the linear depen-
dence of the integrated intensity depicted in Figure 16-46, indicates thai there is
energy redistribution within the emiucd light and it is a signature of light-induced
nel gain due lo stimulated emission. TI1e shift in emission wavelengt h compared
lu the Ooct-OPV5 single crystal can be allrihuted to the dill'crencc in crystal pack-
ing (Section 16.3.3.2. 1), whid1 allers the emission propc11ies.
606
16 A Model Oligomer Approuclr 10 Semiconducting Polymers
Energy (eV)
2.8 2.7 2.6
e
440 480
Wavelength (nm)
Energy(eV)
2.4 2.3 2.2
520 540
WavetengUl (nm)
2.5
500

Figure 16-44. Emission spectra of a vacu-
thin (400 11m) lilm of Ooct-
OI'V3 afier annealing at 70C for 30 min.
Excitation energy: (a) 7.3 (b) 45 (c)
46 (d) 48 (c) 210 cxcitatioo
beam diameter 1.1! mm.
Energy (eV)
2.4 2.3 2.2 21
soo 540 600
Waveleoglh (nm)
'igurc 16-45. Emissioo spectra of a vacuum-dcposiuxl thin (300 nm) film of Ooct-OPVS ul'll:r anneal-
ing al J20C for 1 min. Lcfi: excibtion energy: (a) 0.9 ml, (b) 1.6 m.J, (c) 2.1 rn.J, (Ill 3. 1 J_U. (c)
3.9 ml; excitation beam diameter 1.8 mm. Right: excitation energy: (a) 6 (b) 180 cxcnalloo
beam diameter 30 IJm.
r-----------------------------,40
30I

:X:
20i!E
.s::.
6
10
c
:::::i
0
0
2 3 4
Excitalion energy (mJ)
ligurc 16-46. lmcgmtcd intensity of
< >. hroad ( 0 ), niiiTOw (I I), and
lincwidlh of total <e ) and narrow
(0 ) as a function of excita-
tioo energy for an annealed thin (300
nm) film of 0oct-0PV5: Cl'.Citatioo
bcmn dimncter :::: 1.8 111111.
16.4 Emissiou Applicutions of OPVs 007
Waveguiding inside the film is crucial: mirrorlcss lasing has not been observed
in annealed films of I 00 nm thickness, a thickness which is below the cut-off val-
ue for waveguiding in this asymmetric layered structure.
For the Ooct-OPV3 film, the energy threshold for gain narrowing is approxi-
mately 45 J.LI, while that for Ooct-OPV5 is much higher, 1.6 mJ . The latter value
corresponds to a threshold tluence of (:fJ mJ cm-
2
and is three orders of magni-
tude higher 1han that reported for polymer lilms [64, 105- 110), which
have values in the range of 10 f.d em- to a tew hundred J.LI cm-
2
. The
can be attributed to the polycrystall inc struct ure of the thin films. We conclude
that mirrorless lasing occurs only wi thin the individual crystalline domains. Scat-
tering at grain boundaries results in high optical losses, which prevents sufticient
net gain to be realized across muhiple domains. The amplification length is thus
restricted by lhc size of the crystalline domains. The domain size in as-deposited
lilms, below 10 is found to be too small to achieve observable gain at all. In
the case of the annealed film of Ooct-OPV5, the domain size is approximately
20 which is apparently suflicient for gain to be obtained. The domains of
Ooct-OPV3 arc much larger, in the order of I mm (sec Fig. 16-35), and the
threshold for gain narrowing is concomitantly lower. In these experiments, where
the domain size is smaller than the beam diameter (ca. 1.8 mm), the threshold in-
tensity varies inversely proportionally to the domain size. As a result of the broad
size distribution of the crystalli tes in the polycrystalline films, the luminescence
background observed at energies above the experimental threshold energy remains
much higher for these films than for single crystals.
Our interpretation was veri fied by experi ments in which a smaller area of the
annealed Ooct-OPV5 lilm was excited. For this purpose the excitation spot size
was reduced from 1.8 mm to 30 in diameter, only a little larger than the typi-
cal domain size. Sample alignment was found to be cntcial with such a small spot
size. Mirrorless lasing was not observed at each spot excited on the sample, indi-
cating that the excitation beam should be well aligned above a crystalline domain.
The best results of these experiments at low and high excitation energy (6 and
um respectively) arc shown in Figure 16-45 (right). It is evident from these
spectra that the energy threshold is dr.mtatically reduced. The threshold flucnce
estimated from these experiments is roughly 100-200 mJ cm-
2
, which is a few
times as high as that obtained with an excitation spot size of 1.8 mm, while one
would expect the threshold tluencc to be constant for beam diameters larger than
the domain size. The explanation of this discrepancy between the threshold values
lies in the fact that the experiment using a spot diameter of 1.8 mm involves
roughly 10000 crystal domains of varying size and perfection; obviously, with a
spot diameter of roughly the size of a single crystalline domain, the chance of
positioning the spot over the optimum domain is extremely small .
A further conlirmatiun that minorlc.-;s lasing is restricted to single domains
comes from an experiment in which an Ooct-OPV5 film has been crystallized
from the isotropic melt phase (above 204 "C). Melt crystall ization rcsullcd in the
fonmttion of large domains wilh dimensions up lo scver.ll millimeters (see
Fig. 16-29C). The nonnalizcd emission spectr..t for dillen.:nt excitation energies
are shown in Figure 16-47. The excitation spOI diamelcr was I mm in lhl'Sl. ex-
608
>-
ii5
c:
Q)

