Outline

1. 2. 3. 4. 5. Chronology of display technology Advantages of LEDs Definition of OLED Principles of operation Technology Branches SMOLEDs LEPs Effect of dopant Other applications Corporations in this field Conclusion

6. 7. 8. 9.

Basic Idea Behind Emission

Molecular Energy Systems

Light

Beginning of LED

www.kodak.com

Advantages of LEDs over LCD

1. Brighter, thinner, lighter, faster 2. Bright from all viewing angles 3. Need less power to run 4. A lot cheaper to produce 5. Expanding memory capability - coating new layer on top of existing one 6. Wider temperature range

7. Doping or enhancing organic material helps control Brightness Color of light.

Semiconductor LEDs
LEDs work on the principle of injection luminescence. Conventional LEDs are made of : (AlGaAs) - red and infrared (GaAs/P) - red, orange,yellow (GaN) - green (GaP) - green (ZnSe) - blue (InGaN) - blue (SiC) - blue diamond (C) - ultraviolet

OLED is a display device that sandwiches carbon based films between the two electrodes and when voltage is applied creates light.

www.ol-ed.com

Single Layer Device

Organic electroluminescene (EL) is the electrically driven emission of light from non-crystalline organic materials

Energy level diagram of a two-layer OLED

HOMO, LUMO of the HTL is slightly above that of the ETL

L.S.Hung et al.,Materials Science and Engineering R 39, (2002), 143

Chemistry behind Emission

Electrons and holes recombine : singlet state, triplet state

- +

S+T S0 + h

S+T

Formation of triplet is 3 times more feasible than singlet

Photoluminescence vs. Electroluminescence

When a radical anion and a radical cation combine on a single conjugated segment, singlet and triplet excited

states are formed, of which

the singlets can emit light.

A.B.Holmes et al., Angew. Chem. Int. Ed. 37, 1998, 402

R.H.Friend et al., Nature 413, 2001, 828

Thermodynamics of Electroluminescence
A + eA +e +

AA A*

E reduction E oxidation E emission

(- ) (+)

A + hv A+ + AWhen E oxidation -

2A or A + A* E reduction > or = E emission

Ru(bpy)32++ eRu(bpy)33++ e

Ru(bpy)3+

E reduction

-1.4 V + 1.2 V 2.05 V

Ru(bpy)32+ E oxidation Ru(bpy)33* Eemission

Ru(bpy)3 + hv

Factors influencing efficiency

1. 2.

Efficiency of electrons and holes recombination Efficiency of excited state formation upon annihilation.

3.

Quantum yield of emission of excited state.

Two Principle Branches

1. Light-Emitting Polymers (LEPs) Or Polymer Light Emitting Diode (PLEDs) Using relatively large molecules

2. Small Molecule Organic Light Emitting Diodes (SMOLEDs). Using relatively small molecules (even monomers)

eg :Conjugated molecules

eg: Metal chelates

SMOLEDs
Criteria Metal chelates must satisfy

Thermally stable, Highly luminescent in the solid state,

Thin-film forming upon vacuum deposition

Capable of transporting electrons

C.H.Chen et al., Coordination Chemistry Reviews 171, (1998), 161

Early thin film organic device

Mg:Ag 10:1 Luminescent film - 600A Diamine 750A

Relatively High voltage (80-100 V) - Inject charge into organic crystals Low work function alloy-cathode Organic layers, cathode were vacuum deposited.

C.W. Tang & S.A. VanSlyke, Kodak Research Laboratories

Emission Spectrum of the EL Diode.

EL emission spectrum is sensitive to thickness of organic layer.

Diamine layer transports holes and blocks electrons injected from Mg:Ag electrode.

Brightness-Current-Voltage Characteristics

Most of the bias voltage is across AlQ3

EL diode can be driven to produce high brightness.

Key Factors
Morphological properties of organic layers are critical. Thin films must be smooth and continuous . Mg is susceptible to atmospheric oxidation and corrosion

Ag improves the sticking coefficient of the metal to the organic layer.

A dc voltage of less than 10V drives the diode.

Full-Color Displays

Development of red, green, and blue emitting electroluminophores

Photophysical properties of Alq3-type complexes are dominated by ligandcentered excited states

Pavel Jr.et al., J. Org. Chem. 69, 2004, 1723

Varying degree of electronic density in the quinolinolate ligand,

Excitation of dichloromethane solutions at 365 nm.

Preliminary experiments with fabrication of OLED devices

All complexes are electroluminescent They can be processed via vapor deposition The emission maxima of the OLEDs are very close to the maxima recorded in solution

Other Materials

Abhishek et al., Chemistry of Materials, 2004 ASAP

Rules governing the fluorescence of metal chelates

(1) Paramagnetic metal ions : Essentially non-fluorescent

(2)

Increasing atomic number : Fluorescence reduced InQ3 < GaQ3 <AlQ3 Covalent nature of the metal-ligand bonding increased : Emission shifts to longer wavelength.

