12 Thesis

Molecular Organic Semiconductors
for
Electronic Devices
Oana Diana Jurchescu
MSC PhD thesis series 2006-15

issn: 1570-1530
isbn: 90-367-2708-1
The work described in this thesis was performed in the research group Solid State
Chemistry of the Materials Science Centre at the University of Groningen, the
Netherlands.
Printed by: PrintPartners Ipskamp B.V., Enschede, the Netherlands
Rijksuniversiteit Groningen
Molecular Organic Semiconductors for

Electronic Devices
Proefschrift
ter verkrijging van het doctoraat in de
Wiskunde en Natuurwetenschappen
aan de Rijksuniversiteit Groningen
op gezag van de
Rector Magnificus, dr. F. Zwarts,
in het openbaar te verdedigen op
vrijdag 6 oktober 2006
om 14:45 uur
door

geboren op 1 maart 1979
te Timisoara, Roemenie
Promotor:
Prof. Dr. T.T.M. Palstra
Beoordelingscommissie:
Prof. Dr. Y. Iwasa

Prof. Dr. G. G. Malliaras
Prof. Dr. P. Rudolf
Contents
1 Introduction
1.1 Organic conductors - general aspects . . . . . . . . . . . . . . . . .
1.2 Charge transport in organic semiconductors . . . . . . . . . . . . .
1.3 Organic electronic devices . . . . . . . . . . . . . . . . . . . . . . .
1.3.1 Field effect transistors - operation principles . . . . . . . . .
1.3.2 Fabrication of OFETs . . . . . . . . . . . . . . . . . . . . .
1.3.3 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.4 Organic molecular crystals . . . . . . . . . . . . . . . . . . . . . . .
1.5 Single crystals - model systems for investigation of intrinsic properties
1.6 Aim of the present research . . . . . . . . . . . . . . . . . . . . . .
1.7 Outline of the thesis . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
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2 The Effect of Impurities on the Mobility of Single Crystal Pentacene

2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 Control of the defects and impurity states in organic crystals . . .
2.2.1 Spectroscopic evidence for the presence of impurities . . . .
2.2.2 Purification of the starting material . . . . . . . . . . . . .
2.2.3 Single crystal growth . . . . . . . . . . . . . . . . . . . . . .
2.2.4 Quantitative analysis of 6,13-pentacenequinone content . .
2.3 Electronic response to structural and chemical properties . . . . .
2.3.1 Space charge limited currents . . . . . . . . . . . . . . . . .
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vi
Contents
2.3.2 Evaluation of the bulk mobility of the high quality crystals
2.3.3 Band transport in pentacene single crystals . . . . . . . . .
2.3.4 Origin of traps . . . . . . . . . . . . . . . . . . . . . . . . .
2.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3 Interface Controlled High-mobility Organic Transistors

3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 Current status of the field . . . . . . . . . . . . . . . . . .
3.3 Novelty . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4 Single crystal growth . . . . . . . . . . . . . . . . . . . . .
3.5 Surface morphology of pentacene single crystals . . . . . .
3.5.1 Surface mapping . . . . . . . . . . . . . . . . . . .
3.5.2 AFM measurements . . . . . . . . . . . . . . . . .
3.6 Comparison between different FETs . . . . . . . . . . . .
3.6.1 FETs fabricated with conventional dielectrics . . .
3.6.2 FETs fabricated with pentacenequinone dielectric
3.7 Device fabrication . . . . . . . . . . . . . . . . . . . . . .
3.8 Properties of FETs fabricated with
pentacenequinone gate dielectric . . . . . . . . . . . . . .
3.9 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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4 Cross-over from 1D to 2D - Space Charge Limited Conduction

in Pentacene Single Crystals
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2 Space-charge-limited-current theories for semiconductors . . . . . .
4.2.1 Mott-Gurney model . . . . . . . . . . . . . . . . . . . . . .
4.2.2 Geurst model . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3 Space charge limited currents in pentacene single crystals with planar contacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.1 Experimental procedure . . . . . . . . . . . . . . . . . . . .
4.3.2 Charge transport in the SCLC regime . . . . . . . . . . . .
4.3.3 Evaluation of mobility for sandwich-type and gap-type structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.4 Resistivity anisotropy effects - effective thickness . . . . . .
4.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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vii
Contents
5 Electronic Transport Properties of Pentacene Single Crystals

upon Exposure to Air
77
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5.3 Exposure to dry and ambient air . . . . . . . . . . . . . . . . . . . 79
5.3.1 I-V characteristics in the dark - in vacuum and after exposure to air . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.3.2 Gas diffusion in pentacene single crystals . . . . . . . . . . 80
5.3.3 Effect of Oxygen and water in dark . . . . . . . . . . . . . 84
5.3.4 Effect of Oxygen and water in light . . . . . . . . . . . . . 86
5.3.5 Effect of high O2 pressure . . . . . . . . . . . . . . . . . . . 87
5.4 O2 and H2 O effects - experimental observations . . . . . . . . . . . 88
5.4.1 Electrical measurements . . . . . . . . . . . . . . . . . . . . 88
5.4.2 UPS spectroscopy . . . . . . . . . . . . . . . . . . . . . . . 89
5.5 Mechanism of oxygen doping . . . . . . . . . . . . . . . . . . . . . 91
5.5.1 Formation of the charge transfer complex between pentacene
and O2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.5.2 Reversible oxidation of pentacene . . . . . . . . . . . . . . . 92
5.5.3 Calculation of the oxygen-induced dipole moment . . . . . 93
5.6 Quantitative analysis of the effect of O2 and H2 O . . . . . . . . . . 96
5.7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
6 Low Temperature Crystal Structure of
Rubrene Single Crystals Grown by Vapor Transport
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.2 Polymorphism in rubrene . . . . . . . . . . . . . . . . . . .
6.3 Growth of rubrene single crystals . . . . . . . . . . . . . . .
6.4 Single crystal diffraction . . . . . . . . . . . . . . . . . . . .
6.4.1 Experimental details . . . . . . . . . . . . . . . . . .
6.4.2 Orthorhombic rubrene . . . . . . . . . . . . . . . . .
6.5 Relation between molecular stacking and electronic mobility
6.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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A Crystal structure of pentacene
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B Crystal structure of rubrene
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viii
Contents
Summary
131
Samenvatting
135
List of Publications
139
Introduction
1.1
Organic conductors - general aspects
Organic semiconductors are a fascinating class of materials, with a wide range

of properties [17]. The interest in organic electronics is motivated by increasing
demands of supplementing Si-based electronics with materials that offer easier
processing methods completed with functionalization by chemical manipulation.
Typical deposition techniques for organics are readily available or not very difficult
to implement (spin-coating, drop-casting, direct printing via stamps or ink-jets).
Their compatibility with light-weight, mechanically flexible plastic substrates,
completed by new, innovative fabrication routes, make them possible candidates
for future electronic devices. Moreover, due to different molecular tailoring possibilities via chemical synthesis, organic materials present an infinite variety in
functionality. The design of the molecular structures can be engineered to enhance
particular properties (solubility in different solvents, color of light emission, crystal
packing). In particular, addition of polar groups in polymers (e.g. polyvinylidene
fluoride and its copolymers with trifluoroethylene and tetrafluoroethylene) leads
to rich systems for investigation of ferroelectricity [8]. By incorporating them in
transistors (ferroelectric field-effect transistors - FeFETs), combined functionality
can be achieved for non-volatile memory devices that are compatible with flexible plastic substrates [9]. Modification of the chemical end-groups also allows
fabrication of large transistor arrays for organic sensors. Different methods are
developed to increase the sensitivity and selectivity of organic sensing transistors
to different chemical or biological species. Applications include environmental
issues (e.g. air pollution), pH indicators [10], food freshness, toxic compounds,
1
Chapter 1. Introduction
stress and pressure indication in clothes [11].

Rapid progress is being made in the industrial development of the organic
electronic devices. Organic devices can be implemented on large scale application
area when their operation offer high performance, reliability, stability, long life
time, good control and reproducibility. Impressive steps have been accomplished
towards incorporation of organic conductors in devices, as constituents of plastic
electronic components, by continued innovation in materials, processing methods
and device design. For example, Philips and Polymer Vision already presented
their prototype rollable display based on pentacene FETs that will be used for fabrication of mobile phones [12]. OLED1 technology has already been incorporated
in commercial applications such as small displays for mobile phones, car radios,
and digital cameras [13]. It was suggested that if the field continues to progress
at its current, rapid pace, electronics based on organic thin-films materials will
soon become a mainstay of our technological existence (S. Forrest [14]).
In the academic community, the interest in electrical properties of organic materials has grown enormously in the last years [1626]. Different materials and
structures are actively being investigated. On the one hand, the research is motivated by new applications for organic (plastic) electronics that can overcome
limitations of inorganic materials. On the other hand, the effort is driven by
the intellectual challenges that the investigations of new generation of functional
materials offer. This implies addressing new questions, concepts and models that
allow the manipulation of chemical, structural, physical properties and device
performance. The field is moving very fast; at the moment researchers are able to
control the material properties at the molecular level. They can impose different
molecular packing during growth, add side groups that enhance particular properties, as a result of the understanding of the various microscopic contributions to
the charge transport. Past investigations were hindered by material instabilities
(to environmental conditions and/or processing methods) and structural defects
that prevented the measurement and understanding of the intrinsic properties of
the organic materials. In the last years, by careful design of new methods that
enable the exploitation of the fascinating properties of carbon-based semiconductors, good control of the structural properties and charge density distribution in
organic materials is achieved (both by electrostatic and chemical doping). The
degradation is avoided as a consequence of a better understanding of the material
behavior in different conditions (temperature, moisture, light) and interactions
during processing.
1 OLED
- organic light emitting diodes
1.2. Charge transport in organic semiconductors
1.2
Charge transport in organic semiconductors
Organic semiconductors are wide-band-gap and small bandwidth semiconductors.

The HOMO2 -LUMO3 gap is in the range of 1-4 eV [27]. With such a large gap,
it might be expected that the organic materials are insulators (an electron would
have to acquire a large thermal energy to make the jump from the valence band
to the conduction band). There are some effective methods that can generate
charge carriers in the organic semiconductors:
injection of carriers from metallic electrodes;
optical excitation (creation of electron-hole pairs);
electrostatic or chemical doping.
Different organic molecular structures are of current interest for the continued search for novel and useful properties. Carbon nanotubes (CNTs) are onedimensional, cylindrical systems that are attractive for nanometer-sized electronics because they combine the high electrical and thermal conductivity with good
mechanical strength and flexibility [28]. The physical properties of nanotubes
are imposed by their diameter, length, and chirality, or twist. For example, they
can be both metallic and semiconducting, depending on the chirality [29]. Nanotubes are attractive also for the field emission properties [30] because they are
long and very thin, conductive, with high mechanical strength, and have a low
work-function. As the CNTs are generally accepted as being the bridge between
the nano- and microscopic length scales, a step further was done in coupling them
to biological systems aiming the fabrication of biosensors [31, 32]. More recently,
superconductivity has been observed in nanotubes [33].
When the carbon sheet is not rolled into a tube, it forms a graphene sheet.
Graphene is a candidate for nanometer-scale electronic devices that combine the
properties of carbon nanotubes with the compatibility with established microelectronics manufacturing techniques. Low scattering yields mobilities up to 104
cm2 /Vs [34]. This value gives ultra-fast-switching transistors for electronics. Also,
the quantum Hall effect was recently reported in graphene [35].
The most common 3D structure in the fullerene structural family is C60 ,
the spherical buckyball (Fig. 1.1(d)). Because of its particular electronic structure, C60 exhibits semiconducting properties, but it reveals one amazing property after another upon doping [36]. It can be tuned to a metallic or insulating
2 HOMO
3 LUMO
- highest occupied molecular orbital

- lowest unoccupied molecular orbital
state by transferring charge on the molecule through doping. At low temperature this metallic state often exhibits superconductivity, with transition temperatures only exceeded by the high-temperature superconducting copper oxides [37]. This is not an unique type of organic superconductor. Several organic
superconductors have been identified, such as the quasi-one-dimensional Bechgaard salts ((TMTSF)2 X4 and (TMTTF)2 X5 , with X= PF6 , FSO3 , ClO4 ,
etc.), and quasi-two-dimensional salts derived from the donor group BEDT-TTF6
(Fig. 1.1(a)) [38]. Organic superconductors are charge transfer compounds, unconventional superconductors, in which the interchain transfer integral can be
changed with pressure, temperature, and composition (the nature of the anion
X controls the chemical pressure), leading to a delicate balance of interactions
that gives rise to a rich variety of physical phenomena. These include charge ordering, spin-Peierls ground state, antiferromagnetism, spin density waves (SDW),
metallicity and superconductivity [38].
In polymers, the electrical properties are dominated by disorder that localize
the charges at low temperature. Still, these materials present fascinating properties that make them attractive for organic electronic devices [1,2,6]. We presented
in Section 1.1 the potential of polymers, that were already incorporated in commercial devices, as components of the OLEDs. Their semiconducting properties
are also used in FETs and solar cells [1618]. In OLEDs and solar cells an exciton
(excited electron - hole pair) is generated in the organic material. In OLEDs
light is generated through radiative recombination of electrons and holes and it
is emitted through the transparent electrode. Two distinct processes, equally important, govern the operation of the device: charge transport and recombination.
The color of the emitted light is tuned by the band gap of the active material that
is used. In solar cells light is absorbed through the transparent electrode and the
photons absorbed in the semiconductor create mobile excited electron-hole pairs.
These excitons subsequently undergo dissociation yielding free electrons and holes
that are collected at the contacts. The efficiency of the solar cell is given by the
photon absorption efficiency, exciton dissociation efficiency and charge collection
efficiency. Organic photovoltaic devices are limited by exciton lifetime, and low
charge carrier mobilities; only a fraction of the light-induced excitons contribute
to the current generation. Tang et al. demonstrated that the efficiency can be increased considerably if a heterojunction of a electron donor and electron acceptor
material is manufactured [39]. To enhance the quantum separation efficiency, a
4 TMTSF
stands for tetramethyltetraselenafulvalene

stands for tetramethyltetrathiafulvalene
6 BEDT-TTF stands for bis(ethylenedithio)tetrathiafulvalene
5 TMTTF
Figure 1.1: Chemical formulae of organic molecules with different functionalities.
network of internal heterojunctions, with a large contact area between donor and
acceptor species (referred to as bulk heterojunctions) was proposed [40].
Despite the fast developments in the field of organic electronics and dramatic
improvement in knowledge and manipulation of the charge injection and transport in organic semiconductors, a reliable relation between microscopic properties
and their effect on the physical properties is still under development. There is
significant work done in understanding the mechanism of conduction in organic
semiconductors. Correct correlations between morphology, molecular packing and
the resulting electronic properties are essential, in order to elucidate fundamental
questions regarding charge transport in these materials. Small molecule conductors allow these type of studies. Because of a higher degree of order than
solution-processed polymers, they can be structurally characterized straightforward using diffraction, and microscopy techniques. Complementary to this, the
theoretical modelling can be easier implemented because of the lower complexity
of these systems.
In organic molecular solids, the intermolecular forces are weak (van der Waals
and electrostatic type). A detailed description of these issues will be developed
in Section 1.4. The bonding energies are considerably lower than in covalent and
ionic inorganic semiconductors [27, 41]. For this reason, the mechanism of charge
transport is fundamentally different. In organic conductors, the charge carriers
interact strongly with the lattice environment leading to polarization effects and
tendency of charge carrier localization. The weak van der Waals interactions result
in a small electronic bandwidth, strong electron-lattice interaction, and polaron
formation. For example, calculations performed on organic molecular crystals
that are free of defects, yield bandwidths in the order of 0.1-0.5 eV [4247]. This
is more that one order of magnitude lower than the bandwidth in silicon ( 10
eV, [48]). The small bandwidths is reflected in low charge carrier mobilities (105 10 cm2 /Vs [1626] for organic semiconductors, compared to 50-500 cm2 /Vs in
silicon [49]), and strong interactions between free charge carriers and the lattice.
This interaction facilitates the localization of the charge carriers and narrowing
of the bandwidths even further, and thus are expected to crucially affect the
transport properties. Considerable effort is involved in describing the polaron
dynamics, lifetime, binding energies, and diffusion in the lattice [50, 51].
The mobility of the charge carriers reflects the drift velocity of the charges in
the lattice, thus it is influenced by all interactions that it encounters:
=
vd
E
(1.1)
where is the drift mobility, vd is the drift velocity and E the electric field.
Scattering by defects, impurities and phonons (lattice vibrations) will decrease

the drift velocity of charges, thus the electronic mobility. The conductivity of the
material is given by charge carrier density n and charge carrier mobility .
= ne
(1.2)
where e is the elementary charge. The mobility is influenced by the scattering

events, so that [52]:
e
(1.3)
=
m
where is the time between two consecutive scattering events, and m is the
effective mass. This provides a direct relation between the morphology of the
materials and their mobility. In polymers the conduction ( = 108 104
cm2 /Vs) [16, 17] is limited by disorder and hopping of charges between polymer
chains, and thus is lower than in oligomers ( = 103 10 cm2 /Vs). Even for
the class of oligomer devices, the mobility increases with the degree of structural
order. Structural defects and chemical impurities present in the crystal lattice
promote the localization of the charge carriers. They can either form new states
in the semiconductor band-gap, leading to electronic traps, or scatter the charges.
Both processes result in a decrease of the mobility.
The value of the mobility directly affects the performance of the material in
devices, as it is related with the switching speed. Dramatic improvement in control and understanding of the transport mechanism in organic materials, on the
molecular level, together with the knowledge on the influence of intrinsic and extrinsic factors on a good performance, has been achieved lately (the value of the
mobility increased 5 orders of magnitude in the last 15 years, reaching the value
of amorphous silicon [49]). This is very important, as some of the possible applications, like switching devices for active-matrix flat-panel displays (AMFPDs)
based on OLED displays, active-matrix backplanes of OTFTs (organic thin film
transistors) for electronic paper displays, or radiofrequency identification tags
(RFID) require mobilities greater than 1 cm2 /Vs [53], values already exceeded in
devices built on organic single crystals [19]. Parallel to organic electronic devices,
organic-inorganic hybrids emerge as new applications by coupling high carrier
mobilities inorganic semiconductors with the flexibility of organic materials [54].
Most organic semiconductors behave as either p-type or n-type semiconductors (they have either holes, or electrons as majority carriers) (see Fig. 1.1 c, d).
The absence of ambipolar behavior is a severe limitation for the organic electronic
devices for the fabrication of CMOS7 -like circuits. Different strategies were proposed to overcome this problem. Most of them involve separate steps to fabricate
7 CMOS
- complementary metal oxide semiconductor
n-type and p-type transistors [17,55]. However, for many materials it is generally
accepted that this is not an intrinsic property, but rather a result of trapping of
one type of charge carriers [16] or due to a high energetic barrier for either electron or hole injection from the metal electrodes, which is caused by the relatively
large bandgap of organic semiconductors.
1.3
1.3.1
Organic electronic devices