'0
Q)
.!::!
(ij
E
0
z
16 A Model Oligomer Approocll to Semiconducting Polymers
Energy (eV)
2 .4 2.3 2.2
520 540 560 580
Wavelength (nm)
2.1
Figure 16-47. Emission spectr.s of a melt-
crystallized thin (300 nm) film of Ooct
OPV5. Excitation energy: (a) I (b) 10
600 (c) 50 (II) 70 excitation beam di-
ameter I mm.
periment-; and the beam was focused within one domain. The were ex-
cited with the pump light polarized parallel to the molecular ax1s. The lowest
measured energy threshold for lincwidth collapse is approximately 4 j.U. corre-
sponding to a threshold lluence of jlJ
which is substantially
than that measured for the annealed films. Th1s lowenng cannot be explmned
solely on the basis of the differences in optical density, since the O.D. at 355 nm
for the melt-crystallized films was approximately twice as high as that of the an-
nealed film.
The energy threshold appears to be dependent on the excitation spot size at
constant pump intensity, which indicates that occurs ?ver the
illuminated area. It should be stated that, desp1te the large domruns, the optical
quality within the domains is lower than that of the anne?led films. This
rise to additional scattering losses which decrease the magmtude of the amphhca-
tion.
16.5 Summary and Outlook
We have developed new PPV-type copolymers of two different architectures. In
one of these, the presence of substituted tcrphenylene units in the chain leads to
the isolation of PPV-type chromophorcs through steric interactions. These poly-
mers possess a reduced and controlled n-conjugation and have the optical
ties of small oligomers, but they still have a rigid-rod structure and correspondmg
properties. In the second architecture, the optical_ arc
trolled by the introduction of dimethylsilylene umts m the backbone. Tius g1ves
amorphous polymers with enhanced solubility and superior proccssability. With a
chromophore length or live rings. the spectral features or these copolymers (and
16.5 Summary aud Owlook 609
of the related model oligomers) are already close to those of a similarly substi-
tuted fully conjugated PPV.
The optical properties can be tuned by variations of the chromophorcs (e.g.
type of side-chains or length of chromophore). alkyl- and alkoxy-substitutetl
polymers emit in the bluc-gn.>cn range of the visible spectrum with high photolu-
quantum yields (0.4-U.H in solution), whi le yellow or red emission is
obtained by a further modilication of the chemical structure of the chromophores.
For example, cyano substitution on the vinylene moiety yields an orange emitter.
In order to tint! relationships between substitution patterns, packing of the chro-
mophores in the solid state, and emission properties, we have studied a variety of
three-ring and five-ring oligo(paru-phenylene vinylcne)s (OPVs) that closely re-
semble the chromophores in polymers. In many cases, single crystals have been
obtained, and the molecular anangement could be derived from a crystallographic
analysis. Particular attention has been paid to the influence of the position of cya-
no substituents. Intermolecular n-stacking was found when the cyano group was
placed not tlircl:lly adjacent to the central ring, and this resulted in strongly red-
shifted, excimer-type emission.