(3)

Light Emitting Polymers

1. Dendrimers: They are highly branched structures built up from monomer units with precisely controlled architectures. 2. Long chain conjugated molecules:

Semiconducting property

Electroluminescent behavior
Semiconducting properties :delocalised -electron bonding

and * orbitals form delocalised valence and conduction wavefunctions, which support mobile charge carriers.
Electrons and holes capture : polymer film Form neutral bound excited state: Exciton Due to confinement, energy difference between singlet and triplet may be large.

R.H.Friend et al., Nature 397, (1999), 121 J.H. Burroughes et al., Nature 347, (1990), 539

Perfluorinated Phenylene Dendrimers

Good Electron-transport materials for OLEDs

(1) Low-lying LUMOs and HOMOs (2) Relatively low sublimation temperature (3) Good thermal and chemical stability (4) Soluble in CHCl3, THF and aromatic solvents such as toluene.

Suzuki et al.,J. Am. Chem. Soc. 122, 2000, 1832

Luminance-voltage characteristics

Performance of the devices 3 < 2 < 4 < 5.

2 and 3 (biphenyl)< 4 (p-terphenyl) < 5 (p-quaterphenyl) When the LUMO energy level of the electron-transport material becomes lower, the electron injection from the metal layer to the electron-transport layer should be easier

www.iitk.ac.in

Perfluorinated Oligo(p-Phenylene)s:

PF-5P <1< PF-6P = PF-7P = PF-8P <2

A perfluoro-2-naphthyl group turned out to be an excellent building block for constructing n-type semiconductors

This might indicate that the LUMO level is low enough rate of electron injection is not affected by the LUMO energy

Sophie B. Heidenhain et al.,J. Am. Chem. Soc.122, 2000, 10240

Inorganic semiconductors , organic dyes : deposited sublimation or deposition

vapor

Fluorescent conjugated polymers : deposited from solution by spin-coating or Langmuir Blodgett technique

A.B.Holmes et al., Angew. Chem. Int. Ed. 37, 1998, 402

Multilayer Devices

Increase efficiency of devices electron injection has to be significantly boosted.

Electron-conducting/holeblocking (ECHB) layer

Design of ECHB
Electron-deficient and poor hole acceptor

Work on electron hopping mechanism

Fu Wang et al., Adv. Mater. 11, 1999, No. 15

Polymers with higher electron affinity

Ideal light-emitting polymer should be both fluorescent and avoid the need for an extra electrontransporting material.

Electron-withdrawing groups on the ring or vinylene moiety of PPV

A.B.Holmes et al., Angew. Chem. Int. Ed. 37, 1998, 402

Effect of Dopant (Organic Fluorescent dyes)

Dyes in solid state suffer from Quenching Broadening of emission bands Bathochromic Shifts Doping fluorescent dye as guest in a host matrix

Rubrene

Increase in lifetime

Peter Baeuerl et al.,J. Mater. Chem., 10, 2000 , 1471

Other applications

FOLED: Flexible OLED

PHOLED :Phosphorescent OLED TOLED: Transparent OLED

SOLED: Stacked OLED

PMOLED: Passive Matrix OLED

AMOLED: Active Matrix OLED

Future Research
Solutions for the following:

Susceptibility towards oxidative degradation

Lifetimes remains lower

Photooxidation produces carbonyl defects that quench fluorescence

Corporations in OLEDs

Small Molecule Kodak IBM UDX Ritek

Polymer CDT Dupont Philips Dow Chemicals

Conclusion
OLED is a display device that sandwiches carbon based films between the two electrodes and when voltage is applied creates light SMOLEDs & LEPs are its technology branches. Chemical modifications to the structure can tune the emission over the entire visible region. Multilayer devices and dopants also play a role in tuning emission.

The dynamic interplay of chemistry with device physics results in these remarkable displays.

Acknowledgments
Prof. Russell.H.Schmehl
Group Members : Dr.Sujoy Baitalik Heidi Hester Kalpana Shankar Rupesh Narayana Prabhu David Karam

Chemistry Department
All of You

Different forms of luminescence

Luminescence type Excitation Source Application

Catholuminescene Photoluminescene Chemiluminescene Bioluminescence Electroluminescene Triboluminescence

Electrons (UV) Photons Chemical reaction energy

TV sets, monitors Fluorescent lamps, plasma displays Analytical chemistry

Biochemical reaction energy Analytical chemistry Electric field Mechanical energy LEDs, EL displays

Hole-Injection Materials
Anode buffer layer- reduces the energy barrier in-between ITO/HTL. Enhances charge injection at interface.

CuPc,p-doped aromatic amines,