Field effect transistors - operation principles
Organic semiconductors are active materials in different devices. Field effect transistors, light emitting diodes and solar cells are intensely studied. Organic materials are soft, fragile and relatively reactive, thus the conventional semiconductors
device fabrication technologies are not always compatible with these compounds.
For this reason the intrinsic electronic properties could not be reached in devices for a long period of time. They were explored with different techniques
(e.g. time of flight [56]). Only lately, using innovative approaches, the fabrication
of organic electronic devices was successful and a good reproducibility between
research groups was achieved [19, 24, 25].
Figure 1.2: Structure of a field effect transistor (FET) with organic semiconductor
as active material. The source electrode is connected to the ground.
This convention is valid for all the devices presented in this thesis.
1.3. Organic electronic devices
The field effect transistor (FET) is a three terminal device. The three contacts
are referred to as gate (G), drain (D) and source (S, connected to ground). The
schematic picture of a a FET is drawn in Figure 1.2. The active channel forms at
the semiconductor-insulator interface. The gate insulator acts like a capacitor and
the electric field applied at the gate electrode determines the density of the charge
carriers accumulated at the interface. The current between source and drain is
modulated by the gate voltage (VG ). The operation principle of a FET was
introduced by Lilienfeld [57], in 1930, and later developed by Shockley and Pearson
[58]. In 1947 Bardeen, Brattain and Shockley (Bell Laboratories) discovered the
transistor effect and fabricated the first device [59]. They were awarded the Nobel
Prize in physics in 1956 for their discovery. The first metal-oxide-semiconductor
field-effect transistor (MOSFET) was introduced in 1960 by Khang and Atalla
[60].
MOSFETs, built at the surface of inorganic semiconductors, were intensively
studied, and they are incorporated in integrated circuits [41]. Owing to similar
experimental I-V characteristics between organic field-effect transistors (OFETs)
and MOSFETs, the theory developed for MOSFETs is used as starting point
in modelling the OFET behavior. However, the electrical transport in organic
semiconductors is different than in the covalently bonded inorganic semiconductors. Some attempts to describe the operation principle in OFETs were performed [61, 62].
The transistor channel is active only when the gate voltage (VG ) value exceeds
the value of the threshold voltage (VT ). Below this point, the transistor is turned
off, and there is no conduction between drain and source (sub-threshold region).
In the operation of a FET, two distinct regimes can be distinguished (Fig. 1.3(a)).
In the linear regime (small drain-source VD voltages, VD VG VT ), the current
between drain and source (ID ) depends linearly on the applied voltage (Eq. 1.4).
The device acts as a gate voltage - controlled variable resistor. The value of the
drain current, ID , is given by:
ID =
W
Ci (VG VT )VD
L
(1.4)
where L is the channel length, W is the gate width, Ci is the capacitance per unit
area of the gate insulator. This model assumes constant velocity, electric field,
and inversion layer charge density between the source and the drain. A more
realistic approach accounts for the variation of the inversion layer charge between
source and drain, and yields the following expression for the current:
h
V2i
W
(1.5)
Ci (VG VT )VD D
ID =
L
2
10
Figure 1.3: I V curves for a FET operation. (a) Output characteristics (ID VD )
for different applied gate voltages (VG ). The curves are obtained from
simulating the I V curves that correspond to expression 1.5. The
linear and saturation regimes are indicated. The dotted line points
the pinch-off that separates the linear region of operation on the left
from the saturation region on the right. (b) Transfer characteristics
(ID VG ) for different drain voltages. The curves correspond to experimental points for a pentacene transistor.
At higher VD voltages, the channel is not continuous, but a depletion area forms at
the drain contact. The onset of this region is called pinch-off (Fig. 1.3(a)). Beyond
this point, the operation regime is referred to as saturation regime. The drain
current is now relatively independent of the drain voltage, being only controlled
by the gate voltage, and varies quadratically with the field:
ID =
W
Ci (VG VT )2
2L
(1.6)
Equations 1.4, 1.5, and 1.6 represent expressions that yield the value of the mobility of the semiconductor. The mobility can also be estimated from the gate
voltage sweep (Fig. 1.3(b)), at low drain voltages VD . Here, the expression for
the transconductance (gm ) is:
ID
(1.7)
gm =
VG
From this equation, the value of the mobility can be extracted:
=
L 1 ID
W Ci VD VG VD 0
(1.8)
11
However, all these expressions assume a field independent mobility, and that all
the charges induced by the gate voltage are mobile.
Key parameters in the operation of a FET are the electronic mobility of the
charge carriers and the on/off ratio. The first determines the switching speed and
the maximum current, and the later impose the switching of the device from a
non-conducting (off ) to a conducting state (on).
Good performance organic field-effect transistors (OFETs) were fabricated at
the surface of the organic single crystals using deposition techniques that minimize damage at the interface [19, 24]. Fabrication of devices with competitive
characteristics remains an ambitious task for large-scale applications.
1.3.2
Fabrication of OFETs
Owing to the fragility of organic materials, processing to incorporate them in

electronic devices represents a challenge at this early stage. However, they trigger
interest to develop revolutionary methods that are simple and efficient to be used
for large scale applications. In this section we will describe recent advances in
organic electronic devices, focusing on OFETs fabricated on molecular crystals.
Different device structures were proposed to study the electrical transport at the
surface of organic crystals, in order to measure a high intrinsic mobility, that
is not diminished by disorder introduced during processing. There are many
factors involved in the good performance of the device. In spite of the better
reproducibility that is archived lately, the results reported by different groups
are still not always consistent. This can be attributed in part to the fact that
the performance of the electronic devices depends critically on the quality of the
crystals and the interfaces, as well as on the extrinsic factors (like, for example
the environmental conditions in which the experiments were performed). Organic
semiconductor quality, dielectric properties, contacts, and interface properties are
equally important.
Deposition of the organic semiconductor
The most common method used for the deposition of small molecule conductor
films is vacuum sublimation. The macroscopic electronic properties of the films
are imposed by their crystallinity [53]. Better crystallinity and larger grain size
facilitates higher mobilities. Values of 1 cm2 /Vs were reached in vacuum sublimated pentacene TFTs, after optimization of the fabrication process [85].
We mentioned in Section 1.1 that the highest impact that the organic electronics can produce over traditional Si-based technology, is the relatively easy
12
processing techniques that their deposition requires. Polymers are attractive because they are soluble in organic solvents, thus they can be spin coated or printed
on flexible substrates, forming amorphous or polycrystalline films. Still, the highest mobilities are achieved in devices build with small molecules. A drawback is
that their solubility is limited and they require deposition methods like vacuum
sublimation, or physical vapor deposition. These demands are not straightforward
to accomplish. Because a high electronic mobility is not sufficient for a material
to be competitive for large scale applications, scientists develop different methods
to facilitate the compatibility with cheap and easy solution processing techniques.
Herwig et al. proposed a synthetic concept for fabrication of a soluble pentacene
precursor [63]. The precursor is converted to pentacene via thermal [63] or irradiative [64] treatment, and the obtained thin film transistors (TFTs) exhibit
mobilities of 0.2 cm2 /Vs. A different route to increase the solubility of oligomers
is the attachment of flexible side groups. At the molecular design, careful attention is payed to the interplay between the degree of solubility and the molecular
stacking that the side group induces. Field-effect transistors with maximum mobilities of 0.01 cm2 /Vs were fabricated from quaterthiophene and hexathiophene
end-substituted with 3-butoxypropyl groups [65].
The above mentioned directions represent a compromise, a balance between
performance and cost, because the mobility of materials deposited from solution
remains lower than that of the thermal evaporated material [19, 20]. Moreover,
in polycrystalline films [20, 21, 23], the mobility is lower than in single crystals
[19, 2426]. This is partially caused by a large grain boundary resistance.
Gate dielectric materials
In field-effect transistors the conduction takes place at the surface of the semiconductor, thus the performance is limited by the quality of the interface between
organic and dielectric, and only in part by the bulk properties. This is evident
from experiments that demonstrate that the gate insulator can modify the charge
density at the interface, having a crucial effect on the operation of both polymer [66] and small molecule [67] devices. Particularly important are the roughness
of the semiconductor/dielectric interface, and the density of defects and impurities present in this region. Different treatments of the dielectric were proposed in
order to decrease the trap density (e.g. OTS8 treatment [68]).
General requirements for a high quality dielectric include several parameters.
The introduction of a large capacitance, that governs the magnitude of charge
8 OTS
denotes octadecyltrichlorosilane
13
Figure 1.4: Different geometries of the OFETs. Source (S), drain (D), and gate
electrodes are indicated. The transport takes place at the interface
between semiconductor layer and gate insulator layer. (a) bottomgate geometry; (b) top-gate geometry.
induced in the channel by gate effect, can be done using high-k dielectrics or by
varying their thickness. Besides this, a good insulator in FETs should account
for a large breakdown voltage and low leakage currents, excellent thermal and
chemical stability. There are three classes of dielectric materials incorporated in
OTFTs [69]: inorganic dielectric materials (e.g. SiO2 , Ta2 O5 , Al2 O3 ), organic
dielectric materials (e.g. parylene, PS9 , PMMA10 , Fig. 1.1(e)) and self-assembled
mono-and multilayers. In FETs with top-gate configuration (Fig. 1.4(a)), the
deposition of inorganic dielectrics partially damages the surface of the organic
crystals and introduces chemical and structural disorder, due to violent processing methods (sputtering, e-beam, plasma-enhanced chemical vapor deposition).
This is the reason why organic dielectrics are used only in bottom-gate devices
(Fig. 1.4(b)). The deposition of an organic dielectric requires lower temperatures
(typical deposition techniques are spin-coating, casting, and printing), are not
destructive, and yield remarkably high mobilities (8 cm2 /Vs in rubrene single
crystals transistors with parylene gate dielectric [24]).
Contacts
Contact issues are amply discussed in the field of molecular electronics. Different
models are proposed, as it is believed that the charge transport is either limited by
injection problems due to poorly defined contacts, or by bulk conductivity. Baldo
9 PS
denotes polystyrene
denotes polymethylmethacrylate
10 PMMA
14
et al. elaborated an interface injection model, that accounts for two distinct
injection steps [70]. During the first step, charges are injected from the contacts
into an interface region that contain a broad distribution of states induced by
interface dipoles. In the second, limiting step, the charges migrate from the
interface to the bulk region.
Two types of device geometries are used in the fabrication of the field-effect
transistors: top-contact and bottom-contact structures. In the first case, it was
observed that the deposition of contacts on the organic semiconductors inflicts
with their chemical and mechanical fragility, and introduce traps locally, at the
metal/organic interface [71]. Different deposition methods are used, depending
on the nature of the contact. Metal contacts are usually evaporated or sputtered
using shadow masks, or painted (the latter method is also applied for colloidal
graphite paste). The choice of the metal contact gives the value of the Schottky
barrier, thus the deviation from the ohmic regime, and also the type of the majority carriers. Alternative contact materials, with specific deposition requirements
were proposed and successfully applied. Room temperature lamination of metal
coated elastomeric stamps (e.g. PDMS11 [19]) represents a non-destructive, high
resolution method to fabricate contacts. The polymer PANI12 and the copolymer
PEDOT:PSS13 (Fig. 1.1(b)) are currently widely used in organic devices, especially OLEDs and solar cells because of their excellent transparency in the visible
region, but also in FETs due to good electrical conductivity, and environmental
stability [72].
1.3.3
Outlook
Reviewing the recent advances in materials, methods and emerging applications,

two very important issues can be mentioned. Firstly, organic semiconductor research is an exciting and interdisciplinary area of current research activity that
raised the interest of theorists, chemists, physicists, and device scientists and is
developing extremely fast. Secondly, organic materials impose a new way of thinking because they exhibit a wide range of electrical properties, being tunable from
insulator (in gate dielectrics) to semiconductor (as active layers in devices), to
metal, and even superconductor. A scheme with the wide range of functionalities
that the organic materials offer can be found in Figure 1.1(a-e). These diverse
properties are spectacular and give the opportunity of building all-organic devices.
11 PDMS
denotes polydimethylsiloxane
denotes polyaniline
13 PEDOT:PSS denotes polyethylene(3,4-dioxythiophene)/polystyrene sulfonate
12 PANI
1.4. Organic molecular crystals
1.4
15
Organic molecular crystals
Characteristic of organic semiconductors are the intramolecular bonds. The

alternation of single () and double () bonds, referred to as conjugation, is typical for organic conductors. The Carbon atoms involved in this type of bonding
are sp2 hybridized. The three hybrid sp2 orbitals form the bonds, with the
-electrons being highly localized. The remaining nonhybridized pz orbitals of
adjacent Carbons form the - orbitals perpendicular to the bonds and delocalized over the molecule. The bonds are very strong (they are positioned lower
in energy). The molecular orbitals that are filled (-bonding orbitals) form the
valence states. The filled orbital with the highest energy is called the Highest
Occupied Molecular Orbital. The vacant orbitals ( -antibonding orbitals) form
the conduction band, with LUMO being the Lowest Unoccupied Molecular Orbital. The -electrons are responsible for an important part of the intermolecular
conduction in these materials. Besides this, the molecular packing in the solid,
imposed by the physical interactions, determine the physical properties, e.g. the
electronic transport.
The intermolecular forces are weak, and result from the cooperation and
competition between and interactions. The interaction energy between molecules originates from several contributions. The electrostatic interaction between permanent multipoles (usually quadrupoles), and the dispersion
(van der Waals) forces between induced dipoles represent the dominant force.
The interaction between the permanent multipoles and the induced multipoles,
called induction, is generally treated as a second order term. In a simple pictorial
model, the van der Waals forces between molecules originate from the instantaneous polarization of the neutral molecules into dipoles [27]. The temporary
generated dipoles promote the formation of new induced dipoles in neighboring
molecules and spread in the lattice. For interplanar separation that characterize
organic molecular crystals (d > 3.4
A [32]), the van der Waals forces are always
attractive. The quadrupolar interactions emerge from the coupling between the
permanent quadrupolar moments of the molecules [73, 74], and can be attractive
or repulsive, depending on the relative orientation of the quadrupoles.
The crystal structure is determined by an interplay between van der Waals
forces and quadrupolar interactions. The two competing interactions promote
different molecular stacking that minimize the energy. The van der Waals interactions are optimized for face-to-face orientation of the molecules, that result
in the maximum overlap. On the other hand, the presence of quadrupolar
moments favor the edge-to-face stacking, in which the hydrogen on one ring
16
Figure 1.5: Crystal structure of pentacene single crystal. Left panel: view along
the [100] axis (the layered structure can be seen). Right panel: the
herringbone arrangement within the layer, view along the long axis of
the molecule. The unit cell orientation is also drawn.
encounter the network of the adjacent molecule. The most common crystal
packing that results from the afore mentioned mechanisms is the herringbonearrangement (Fig. 1.5). Oligomers often crystallize in a layered fashion, and
the molecular arrangement within the layers is imposed by the van der Waals
and quadrupolar interactions. Gavezzotti et al. distinguished four possible herringbone modes in which polynuclear aromatic hydrocarbons pack: herringbone
structure (naphthalene, anthracene, pentacene ), sandwich herringbone structure
(pyrene, perylene), structure (benzopyrene, coronene), structure (trybenzopyrene, tetrabenzoperylene) [75]. Cofacial -stacking in molecular crystals is hardly
ever found. Anthony et al. synthesized these types of structure by substitution
of different groups to pentacene backbone [76]. They showed that different type
and amount of -overlap can be controlled by the nature, size and position of the
substituent, leading to various stacking motifs. Although seldom encountered,
cofacial configurations are particularly attractive because they accommodate the
largest electronic splitting in the HOMO and LUMO levels, promoting the highest theoretical predicted charge carrier mobilities [77]. In the local picture (as
opposed to the band picture) of the charge transport in organic conjugated materials, the efficiency of this process reflects how easy the charges are transferred
1.4. Organic molecular crystals
17
between neighboring sites, and, as expected, is very sensitive to orientation of the

molecules with respect to each other. The electronic coupling between adjacent
molecules, quantified by the transfer integral t, is modulated by the molecular
arrangement and directly associated with the electronic mobility [45, 46, 77]. In
the framework of these calculations, the amplitude of the electronic coupling is
influenced by the intermolecular separation distance, the molecular overlap, the
length of the molecule, and, in the case of herringbone structures, the rotation
of molecular planes [77]. Additionally, the relevance of thermal motions in the
modulation of the electronic coupling between molecules in an an organic solid
was demonstrated [45].
Owing to the weak interaction forces between molecules in the solid, small
variations in the crystal packing can be present, leading to polymorphism. The
term polymorphism refers to the existence of more than one crystal structure
for a particular compound. This phenomenon is frequently displayed by organic
crystals and is driven by the growth conditions and/or subsequent treatment. In
rubrene, different polymorphs can be obtained, depending on the pressure in the
system in which the starting material is sublimed (see Chapter. 6 in this thesis
and the references therein). In quaterthiophene (4T) [79] and sexithiophene
(6T) [80, 81] different molecular arrangements are induced by the source temperature. The general picture is even more complex in pentacene films, where
four polymorphs were detected [78, 82]. The obtained polymorph is dictated by
the substrate type, the substrate temperature and the thickness of the film. For
pentacene single crystals, only one polymorph exists [78].
The existence of different polymorphs for some molecular crystals provides
a unique opportunity to understand the influence of the crystal packing on the
electronic properties, since these systems only differ with the orientation of the
constituent building blocks with respect to each other, the molecule being the
same [42, 46, 81]. For example, Troisi and Orlandi performed band structure
calculations on the four pentacene polymorphs and found that the mobility tensor
is highly anisotropic for three of the four considered polymorphs [83]. This result
is relevant for understanding the fundamental mechanisms of charge transport in
organic crystals.
18
1.5
Single crystals - model systems for investigation of intrinsic properties
The progress in the field of organic electronics requires a good fundamental understanding of factors that influence the electronic behavior. This leads to a better
control of the microscopic properties that determine the conduction of the materials used in the devices. A correct insight on the interplay between the effects of
chemical structure and molecular orientation on the transport process can only
be accomplished when single crystals are used.
Single crystals are not meant to be incorporated in applications, but to provide
a well defined structure, in which the intrinsic electronic properties of the material
can be measured [19,2426,84]. They serve as model systems, for which structureproperties correlations can be explored.
Although thin films (polycrystalline or amorphous) are more attractive for
organic electronic devices, here the intrinsic properties are generally masked by
grain boundaries where structural defects localize and trap the charge carriers.
The major limitation of thin-film transistors (TFTs) comes from the fact that their
performance is severely dependent on the fabrication conditions. Moreover, even
films that are grown in an identical manner can exhibit very different electrical
properties [85].
The electrical properties of organic single crystals have been successfully probed
by time-of-flight (TOF) [56] and space-charge-limited current (SCLC) methods
[26], as well as field-effect transistor (FET) experiments [19, 24, 25].
1.6
Aim of the present research
Motivated by the various properties that organic semiconductors reveal, we evaluate in this thesis a critical analysis of the different factors that determine the
electrical conduction in these materials. Although the progress is fast, both in
performance and reliability, there are still numerous questions that lack an answer,
or for which inconsistent explanations were given.
The questions we address in this thesis concern intrinsic and extrinsic factors
that determine the charge transport in organic conductors. In order to answer
these questions we focus our work on single crystals (the advantages of working
with single crystals are outlined in Section 1.5). We systematically study the effect
of structural defects and impurities (Chapter 2, Chapter 3), geometrical factors
(Chapter 4), molecular stacking (Chapter 6) and exposure to ambient conditions
1.7. Outline of the thesis
19
(Chapter 5).
While the organic field-effect transistor characteristics were improved in the
past years by implementation of novel processing techniques, the charge carrier
mobility remains limited. In this context, our efforts focus on the understanding
of the microscopic processes that determine the value of the mobility in molecular
crystals, in particular the generation and migration of defects. The work aims
not only at improving the performance of organic materials for possible incorporation in devices, but also at satisfying the pressing need for insight into the
relevant physical processes that govern the electrical conduction in these materials. We show that even small defect densities are critical and act as charge traps,
consequently decreasing the mobility significantly. By systematic measurements,
we demonstrate that the origin of defects is of dual nature. The trapping sites
such as crystal defects and chemical impurities are created during crystal growth.
Additional traps are introduced during processing or exposure to ambient conditions. Moreover, we propose successful methods that allow the study of high
quality materials with desired properties.
Furthermore, we incorporate the investigated materials into field-effect devices. Here, the conduction channel is limited to the vicinity of the interface. We
show that the conductivity is strongly influenced by disorder and charge traps
near the interface, and propose a reliable method to overcome this limitation.
Hence, our efforts can broadly be defined as contributions in the area of fundamental and applied studies on the organic molecular crystals properties. By
means of correlations between electrical measurements and structural properties,
determined via X-ray diffraction, or thermodynamic response via thermogravimetric experiments, we wish to cover important features of the chemical, physical
and technological problems that arise in these materials.
1.7
Outline of the thesis
This thesis is organized as follows:

Chapter 2 emphasizes the importance of the control of defects and impurity
states in organic molecular crystals in order to obtain a high electronic mobility. We measure record electronic mobilities as a result of the reduction of the
number of traps by careful crystal growth and subsequent handling. The temperature dependence of the mobility is consistent with the band model for electronic
transport.
In recent studies, little attention is paid to the concentration, distribution
of impurities and their consequences on electronic properties. Thus far, it has
20
been generally assumed that the impurities are evenly distributed throughout
the lattice. In Chapter 3 we will show that this is not the case for pentacene
single crystals, where the impurities are are located preferentially at the surface.
Moreover, we describe a new, reliable method, and demonstrate that in our fieldeffect transistor devices the impurity states at the interface can be made inactive
by incorporating them into the dielectric gate barrier.
In Chapter 4 we give a geometrical description of the electric field distribution
in organic crystals. We report the cross-over from 1D to 2D - space charge limited
conduction in pentacene single crystals with planar contacts. Furthermore, we
establish the parameters for which the conduction is dominated by bulk charges
and show that the transition to a surface-governed transport takes place gradually.
These results incorporate corrections for the anisotropic resistivity.
Chapter 5 is dedicated to the effect of air exposure on the electronic properties of pentacene single crystals. We show experimentally that air can diffuse
reversibly in and out of the crystals. This process is reflected in the electrical
properties. We are able to distinguish two competing mechanisms that modulate
the electronic transport: the doping effect of oxygen and the trapping caused by
the presence of water vapor. By combining the gravimetric and electric measurements, we can describe quantitatively these effects.
The investigations that yield the results presented in Chapters 2, 3, 4, and 5
focused on the study of pentacene single crystals, the first organic crystalline
material already incorporated in prototypes of commercial devices [20]. The measurements discussed in Chapter 6 were motivated by intriguing changes observed
in the values of electronic mobility of rubrene single crystals at low temperatures.
We relate this changes with the structural transformations in the material.
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[62] G. Horowitz, and P. Delannoy, J. App. Phys. 70, 469 (1991)
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[65] H. E. Katz, A. J. Lovinger, J. Johnson, C. Kloc, T. Siergist, W. Li, Y.-Y.
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26
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Lett. 72, 1854 (1998)
The Effect of Impurities on the Mobility

of Single Crystal Pentacene
We have obtained a hole mobility for the organic conductor pentacene (in the
single crystal form) of = 35 cm2 /Vs at room temperature increasing to = 58
cm2 /Vs at 225 K. These high mobilities result from a purification process in which
6,13-pentacenequinone was removed by vacuum sublimation. The number of traps
is reduced by two orders of magnitude compared with conventional methods. The
temperature dependence of the mobility is consistent with the band model for
electronic transport.
This Chapter is adapted from O. D. Jurchescu, J. Baas, and T. T. M. Palstra, Appl. Phys.
Lett. 84, 3061 (2004).
27
28
2.1
Chapter 2. The Effect of Impurities on the Mobility
Introduction
Organic materials are presently being investigated and incorporated in semiconductor devices for a new era of the electronics industry. The understanding of the
electrical conduction mechanism in these materials and at their interfaces represents a challenge, for which various, often conflicting models have been proposed.
Molecular crystals are formed by relatively weak van der Waals interaction between molecules, and the molecular packing determines the electronic behavior.
Thus the charge carrier transport must be described using completely different
models than for covalently bonded semiconductors. Of the many molecular conductors, pentacene is a promising candidate for future electronic devices and an
interesting model system. Recent improvements in electronic applications showed
that this material exhibits mobilities higher than 1 cm2 /Vs for TFTs made from
highly ordered films [1,2]. A mobility up to 8 cm2 /Vs was measured in single crystals of rubrene using a complete organic field-effect transistor [3]. The anisotropy
of mobility, and a band-like temperature dependence was demonstrated in rubrene
FETs with PDMS flexible elastomeric stamps as substrate, and air-gap as gate
dielectric. This fabrication method yields mobilities as high as 15 cm2 /Vs at
room temperature [4] and 20 cm2 /Vs using the 4-probe measurements [5]. The
above mentioned values for mobilities reflected hole transport. By using the last
mentioned approach, electron mobilities of 1.6 cm2 /Vs were measured for TCNQ
(7,7,8,8-tetracyanoquinodimethane) single crystals [6]. The importance of impurities for the limitations in device performance has been emphasized during the
last few years. However, little quantitative analysis concerning the consequences
of impurities is incorporated in recent studies [7].
2.2
Control of the defects and impurity states in

organic crystals
We report a mobility of = 35 cm2 /Vs at room temperature increasing to = 58

cm2 /Vs at 225 K for ultra-pure pentacene single crystals. The crystals were
obtained by vapor transport growth in argon flow after purification of the material
by a vacuum sublimation technique designed to remove pentacenequinone. The
content of the quinone impurity in pentacene was determined using high pressure
liquid chromatography technique (HPLC), indicating a reduction by almost one
order of magnitude. The structures of pentacene and 6,13-pentacenequinone,
respectively, are shown in Figure 2.1.
2.2. Control of the defects and impurity states in organic crystals
2.2.1
29
Spectroscopic evidence for the presence of impurities
Figure 2.1: Molecular structure of pentacene (a) and 6,13-pentacenequinone (b).
Figure 2.2: Left panel: IR spectrum of pentacene powder without any additional
purification. The presence of the peak around 1697 cm1 is due to
quinone impurities. Right panel: mass spectrum of the starting material. The peak at m/z = 278 corresponds to pentacene and the one
at m/z = 308 is a result of the presence of 6,13-pentacenequinone.
The starting material for the experiment was pentacene obtained from Aldrich.
Infrared absorption measurements (Nicolet Nexus spectrometer) show that 6,13pentacenequinone is present as an impurity. The evidence for this is the absorption
peak at 1697 cm1 which is assigned to a C=O bond vibration (Fig. 2.2 - left
panel). The pure material does not have significant absorption in this region. The
infrared experiments were complemented by mass spectrometry analysis, which
30
confirmed that the C=O vibration originates from a pentacenequinone molecule

(Fig. 2.2- right panel).
2.2.2
Purification of the starting material
We have used vacuum sublimation under a temperature gradient as purification

method. This technique is effective for the separation of impurities from a solid
if these impurities have a vapor pressure that is sufficiently different from the
desired product [8]. The cleaning tube is shown in Figure 2.3. The pentacene
powder is placed in an alumina boat inside a glass tube that is thoroughly cleaned
chemically, and then heated in a furnace under vacuum to remove the solvents
used for cleaning. A controlled temperature gradient is applied along this tube.
The purification takes place at T = 430 K for 70 h under a dynamic vacuum
of a membrane pump. Special attention is paid to avoid contamination due to
vacuum connections. The sublimated molecules will condense in the cold zone
of the tube. The entire set-up is placed in the dark to prevent UV degradation
of the acene molecules. The carbonyl groups at each side of the middle ring
reduce the sublimation enthalpy compared to the host molecule, thus at T = 430
K pentacene will not sublime and only quinone will be removed. This can be
detected as a brown powder on the walls of the tube. The violet powder that
did not sublime is purified pentacene that is used as the starting material for
the single crystal growth. We repeat this purification process several times to
minimize the impurity content. We will present in Section 2.2.4 the effect of the
different sublimation steps on the degree of purity.
Figure 2.3: Schematic overview of the vacuum sublimation set-up used to remove
the 6,13-pentacenequinone from pentacene.
2.2.3
31
Single crystal growth
Pentacene single crystals were obtained using physical vapor transport in a horizontal glass tube [9] under a stream of argon. The use of ultra-pure argon without
hydrogen as the transporting gas is motivated by the need to prevent the introduction of other impurities, like 6,13-dihydropentacene in the crystal, which can form
by the hydrogenation of the acene at the middle ring (most reactive positions).
Figure 2.4: Crystal growth setup. The source material is placed in the boat in
the hot part of the tube and it is transported by the inert gas to the
crystallization region. The temperature profile of the growth tube is
shown in the lower panel.
The gas was obtained from AGA, with purity of 99.999%. A drying column
was inserted in the system for additional purification of the gas. We paid attention
to the quality of the transporting gas because the quinone can be re-introduced by
residual water or oxygen as ppm impurities in the carrier gas during growth. The
growth tube set-up is presented in Figure 2.4 (upper panel). Prior to growth, the
inner tube was cleaned with soap, type II water (
= Mcm at 25 C), acetone
and alcohol. The empty tube was heated in argon flow at T = 620 K for 15 hours
32
to remove possible water and other solvents. 30 40 mg of the source pre-cleaned

material was placed at the end of the tube in an alumina boat. A temperature
gradient was applied by resistive heating of two heater coils around the tube. The
temperature profile is shown in Figure 2.4 (lower panel). The temperature was
controlled using two thermocouples, placed at positions marked with labels T1
and T2 . The sublimation temperature, Ts = 545 K, was kept as low as possible,
in order to obtain a low crystallization rate that ensures a minimum formation
of defects and avoids side reactions [10]. The setup was placed in the dark to
protect against oxidation. The molecules, in the vapor phase, are transported by
the argon gas and will crystallize in the cold part of the tube (approx. 30 cm from
the sublimation point. The crystals are platelet-shaped and their dimensions can
be controlled by the growth time. Typical growth time is around 3 days. This
yields crystals of maximum 4 4 mm in plane and 50 m thickness.
After obtaining ultra-pure crystals, they were annealed for 50 h at a lower
temperature (Th = 450 K) than the crystallization temperature (Tc = 490 K).
This treatment diminishes the number of dislocations and the stress in the crystal.
The crystal structure of pentacene single crystals at room temperature is given
in the Appendix A of this thesis.
Without pre-purification of the pentacene, pentacenequinone will sublime together with the host molecule. Part of it will be introduced in the pentacene
matrix in the crystallization process at the low temperature part of the tube.
2.2.4
Quantitative analysis of 6,13-pentacenequinone content
We used HPLC (Agilent 1100 LC/MSD) [11] to determine the impurity concentration of the pentacenequinone in pentacene single crystals. Pentacene crystals
were dissolved in 1,2,4-trichlorobenzene by stirring for 24 h at 45 C under inert
atmosphere (in the glove-box).
Pentacene (P) and pentacenequinone (PQ) were separated on a silica column.
The selectivity for retention was controlled with a 3 : 1 v/v mixture of 1,2,4trichlorobenzene and cyclohexane used as mobile phase, at 80 C. The volume
of the sample injected was 50 l. We used the Beers law [12] to determine the
concentration of pentacenequinone impurity in pentacene single crystals. The
absorbance A at a particular wavelength is proportional to the concentration c
of the constituent species:
A() = b()c
(2.1)
where b is optical path length and () is the extinction coefficient at . Com-
33
Figure 2.5: Retention times for pentacene (P) and pentacenequinone (PQ) at =
390 nm. Upper panel: P with 0.4% PQ. Lower panel: P enriched with
30% PQ
bining the expressions for the absorbance of P and PQ, corresponding to the two
peak areas in Figure 2.5, we obtain the relative concentration (c%) of PQ in P.
The expression that allows the calculation of concentration involve the extinction
coefficients (P , P Q ), peak areas (AP , AP Q ) and molar masses (MQ , MP Q ) of
the two components:
H
(2.2)
cP Q (%) = 100
1+H
where we define H:
AP Q P MP Q
(2.3)
H=
AP P Q MP
The amount of quinone was determined from the integrated intensity of the
chromatogram, using a diode array UV-Vis detector that can be tuned at different absorption lines (Fig. 2.5). We have chosen = 390 nm because it corresponds to a low extinction coefficient for pentacene, and much higher value for
pentacenequinone [13]:
(
log(P ) = 2.75
(2.4)
log(P Q ) = 4.389
Figure 2.5 presents typical HPLC measurements from which pentacenequinone
concentration in pentacene was calculated. The retention times for pentacene and
pentacenequinone were 2 min, and 11 min respectively. The upper panel
corresponds to 0.4% PQ in P. We deliberately introduced pentacenequinone in
34
Figure 2.6: 6,13-pentacenequinone concentration in pentacene in different stages

of purification: 1- as received, 2- single sublimation clean, 3- double
sublimation cycle, 4- crystal grown from untreated powder, 5- crystal
grown from doubly cleaned powder.
the solution obtained from the solvation of a pentacene single crystals. This can
be seen as an enhanced signal at time = 11 min in the lower panel of Figure 2.5,
that corresponds to 30% PQ content. Additional peaks, of lower intensity, arising
from other impurities can be detected in both panels of Figure 2.5. However, in
this study we did not concentrate on the quantitative evaluation of their content,
but we focus only on the majority impurity.
The quinone concentration was reduced from the as received material containing 0.68% in two sublimation steps to 0.17%. Subsequent crystal growth reduces
the quinone concentration to 0.028%(0.004) compared with 0.11%(0.006) in
crystals grown from untreated powder (Fig. 2.6). The characteristic absorption
of C=O is observable even for the purest crystals (stage 5 in Fig. 2.6). We will
show in Chapter 3 that this small quantity of pentacenequinone impurity still
present in pentacene single crystals is critical for the fabrication and operation of
the field-effect transistors.
2.3. Electronic response to structural and chemical properties
2.3
35
Electronic response to structural and chemical properties
2.3.1
Space charge limited currents
We determined the electrical properties of the pure pentacene single crystals using
space-charge-limited current (SCLC) measurements (Fig. 2.7). Gold was used as
hole-injecting electrode. The samples were measured in dark and a vacuum of
2 107 mbar.
In the analysis of the evolution of the current density J with respect to the
applied electric field E several assumptions are made. Following the standard
analysis [7, 14, 15], we consider:
a 1-dimensional, unipolar current flow (holes are injected from the contact
placed at position x = 0 and collected at the contact at x = L);
the contacts are ohmic;
the mobility of free charge carriers is independent of the magnitude of the
applied electric field;
the diffusion of charge carriers inside the crystal is neglected;
the injecting contact is an infinite source of charge carriers;
the traps are homogenously distributed in space and all correspond to one
discrete energy level;
the density of free charge carriers (nf ) is described by Boltzmann statistics,
and the density of the trapped (localized) carriers (nt ) follows the FermiDirac statistics, as follows:
E (x)
F
nf = NV exp
kT
(2.5)
nt =
(2.6)
h(E)

F (x)
1 + exp Ei E
kT
Here NV is the effective density of states in the valence band, EF the Fermi
level, Ei stands for the energy, h(E) describes the energetic distribution of
localized states, and k is Boltzmanns constant.
36
Figure 2.7: Current density (J) vs. electric field (E) for pentacene single crystal
at room temperature. The solid lines represent the fits for the three
different regimes. The value of the electric field that corresponds to
the transition to the trap-free regime (ET F L ) is shown. The inset
shows experimental configuration of the a, b, and c*-axis, and the
contacts.
Four distinct regimes can be distinguished in the evolution of the current with
the applied electric field (see Fig. 2.7). At small electrical fields the transport is
ohmic, and the current density depends linearly on the electric field. The current
is space charge limited (SCLC) at high electric fields. In the first part of the SCLC
regime, the injected carriers are trapped and the current is reduced by a factor
, which represents the ratio between free and total number of charge carriers
introduced in the solid (Eq. 2.7):
=
nf
nf
=
ntot
nf + nt
(2.7)
where nf and nt are the free and trapped carriers density, respectively, and ntot
is the total carrier density. At VT F L /ET F L (trap-filling voltage) the current rises
abruptly. After this point, all the traps are filled and the trap-free regime is
reached ( = 1).
The expression that describes the current-voltage (density of current - electric
field) are obtained upon combining several expressions:
37
the continuity equation (Eq. 2.8) [14, 16]:

J(x) = enf (x)E(x)
(2.8)
where J(x) is the current density at distance x from injecting electrode, e is

the elementary charge, is the charge carrier mobility and E is the electric
field,
Poissons equation (Eq. 2.9):

dE(x)
e
e
ntot (x) =
[nf (x) + nt (x)]
=
dx
0 r
0 r
(2.9)
Combining equations 2.7, 2.8, and 2.9, the expression of the current becomes:
J = 0 r E
dE
dx
(2.10)
By integrating this expression, one obtains:

Jx
E 2 (x) E 2 (0)
=
0 r
2
(2.11)
Taking into account the assumption made previously, the electric field at the
injecting electrode (x=0) is E(0)=0, Eq 2.11 becomes:
s
2Jx
(2.12)
E(x) =
0 r
Integration of Eq 2.12, together with the use of the boundary conditions imposed
in the beginning, yields the expression of the density of current versus electric
field (Mott-Gurney law) [7, 14]:
JSCLC =
9
V2
0 r 3
8
L
(2.13)
where JSCLC is the current density in the space-charge-limited regime, V is the

applied voltage across a length L, r is the dielectric constant of the conductor (for
which we use the literature value r =3), and the ratio between the concentration
of free carriers and the total numbers of carriers (see Eq. 2.7).
The mobility in our experiments was calculated from the trap-free region of
the space-charge-limited-current regime, using the Mott-Gurney model (Eq. 2.13).
We note that this formula was derived for the sandwich-type electrode geometry,
38
Figure 2.8: Temperature dependence of the electrical hole mobility for a pentacene single crystal using the actual crystal thickness () and the
effective thickness ().
whereas we use a gap-type geometry. A description of the two types of structure,

and a detailed study on the evaluation of the current-voltage characteristics will
be presented in Chapter 4. The value of the number of traps Nt can be calculated
from the value of the trap-filling voltage (VT F L ):
VT F L =
2 eL2
Nt
3 0 r
(2.14)
The SCLC measurements show that the pentacene single crystals grown after precleaning of the starting material are very pure, with Nt = 1.74 1011 traps/cm3 .
This is almost two orders of magnitude lower than the number of traps obtained
for crystals grown with the conventional procedures [17].
2.3.2
Evaluation of the bulk mobility of the high quality

crystals
If we assume a homogeneous current flow through the sample, the mobility is

= 11.2 cm2 /Vs. However, as the mobility in the basal plane ab is much larger
than the mobility along the c* -axis (perpendicular to ab plane), the current will
be confined to the contacts side of the crystal. The measurements of the ohmic
39
regime of the current-voltage characteristic showed different values for the resistivity for different directions (a = 1.3 106 m, b = 4.7 105 m, c = 2.1 108
m). We have used Montgomerys method [18, 19] for analyzing anisotropic
materials, transforming an anisotropic sample with resistivities a , b , and c
and dimensions x, y, and z, to an isotropic solid with dimensions x , y and z .
For the isotropic solid, the normalized effective thickness is determined to be
zef f /(x y )1/2 = 0.7 for normalized sample thickness z /(x y )1/2 = 2.19 and the
ratio for the in-plane directions y /x = 0.535. Using this procedure, the relation
between the effective thickness (zef f ) and the real thickness of the crystal (z) is
calculated. Eq. 2.15 expresses the conversion for the two dimensions:
zef f = 0.32 z.
(2.15)
With the effective thickness introduced in the current density JSCLC,tf in