The substituted five-ring OPVs have been processed into polycrystalline thin
lilms by vacuum deposition onto a substrate from the vapor phase. Optical ab-
sorption and photoluminescence of the lllms arc significantly ditTerent from dilute
solution spectm, which indicates that intennolecular imeractions play an important
role in the solid-state spectra. The molecular orientation and crystal domain siz.e
can be increased by thermal annealing of the tilms. This control of the microstruc-
ture is essential for the usc of such films in photonie devices.
Electroluminescence was achieved in the green and orange wavelength regions
with devices consisting of a single active layer between a transparent indium-tin
oxide anode and an air-stable AI cathode. The etliciencies of the single-layer oli-
gomer LEOs arc comparable to those reported for fully conjugated PPVs. Fowler-
Nordheim tunneling theory was used to detennine the barriers for hole injection
in the single-layer devices. The inlluence of the morphology of the active layer
on LED pcrfommnce has been investigated. Annealed layer.; showed a higher effi-
ciency; this was attributed to enhanced electron mobility. Device optimization by
means of additional charge-tmnsport layers to enhance the efticiency has been ap-
plied successfully. Balanced hole and electron cuJTents, and e-h recombination
away from the metal cathode arc probably achieved in such devices. The best-per-
forming double-layer LEOs were based on the electronegat.ive cyano-substituted
oli gomers as the electron-tmnsport/emissive layer. In this case. external electrolu-
minescence efficiencies exceeding 0.3% are attained.
In both single crystals and thin lilms of oligomers. spectral gain narrowing h;L<;
been observed above a t1uence threshold and at a wavelength ncar the maximum
of Scallering losses at the domain boundaries in polycrystal-
line oligomer tilms prevent amplificat ion across thoscboundarics, and the domain
size therefore limit-; the length of interaction. For net gain to be observable, the
domain size must exceed a critical value at a given lluence.
Luminescence from the solid state is strongly subject to packing eff<x:ts. Some
arc related ll> mukcular conform;Jtion, some resuh from electronic be-
610 16 A Model Oligomu Approach 10 Semiconducting Pv/ymers
tween molecules. In particular, our study of luminescence from single crystals has
suggested a correspondence between n-stacking and excimer-type emission. It has
turned out to be difficult to establish cl{!ar-cut relationships and, admittedly, the
gap between model oligomers and polymers has not yet been bridged. What the
studies of oligomer films have clearly pointed out, however, is the importance of
the structural organization at higher levels for the optical and electrical properties.
Morphology should therefore be of primary concern to anyone working on the op-
timization of photonic devices based on films of organic compounds. Oligomer
thin films are suitable model systems for studying the strong influence of mor-
phology on the opto-electronic properties of organic semiconductors.
Acknowledgements
The authors acknowledge Hendrik-Jan Brouwer, Richard E. Gill, Alain Hilbcrer,
and Victor V. Krasnikov for carrying out the work described here as well a-; for
contributing to major parts of the text. We thank Gecrt Berentschot, Eddy (F.J.).
Esselink, Frank Garten, Valerie Gmycr, Jan K. Hcrrema, Auke Meetsma, George
G. Malliaras, Marc Moroni, Thuy-Anh Pham, Ulf Stalmach, Sjocrd C. Veenstra,
Michel P.L. Werts, Reinier H. Wieri nga, ami Jurjen Wi ldeman for their experi-
mental contributions.
We are indebted to Francis Gamier and Philippe Lang (Labomtoire des Materiaux
Moleculaires, CNRS, 2 rue Henri-Dunant, 94320 Thiais, Fmnce) and Jean Claude
Wittmann (CNRS, lnstitut Charles Sadron, 6 rue Boussingault, 67083 Strasbourg,
France) for their collaboration.
This research was financially supported by the Netherlands Organization for
Scientific Research (NWO-SON/STW/FOM) and by the EU (fMR program).
References
I. J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L
Bum. A.B. Holmes. Nature, 1990,347, 539.
2. G. Gustafsson, Y. Cao, G. M. Treacy, F. Klaveuer, N. Colancri, A. J. Hccger, Nature 1992, 357,
471.
3. P. L. Bum, A. B. Holmes, A. Kraft, D. D. C. Bradley, A. R. Brown, R. H. Friend, R. W. Gymer, Na-
ture 1992, 356. 41.
4. Z. Yang, I. Sokolik, F. E. Karasz. 1993, 26, 11 811.
5. A. Hilbcrer, H.-J. Brouwer, B.-J. van dcr S.:IICCr, J. Wildeman, G. Hadt.iioannou, Mllcmmo/ecule.r
1995, 28, 4525.
6. N.C. Grccnham, S.C. Mor.llli, D.D.C. Bradley, R.H. Friend, A.B. llolmc!>, Nt11ure 1993, 365,
628.
7. I. D. W. Samuel, G. Rumbles, C. J. Collison, l'lrys. Rrn 8 1995, 52, R 11573.
8. E. M. Conwell, J. Perlstein, S. Shaik, l'hy.. Rev. IJ 1996, 54, R23ffil.
9. T. Granier, E. L. nlolllaS, D. R. Gagnon, F. E. Karasz. R. W. Lcnz., J. l'ulym. &i., 1'1. 8: 1'<1/ym.
Phy.r. 19116, 24, 2793.
10. D. Chcu, M. J. Winokur, M. A. Malo!><:, F. E. 19'J2. JJ. 31 1(>.
References 611
II . J. H. F. Martens, E. A. Marscglia, D. D. C. Bmll ley, R. H. Friend, P. L. Bum, A. B. Holmes, Symh.
Met. 1993, 55- 57, 449.
12. J. K. Hcrrcma, J. Wiklcman, F. van Bolhuis, G. Hadt.iioannoo, Symll. Met. 1993, 6(), 239.
13. G. HoruwiiL, B. BadJCt. A. Ya'l.o;ar, P. L:111g. F. Dcmanzc, J.-L. fave. F. Gamier. Chcm. MutC'T.
1995, 7, 1337; CITmum: Cllcm. Mtttct: 19%. 8. 915.
14. B. Servct. S. Ric:., M. Trutel, P. Alnm, G. HorowitL. F. Garnier, Adv. Moler. 1993, 5, 461.
15. P. Lang, G. Horowitz. P. Valat, F. Gamier, J. C. Willml111n, B. Letz. J. 1'/lys. Owm. IJ 1997, WI,
8204.
16. A. Hilbcrcr, P.F. van Huncn, J. Wildeman, G. Hadziioannoo, Muuomol. Otem. Phys. 1997, 1118,
2211.
11. J.-L. Bred<L,, J. Comil, A. J. Hccgcr, Atll: Muter. 1996, 8, 447.
18. F. Ca.cialli, X.-C. Li , R H. Friend, S.C. Moraui. A. B. Holmes. S1111h. Mcl. 1995, 75. t 6 1.
19. P. lle..:mann. H. Vc,twcht.-r. J. J>ununel'chnc. R. F. Mahrt, A. Greiner, At/1: Meller. 1995, 7, 31lll.
20. M. Moroni. A. 1-lilbcrcr, G. Hadzi iuannuu, Macnmwl. Htltlitl Comnum. 1996, 17, 693.
21. G. G. J. K. Hcrrcma. J. Wil<lcm:m. R. ll. Wiering:l. R. E. Gill. S.S. Lampuuro1, G. Had-
;jioannou. At/1. Mater. 1993. 5, 721.
22. J. K. Hcrn:ma, P. F. van l luucn. R. E. Gill, J. Wildcm<m, n. H. Wieringa, G. Hadziioannoo, Mucm-
molccu/c:.{ 1995, 28, 8 102.
23. 'L Yang, F. E. Karast.. H. J. Geise, MacnmwiC"cules 1993,26, 6570.
24. Z. Yang, F. E. H. J. Geise, Pulymt!r 1994, 35. 391.
25. J. Obcr.;ki, R. C. Sduuidt. G. J. H. Wentlurll'. A. Greiner, M. Hopmcier, F. Mota-