Eq. 2.13, for the trap-free regime, the calculated mobility increases by more than
a factor of three (see Fig. 2.8). Therefore, a more accurate value for the mobility
is = 35 cm2 /Vs at 290 K and = 58 cm2 /Vs at 225 K. We note that the
Montgomery method is only valid in the linear part of the I V regime. For
I V 2 the effective thickness (zef f ) should be considered as the upper limit.
Thus, this analysis provides a lower limit of the intrinsic mobility.
2.3.3
Band transport in pentacene single crystals
Fig. 2.8 shows that below room temperature the mobility increases with decreasing
temperature following the relation:
= C T 2.38
(2.16)
This behavior is noticed in several samples and it is consistent with a band model
for charge transport in pentacene [14], with the interaction of the delocalized carriers with the phonons, the main scattering process. Above room temperature a
different transport mechanism dominates the mobility. This low temperature dependence was earlier suggested by time-of-flight experiments on single crystals of
naphthalene and anthracene [20]. In this Chapter we present the low-temperature
electrical measurements performed on organic single crystals pentacene, that also
point to a band-type conduction. We were able do reproduce the early TOF experiments in electrical measurements using crystals with a high degree of purity
(Nt = 1.74 1011 traps/cm3 ). The metallic-like behavior was also demonstrated in field-effect transistors built at the surface of high quality rubrene single
crystals [4, 5]. Previous electrical measurements on organic crystals were dominated by defects and impurities that severely localized the charges. This was
40
reflected in a lower mobility than the intrinsic one, and a thermally activated
charge transport, which is also not of intrinsic origin. In the band-like picture
of the transport in molecular crystals (Fig. 2.9(a)), the mobility decreases with
increasing temperature due to electron-phonon coupling. The scattering events
involve interactions with defects and lattice vibrations. The vibration of the lattice increases with temperature, causing more scattering, and thus reducing the
mobility. Moreover, following Holsteins theory of small-polarons, at low temperatures the electronic mobility decreases with increasing temperature due to
bandwidth narrowing. Hannewald et al. expanded the local approach developed
by Holstein with nonlocal (Peierls-type) couplings using first-principles densityfunctional calculations [22, 23]. Their theory is in good agreement with the low
temperature behavior of charge-carrier mobility shown in Figure 2.8. At high
temperature, due to phonon-assisted hopping (Fig. 2.9(b)), the mobility increases
with temperature (as seen in Fig. 2.8 above room temperature) [21].
2.3.4
Origin of traps
In the following, we will focus on the origin of the trapping factor () in Eq. 2.7.
The traps in the crystal are mainly caused by structural imperfections and chemical impurities (see the scheme in Fig. 2.10). In our crystals varies from = 0.3
at 225 K to = 0.82 at 340 K. With increasing electric field the density of injected carriers will increase, and above the trap-filled limit voltage (VT F L ) the
mobility is not affected by impurity states and defects [24], as shown in Fig. 2.7.
This part of the curve was used to calculate the mobility of pentacene.
Extended defects, such as edge dislocations or screw dislocations modify the
available energy levels in their vicinity, often leading to the presence of accessible vacant orbitals in the band gap. We minimized the number of traps by a
careful crystal growth and subsequent handling. Heating the as grown crystals in
an inert argon atmosphere will reduce the dislocation density. These defects are
introduced during the crystallization process and are thermodynamically unstable. Thus their number decreases by annealing. Dislocations will also enhance the
chemical reactivity in their vicinity. Under the influence of light and temperature,
reactions that oxidize pentacene to pentacenequinone will occur preferentially at
dislocations [7]. So, even if the quinone is not present after crystal growth, it can
be formed at defects after exposure to air and light.
We found that 6,13-pentacenequinone is the dominant chemical impurity. We
did not observe C22 H15 and C22 H13 O impurities that were calculated to form gap
states in our pentacene, C22 H14 [25]. Moreover, we argue that these molecules
41
Figure 2.9: Charge transport mechanisms in organic conductors. (a) Band-type

conduction. In a perfect crystal, a free charge carrier is delocalized.
As the temperature is increased, the lattice vibrations scatter the
charges. This limits the charge carrier mobility. The mobility for
band transport increases with decreasing temperature. (b) Hopping
conduction. If the carrier is localized (e.g. due to defects), the lattice vibrations promote a carrier to hop over barriers of height Eb
between the localized sites. For hopping transport the mobility
increases with increasing temperature. The figure is adapted from
ref. [27].
42
Figure 2.10: Origin of traps for the injected charges in pentacene single crystals
2.4. Conclusions
43
are irrelevant as these radicals are highly reactive. We were able to prevent the
formation of the dihydropentacene C22 H16 by using argon as transport gas during
the crystal growth. We have shown that the reduction of 6,13-pentacenequinone
(C22 H12 O2 ) impurities in pentacene by a factor five reduces the number of traps by
almost two orders of magnitude. These impurities have different energy levels from
pentacene, but they are energetically inert as a hole trap because their HOMO
level is positioned below that of the host molecule ( [25] for C22 H16 and [26] for
C22 H12 O2 ). This is distinctly different from experiments performed on smaller
acenes, where the impurities yield states in the gap [7]. For this reason, the
number of traps in our measurements is different from the number of chemical
impurities. Although the impurity molecules do not act as trapping centers, they
will induce a local deformation by distorting the pentacene lattice locally and
create a scattering center. The quinone molecule is non planar and larger than
pentacene. The middle ring has a flattened-chair shape with the bond length
of 1.216
A and planar inclined at an angle of 3.1 to the molecular plane [27].
Thus, it will induce a local deformation leading to an increase in potential energy
because of changes in molecular density. The quinone will strongly influence the
number of such scattering sites, and thus the charge transport through organic
single crystal.
2.4
Conclusions
In conclusion, we have reduced the impurity concentration of pentacenequinone

in pentacene by a pretreatment consisting of vacuum sublimation of the impurity
under a temperature gradient. The crystals exhibit a trap-free space charge limited current behavior. The mobility increases with decreasing temperature with a
power law T n from = 35 cm2 /Vs at room temperature to = 58 cm2 /Vs
at 225 K, indicating band transport. These results incorporate corrections for the
effective thickness of the crystal for the anisotropic resistivity, where the effective
thickness is at least three times smaller than the crystal thickness. Our results
emphasize the importance of the control of defects and impurity states in molecular organic crystals in order to obtain a high electronic mobility, and allow studies
of the band transport regime [28].
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[5] V. Podzorov, E. Menard, A. Borissov, V. Kiryukhin, J. A. Rogers, and M.
E. Gershenson, Phys. Rev. Lett. 93, 086602 (2004)
[6] E. Menard, V. Podzorov, S.-H. Hur, A. Gaur, M. E. Gershenson, and J. A.
Rogers, Adv. Mat. 16, 2097 (2004)
[7] M. Pope, and C. E. Swenberg, Electronic Processes in Organic Crystals and
Polymers 2nd ed. (Oxford Univ. Press., New York, 1999)
[8] A. R. McGhie, A. F. Garito, and A. J. Heeger, J. Cryst. Growth 22, 295
(1974)
[9] R. A. Laudise, C. Kloc, P. Simpkins, and T. Siegrist, J. Cryst. Growth 187,
449 (1998)
45
46
References
[10] L. B. Roberson, J. Kowalik, L. M. Tolbert, C. Kloc, R. Zeis, X. L. Chi, R.

Fleming, and C. Wilkins, J. Am. Chem. Soc. 127, 3069 (2005)
[11] The measurements are done in collaboration with P. van t Hof, and J. C.
Hummelen (RuG)
[12] J. R. Dyer, Applications of Absorption Spectroscopy of Organic Compounds
Prentice-Hall, Inc. (1965)
[13]
http://webbook.nist.gov/chemistry/
[14] K. C. Kao, and W. Hwang, Electrical Transport in Solids, vol. 14, Pergamon
Press, New York, (1981)
[15] S. Nespurek, and J. Sworakowski, Phys. Stat. Sol. (a) 41, 619 (1977).
[16] S. M. Sze, Physics of Semiconductor Devices Wiley, New York, (1981)
[17] C. C. Mattheus, A. B. Dros, J. Baas, G. T. Oostergetel, A. Meetsma, J. L.
de Boer, and T. T. M. Palstra, Synth. Met. 138, 475 (2003)
[18] H. C. Montgomery, J. Appl. Phys. 42, 2971 (1971)
[19] J. D. Wasscher, Philips Res. Repts. 16, 187 (1961)
[20] W. Warta, and N. Karl, Phys. Rev. B 32, 1172 (1985)
[21] T. Holstein, Ann. Phys. 8, 343 (1959)
[24] G. Horowitz, M. E. Hajlaoui, and R. Hajlaoui, J. Appl. Phys. 87, 4456 (2000)
[25] J. E. Northrup, and M. L. Chabinyc, Phys. Rev. B 68, 041202(R) (2003)
[26] G. de Wijs, private communication
[27] A. V. Dzyabchenko, V. E. Zavodnik, and V. K. Belsky, Acta Cryst. B35,
2250 (1979)
[28] V. Y. Butko, X. Chi, D. V. Lang, and A. P. Ramirez, Appl. Phys. Lett. 83,
4773 (2003)
Interface Controlled High-mobility Organic

Transistors
We report the fabrication of Organic Field-Effect Transistors (OFETs) in which

it is possible to reach the intrinsic bulk mobility. This was accomplished by
minimizing the trap density at the semiconductor-insulator interface. We obtain
low defect density interfaces by converting impurity scattering centers into the
gate dielectric. High mobilities (= 1440 cm2 /Vs), large on/off rations (Ion /Iof f
= 106 ) and good reproducibility of the measurements characterize the transistors
fabricated with present method.
This Chapter is adapted from O. D. Jurchescu, M. Popinciuc, B. J. van Wees, and T. T.

M. Palstra, submitted
47
48
Chapter 3. Interface Controlled High-mobility Organic Transistors
3.1
Introduction
Electronic devices based on organic semiconductors have gained prominent industrial and academic interest in recent years [118]. Organic materials represent new
semiconductors for flexible, low-cost, light-weight electronic devices. The device
functionality remains limited by the relatively low electronic mobility, which for
thin film devices is partially caused by a large grain boundary resistance [19]. Only
single crystal based devices allow the determination of intrinsic properties. Rapid
technological progress has been made in the fabrication of field-effect transistors
(FET) at the organic - semiconductor interface [2025]. However, the electronic
mobility of such FET devices is typically much smaller than can be obtained
in bulk materials 1 [2628]. We demonstrate that for pentacene-derived devices
this can be related to surface properties of the crystal. We use a new method
to inactivate the impurity states at the interface in the single crystal devices by
incorporating them into the dielectric gate barrier. Thus, high mobility devices
in which the bulk mobility is reached can be reproducibly constructed.
Recent progress in organic single crystal FET devices has shown that the
semiconductor interface layer, which forms the conduction channel between the
source and drain electrode, contains a broad distribution of interface states [2].
In order to minimize the trap density, organic dielectrics such as parylene have
been used as gate dielectric [1, 20, 21, 26]. Previous attempts using more robust
dielectrics such as SiO2 and Al2 O3 involve to many chemical reactions and lead
to structural disorder. Nevertheless, even organic dielectrics often yield limited
mobilities, which is partially attributed to damage below the metal electrodes [6].
However, little detailed knowledge is available on the nature of the defect states
and traps.
3.2
Current status of the field
The mobility of high purity organic field-effect transistors, is usually much lower
than the value determined from SCLC measurements. This can be attributed
to the fact that in FET devices the surface conduction is probed, whether in
SCLC the bulk mobility is measured. The mobility in the bulk can be increased
by reducing the number of traps through controlled processing. We have chosen
to investigate pentacene. This material has become a prominent choice, both
for industrial applications and for fundamental studies. Moreover, it is used in
rollable displays in prototypes of commercial devices [3], and exhibits the highest
1 By
bulk mobility we denote the mobility obtained from SCLC measurements
3.3. Novelty
49
reported electronic mobility: = 35 cm2 /Vs at room temperature in bulk single

crystals [28]. However, for FET devices built on pentacene single crystals, a
mobility of 0.3 cm2 /Vs was measured when using a parylene gate dielectric [26].
This value was improved to 2.2 cm2 /Vs for purified pentacene [8]. A mobility of
1.4 cm2 /Vs was measured for pentacene single crystal FETs using a SiO2 gate
dielectric treated with self-assembled monolayers [27]. The different mobilities of
the bulk and FET devices built on pentacene single crystals indicate the relevance
of a structurally and chemically clean interface. The morphology, spatial ordering
and roughness at the interface are as important as the purity of the active area
of the devices [1416].
3.3
Novelty
Our OFETs, fabricated using the method described in this work, have a typical
charge carrier mobility of = 15 - 40 cm2 /Vs at room temperature, similar to the
value measured in bulk, ultra-pure single crystals [28]. This mobility represents
a record value for the FETs based on organic semiconductors. The on/off ratios
are as high as Ion /Iof f = 106 . The large values of the mobility and on/off ratio
result from a reduction in the number of scattering sites at the interface between
the semiconductor and insulator. The method developed in this work leads to
remarkably good reproducibility of the devices.
3.4
Single crystal growth
We have grown pentacene single crystals with a high degree of purity using physical vapor transport [7]. The starting material was obtained from Sigma Aldrich
and was purified using vacuum sublimation under a temperature gradient. We
have described in Section 2.2.3 of Chapter 2 the details concerning this step.
This growth method yields platelets of pentacene single crystals with in-plane
dimensions of 1 4 mm and thicknesses of 10 50 m.
50
3.5
3.5.1
Surface morphology of pentacene single crystals

Surface mapping
We have previously established that 6,13-pentacenequinone (PQ) constitutes the

largest impurity fraction in pentacene single crystals [28]. The quinone is easily
formed upon oxidation of the relatively reactive conjugated pentacene molecule.
Moreover, pentacene is routinely synthesized from PQ, thus small fractions of
the quinone can remain in the final reaction product. The purity of the material
can be improved by vacuum sublimation treatment of the starting material [28]
or repeated vapor transport crystallization [21]. In typical crystals, PQ may
be present at a concentration of 0.11% and even after repeated distillation we
observed a fraction of 0.028% [28]. Thus far, it has been commonly assumed that
such an impurity is evenly distributed throughout the lattice. We will show that
this is not the case, rather that PQ is located preferentially at the surface. This is
reasonable and can be expected from the dynamics of the crystal growth process.
At the interface, PQ molecules form scattering centers, reducing the mobility or
even preventing transistor action altogether. However, PQ can be incorporated
into the gate dielectric by growing additional quinone layers on the surface. Thus,
the PQ can form a pinhole-free gate barrier and considerably minimize the trap
states.
Pentacene is a layered material characterized by a herringbone pattern within
the layers, while adjacent layers are bonded by van der Waals forces. Pentacene
has several polymorphs, each with a particular d(001)-spacing along the c*-axis
(Fig. 3.1). This length varies from 14.1 to 15.5
A, but for pentacene single crystals
it is unique: dP (001)=14.1
A [29]. This polymorph is already adopted in the first
monolayers. The d(001) spacing is significantly different in 6,13 pentacenequinone:
dP Q (001)=17.79
A [30] (Fig. 3.1). This allows us to distinguish between the two
types of molecules present at the surface by Atomic Force Microscopy (AFM).
3.5.2
AFM measurements
In order to characterize the surface morphology of pentacene single crystals, we

investigated several crystals using the AFM technique and measuring on different
areas of the crystals. The AFM measurements were performed in the tapping
mode using a MultiMode Scanning Probe Microscope, the NanoScope IV, from
Digital Instruments. On the surface of pentacene single crystals we observed
3.5. Surface morphology of pentacene single crystals
51
Figure 3.1: Pentacene crystal packing. Pentacenequinone impurity is located randomly at the surface. The molecular structure, as well as the interlayer
separation for pentacene (14.1
A) and pentacenequinone 17.79
A are
indicated.
Figure 3.2: AFM picture at the surface of pentacene single crystal showing characteristic steps. The step height reveals the inter-layer separation
distance d(00l).
52
and 18
Figure 3.3: Upper panel: histogram showing the occurrence of the 14 A
A
steps at the surface of the pentacene single crystals. The Gaussians
peaking at 14
A and 18
A are a guide to the eye. Lower panel: step
distributions characteristics for the bulk (obtained after cleaving the
crystals), where only the 14.1
A step is observed.
3.6. Comparison between different FETs
53
terraces (see Fig. 3.2), which exhibit steps heights with predominantly two values: 14
A and 18
A. The former value corresponds to the d-spacing of single
crystal pentacene, and the latter to that of PQ. Although we have no detailed
quantitative analysis over the entire crystal, we observe that the 14
A step occurs approximately five times more often than the 18
A step. The results differ
slightly between crystals, depending on the surface area that is measured. The
occurrence of the 14
A and 18
A steps at the surface of the pentacene single crystals, corresponding to pentacene and pentacenequinone, respectively, is shown in
Figure 3.3-upper panel. The crystals were then cleaved and the new surface was
mapped (bulk material). There, we observed only terraces with 14.1(5)
A steps,
characteristic of pentacene (Fig. 3.3-lower panel). We conclude that the impurity PQ molecules agglomerate in patches that are distributed over the surface
of the pentacene crystals. Similar effects were reported for acenes with a lower
number of benzene rings. Quantitative analysis via Gas Chromatography (GC)
on tetracene single crystals allowed the detection of the tetracenequinone surface
concentration larger by one order of magnitude with respect to the bulk [31].
Both in pentacene and tetracene single crystals, because the pentacenequinone
and tetracenequinone, respectively, are preferentially located at the surface, many
more scattering sites are formed in the FET geometry than we determined for the
bulk [28]. This is critical for the performance of the FETs because the traps are
located at the interface with the gate insulator, where the active channel forms.
3.6
3.6.1
Comparison between different FETs

FETs fabricated with conventional dielectrics
In the case of OFETs built on the surface of pentacene single crystals using conventional methods (Fig. 3.4(a)) [8, 26, 27], the charge transport is dominated by
disorder, thus the mobility is lower than the bulk value. This reduction can originate from the presence of pentacenequinone molecules at the surface. The interactions between the systems of the host and impurity molecules introduce
additional scattering sites to the inevitable traps formed during the deposition
of the gate insulator. The electric field applied at the gate electrode has to fill
first these trap states. Only a higher gate bias can populate the density of states
(DOS) of pentacene and modulate the drain current for a proper FET operation. Moreover, random dipoles and quadrupoles [32] are locally introduced at
the interface due to the presence of the impurity molecules. This leads to energetic disorder and an increase in carrier localization by electronic polarization. It
54
has been shown by Lang et al. [2] that even high quality pentacene single crystals have a relatively broad distribution of states ( 1eV ) above the edge of the
valence band. The different intermolecular interactions between pentacene, pentacenequinone and the gate insulator material modulate the energy levels of the
states. This results in a broadening of the DOS and the formation of an increased
number of tail states.
3.6.2
FETs fabricated with pentacenequinone dielectric
We replace the conventional gate dielectrics (SiO2 , parylene, polymers) with ordered 6,13 - pentacenequinone films (P-PQ OFET: Fig. 3.4(b)). This method
presents the unique advantage of being able to transform the scattering sites
present at the surface of pentacene single crystals into an extremely good layer at
the semiconductor-gate interface. A slow deposition rate ensures a small surface
roughness. Once the pentacenequinone layer at the surface is completed, an uniform, extremely good-quality heterointerface is built. This ensures the uniformity
of the conduction path. In this device, the electric field applied at the gate is
able to inject directly into the DOS of pentacene. This is reflected in a smaller
value of the threshold voltage (VT = 2 V) of devices built with the geometry in
Figure 3.4(b), compared with devices fabricated with conventional methods (VT
= 5 V in ref. [26] and VT = -10 V in ref. [27]).
3.7
Device fabrication
We paid special attention to the fabrication of the field-effect transistors on the

organic crystal surface, in order to avoid damaging the surface of the semiconductor. Silver epoxy source and drain contacts were painted on the crystal at
different separation lengths, L. A film of 6,13-pentacenequinone was deposited
on top. The deposition of the insulator was carried out in a clean environment, in
high-vacuum (107 mbar), and the growth was carefully controlled. The source
material was obtained from Sigma Aldrich. No further purification was done.
The sublimation rate was low (5
A/min) to ensure the homogeneity of the film.
A shutter was inserted between the quinone source material and the pentacene
crystal. First the evaporation rate was stabilized, and only after that the device
structure was exposed to the molecules. The thickness of the film was determined
very precisely during the growth by a quartz crystal balance. The silver epoxy
gate electrode was then painted on top of the device.
3.7. Device fabrication
Figure 3.4: Schematic cross-section of a FET fabricated on a pentacene single crystal. The bondline chemical formulae for 6,13-pentacenequinone and pentacene are drawn. (a) Conventional gate dielectric is deposited on the surface of the pentacene crystal. Here,
pentacenequinone molecules present at the interface form scattering sites and decrease the mobility. (b) P-PQ OFET: highly ordered pentacenequinone films act as
gate insulators and reduce the number of scattering sites at the interface.
55
56
3.8
Properties of FETs fabricated with

pentacenequinone gate dielectric
Field-Effect Transistor measurements were performed in the dark and a vacuum of