nll!di , Mtttnm!uiC't'U/es 1995, 28, !!C>76.
26. H. von Scggcm, P. Schmidt-Winkel, C. Zhang, H.-W. Schmidt, Mmmmol. Oll!m. Pily.r. 1994,
1115, 202J.
27. R. E. G1ll, G. G. Malliamll, J. Wildeman. G. H<KI:t.iioanmm, Mllln: 1994. 6, 132.
2!!. J. K. Hcm:ma, 7imiug ll/ t/11 Lumillc:sccmcc ;, Pllly/{silwyiC!IIe)tltiopltmejs, Ph.D. Gronin-
gcn. 1996.
29. A. Pohl, J.-L Bni<las, lm. J. Qua111. Cht!m. 1997, 63, 437.
30. R. E. Gill, A. Mcctsma. G. Had:tiioannou. Adt. Mma 1996. H. 212.
31. R. E. Gill, P. F. van HutiCn, A. G. Hadziioannou, Cllem. Mater. 1996, X, 1341.
32. P.F. van Bullen, V. V. H.-J. Brouwer, G. Hadt.iioannoo. Chem. l'lt1s. 1999,241, 139.
33. F. Gamier, A. H. HajkiUui, G. 1-lorowit:t., F. D.:lull'rc. B. Scrvet, S. Rics, P. Alnol, J. Am.
C/1<'111. Soc. 1993, 115, !!11(>.
34. A. Yassar, G. HoruwiiL. P. Valat. V. M. Hmycno.:, F. Dcloffrc, P. Srivastava, P. Lang, F.
J. Pt.y.v. C!ltm. 1995, W, 9 155.
35. G. Horowitz, S. Romdhanc, H. Boochriha, P. Delwmoy, J.-L. Monge, F. Kouki, P. Valai, S}711h.
Met. 1997, 90, 1!!7.
36. F. Gamier, G. Hurowitz, X. Peng, D. Fichou, Ac/1. Muwt: 1990, 2, 592.
37. L. Torsi, A. Dodabalapur, L.J. Rothberg. A W. P. fung, H. E. St:iezzu 1996, 272, 1462.
38. G. Horowitz.. F. Gamier, A. Yassar, R. Hajlaoui, F. Kouki, Adl( Muter. 1996, 8, 52.
39. K.B. Becker, Svmllesi.r 191!3, 341.
40. G. Drcfahl, R. H. H.-H. Horhold. Mukmmul. Cllem. 1970, JJI. 89.
4 1. M. Hartel . G. Ko."<SniChl, G. Manccke, W. Wille, D. Wbhrlc. D. Zcrpncr, Angcw. Mukrrmwl.
1973, 2Y/.W, J07.
42. Z. Yang, H. J. M. Mehbo<l, G. Dcbruc. J. W. Visser, E..J. Sonnevcld, L. Van' t Dack, R. Gij-
bcls, Sym/1. Mn 1990, JY, IJ7.
43. R. Schenk, H. Gregorius, K. Mccrholt, J. Heinze, K. Mullen, J. Am. Chcm. S.K. 1991, 1/J,
2634.
44. N. N. D. J. Guerrero, H. J. Olivos, J.P. FCIT.lCi:.. !!J)'mfl. Met. 1995, 75, 153.
45. H. E. Kutz. S. F. nc111, W. L Wilson. M. L. Schilling, S. B. J. Am. Clm11. St>c. 1994, //6.
6631.
46. s. KlingdhOfer. c. Schellenberg, J. Pununcrcluk!, H. na. ... ,lcr. A. Greiner, w. Mae'IWIIU/.
Cllem. l'hys. 1997. I Y.'l, 1511.
47. R.F. Hc.:k. in Orxauic Htllctitms (Eds.: W. G. et al .)., Jolm Wiley & Sons hlC., New
York. USA. 191!2, Vol. 27, Chapter 2.
4!!. T. W. Li, L. Yu. J. Am. C/wm. Sue 19\11. //Y. 1144.
\
612 16 A Model Oligomer Approuch to Semicunductiug Polymers
49. U. Stalmach, H. Kolshom, I . Brehm, H. Meier, Licbigs Am1. 1996, 1449.
SO. E. Thom-Csoinyi, K.P. POug. J. MoL Cato/. 1994, 90, 69.
51. H. Krcusctunann, H. Meier, J. Prald. Chon. 1994, JJ6, 247.
52. S.E. [)Ottinger, M. Hohloch, J.L E. Steinhuber, M. Hanack, A. Tompcrt. D. Oclkrug,
Adv. Mater. 1997, 9, 233.
53. W. Heitz, W. Briigging, L Freund, M. Gai lberger, A. Greiner. H. Jung, U. Kampschultc, N.
Niessner, F. Osan, H. W. Schmidt, M. Wicker, Makrrmwl. Chem. 1988, IH9, 11 9.
54. H.-P. Weitzel, K. Mullen, MakrtmwL Che111. 1990, /91, 2837.
55. J. Kiji, Macromol. S>'"P 1996, 105, 167.
56. R. E. Gill. Desigll, Sylllllesis U/10 Clrara,terizatiOII of umrillescmt Orgullic Semicvnductors,
Ph.D. Thesis, Groningen, 1996.
57. G. Manccke, S. Uittke, Chem. Ber. 1970, /OJ, 700.
58. J. N. Delllal>, G. A. Crosby, J. l'lry.f. Clrem. 1971, 75, 991.
59. Pruttical Fluuresce11ce (Ed.: G. G. Guitbauh), 2nd ed., Marcel Dekker Inc., New York. USA
1990.