106 mbar [9], in a home-built probe station. The characterization was done using
a Hewlett Packard 4155B Semiconductor Parameters Analyzer. We investigated
several FETs built on pentacene single crystals obtained from different batches.
The electrical properties of the devices were similar. We performed I V measurements on pentacenequinone single crystals in order to estimate the electrical
breakdown field of the gate dielectric. We obtained a value of 3 MV/cm for the
PQ single crystal insulator. Pinhole-free insulation was obtained for film thicknesses greater than 200 nm. We performed capacitance measurements on single
crystals of the PQ gate dielectric material and evaluate the dielectric constant
r (PQ)= 3.5. An Andeen-Hagerling 2500A Ultra Precision Capacitance Bridge
was used for the dielectric measurements performed on pentacenequinone and a
Keithley 237 Source Measure Unit was used to determine the insulator breakdown
voltage.
The procedure we utilize for pentacene may be applied for the fabrication of
FETs of similar materials. Surface oxidation is widely encountered in conjugated
organic materials. Pentacene is highly susceptible to oxidation at the most reactive positions, leading to 6,13-pentacenequinone. The larger acenes are even less
stable. The attachment of substituents on the acene backbone (e.g. phenyl in
the case of rubrene) makes these positions less reactive and protects the molecule
from unwanted oxidation. In this case the interaction of the oxygen with the
crystal is significantly different; the oxidation is reversible yielding endoperoxide
instead of quinones [38].
The transistors built using this method, on the surface of ultra-pure pentacene single crystals, exhibit p-type conduction. We did not observe ambipolar
transport for this configuration. The sharp increase in the drain current ID in
the transfer characteristics presented in Figure 3.5 is a typical feature of a highperformance field-effect device.
We calculate the field-effect mobility from the I V characteristics presented
in Figure 3.5 and Figure 3.6. We observe typical mobilities in the range = 15 - 40
cm2 /Vs for the transistors fabricated using the PQ gate dielectric. The variations
in mobility are caused by different crystal quality, contact injection issues, and
contact resistance. The on/off ratio is of the order of 106 . We measured 20 devices
built on 8 different crystals and observed consistent behavior. The expression of
3.8. Properties of FETs fabricated with pentacenequinone gate dielectric
57
Figure 3.5: OFET fabricated on a high purity pentacene single crystal with 250
nm thick pentacenequinone film gate dielectric. The geometry of the
device is L W = 250 m 4 mm. The graph shows the variation
of the drain current (ID ) with respect to the applied gate voltage
(VG ) (relative to the source contact) for VD = 1V and VD = -1V. The
properties of the transistor are included in the inset.
the mobility from transconductance (Fig. 3.5) is:

ID
VG
(3.1)
L 1 1 ID
W Ci VD VG
(3.2)
(logID )
VG
(3.3)
gm =
At low drain voltages VD :
=
where L is the channel length, W is the gate width, and Ci is the capacitance per
unit area of the gate insulator. The expression for the subthreshold slope is:
S=
The normalized subthreshold slope:
Si = S Ci
(3.4)
has a value Si = 33.7 V nF/dec cm2 . This value is higher by a factor of 6 - 8

than the value obtained for the best rubrene transistors [20].
58
Figure 3.6: Drain current (ID ) versus drain voltage (VD ) for different negative
gate voltages VG for a device with L W = 250 m 4 mm, and
250 nm thick pentacenequinone film gate dielectric.
Typical output characteristics of the P-PQ transistors are plotted in Figure 3.6.
The curves are stable with time, even if the device is stored in ambient atmosphere
and light. The current in the channel increases as the negative gate bias (VG )
is increased, and saturates at VD = VG VT . For each curve of Figure 3.6,
corresponding to a gate voltage, when the drain voltage reaches the value VD =
VG VT , a depletion region will start to form around the drain contact. As
VD VG VT , this region increases and the drain current becomes saturated,
independent of the applied voltage. We attribute the nonlinearities in the low VD
regime to the contact injection issues. This is consistent with previous studies that
assigned the superquadratic-like behavior at low drain voltages to the presence
of the Schottky barrier between Fermi level of the metal contact and HOMO
of the organic semiconductor (LUMO in the case of electron conduction) [33],
the (diffusion-limited) thermionic emission and the recombination at the metalorganic interface [34], or the presence of a depletion area in the vicinity of the
top contacts, with a high density of localized states, that induces a parasitic
resistance in the FET circuit [6, 35, 36]. The quality of the manually deposited
contacts is not very good, and this is reflected even in the I V characteristics
of the best devices of both VG and VD sweeps. Moreover, the contacts are not
equivalent and the device shows an asymmetry in the VG sweep between VD =
+1 V and VD = -1 V.
3.9. Conclusions
59
Small shifts in the threshold voltage were recorded for different devices, between positive and negative values. As for devices fabricated with identical methods, VT is both positive and negative, we suggest that this is not of intrinsic origin
(the negative VT is not caused by bulk defects, and the positive VT is not a result
of bulk crystal doping). More probably, during the deposition of the contacts and
the gate insulator, traps/additional charges are accumulated at the surface of the
crystal, randomly.
The field-effect-mobility estimated from Figure 3.6, from the linear regime,
as well as from the saturation regime (using Eq. 1.5, and Eq. 1.6, respectively),
increases with drain and gate voltage. This feature has also been reported by
Goldman et al. [27] and Podzorov et al. [37]. This can result from a field dependent
mobility, while in all the assumptions we considered that this parameter does not
vary with the electric field. Also, in the part of the graph that corresponds to the
linear regime of the FET operation, the channel resistance (Rc ) varies linearly
with the applied voltage for a standard FET. The parasitic resistance introduced
at the contacts is field-independent. The total resistance (Rt ) of the channel
is thus: Rt = RS + Rc + RD , where RS , RD are the resistance of the Source,
respective Drain contacts, and will not have a linear dependence of the field. This
will introduce additional variations from the already available models.
3.9
Conclusions
In conclusion, we have been able to incorporate the interface scattering centers of

pentacenequinone into the gate dielectric of Organic Field Effect Transistors built
on pentacene single crystals. Thus, we obtain a semiconductor/dielectric interface
of extremely high quality. The FET mobility = 15 40 cm2 /Vs can reproduce
the value obtained in ultra-pure single crystal bulk devices. This demonstrates
that we are able to measure the intrinsic properties of the single crystal by careful
control of the interface properties, which imply minimizing the trap density in
the active channel.
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Cross-over from 1D to 2D - Space Charge

Limited Conduction in Pentacene Single
Crystals
We report the cross-over from 1D to 2D - space charge limited conduction in

pentacene single crystals with planar contacts. The space charge is confined to
the in plane longitudinal direction for L/h 15, with L the contact separation
and h the sample thickness. For L/h > 250 the space charge is dominated by the
transverse component of the electric field.
This Chapter is adapted from O. D. Jurchescu, and T. T. M. Palstra, Appl. Phys. Lett.
88, 122101 (2006)
65
66
Chapter 4. Cross-over from 1D to 2D - SCLC in Pentacene Single Crystals
4.1
Introduction
Small molecule organic crystals can exhibit large electronic mobilities at room
temperature, if local impurities and extended defects, such as grain boundaries,
can be minimized. Thus, single crystals can provide information about the intrinsic electronic transport properties [16]. Nevertheless, the evaluation of the
transport parameters can be difficult because of the charge injection at the interface, or the non-uniform nature of charge carrier density, current density, and
electric field under non-ohmic conditions. The evaluation of the electronic mobility depends strongly on the correctness of the relationship between electronic
parameters, including mobility, charge density etc., but also on the associated
geometry that is used.
In this chapter we analyze the current flow across pentacene single crystals
with planar contacts. Our study focuses on the electric field E pattern for parallel
planar contacts with different gap separations L, in the space-charge-limitedcurrent (SCLC) regime. We discuss the effect of the geometric parameter L/h,
with h the crystal thickness, and the anisotropy of the mobility on the electric
field distribution inside the semiconductor. Effects like surface scattering, charge
diffusion, surface traps [7] and surface polarization are neglected. We observe a
gradual transition from a 1- to 2-dimensional (D) space charge limited conduction
as L/h increases.
4.2
4.2.1
Space-charge-limited-current theories for semiconductors

Mott-Gurney model
The charge transport in organic conductors is often limited by the emergence of

space charges. There are two limiting geometries to evaluate the conduction. The
Mott-Gurney theory [8] describes the current-voltage characteristics for sandwichtype contact geometries (Fig. 4.1(a)) for materials with one type of trap (the
majority trap) distributed uniformly in space (density Nt ), having one discrete
energy level (Et ). This is a 1D theory in which the electric field, as well as the
space charge, are confined to the channel. Mott-Gurney model gives an expression
of the current density versus applied voltage:
J=
V2
9
0 r 3 .
8
L
(4.1)
4.2. SCLC theories for semiconductors
67
electrodes
crystal
L
(a)
L
(b)
h
L
(c)
Figure 4.1: Electrode configuration: (a) sandwich-type geometry-side view, (b)

gap-type geometry-side view, (c) gap-type geometry-top view (used
in this study).
Here, J is the current density for the applied voltage V , the trapping factor,
L the electrode separation, r the relative dielectric constant of the material, and
the carrier mobility. A detailed description of this model was presented in
Chapter 2, Section 2.3.1.
4.2.2
Geurst model
Geurst analyzed theoretically space-charge-limited-currents in thin semiconductors layers for a gap-structure geometry [9] (Fig. 4.1(b)). Here, the thickness of
the film is negligible with respect to the separation between the contacts. For this
2D model the longitudinal component of the electric field is responsible for the
charge transport and the transversal component, perpendicular to the conduction
channel, is determined by the magnitude of the space charge. This analysis leads
to an expression in which the value of the current I depends quadratically on
the applied voltage V , is proportional to the relative dielectric constant of the
material, r , and inversely proportional to the square of L, the distance between
the contacts:
V2
2
(4.2)
I = 0 r 2
L
Zuleeg et al. [10] have introduced the width of the electrodes, W , into the
expression of Eq. 4.2. This model improves the approximation of Geurst of infinite
long contact length.
Thus, the space-charge-limited current at high voltages varies with L3 in the
68
Mott-Gurney 1D theory (Eq. 4.1) and with L2 in Geurst 2D model (Eq. 4.2). The
former was used to estimate the hole mobility in tetracene [11] and rubrene [12]
single crystals with parallel plate electrodes. It was also applied for analyzing
pentacene single crystals [5,13] and TCNQ-coronene cocrystals [14] in a gaptype
geometry, with a conduction channel length comparable to the thickness of the
crystals. The model of Geurst was used to describe the charge transport of thin
layers of crystalline Se [15], in which the proportionality of the current with L2
was observed.
4.3
Space charge limited currents in pentacene

single crystals with planar contacts
The question we address is for which parameters the 1D-model can be used for
planar contacts, and when the transition to the 2D-model takes place. We show
experimentally that for small L/h ratios, the Mott-Gurney type behavior is observed. Due to the resistivity anisotropy in different crystallographic directions
and short conduction path, the current penetrates only a fraction of the crystal
thickness (hef f ), and the electric field is homogenous. We find that for pentacene
single crystals the 1D SCLC model is accurate for L/h < 15, whereas the 2D
model applies for L/h > 250. The transition takes place gradually and follows
the changes in the value of L/h.
4.3.1
Experimental procedure
Platelets of high purity pentacene single crystals were grown from double sublimation cleaned [5] powder from Aldrich. Physical vapor transport in a horizontal
glass tube under a stream of argon was used [16], as described in Chapter 2. The
geometry of the crystals is maximally 4 4 mm in plane and thickness typically
of 15 20 m. Silver epoxy contacts were painted parallel on the crystal with
a distance varying between 60 m and 3 mm, limited by the dimensions of the
crystals (Fig. 4.1(c)). We used a Keithley 237 Source Measure Unit to perform
the electrical characterization. All I V curves were taken at room temperature,
in darkness and a vacuum of 106 mbar, to avoid environmental effects [17]. For
each single crystal of thickness h, a voltage Vij was applied across different pair
of electrodes i and j attached to the sample at a distance Lij and the value of
the current Iij was measured. The source contact was kept the same to minimize
contact effects [7], and the drain was changed.
4.3. SCLC in pentacene single crystals
69
Figure 4.2: Double logarithmic plot of the current at constant bias for different
ratios of the planar electrode distance L with respect to the crystal
thickness h. The lines are guides for the eyes and correspond to 1D
model (slope -3) and 2D model (slope -2) respectively. The inset represents the derivative d(logI)/d(logL) versus L/h. The positions with
values of 2 and 3, indicating the two considered models are marked.
The data were obtained for one crystal with multiple contacts at room
temperature.
4.3.2
Charge transport in the SCLC regime
The I V curves are ohmic at small biases (I V ), and quadratic at high volt
ages ISCLC V 2 . Figure 4.2 shows the variation of the electrical current I at
constant bias voltage for a crystal of h = 20 m thickness and different contact
spacings, Lij (60 m < Lij < 3 mm), in the SCLC regime. The width of the
contacts is approx W = 200 m. The results are presented as a function of the ratio L/h. The inset shows the logarithmic derivative, d(logI)/d(logL) versus L/h,
with a value 3 corresponding to the 1D conduction, and 2 to the 2D model.
As it can be observed from this graph, at small L/h ratios the bulk charges are
dominant and at high ratios the surface charges determine the conduction. For
L/h 15, there is a good correspondence between the present experiment that we
performed on a crystal with planar contacts and the analytical solution described
70

by Mott-Gurney for devices with parallel plate electrodes I L3 [8]. This
is due to the fact that at small electrode spacing L, the electric field inside the
semiconductor is relatively uniform (Elong ) and parallel to the conduction path.
Moreover, when this distance is small, and considering the anisotropy of mobility
in pentacene single crystals, the current is confined to the surface of the conductor [18]. We demonstrate that the 1D theory (Eq. 4.1) has a relatively limited
range of validity in case of planar parallel electrodes. It is clear from Figure 4.2
that in this geometry the surface contributions become gradually dominant as
L/h increases. The surface charge density gives rise to the normal component of
the electric field (Etrans ) and the electric field obtains more pronounced 2D characteristics. Thus the 1D space charge approximation is not valid in this regime
and the field distribution within the single crystal must be taken into account [19].
The electric field E becomes not uniform inside the crystal. With increasing L,
the transverse electric field results in I L , with ranging from 3 to 2 (see
the inset in Fig. 4.2). We couldnt reach the I L2 regime, corresponding to
Geursts analysis (Eq. 4.2) [9], as we were limited by the size of the crystals.
4.3.3
Evaluation of mobility for sandwich-type and gaptype structures
In the following section we will use the SCLC technique to calculate the value of
mobility in pentacene single crystals. We compare the results obtained for the
mobility in the ab plane with the two types of contact geometry described in this
study. Pentacene presents one morphology in the single crystal phase: triclinic,
with spacegroup P
1 [20]. The crystals are formed by herringbone-type packing
in layers. The molecular packing determines the electronic behavior. Because of
different bonding and antibonding patterns, the effective mass exhibits different
values for the three crystallographic directions [21]. This results in a strong
anisotropy of the carrier mobility, as is often observed for molecular crystals [1,6].
The mobility is higher along the crystallographic direction in which the bonding
or antibonding is dominant. This anisotropy influences the value of the L/h
parameter at which the transition between 1D and 2D space charges occurs. We
expect that for other molecular crystals the transition from 1D to 2D transport
takes place for different geometrical parameters, due to their different mobility
anisotropy.
Figure 4.3 shows the device configurations and current density J versus applied
bias V for one pentacene crystal within the a b plane, using sandwich-type and
gap-type architectures. The ratio L/h = 25 in this case sets the system in the first
4.3. SCLC in pentacene single crystals
71
Figure 4.3: Current density J vs. applied voltage V for pentacene single crystal
at room temperature, in the dark and a vacuum of 106 mbar for gap
structure contact geometry (), and sandwich structure configuration
()
.
part of the intermediate regime, where the conduction is dominated by the 1D

space-charges. This allows us, in first approximation, to use Eq. 4.1 to estimate the
value of the mobility () for this crystal. At low voltages, the current is ohmic. At
higher voltages, the square law dependence of the current with the applied voltage
is observed, corresponding to the SCLC regime (Fig. 4.3). Small deviations from
the linear and quadratic regimes can be attributed to the non-linear contribution
of Schottky barriers formed at the metal/pentacene interfaces. As the trap-free
limit was not reached, can not be determined, but only the value of the product
can be calculated. For the gap type geometry two contacts are deposited
on top of the crystal and the I V curve is measured. When the measurements
are completed, the parts of the crystal that were covered with metal are removed
and new metal contacts are painted parallel to the thickness of the remaining
crystal (h), for the sandwich-type geometry. The calculation of the mobility with
sandwich configuration is straight forward. The device geometry is similar to
the one of a capacitor and the electric field is constant and oriented along the
direction in which the current is measured. From Eq. 4.1, in which the geometrical
factors of the crystal are introduced (L W h = 500 200 20 m), a value of
()sandwich = 12 cm2 /Vs is obtained. In the case of gaptype structure, we can
72
see from Figure 4.2 that, as L/h > 15, the electric field will exhibit deviations from
the idealized 1D form, and the use of simple Mott-Gurney theory is not valid.
Moreover, this model underestimates the value of the mobility: ()gap = 7.2
cm2 /Vs. This comes from the fact that the current flow is not homogenously
distributed along the entire thickness of the crystal (h), but confined to the surface
due to the anisotropy of pentacene.
4.3.4
Resistivity anisotropy effects - effective thickness
We use the Montgomery method [18] to determine the effective thickness (hef f )
penetrated by the electric field lines in the gap configuration. The input for this
algorithm are the values of the components of the resistivity tensor along the
three crystallographic directions (a, b in-plane and c perpendicular to the plane:
a = 1.3 106 m, b = 4.7 105 m, c = 2.1 108 m), and their correspondent
electrodes separation on the crystal (x, y, z). We transform this anisotropic solid
into the equivalent isotropic system of dimensions x , y , z , using van der Pauws
expression [22]:
1
zef
(a b ) 4
zef f
f
=
.
(4.3)
1
1
y ) 21
2
(x y) 2
(x
c
Here zef f and zef

f are the effective thickness for the anisotropic and isotropic
system, respectively. The second factor of the expression is the normalized effective thickness in the isotropic material, which is the abscissa of the graph
proposed by Montgomery (Fig. 2 in Ref. [18]). The normalized sample thickness
in the isotropic space can be calculated from:
1
z
1
(x y ) 2
c2
1
(a b ) 4
z
1
(x y) 2
= 1.036.
(4.4)
The effective thickness depends on the ration x/z, in the anisotropic pentacene
single crystal (Eq. 4.4, Eq. 4.5), which corresponds to the order parameter L/h
that we have used. Different curves are obtained for different ratios of the in
plane directions. For this particular geometry:
y
b 1 y
= ( ) 2 = 0.24.
x
a
x
(4.5)
Thus, the normalized effective thickness of this system is 0.715. This leads
to the value of zef f = 0.33 z, corresponding to hef f = 0.33 h. From Eq. 4.1,
the value of ()gap,hef f = 20 cm2 /Vs can be calculated [18]. This value should
4.4. Conclusion
73
be considered an overestimate of the mobility. This arises mainly from the fact
that in this regime small deviations appear from the 1D model that was assumed
in the calculations. While the Mott-Gourney theory gives I L3 , for our L/h
ratio of 25, we should have used I L2.7 as better approximation. In the
regime L/h 15,where the current varies with the cube of the contact separation (Fig. 4.2), the values of mobility obtained with the two geometries agree
well [5]. The effective thickness that we obtain represents a upper limit. Montgomerys analysis assumes ohmic conduction in which the equipotential lines are
independent of the magnitude of the electric field, while in the SLCL regime the
current density capacity increases quadratically with the field, leading to a smaller
effective penetration depth.
4.4
Conclusion
In conclusion, we report the cross-over from 1D to 2D type space-charge-limitedcurrent conduction in pentacene single crystals with increasing L/h for gap-type
contact geometry. For L/h < 15 the gap type contact is well approximated by
1D-space charges, whereas for L/h > 15 2D-space charges should be taken into
account. The 1D-space charges are predominant in pentacene because of the
anisotropy in resistivity.
References

[2] D. V. Lang, X. Chi, T. Siegrist, A. M. Sergent, and A. P. Ramirez, Phys.
Rev. Lett. 93, 086802 (2004)
Batlogg, J. Appl. Phys. 96, 2080 (2004)
[4] D. A. da Silva Filho, E. G. Kim, and J. -L. Bredas, Adv. Mater. 17, 1072
(2005)
(2004)
[7] R. W. I. de Boer, and A. F. Morpurgo, Phys. Rev. B 72, 073207 (2005)
[8] N. F. Mott and R. W. Gurney, Electronic Processes in Ionic Crystals, 2nd
Edition, Clarendon Press, Oxford 1948
[9] J. A. Geurst, Phys. Stat. Sol. 15, 107 (1966)
[10] R. Zuleeg, and P. Knoll, Appl. Phys. Lett. 11, 183 (1967)
75
76
References
[11] R. W. I. de Boer, M. Jochemsen, T. M. Klapwijk, A. F. Morpurgo, J. Niemax,

A. K. Tripathi, and J. Pflaum, J. Appl. Phys. 95, 1196 (2004)
[14] X. Chi, C. Besnard, V. K. Thorsmolle, V. Y. Butko, A. J. Taylor, T. Siegrist,
and A. P. Ramirez, Chem. Mater. 16, 5751 (2005)
[15] M. Polke, J. Stuke, and E. Vinaricky, Phys. Stat. Sol. 3, 1885 (1963)
(1998)
(2005)
[18] H. C. Montgomery, J. Appl. Phys. 42, 2971 (1971)
[19] S. Hirota, J. Appl. Phys. 50, 3003 (1979)
M. Palstra, Acta Cryst. C 57, 939 (2003)
[21] G. A. de Wijs, C. C. Mattheus, R. A. de Groot, and T. T. M. Palstra, Synth.
Met. 139, 109 (2003)
[22] L. J. van der Pauw, Philips Res. Repts. 16, 187 (1961)
Electronic Transport Properties of Pentacene Single Crystals upon Exposure to

Air
We report the effect of air exposure on the electronic properties of pentacene

single crystals. Air can diffuse reversibly in and out of the crystals and influences
the physical properties. We discern two competing mechanisms that modulate
the electronic transport. The presence of oxygen increases the hole conduction,
as in dark each four O2 molecules diffused into the crystal introduce one charge
carrier. This effect is enhanced by the presence of visible light. In contrast, water,
present in ambient air, is incorporated in the crystal lattice and forms trapping
sites for injected charges.
This Chapter is adapted from O. D. Jurchescu, and T. T. M. Palstra, Appl. Phys. Lett.
87, 052102 (2005)
77
78
5.1
Chapter 5. Electronic Transport Properties upon Exposure to Air
Introduction
Pentacene is a good material for electronic devices like field effect transistors [1
8]. However, the results obtained by different research groups are not always
consistent. This can be attributed in part to the fact that the performance of
the devices depends critically on the environmental conditions [911]. In many
cases these conditions are not explicitly stated, so a comparison between the
experiments is often not appropriate.
We report the electronic properties of pentacene single crystals under controlled conditions of pressure, gas composition, illumination, and in time. We
provide experimental evidence that the influence of air on the charge carrier conduction consists of two separate, distinguishable contributions. Air diffuses into
the pentacene crystals and can be completely removed by re-evacuation. Thus, no
irreversible chemical reactions, like oxidation of pentacene to pentacenequinone,
can be detected during the diffusion process. We demonstrate that oxygen absorption is responsible for an increase in the conductivity, and its effect is enhanced
by the presence of visible light. In contrast, water present in ambient air will
form trapping sites for the injected charges. This will reduce the number of free
charge carriers, and thus the value of the conductivity. These opposite effects
may account for the contradicting reports on the influence of ambient conditions.
5.2
Experimental
Pentacene single crystals of high purity were grown using the vapor transport
technique [12]. The growth was preceded by the purification of the starting material using a two-step vacuum sublimation process under a temperature gradient.
Details about purification and crystal growth are included in Chapter 2 of this
thesis. We performed thermo-gravimetric analysis (TGA) on pentacene single
crystals at room temperature to determine the changes in mass. The increase in
weight at normal pressure in the presence of different gas flows (air, O2 , N2 , and
Ar) were measured using a SDT 2960 from Thermal Analysis Instruments.
The crystals are platelets with dimensions of approximately 3 x 3 mm in plane
and thickness of 15 20 m. Silver epoxy stripe contacts were painted on the
crystal, with a distance of 3 mm. The electrical measurements were performed in
a home built micromanipulator probe station, connected to a turbo pump and to
gas supplies. The system is equipped with a glass window for optical inspection.
This window was covered for the experiments performed in dark. Otherwise, the
samples are exposed to ambient fluorescent light, with no additional illumination.
5.3. Exposure to dry and ambient air
79
A Hewlett Packard 4155B Semiconductor Parameters Analyzer was used to perform electrical measurements. The typical hold and delay time for these scans
were 10 ms in order to avoid charging of the material. All measurements were
performed at room temperature.
5.3
5.3.1
Exposure to dry and ambient air

I-V characteristics in the dark - in vacuum and after
exposure to air
Figure 5.1: Current density J vs. applied voltage V for pentacene single crystal at
room temperature in vacuum and after exposure to dry air (increase
in J) and ambient air (decrease in J). The different curves represent
different exposure times. In dry air : 250 min, 200 min, 150 min, 100
min, 50 min, 10 min, 0 min, in vacuum, in ambient air : 0 min, 10
min, 20 min, 30 min, 50 min, 100 min, 150 min, 200 min, 250 min.
80
To understand the effect of environmental exposure on the transport in organic

crystals, we separate the two competing effects (doping by O2 and trapping by
H2 O), by measuring systematically in dry and ambient air. Figure 5.1 shows
the evolution in time of the current density J versus applied voltage V for single
crystal pentacene in dark, after venting the system with dry and ambient air,
respectively. We associate the behavior at low bias with Ohmic behavior: J
V x , with x = 1. The observed values of x range from 0.7 to 1.3 for different
samples, which we relate to the quality of the contacts. In this regime, no marked
changes in the conductivity are induced by the presence of oxygen or water vapor.
Apparently, no free charge carriers are introduced by O2 absorption.
However, the space-charge-limited current regime SCLC (J V 2 ) is influenced
by exposure to air. Here, J increases upon exposure to dry air, and decreases upon
exposure to ambient air. We interpret this behavior that the induced carriers are
located in shallow trapped states and are only released beyond a critical field.
The quantitative analysis of the transport changes, introduced by absorbing air,
are performed in the SCLC regime (V = 100 V ). In dry air, the number of holes
introduced by the O2 molecules increases in time, leading to an increase in the
charge carrier density. The system will reach the SCLC regime at smaller bias
voltage.
5.3.2
Gas diffusion in pentacene single crystals
We performed in parallel gravimetric and electrical measurements to be able to

give a quantitative description of the effect of gas diffusion on the properties of
organic crystals. In Figure 5.2 we plot the weight increase of pentacene single
crystals upon exposure to 5N dry air (< 17ppm water vapor), at room temperature and atmospheric pressure, expressed as a molar fraction of air in pentacene.
For each situation presented in this chapter, we performed 3 experiments and
they are reproducible within an accuracy of 15%. The mass of the accumulated
air in the crystal structure of pentacene was calculated assuming that the change
in mass is caused only by absorption of gases. This assumption is supported by
the observation that the process is completely reversible.
The same trend is observed for the measurements performed in pure O2 , N2 ,
and Ar. The time constants are determined by the size and shape of both crystals and diffusing molecules. As the diffusion coefficients have similar values, we
conclude that there is no selectivity with respect to any of the gases. The saturation values are within experimental accuracy the same for the different gasses:
2.0% 0.3%.
81
Figure 5.2: Evolution in time of the molar fraction of air in pentacene upon exposure of single crystals to dry air at room temperature and the fit
with a 1D diffusion model. This is a lower limit of the molar fraction,
as it is assumed that the gas molecules diffuse homogenously over the
crystal.
We used Ficks second law (Eq. 5.1) to model the diffusion of gases into pentacene single crystals:
N
2N
(5.1)
= D( 2 )
t
x
Here N is the number of gas molecules at a particular time t and position x.
We use the solution of this equation for the one-dimensional case, constant diffusion coefficient D, and an inexhaustible source. We use two boundary conditions
to obtain a unique solution:
no gas molecules are accumulated in the crystal in the initial stage (N = 0,
for x > 0, at t = 0), we will add an extra term later;
at x = 0, Nsource , induced by the gas flow, is maintained constant for t > 0.
These boundary conditions are represented by the following expressions:
(
N (x, 0) = 0
(5.2)
N (0, t) = Nsource
82
The solution of Eq. 5.1, with the boundary conditions of 5.2, is:
x
N (x, t) = Nsource erfc
2 Dt
(5.3)
where the erfc (z) function, complementary to the error function, erf(z), is defined
as:
Z z
2
2
erf c(z) = 1 erf (z) = 1
ey dy
(5.4)
0
The evolution of the concentration of the gas molecules versus distance, in
time, is shown in Figure 5.3. The distribution of gas molecules, N (x, t), depends
on both distance, x, and time, t. The total quantity of gas molecules in the
Figure 5.3: Evolution of the number of gas molecules absorbed in the crystal
lattice versus distance and in time.
pentacene crystal is obtained by integrating this solution over the length of the
diffusion profile. The result is normalized and expressed in molar fraction of gas
molecules in pentacene. An extra term needs to be added in the solution (Nstart ).
This term reflects the fact that the measurement starts at t = 0 with a quantity of
gas that was accumulated in crystal during venting to atmospheric pressure and
subsequent handling. Because of experimental limitations, we could not evacuate
the gases in the TGA-DSC set-up. The equation that models the diffusion of
gasses in pentacene is thus:
h
d
N (t) = Nstart + Nsource d 1 erf
2 Dt

d2 i
2
Dt 1 exp
+
4Dt
(5.5)
83
where N (t) is the molar fraction of gas at time t, d is the length of the crystal
in the direction in which the 1D diffusion occurs, and Nstart is the value of the
molar fraction accumulated before the TGA measurement. For the case of dry air
(Fig. 5.2), fitting the diffusion curve yields d = 17.5 m, D = 1.81010 cm2 /s and
Nstart = 1.37 103 molecules air/molecules pentacene. Pentacene has a layered
structure with a herringbone arrangement within the layers (Fig. 5.4). Our results
show that the diffusion length is similar to the thickness of the crystal. Therefore,
the diffusion proceeds via the largest surface area, perpendicular to the layers.
We will discuss in Section 5.5 the possible microscopic form adopted by oxygen
molecule in pentacene lattice .
Figure 5.4: The herringbone arrangement of the pentacene molecules in the crystal. The alternation of molecular layers is visible. d is the spacing
between the layers (d=14.1
A for pentacene single crystal). The orientation of the c and a + b direction of the unit cell are drawn.
84
5.3.3
Effect of Oxygen and water in dark
Figure 5.5: Pressure dependence of the current at fixed bias voltage for single
crystal pentacene in the dark. The effect of dry air is shown in 5.5(a),
and that of ambient air in 5.5(b). The experiments are reproducible
for different samples with an accuracy of 15%.
We investigate the influence of the absorbed gas molecules on the changes in
the electrical current. Prior to the experiments, the samples were outgassed in
vacuum (p = 5 107 mbar) in the measurement chamber for at least 100 min.
The measurements can be reproduced after re-evacuation, as the gases diffuse reversibly in and out of the crystal. In order to study the influence of environmental
conditions on the electrical properties, the pentacene single crystals were exposed
to both 5N dry air and ambient air, using a leak-valve connected to the measurement chamber. For the experiments performed in the dark, where the effect is
weaker, we measured both while outgassing and venting the chamber to ensure
that the changes originate from diffusion and not from charging. The evolution
of the electrical properties in time was recorded immediately after venting the
system to atmospheric pressure. The initial time, t = 0, is taken when pressure
equals atmospheric pressure.
Figure 5.5 and 5.6 present the evolution of the electrical current at fixed bias
versus pressure (5.5) and versus time (5.6) at atmospheric pressure in the dark,
85
Figure 5.6: Time dependence of the current at fixed bias voltage for single crystal
pentacene in the dark. The effect of dry air is shown in 5.6(a), and
that of ambient air in 5.6(b). The experiments are reproducible for
different samples with an accuracy of 15%.
respectively. The effect of oxygen exposure is studied when venting with dry
air (Fig. 5.5(a), Fig 5.6(a)). As the pressure increases (Fig. 5.5(a)), oxygen will
diffuse into the crystal, and the conductivity increases. The I V curves are
measured immediately after the desired pressure is reached. Once the system is
at atmospheric pressure, the current continues to increase (Fig. 5.6(a)) because
the diffusion still continues. When venting with ambient air, both water vapor
and oxygen are introduced into the chamber (Fig. 5.5(b), 5.6(b)). We noticed
that in ambient air, the effect of oxygen exposure is counteracted by the exposure
to water. Analyzing the magnitude of the induced changes in the current by
combining oxygen and water effects, one can distinguish two pressure regimes
(Fig. 5.5(b)). At low pressure (p < 102 mbar), the conduction is independent
of air pressure. This leads us to conclude that the two effects are opposite and
of the same magnitude. At p = 102 mbar, a sudden drop in the current is
observed. Apparently, for p > 102 mbar the introduction of scattering sites
exceeds the creation of holes, and this has a major effect on the conduction. This
is reflected also in the results at atmospheric pressure, where diffusion of dry air
causes a current increase (Fig. 5.6(a)), whereas ambient air diffusion cause a drop
(Fig. 5.6(b)).
86
5.3.4
Effect of Oxygen and water in light
Figure 5.7: Pressure dependence of the current at fixed bias voltage for single
crystal pentacene in the light. The effect of dry air is shown in 5.7(a),
and that of ambient air in 5.7(b). The experiments are reproducible
for different samples with an accuracy of 15%.
Figures 5.7 and 5.8 show the evolution of the current under the same conditions, but now in the presence of light. The effect of oxygen diffusion in time is
stronger than in dark (Fig. 5.7(a), 5.8(a)). As the effect of water is independent
of the presence of light, the total influence of ambient air on the crystal properties
will be different in the presence of light. Consistent with the measurements in
dark, we find two pressure regimes. At low pressure (p < 102 mbar), when only
an insignificant amount of water vapor is present, the oxygen doping is the dominant factor of the conduction mechanism. At p = 102 mbar, when water vapor
diffuses considerably into the pentacene crystal, the effect of oxygen is decreased,
and therefore a change in slope is observed (Fig. 5.7(b)). However, the presence
of oxygen remains the most important factor, as the value of the current increases
with pressure. After venting with ambient air, the doping caused by oxygen, activated by illumination, gives a stronger effect than the trapping of charges by
water. The hysteresis in figures 5.5b and 5.7b is very small. This indicates that
the variation in the values of the current is caused by the diffusion and not by
charging.
87
Figure 5.8: Time dependence of the current at fixed bias voltage for single crystal
pentacene in the light. The effect of dry air is shown in 5.8(a), and
that of ambient air in 5.8(b). The experiments are reproducible for
different samples with an accuracy of 15%.
5.3.5
Effect of high O2 pressure
In this section we discuss O2 high-pressure measurements of the electrical properties of pentacene single crystals. The experiments were performed in situ, in a
cubic anvil press [13]. The system was first evacuated, then O2 with controlled
partial pressure was introduced. 30 min was taken to reach the loading for each
pressure, and then I-V curves were taken. In contrast with experiments performed in air, at 106 mbar < p < 103 mbar (Section 5.3.3, 5.3.4), at high O2
pressure (103 mbar < p < 2106 mbar) an increase in current is observed also in
the linear regime as the O2 pressure is increased. Here, the resistance decreases
with 20% between the two extreme pressures mentioned above. The relative
changes in the resistance of the pentacene crystal, with respect to the resistance
in vacuum, versus O2 pressure, is plotted in Figure 5.9. Similar to the case of
hole doping by iodine [14, 15], the resistivity decreases, but no metallic state is
reached. Contrarily, when doping pentacene films with electron donors (e.g. alkali
atoms), a high electrical conductivity and a metallic temperature behavior was
reported [16, 17].
The
measurements are done in collaboration with J. Jun, and J. Karpinski (ETH Zurich)
88
Figure 5.9: Evolution of the resistance with O2 pressure. The results are normalized with respect to the resistance R0 in vacuum. The line is guide
for the eye.
For pentacene loading with O2 at high-pressure, after 2106 mbar, an precipitous decrease in current is observed, both in the linear and quadratic regime. It
is possible that pentacene is transformed irreversibly to pentacenequinone, as the
electrical characteristics cannot be reproduced after evacuation. Moreover, the
sample becomes amorphous.
5.4
5.4.1
O2 and H2 O effects - experimental observations