CJO. H.-J. Urouwer, V. V. Krasnikov, A. Hilbcrcr, J. Wikleman, G. H:xlljioaonou, AllfJI. /'lty.,. u /1.
1995, 66. 3404.
61. J. M. Tour. Adl\ Muter. 11194, 6. 190.
62. K. N. Baker. A. V. Fmtini. T. H. C. Knacbcl, W. W. Ad:un,. E. I'. Socci, U. L Fanner. Pllly
mer 1993. 34, t57l.
63. M. J. S. Dewar, e.G. Zocbisch. E. F. llcaly. J. J. l'. Stewart, J. Am. Cltt'm. Sm. 19!15. 1()7, 31)(12.
64. H. J. Urouwer. V. V. Kr.s.,nikuv, A. Hilbcrcr, G. HaoJtj iuannou. Ad" Mm"r. 1996, li, 935.
65. H. J. Brouwer, A. Hilbcrer, M. Werts. J. Wi ldeman, G. Hadt.iioannou, S/'1 Pmat'dirrgx 1996,
2852, 170.
66. F. Garten, A. Hilbcrcr, F. C...:ialli, E. Essclrnk, Y. van Dam, B. &lrlaJmann, R H. Friend, T. M.
Klapwijk, G. Haoltiioannou, Adv. Muter. 1119'7. 9. 127.
67, F. Garten. A. Hilbcrer, F. Cacialli, F. J. E.'i...clink. Y. van Darn, A. R. Schlaunann, R. H. Friend,
T.M. Klapwijk, G. Hadz.iioannou, Symlt. Met. 1997, H5, 1253.
68. HJ. Brouwer, A. Hitbcrer, V. V. Krasoikov. M. Werts, J. Wildeman. G. Hadziioannou. SytiiiL Met.
1997, 84. 881.
69. H. J. Brouwer, Semiconductilrg l'olymer:r /11r Uglu-emittinx Diodes uml Ut.Yers; a Structural,
Photopltysical wad Electrical Study ll/ PI'V-tJPe Allernating Copolymers wuJ Oligomers, Ph.D.
Thesis, Grooingen. 1998.
70. C.M. Heller, I. H. Campbell. B. K. Laurich, D. L Srniah, D. D.C. Bradley, P.L. Bum, J. P. Ferraris,
K. MUllen, f'hys. Rev. 8 1996. 54, 5516.
71. l. lJ. Berlman, J. Plrys. C#tc11L 1970,74,3085.
72. D.C. Todd, J. M. Jean, S. J. Rosenthal, A.J. Ruggiero. D. Yang, G.R. Acming, J. ClteiiL Pltys.
1990, 93, 8658.
73. J. Comi l, D. A. dos Samos, D. Beljonnc. J. L J. Pltys. 1995, 99, 5604.
74. Conjugated Conducting Pulymers (Ed.: H.G. Kiess}, Springer, Berlin Germany, anti New York,
USA, 1992.
75. J. L. Bredas, G. B. Street , A,c. Clrcm. Res. 11185, IX, 309.
76. H.S. Woo, 0. Lho!.1.. S.C. Gmham, D. D. C. Bmdley, R. H. Friend, C. Quaurocchi, J. L BrCtlas.
R. Schenk. K. Mullen. Sym/1. Met. 1993, 59, 13.
77. K. Mccrholz. H. Gregorius, K. MUllen. J. lieinze, Ad\\ Mmrr. 1994,6, 671.
78. C. Adachi, T. Tsu1sui, S. Saito, 1\JIII/. P/1v:r. Le11. 1990. 56, 799.
79. M.D. Joswick, I. H. Campbell, N. N. J. P. Ferr.1ris. J. Awl. Phys. 1996, XU, 21183.
1!0. M. Verbruggen, Y. Zhou, A. T. H. Lenstm, H. J. Geise. Actu Crysr. 1988. C44, 2120.
81. G. Wu, S. Jacobs. A. T. H. Lenstra, C. van Alseuoy. H. J. Geise, J. Comput. O reiiL 1996, 17,
11!20.
1!2. M. Hohloch. C. Maichle-M6ssmer, M. Hun:1ck, C/rem. Muter. 1998, /0, 1327.
1!3. S. Karabunarliev, M. Baumgarten, N. Tyutyulkov, K. Mullen, J. Pltys. Cltem. 1994, 9X, 111!92.
1!4. J. Comil. D. Bcljonne. 'L Shuai, T. W. Hagler, 1. Campbell, D. D. C. Bmlllcy. J. L UrCdas, C. W.
Spangler. K. MUllen. Cltcm. Plty.v. Utt. 1995. 247. 425.
85. M. fahlman. P. Urorns. D. A. dos Santos. S.C. Muraui. N. Johansson. K. Xi ng. R. H. Fricnt!,
A. B. J L. BrCdas. W. R. Salan.:ck. J. Cltelll. Plt.vs. 1995. /02,1!167.
References 613
86. M. S. G. Drcsselhaus, AtlVCJIICes in 1981, 30, 139.
87. M. Pope, C.E. Swenbcrg, in Elcclronic Processes m Orgunic Crystals, Clarendon Press, Ox-
ford, UK, 1982.
88. S. A. Jenekhe. J. A. Osaheni. S.:ience 1994, 265, 765.
K9. L Yu, 'L Bao, Mmtr. 1994. 6. 156.
9<). D. Demus, L. Richter, Textures of Liquid Cryswl.r. 2nd ell., VEB Deutscher Verlag fUr Gruno-
stollinduslrie, LeipZ-ig. Gernlimy, IIIHO.
91. B. Servea, G. Horowitz. S. Riel>. 0 . Lagors:1e, P. AlllOI, A. Yassar, F. Deloffre, P. Sriva...Wva., R.
Hajlaoui, P. Lang. F. Garnier, Clwm. Mater. 1994, 6, l!l(l9.
92. S. Holla, K. War.1gai , J. Muter. Cllem. 1991, / , 1!35.
93. A. Yassar, P. Valat, V. Wintgcns, M. Hmyenc, F. DcloiTre, G. Horowitz, P. Srivastava, F. Gar-
nier, S.!'lllr. Mt!t. 1994, fl7, 277.
94. R. E. Gill. G. H:.dziiow1nou. P. Lang. F. Gw11ier. J. C. Willmann. Ad1. Matn: 11197. 9. 331.
9.'i. 0 . Bohme. C. l.icgler, W. GQpcl, Ad1. Mawr. 1994, 6, 5ll7.
96. L.J. Rolhhcfl!.. 1\.J. l.uvingcc J. Moftor. Ht.. 199(,. II . 3174.
'J7. lUI. Friend. G. J. Denton. J. J. M. Halls. N. T. Harrison. A. B. Holmes. A. Kohler, A. Lux, S.C.
Moraui. K. Pichler. N. K. Town,, H. F. Wiurn:um, Soli<! State Cammu11. 11197. 102, 249.
9K. D. Braun. A. J. Hcq!cr. Appl. l'ltys. Uu. 1991. 5X, 191!2.
1
J9. J. K. Hcm:nra. J. Wildeman. R. ll. Wictinga. G. G. Malliarus. S. S. l<lmpoura. G. H:rdt:iiiMnnou.
f'olym. l'nt"im. I'J4J.\ . .1-1( I ). 2X2.
ICJ(I. C. Zhang. II. VIll i K. B. 11.-W. Sduuit.lt. A. J. l k-cgcr, Syutlt. 11/tf.
11194, (12, 35.
101. R. M. Gurgc, A.M. Sacker, P.M. Lahti , B. l lu, F. E. Kara.,z. Macmmoll.'cult'l", 1997, 30, 821l6.
W2. H. Becker. S. E. UurrL\, R. H. Friend. Plt1.v. Rt'l'. IJ 1991. 56, 11\93.
11)3. D. Moses, Atltll. l'l_l'l . Len. 1992. 6(), 3il5.
104. F. Hide. B.J. Schwartz. M. A. A. J. Hccgcr, Ctu:m. Phys. Leu. 1996,256,424.
105. F. Hide, M. A. B. J. Schwm1.z.. M. R. Andersson, Q. Pei, A. J. Heeger, Scie11ce
1996, 273, 11!33.
ltl<1. N. Tessler. G. J. Denlon, R. H. Friend, Nutmr 1996. JX2, 695.
107. S. V. Frolov, W. Gcllo.:rmann, M. Ozaki. K. Yoshino, 'LV. Vanleny, Pltyl. Rt'v. Lt'tt. 1997. 78.
729.
101!. G. H. GelirK:k, J. M. Wdl11Jao, M. Remmers, D. Neher. Clrt'm. Pltys. Lett. 1997, 265, 320.
109. G. J. Denton, N. Tessler, M.A. Stevens, R. H. Friend, Atlv. Mmer. 1997, 9, 547.
110. X. Long. A. D. D.C. Bradley. M. lnb:L\Ckarwl. E. P. Woo. Cft<m. Pltys. Lell. 1997.
272. 6.
Ill. D.G. Lidzey, D. D.C. Unx.llcy, S. F. Alvamdu, P. F. Seidler, Natun 1997. 3H6, 135.
11 2. 0. S. AvWIC.\j;m. V. A. Be111krskii, V. Kh. Briken,tein. V. L Bruudc, L. l. Korshunov, A. G. Lav-
1.1. ' lartakovskii. Mol. Crpt. Uq. Crpt. 1974, 29, 165.
11 3. G. Horowill.. P. Dclannvy, H. Bouchriha, F. Deloffrc. J.-L. Fave, F. Gamier, R. Hajlaoui, M.
Heyman, F. Kouki. P. Valat, V. Wintgens, A. Yasl.ar. Ad1\ Mat. 1994, 6, 752.
114. F. Meghdadi, G. Leising, W. Fischer, F. Stelzer. Symlt. Mel. 1996. 76, 11 3.
115. P. Le Rcodu. T. P. Nguyen. 0 . Gaudin. V. li. Tr-.11\. Smth. Met. 11196. 76. 187.
116. U. Stalrnm:h, 1. Detert. H. Meier, V. D. i.taarcr, A. Bacher, H.-W. Schmidt , 0 111. Ma-
l('t: 19118. 9, 77.
117. H. J. Brouwer. V. V. KrJ.Snikov, T. A. Pham. R.E. Gill, P.F. van Huucn, G. Hadt.iioannou, O t t'l/1.
Pltys. I \198, 227, 65.
Il K. S.C. Veenstra. G. G. Mulliaras. li.J. Bmuwer. EJ. lfssclink, V. V. P. f . van Hullcn, J.
Wildeman, H. T. Jonkn1an. G. A. SuwaW.y. G. Haolziiuannou, Symlt. Mel. 11197. 84, 971.
119. l. D. Parker, J. Appl. Pltys. 11194. 75. 16.56.
120. P. S. Davids, Sh. M. Kog:.u1, I. D. Parker, D. L. Smi lh, Attl. l'hy.<. uu. 1996. 69, 22711.
121. P. F. vm Huuen. J. Wildeman, A. G. l lud:Uiommc1u, J. Am. Clte111. Svc. I 999, I 21,
5910.