Electrical measurements
The changes in the electrical properties of the organic semiconductors upon exposure to ambient conditions have not been given much attention in the past.
Only lately, it was stressed that there is a fundamental need to understand these
effects, especially if they are not reversible, because they can affect the performance and the lifetime of the electronic devices in products built for large scale
applications [18].
5.4. O2 and H2 O effects - experimental observations
89
We relate the changes that we observe in the electrical properties and describe in Section 5.3.3 and Section 5.3.4 to the diffusion of gases into the crystal.
Our model includes two competing mechanisms associated with the two different
chemical species that influence the conduction, affected by external factors such
as light. On the one hand, water absorbed by exposure to ambient air [19], will
create new trapping sites for the charges that are injected from the electrodes [20].
This will decrease the value of the electrical conductivity. The afore mentioned
effect is, as expected, independent of the exposure to light. The polar nature
of the H2 O molecules causes interactions with the injected charges and increases
the energetic disorder [21]. This will lead to a decrease of the conduction. Oxygen present in the air will be incorporated in the crystal structure, as shown
in Figure 5.2 and this process will generate holes (a description of the possible
doping mechanism will be provided in Section 5.5 and a quantitative analysis in
Section 5.6 of this chapter). The density of charge carriers responsible for the conduction will thus increase, and accordingly the value of the current will increase.
This process is enhanced by the presence of light. The measurements performed
in pure N2 and Ar under identical conditions show insignificant changes in the
electrical properties, despite a similar amount of absorption.
5.4.2
UPS spectroscopy
We use ultraviolet photoelectron spectroscopy (UPS) to investigate the effect of

oxygen and air exposure on the electronic structure of pentacene single crystals [22]. The oxygen doping should induce a shift of the Fermi-level (EF ) in the
organic towards the highest occupied molecular orbital (HOMO). Photoemission
experiments were performed at the end-station SurICat (beamline PM4) at the
synchrotron light source BESSY GmbH. The ultrahigh vacuum (UHV) system
consists of interconnected sample preparation (base pressure: 1 108 mbar) and
analysis (base pressure: 51010 mbar) chambers. Sample transfer between chambers proceeded without breaking UHV conditions. Pentacene single crystals were
grown ex situ, then mounted on metal sample holders with conducting adhesive
tape, and cleaved in situ (in the preparation chamber) by peeling off the top layers
with a piece of adhesive tape stuck to the crystal surface. Pentacene molecules
crystallize in a layered structure. The interactions between the layers are less
strong than the interactions within the layers, as they are van der Waals interac The experiments were performed in collaboration with the groups of N. Koch and P. Rudolf
and published as The effect of oxygen exposure on pentacene electronic structure, Eur. Phys.
J. E 17, 339 (2005).
90
Figure 5.10: UPS spectra of a pentacene single crystal measured under the following conditions (and in this time-sequence): (a) 3 108 mbar partial
O2 pressure, (b) 2 109 mbar total residual pressure, (c) 3 108
mbar partial O2 pressure after exposure to 5 106 mbar O2 for 30
min., and (d) again at 2 109 mbar total residual pressure.
tions. Therefore, the crystal will cleave easily along the a b plane (perpendicular
to the c direction).
The valence region UPS spectra (Fig. 5.10) recorded on a pentacene single
crystal under different residual oxygen pressures during the measurement and total oxygen exposure clearly show no influence of molecular oxygen on the position
of the energy levels at the given conditions. All four spectra in Figure 5.10 exhibit the same characteristic photoemission features of pentacene, comparable to
previous reports [23]. If doping (i.e., p-type) of pentacene by O2 were the case
(to a significant degree), a clear shift of all levels towards lower binding energy
(BE) would be observed. However, the total in situ exposure of the single crystal
to O2 was rather limited (up to a pressure of 3 108 mbar; for experimental lim-
5.5. Mechanism of oxygen doping
91
itations). Oxygen diffused into pentacene at atmospheric pressure and diffused

out again rapidly after re-evacuation, and does not lead to irreversible changes
(detectable by UPS) in the electronic structure, like, e.g., p-type doping.
In extensive tests we have observed no irreversible reaction of pentacene with
molecular oxygen and water, even if pentacene is optically excited. More importantly, it is found that oxygen diffusion through pentacene single crystals is
reversible, and does not leave behind - after re-evacuation - electrically active
electronic states that would lead to doping of the organic bulk material. This is
evidenced by a lack of energy shifts in UPS spectra of pentacene before and after
exposure to O2 and to air.
5.5
Mechanism of oxygen doping
In the following section we propose a microscopic description of the effect of

oxygen absorption in pentacene. We discuss the nature, on a molecular scale, of
oxygen-induced changes in charge transport properties. Under the experimental
conditions explored here, these changes are reversible. This is fundamentally
different from the experiments in which oxygen creates irreversibly new chemical
species in pentacene, leading to trapping states in the energy gap of pentacene [8].
It should be stressed that oxygen doping is widely observed in organic semiconductors. Therefore, it is likely that this interpretation holds for other similar
materials. The exact nature of the origin the phenomena encountered here is not
known. We propose two possible mechanisms for oxygen doping in pentacene singe
crystals. Further experimental and theoretical studies should elucidate which of
them is correct, or if they can coexist.
5.5.1
Formation of the charge transfer complex between

pentacene and O2
When oxygen is inserted in the pentacene lattice, it can generate a charge transfer
complex (CT complex) with the host material. The direction of the charge transfer
can be established by comparing the values of the electron affinities of the two
neutral molecules. As the value of the pentacene electron affinity (Ea (C22 H14 )
= 2.7 eV [24]) is higher than that of O2 (Ea (O2 ) = 0.45 eV [25]), pentacene is
electron-donating in this complex, and O2 is electron-accepting. Because of its
electronegativity, oxygen will attract electrons from the electron rich - system
of pentacene molecules, and this process will generate holes. No net charges are
generated, but a partial transfer of charge occurs, from the donor to the acceptor.
92
Figure 5.11: The reversible charge transfer formed between pentacene and oxygen.
Figure 5.12: The reversible reaction of pentacene oxidation to endoperoxide. This

reaction can yield irreversibly hydroquinone and quinone.
We expect that the degree of charge transfer in our system is much weaker
that in typical organic charge transfer complexes (e.g. TTF-TCNQ [26, 27]).
Upon formation of the [pentacene-oxygen] charge transfer complex (Fig. 5.11),
the properties of pentacene single crystals are perturbed.
There are several questions that can be raised. How large is the degree of
charge transfer between the two molecules? Does it induce also magnetism,
besides changes in electrical properties? Is it detectable with impedance spectroscopy experiments and/or Raman spectroscopy?
5.5.2
Reversible oxidation of pentacene
A second possibility is that molecular oxygen in the crystal forms a 6,13-adduct

(pentacene-endoperoxide), via the reversible reaction presented in Figure 5.12.
This possibility is analogous to the behavior of carbon nanotubes in oxygen [28].
In pentacene positions 6 and 13 are likely affected because they are the most reactive. This adduct could yield irreversibly, under conditions not explored here,
93
via the formation of the hydroquinone, the 6, 13-pentacenequinone, which is conventionally the dominant impurity species [8].
The reaction that pentacene undergoes to endoperoxide in the presence of
oxygen is photoinduced [29]. Moreover, it is reversible, in agreement with our experimental observations that the electrical properties in vacuum can be recovered
after evacuation. Still, Raman studies that we performed on pentacene single
crystals exposed to oxygen do not show the signature of any peak present in
the region 800 cm1 , that corresponds to the O O vibration [30]. We find
no evidence for the formation of the endoperoxide, in contrast with the case of
rubrene [29].
5.5.3
Calculation of the oxygen-induced dipole moment
We measure the frequency dependence of the dielectric constant () of pentacene single crystals loaded with oxygen and air (Fig. 5.13). We demonstrate
experimentally that a dipole moment is induced in the pentacene crystal, and we
determine its magnitude.
+
The dielectric function () is increased by the polarizability of [C22 H14
O2 ]
charge transfer. The charge transfer gives rise to dipoles that couple to the ac
electric field. This increases the value of permittivity [31].
We used pentacene single crystals with a high degree of purity, grown from
double sublimated powder. Two contacts were deposited, on top and bottom, in
a sandwich-type geometry, as drawn in the inset in Figure 5.13. The description
of the sandwich-type geometry was explained in Chapter 4. The ac dielectric
measurements were performed in a probe station, in air, using a Agilent 4284A.
The as grown crystals were measured first in ambient air. The dielectric response
is shown in Figure 5.13. A decrease of the dielectric constant by 3% is observed
when the frequency is modified from 1 kHz to 200 kHz. The crystals were then
exposed to pure O2 (AGA, 5N) for a few hours. This is sufficient for maximum
loading, as the diffusion constants for oxygen and air (Fig. 5.2) are similar. The
dielectric constant increases markedly at low frequencies for crystals loaded with
O2 and decreases by 12% from 1 kHz to 200 kHz (Fig. 5.13).
Assuming a Debye response, the dielectric constant will decrease with frequency according to:
(0) ()
(5.6)
() = () +
1 + (d )2
where () corresponds to the high-frequency permittivity of the material, and
(0) is the static dielectric constant, is the angular frequency ( = 2f ), and
94
Figure 5.13: Frequency dependence of the dielectric constant of pentacene single

crystals loaded in air and in oxygen. The inset is a schematic representation of the sample geometry, showing also the orientation of
the crystal (c* is the axis perpendicular to the a-b plane). The line
is a fit of a Debye response with a single relaxation time.
d represents the relaxation time. As it can be derived from Eq. 5.6, this model
considers a single relaxation time.
For the measurements performed on pentacene single crystals exposed to pure
oxygen, fitting the curve in Figure 5.13 with Eq. 5.6 yields:
(
(0) = 3.34
(5.7)
() = 3.07
The fit does not represent very accurately the frequency response of the dielectric constant. At low frequencies, additional contributions increase the permittivity, and the Debye model does not describe the response accurately. Deviations
from the model can also be ascribed to the presence of different relaxation times,
whereas we assume a single value.
We use the Clausius-Mossotti equation [32], that relates the dielectric constant
with the dipole moment inside the solid:
Nd 2
4Nm m
() 1
=
+
() + 2
90 kB T
3
95
(5.8)
Here Nd is the density of dipoles, T is the temperature, Nm is the molecular

density in the solid (Nm = 2.92 1021 cm3 for pentacene), m is the molecular
polarizability, and 0 and kB are the vacuum permittivity and the Boltzmann constant, respectively. We assume one dipole created per each absorbed O2 molecule,
thus Nd 0.02 Nm . Only 2% of the pentacene molecules form a dipole, corresponding to the 2% molar loading. The distribution of the pentacene species
corresponds to the distribution of the oxygen in the lattice (experiments are in
progress to determine the spatial distribution of oxygen in pentacene).
If we assume that the behavior of () is only determined by dipole formation
through O2 -loading, we find that:
() 1
4Nm m
=
3
() + 2
(5.9)
Thus, we can determine value of the dipole moment of this charge transfer complex. At room temperature, we obtain = 4 D. This allows the calculation of the
degree of charge transfer (q), as = q d, where d represents the distance between
the charges.
We do not have structural information concerning the position of the O2
molecule in the pentacene crystal lattice. Thus we cannot give an exact value
of the distance between the charges. For this reason, we can only extract an order
of magnitude for the value of the charge transfer. We obtain q 0.25e, where e
is the elementary charge.
Repeating the same algorithm for the measurements performed in air, and
considering Nd 4 103 Nm (only 20% from the 2% loading represents O2
molecules), we obtain: (0) = 3.2, () = 3.08, and = 5 D. The correspondent
values for the charge transfer is q = 0.3e.
We observed that the values of the dipole moment induce by oxygen in pentacene, calculated for the experiments performed in air and in oxygen are similar,
as expected. We associate the small differences to additional polarization, induced by the interaction of pentacene molecules with other impurity states in
the crystals, and with the metal contacts, and also to experimental errors. The
oxygen-induced charge-transfer mechanism presented here is able to describe the
main features of the frequency dependence of the dielectric constant: the decrease
of the value of with frequency, and dependence on the oxygen content.
96
5.6
Quantitative analysis of the effect of O2 and

H2 O
A comparison of Figure 5.2 with Figure 5.6(a) reveals a remarkable consistency.

The time evolution of the electrical current mirrors that of the oxygen absorption.
We can quantitatively assess the influence of O2 and H2 O. The value of the hole
current is affected by the number of gas molecules present in the crystal and thus
varies in time:
Jp (t) = ep p(t)E
(5.10)
where e is the elementary charge and p is the mobility of holes in pentacene.
The term p(t) is the density of charge carriers and consists of several terms:
p(t) = pinj + pdop ptraps
(5.11)
Here pinj represents the hole density injected from the contacts, and pdop is
the hole density induced by exposure to oxygen, which is a fraction of the number
of air molecules absorbed in the solid:
pdop = 0.2oxygen N (t)
(5.12)
The oxygen efficiency oxygen is thus defined as the inverse of the number of
oxygen molecules required to generate one hole. The term:
ptraps = pdef + pimp + pwater
(5.13)
is given by the density of traps in the band gap. In vacuum a fraction of the
injected charges are trapped by crystal defects, pdef , and impurities, pimp . In
ambient air, an extra term is added in the trapping sites due to the presence of
water molecules,
pwater (t) = N (t)
(5.14)
which is a fraction of total number of the air molecules N (t) accumulated in the
crystal. Combining the measurements performed in dry air (Fig. 5.6(a), 5.8(a))
with N (t) taken from Figure 5.2, we can calculate the oxygen efficiency oxygen ,
which determines the number of holes introduced by one O2 molecule (see upper
panel Fig. 5.14).
As it can be observed in Figure 5.14, this number is constant and independent
of time with oxygen 0.25 in the dark and oxygen 0.5 with light exposure.
This means that the efficiency of the oxygen exposure induced doping is independent of oxygen loading and it is increased by light exposure. Roughly two O2
5.6. Quantitative analysis of the effect of O2 and H2 O
97
Figure 5.14: The upper panel shows the evolution in time of the oxygen efficiency
in the dark () and with light exposure (). For ambient light intensity, this efficiency is constant and time independent. The lower
panel shows the variation of the trapping factor by introducing water
molecules (water ) with time. The values are similar in the dark ()
and with light exposure ().
molecules are needed in light to create one hole, compared with four molecules in
dark.
In ambient air, the number of trapping sites is proportional to the number of
water molecules that diffuse into the crystal. We introduce the ratio (Eq. 5.15):
water =
pinj pwater
pinj
(5.15)
that quantifies the fraction of untrapped charge carriers: water = 1 in vacuum.

After exposure to ambient air, the value of water is reduced. water is calculated
by subtracting Figure 5.6(a)/ 5.8(a) from Figure 5.6(b)/ 5.8(b), using appropriate
geometrical factors. The lower part of Figure 5.14 shows water versus time. The
effects of water in the dark and with light exposure have similar magnitudes, and
they follow the diffusion of water, introduced from ambient air.
The changes of the conductivity with time and pressure are the electronic
response to the diffusion of gases in pentacene crystals. They are fully reversible.
The p-doping by molecular oxygen increases the concentration of charge carriers.
98
Water molecules form new electronic states in the gap that trap the injected
charges. It should be noticed that experiments under UHV conditions will not
be influenced by exposure to an ambient atmosphere, as the absorbed gas can be
fully removed by evacuation [22]. We expect that these effects are even larger in
thin films, in which the presence of grain boundaries facilitates the diffusion.
5.7
Conclusion
In conclusion, we have investigated the intercalation of gases in pentacene single

crystals and its effect on the electronic properties. We differentiate between the
exposure to oxygen and water. Absorbed oxygen enhances the conduction by
introducing holes near the valance band. Absorbed water molecules create new
defect states, which trap the injected charges. This insight in the relationship
between the macroscopic diffusion of gas in organic conductors and the effect on
the physical properties may lead to an improved control of the device performance.
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Low Temperature Crystal Structure of

Rubrene Single Crystals Grown by Vapor
Transport
The study presented in the following chapter is promoted by reports of a precipitous drop in the electronic mobility of rubrene single crystals below 175 K. We
assign this change to a phase transition. We perform the crystal structure determination for rubrene single crystals, C42 H28 (5,6,11,12 - Tetraphenyltetracene),
in the temperature interval 100 K - 300 K. The crystals are grown by physical
vapor transport in an open system. The crystal structure is orthorhombic over
the entire temperature range. We find evidence for a phase transition from Differential Scanning Calorimetry measurements, but see no evidence for a structural
phase transition in the diffraction experiments.
This Chapter is adapted from O. D. Jurchescu, A. Meetsma, and T. T. M. Palstra, Acta

Cryst. B 62, 330 (2006)
103
104
6.1
Chapter 6. Orthorhombic Rubrene Single Crystals
Introduction
The electronic properties of polymers and molecular crystals are of much current
interest due to fundamental questions regarding electron transport and associated
applications. The present focus is in developing novel chemical structures, as well
as improved fabrication techniques that are able to open new fields for electronic
applications based on organic materials.
A number of molecular conductors are of current interest. Rubrene (Fig. 6.1)
exhibits interesting physical properties such as having one of the highest reported
electronic mobilities at room temperature [1] (20 cm2 /Vs). Emerging new applications based on rubrene are organic field effect transistors (OFETs) [14] and
organic light emitting diodes (OLEDs) [5, 6].
Figure 6.1: Bond-line formula of rubrene

.
Although the technological development is relatively fast, fundamental questions concerning the intrinsic mechanism of conduction have still not been answered. Moreover, for the title compound, little attention has been paid to the
interplay between its crystal structure and electronic properties. The interest in
the present work is guided by intriguing changes which have been observed at
low temperature in the mobility of field-effect transistors built on rubrene single
crystals [2, 3].
6.2
Polymorphism in rubrene
In this study, we investigate the structure of rubrene single crystals and correlate
it with the electrical properties. The crystals are formed through competition
6.3. Growth of rubrene single crystals
105
between - stacking and quadrupolar interactions. Owing to these weak interactions, different growth conditions can lead to different polymorphs. This feature
is widely encountered for molecular crystals. Several polymorphs of rubrene have
been reported. A monoclinic phase was described by Taylor (1936) [7] and a triclinic polymorph was explored by Akopyan et al.(1962) [8]. Unfortunately, these
reports do not mention the growth method. An orthorhombic form of rubrene
(space group Aba2) was reported by Henn et al. (1971) [9] for crystals grown
from vapor in vacuum using sealed ampoules. For crystals obtained in a closed
system, in a two-zone furnace, at ambient pressure, Bulgarovskaya et al. (1983)
reported a second orthorhombic polymorph, with space group Bbam [10]. For all
the polymorphs investigated previously, only the room-temperature structure is
reported, thus no relation with the physical properties at low temperature can be
made.
6.3
Growth of rubrene single crystals
Rubrene single crystals investigated in this work were grown using physical vapor
transport under a temperature gradient, in a horizontal tube [11]. The inner
tube, in which the crystallization takes place, was cleaned and heated afterwards
at T = 600 K under Ar flow for 10 hours to evaporate the solvents. The source
material, with nominal 98% purity, was obtained from Sigma Aldrich. Prior
to crystal growth, the powder was purified using vacuum sublimation under a
temperature gradient process [12], designed to remove the light impurities1 . The
purified powder was placed in the hot part of the growth tube in a alumina
boat. The sublimation temperature (T = 553 K) was kept as low as possible
(close to the sublimation threshold). This was done to prevent the sublimation
of heavy impurities and to ensure the slow sublimation rate that yields crystals
with a minimum number of structural defects. Crystals grown at slightly higher
temperatures were of significantly lower quality and gave weak diffraction pattern.
The growth set-up was placed in dark to avoid oxidation. The transport gas was
a mixture of H2 (AGA, 5N ) and Ar (AGA, 5N ), with a volume percentage of
5.25% H2 .
The crystals are orange-colored and needle- or platelet-shaped. The typical
in-plane dimensions are 200 m 1 cm for the needles and 3 5 mm for platelets.
The thickness of the crystals is 3 20 m.
1 We
refer to the species present in the system that have lower/higher molecular masses than
the parent compound as light/heavy impurities.
106
6.4
6.4.1
Single crystal diffraction

Experimental details
The single crystal diffraction experiments were performed on a Bruker SMART

APEX CCD diffractometer. A crystal fragment, cut to size to fit in the homogeneous part of the X-ray beam, with dimensions of 0.51 x 0.45 x 0.03 mm was
mounted on top of a glass fiber and aligned on the diffractometer. The diffractometer was equipped with a 4K CCD detector set 60 mm from the crystal.
Intensity measurements were performed using graphite monochromated Mo-K
radiation. The crystal was cooled fast using a Bruker KRYOFLEX (1h was taken
to reach 100 K) and the measurements were performed during heating, after the
temperature was stabilized. For each temperature investigated in this chapter,
a total of 1800 frames were collected with an exposure time of 30.0 seconds per
frame. The overall data collection time was 18.0 h. During this time, the variations in the temperature were 0.5 K at 100 K, and at most 2 K at higher
temperatures.
The structure was solved by direct methods with SHELXS-97. The positional
and anisotropic displacement parameters for the non-hydrogen atoms were refined.
Experimental details about the structure determination, data collection and
refinement are summarized in the Appendix B of the thesis. The data collection
(radiation type, monochromator, data collection method, range) and refinement parameters (number of reflections, number of refined parameters, weighting
scheme, goodness of fit) are similar for the structures corresponding to the eight
temperatures investigated in this study.
6.4.2
Orthorhombic rubrene
Crystals grown from physical vapor transport in an inert gas, in an open system
and continuous flow [11] are preferred for electronic applications, because they
present the highest purity and thus the largest mobility. Still, no crystal structure
determination is available for crystals obtained by this method. In this study we
report the crystal structure between 100 K and 300 K of rubrene single crystals
grown from physical vapor transport (PVT). This growth method yields orange
crystals with orthorhombic symmetry, space group Cmca. We notice that the
polymorph of the crystals grown with this method coincides2 with that obtained
2 We used the standard settings of the International Tables for Crystallography. The transformation to Bbam (Cmca Bbam) is: b a, c b, a c. For the crystal orientation in
the electronic measurements [2, 3], the Bbam setting was used.
6.4. Single crystal diffraction
107
Figure 6.2: Perspective ORTEP drawing of the rubrene molecule illustrating the
configuration and the adopted labelling scheme for the non-hydrogen
atoms at 100 K (a), and room temperature (b). Displacement ellipsoids for non-H are represented at the 50% probability level.
.
108
Figure 6.3: Lattice parameters a, b and c, and unit cell volume V versus temperature for rubrene single crystals. The lines are guides for the eyes.
for the crystals grown in sealed ampoules by Bulgarovskaya et al. [10].