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Georges Hadziioannou, Paul F. van Hutten (Eels.

is the dimensionless electron-lattice coupling constant and

bare optical phonon frequency at q=nl1.

one obtains the self-consistency equa-

the electron spec-

Such an approach is, essen-

(x)=L\,. In particular, the on-site

both types have the same en-

.. , (one Ca awm per munumcr) OIIPt>v with u

dtsplaycd m. F1gure 5-4. Three base (neutral) forms of polyaniline have

Salan.:.:k. C. B. Duke. E. W. Plununer, A. J. 11e.:gcr, A. G. MacDiarmid, Po/r-

wtl Neluted 1'/aelllllllt'IIU I""" '

c. Scou J. R. Salem, M. Angclopoulos, SymiL Met. 1996, IJ(), Ill .

where the operator Vt . l is the intennolecular potential

In view of the exciton structure obtained from the

The power spectral density (PSO) of the Fast Four-

j df1Jil;(f cos fiJ.! sin fiJ) j

. lcmpcr.uun: (4 K) lluorc.-.ccncc l>pcclm of lwn uiiTcrcnt films of 1: prepore' u----

emrOsston properties of a lumincscem material within an ,. uhcttbth!Y. of

the of lilting the

and simulate the transient PM and EA spec-

Ftgure 7- 12, agrees very well with the experimental PA

20 ns. The slower ISC mte in solu-

wfth ump polariz.ation parallel and

S_mce Y 1:. not hnear tn r '?D

fowler Nordheim Iii <1., =0.2

the hole SLC accord-

'{;-quantifies of the for-

_of an llle pa-

LEOs. This etlect has been

K R. ll. Frknd, P. L Bums.

Bem" a St"'"lla t " " s

of (Rd. I?21J. <:Ill The dashed hnc c..-or-

tor eV, notably at lower temper.llurcs. It is noteworthy

which a complicated crystal

In Figure 13- 11 b, the of the

the mobt hty ol wluch can be as hagh as 0.08 em v- s

then the siOJX:

and the HOMO-LUMO gap, respectively [ 1191. 1l1c results of

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