The molecule presents 2/m symmetry, with the asymmetric unit consisting of
one quarter of a rubrene molecule. A twofold axis is located along the C1 C1b
bond. There is a mirror plane perpendicular to the planar tetracene fragment of
the molecule, through the inversion center positioned in the middle of the C1C1b
bond. The adopted labelling scheme and the molecular geometry are illustrated
in the ORTEP drawings of Figure 6.2(a, b). The plots show graphical representations of the atomic positions and their anisotropic displacement ellipsoids at the
minimum and maximum temperatures investigated in this study (T=100 K, and
room temperature). These images provide a visual description of the vibrational
motions of each atom around its equilibrium position.
The crystal structure determination reveals a 2.157% volume thermal expansion of the crystal between 100 K and 300 K, in agreement with typical values
measured in organic crystals. The thermal expansion is anisotropic for the three
crystallographic directions (a = 0.410%, b = 0.320%, c = 1.562%) and oc-
6.5. Relation between molecular stacking and electronic mobility
109
curs predominantly along the weakest bonding c-axis (see Fig. 6.3). The lattice
parameters together with other crystallographic parameters for all eight temperature structures investigated in this study can be found in the Appendix B of the
thesis.
6.5
Relation between molecular stacking and electronic mobility
We relate the behavior of electronic mobility versus temperature with structural

changes. Electronic measurements performed on rubrene single crystals show
that the field effect mobility increases with decreasing temperature down to 175
K, consistent with band-like behavior [2, 3] (the results differ slightly between
groups). Below 175 K the mobility drops precipitously. The dramatic decrease
in the field-effect mobility can be a consequence of a structural phase transition
in the material. Our diffraction experiments show that the crystallographic symmetry does not change when passing in this temperature interval. It can also
be observed from Figure 6.3 that the unit cell volume and unit cell parameters
are continuous with temperature within our resolution. Also, the evolution of
the fractional coordinates of the Carbon atoms do not signal the presence of a
phase transition. However, differential scanning calorimetry (DSC) performed on
the crystals exhibit the signature of a phase transition around T = 175 K (see
Fig. 6.4). It is likely that there is a phase transition at this temperature, but it
is not observable from our X-ray diffraction experiments.
We use the model proposed by da Silva Filho et al. [13] to explain the changes
in electronic properties as a response to the structural changes in the crystal.
They associate the intrinsic transport properties of rubrene single crystals with the
electronic coupling between adjacent molecules. The measure for this interaction
is the interchain transfer integral, t, which varies with molecular packing. The
electronic coupling is maximal if the molecules are perfect cofacial in the crystal,
oscillates when the molecular displacement increases (with positive and negative
values) and becomes zero at large shifts. This translates to the direct influence of
the molecular stacking on the electronic properties.
It can bee seen in Figure 6.5 that the molecules are not perfectly cofacial, but
they are shifted with respect to each other. We define the molecular displacement
d that quantifies the shift between two molecules. From the calculations of Silva
Filho et al. it is obvious that the molecular displacement, d, is the relevant
parameter, relating the crystal structure with the electronic mobility, similar to
110
Figure 6.4: Differential Scanning Calorimetry of crushed rubrene single-crystals.

The measurement has been carried out in N2 atmosphere. The enthalpy associated with the transition is 3.13 kJ/mole. The arrow
indicates the position or the peak.
the model proposed by Mattheus et al. [14]. This parameter is complementary

to molecular overlap and given by the orientation of the tetracene backbone with
respect to the b - crystallographic direction.
In order to calculate the value of molecular displacement at each temperature,
we show the projection of two rubrene molecules on the b-c plane (see Fig. 6.6).
From geometrical considerations, the value of the molecular displacement (d) is
given by: (Eq. 6.1):
d=r+q
(6.1)
where r represents half of the length of the rubrene molecule, and q the distance
from the extremity of the one molecule to the perpendicular taken from the middle
of the molecule to the long axis of the other one. The simplified expression for d
at each temperature is:
d = b cos
(6.2)
where b is the value of the unit cell parameter (Fig. 6.3) and is the angle that
the linear part of the molecule makes with this axis.
The maximum deviation from planarity in the tetracene backbone of the
molecule corresponds to C2 and is 0.0714(11)
A at 100 K and 0.0731(14)
A
6.5. Relation between molecular stacking and electronic mobility
111
Figure 6.5: Schematic representation of two rubrene molecules in the crystal.

The - stacking distance is similar to van der Waals distance. The
molecules are shifted with respect to each other along the tetracene
backbone.
.
Figure 6.6: Arrangement of the rubrene molecules in the unit cell: view along
the [100] axis. The drawing includes schematic representation of the
parameters (r, q) used in the calculation of the molecular displacement
(d). Unit cell b and c axis are also indicated. is the angle between
the long axis of the molecule and b-axis.
112
Figure 6.7: Evolution of the molecular displacement along the long axis of the
rubrene molecule with temperature. The inset represents rubrene
molecular packing viewed along the [100] direction, and defines the
length d of the molecular displacement.
at room temperature. The interplanar separation between two adjacent parallel molecules, along the -stack, increases from 3.654(3)
A to 3.715(3)
A between
100 K and 300 K. This length is slightly larger than the typical van der Waals
interaction distance in a C C -stack [15].
The molecules slide with respect to each other along their long axis when the
temperature is modified. Figure 6.7 shows the temperature dependence of the
molecular displacement, d along the long axis of the molecule in rubrene single
crystal. The value of the shift increases between 100 K and 300 K (Fig. 6.7). The
changes of d with temperature are dominated by changes in the lattice parameter
b (see Fig. 6.3). However, it can be seen from Figure 6.3 and Figure 6.8, that the
temperature dependence of b and cos() individually do not present any discontinuity or change of slope at T = 175 K. In spite of the fact that a different picture
is suggested by their combination in the molecular displacement (see Eq. 6.2), we
cannot assign this to a crystallographic phase transition.
The variations in molecular displacement induce changes in the transfer integral (t), and determine the electronic mobility (see Figure 4, da Silva Filho
6.6. Conclusions
113
Figure 6.8: Variation of the angle between the tetracene backbone of rubrene
molecule and the b crystallographic axis.
et al., [13]). The molecular displacement has a large value due to the effect of
the interactions between phenyl side groups of neighboring molecules. They are
arranged two by two, on different sides of the planar tetracene part of rubrene
and the position is restricted by the inversion center. Their torsion with respect
to the acene linear part ranges from 80.30(5) at 100 K to 80.88(7) at room
temperature. The phenyl rings positioned on the same part of the molecule make
a dihedral angle of 25.32(6) at 100 K and 25.14(10) at 300 K. The connection
between the phenyl rings and the tetracene fragment is the C2 C6 bond. At
100 K this bond makes an angle of 12.57(8) with the tetracene fragment of the
molecule and 6.13(9) with the phenyl-plane. The corresponding angles at 300 K
are 12.74(9) and 6.00(10), respectively.
6.6
Conclusions
We conclude that rubrene single crystals grown from physical vapor transport
in ambient pressure exhibit an orthorhombic symmetry. We find evidence for a
phase transition from DSC measurements, but see no evidence for a structural
phase transition in the diffraction experiments. Further investigations concerning
the mechanism that drives the dramatic changes in electronic mobility at T = 175
K in rubrene are required.
References

[2] R. W. I. de Boer, M. E. Gershenson, A. F. Morpurgo, and V. Podzorov,
Phys. Stat. Sol. A 201, 1302 (2004)
[4] V. Y. Butko, J. C. Lashley, and A. P. Ramirez, Phys. Rev. B 72, 081312
(2005)
[5] T. Oyamada, H. Uchiuzou, S. Akiyama, Y. Oku, N. Shimoji, K. Matsushige,
H. Sasabe, and C. Adachi, J. Appl. Phys. 98, 074506 (2005)
[6] C. N. Li, C. Y. Kwong, A. B. Djurisic, P. T. Lai, P. C. Chui, W. K. Chan,
and S. Y. Liu, Thin Solid Films 477, 57 (2005)
[7] W. H. Taylor, Z. Kristallogr. 93, 151 (1936).
[8] S. A. Akopyan, R. L. Avoyan, and Yu. T. Struchkov, Z. Strukt. Khim. 3, 602
(1962)
[9] D. E. Henn, and W. G. Williams, J. Appl. Cryst. 4, 256 (1971)
[10] I. Bulgarovskaya, V. Vozzhennikov, S. Aleksandrov, and V. Belsky, Latv.
PSR Zinat. Akad. Vestis, Fiz. Teh. Zinat. Ser. 4, 53 (1983)
115
116
References
(1998)
[12] O. D. Jurchescu, J. Baas, and T. T. M. Palstra, Appl. Phys. Lett 84, 3061
(2004)
[13] D. A. da Silva Filho, E. G. Kim, and J.-L. Bredas, Adv. Mat. 17, 1072 (2005)
[14] C. C. Mattheus, G. A. de Wijs, R. A. de Groot, and T. T. M. Palstra, J.
Am. Chem. Soc. 125, 6323 (2003)
[15] A. Bondi, J. Phys. Chem. 68, 441 (1964)
Crystal structure of pentacene
Pentacene T = 100 K
Chemical formula
Formula weight
Cell setting
Space group
a (
A)
b (
A)
c (A )
A3 )
V (
Z
calc (g cm3 )
Crystal form, colour
Crystal size (mm)
C22 H14
278.35
Triclinic
P 1, 2
6.277(1)
7.663(2)
14.363(3)
669.5(2)
76.893(3)
88.182(3)
84.326(3)
2
platelet, violet
0.430 0.210 0.050
Table A.1: Crystal data and details of the structure determination of pentacene at 100
K
Diffractometer
Radiation type
Monochromator
Data collection method
range ( )
Unique data
Data with criterion F0 > 4(F0 )
Rint
Range of h, k, l
Bruker Smart Apex;

CCD area detector
Mo K
Graphite
and scans
2.74 25.03
2310
1683
0.0245
7 h 7
9 k 9
16 l 17
Table A.2: Data collection for pentacene at 100 K
117
118
Appendix A. Crystal structure of pentacene
No. of reflections
No. of refined parameters
Final agreement factors:
Weighting scheme R(F )
wR(F 2 ),
Goodness of Fit (S)
Residual electron density
min
max
2310
255
0.0504
0.1722
1.050
0.2 (e
A 3 )
0.33 (e
A3 )
Table A.3: Refinement for pentacene at 100 K
Atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
H1
H3
H5
H6
H7
H8
H10
H12
H14
H16
H17
H18
H19
H21
x
0.7010(2)
0.5432(2)
0.5778(2)
0.4214(2)
0.4559(3)
0.3002(2)
0.0949(3)
0.0542(2)
0.2132(2)
0.1761(2)
0.6654(2)
-0.1816(2)
-0.1558(2)
-0.3059(2)
-0.2788(2)
-0.4297(2)
-0.3994(3)
-0.2153(3)
-0.0673(3)
-0.0911(2)
0.0573(2)
-0.0321(2)
0.843(3)
0.720(3)
0.599(3)
0.325(2)
-0.013(3)
-0.085(3)
0.030(3)
-0.308(3)
-0.434(3)
-0.555(3)
-0.496(3)
-0.199(2)
0.062(3)
0.187(3)
y
0.40059(1)
0.37090(9)
0.24511(9)
0.21774(9)
0.0927(2)
0.0696(2)
0.1708(2)
0.2906(2)
0.32033(9)
0.44335(9)
0.52590(9)
-0.04326(9)
-0.09971(8)
-0.19924(9)
-0.25490(9)
-0.35691(9)
-0.4106(2)
-0.3661(2)
-0.2710(2)
-0.21086(9)
-0.11257(9)
0.05508(18)
0.332(2)
0.179(2)
0.026(2)
-0.0141(9)
0.154(2)
0.363(2)
0.512(2)
-0.077(2)
-0.231(2)
-0.389(2)
-0.480(2)
-0.405(2)
-0.240(2)
-0.081(2)
z
0.01612(11)
0.08724(11)
0.17491(11)
0.24535(11)
0.33527(11)
0.40311(11)
0.38655(12)
0.30274(11)
0.22850(11)
0.14271(11)
-0.07033(11)
-0.04185(11)
0.05702(11)
0.11683(11)
0.21458(11)
0.27553(11)
0.37083(12)
0.41408(11)
0.35924(11)
0.25798(11)
0.20025(11)
-0.10063(11)
0.0269(11)
0.1853(11)
0.3450(12)
0.4675(10)
0.4396(11)
0.2899(11)
0.1321(11)
-0.0728(11)
0.0867(11)
0.2455(11)
0.4135(12)
0.4857(12)
0.3904(11)
0.2310(11)
Ueq (
A2 )
0.0151(5)
0.0146(5)
0.0155(5)
0.0159(5)
0.0171(5)
0.0189(5)
0.0189(5)
0.0174(5)
0.0150(5)
0.0158(5)
0.0146(5)
0.0148(5)
0.0144(5)
0.0149(5)
0.0150(5)
0.0161(5)
0.0186(5)
0.0189(5)
0.0172(5)
0.0154(5)
0.0155(5)
0.0143(5)
0.022(4)
0.021(4)
0.030(5)
0.007(4)
0.019(4
0.023(4)
0.024(4)
0.020(4)
0.020(4)
0.022(4)
0.029(5)
0.018(4)
0.028(5)
0.019(4)
Table A.4: Fractional atomic coordinates of pentacene at 100 K
119
Pentacene T = 293 K
Chemical formula
Formula weight
Cell setting
Space group
a (
A)
b (
A)
c (A )
V (
A3 )
Z
calc (g cm3 )
Crystal size (mm)
C22 H14
278.33
Triclinic
P 1, 2
6.275(2)
7.791(2)
14.556(4)
688.7(3)
76.434(5)
87.585(5)
84.707(5)
2
1.342
platelet, violet
0.430 0.210 0.050
Table A.5: Crystal data and details of the structure determination of pentacene at 293
K
Diffractometer
Radiation type
Monochromator
range ( )
Unique data
Rint
Range of h, k, l
Bruker Smart Apex;

CCD area detector
Mo K
Graphite
and scans
2.70 25.02
2376
1417
0.0269
7 h 7
9 k 9
15 l 17
Table A.6: Data collection for pentacene at 293 K
120
Appendix A. Crystal structure of pentacene
No. of reflections
Weighting scheme R(F )
wR(F 2 ),
Goodness of Fit (S)
min
max
2376
255
0.0537
0.1722
1.022
0.14 (e
A3 )
0.25 (e
A3 )
Table A.7: Refinement for pentacene at 293 K
Atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
H1
H3
H5
H6
H7
H8
H10
H12
H14
H16
H17
H18
H19
H21
x
0.7001(3)
0.5428(3)
0.5768(3)
0.4212(3)
0.4551(4)
0.3000(3)
0.0956(4)
0.0554(3)
0.2134(3)
0.1775(3)
0.6654(3)
-0.1807(3)
-0.1557(3)
-0.3056(3)
-0.2795(3)
-0.4302(3)
-0.4006(4)
-0.2173(4)
-0.0691(3)
-0.0920(3)
0.0554(3)
-0.0314(3)
0.842(3)
0.720(3)
0.596(3)
0.326(3)
-0.008(4)
-0.082(3)
0.037(3)
-0.311(3)
-0.436(3)
-0.557(3)
-0.498(4)
-0.199(3)
0.064(3)
0.186(3)
y
0.4027(2)
0.3722(2)
0.2485(2)
0.2209(2)
0.0983(3)
0.0755(3)
0.1745(3)
0.2916(3)
0.3212(2)
0.4426(2)
0.5264(2)
-0.0442(2)
-0.0996(2)
-0.1988(2)
-0.2532(2)
-0.3546(2)
-0.4067(3)
-0.3616(3)
-0.2673(3)
-0.2083(2)
-0.1107(2)
0.0539(2)
0.338(2)
0.184(2)
0.033(3)
-0.004(3)
0.157(3)
0.359(3)
0.507(2)
-0.075(2)
-0.228(2)
-0.387(2)
-0.481(3)
-0.401(3)
-0.235(2)
-0.080(2)
z
0.01486(13)
0.08631(13)
0.17321(13)
0.24388(13)
0.33302(15)
0.40070(16)
0.38514(16)
0.30244(15)
0.22806(13)
0.14323(13)
-0.07069(12)
-0.04027(13)
0.05751(13)
0.11743(13)
0.21392(13)
0.27544(15)
0.36951(16)
0.41105(15)
0.35623(14)
0.25603(13)
0.19804(13)
-0.09933(13)
0.0273(12)
0.1848(12)
0.3435(13)
0.4650(15)
0.4381(15)
0.2904(12)
0.1312(11)
-0.0693(12)
0.0882(12)
0.2455(13)
0.4120(14)
0.4813(14)
0.3850(12)
0.2262(11)
Ueq (
A2 )
0.0321(6)
0.0313(6)
0.0341(7)
0.0338(7)
0.0420(7)
0.0480(8)
0.0476(8)
0.0410(7)
0.0337(7)
0.0343(7)
0.0309(6)
0.0317(6)
0.0300(6)
0.0327(6)
0.0331(6)
0.0389(7)
0.0472(8)
0.0464(8)
0.0407(7)
0.0344(7)
0.0340(7)
0.0302(6)
0.041(5)
0.041(5)
0.055(6)
0.057(6)
0.068(7)
0.052(6)
0.041(5)
0.041(5)
0.044(5)
0.053(6)
0.056(6)
0.053(6)
0.050(6)
0.036(5)
Table A.8: Fractional atomic coordinates of pentacene at 293 K
Crystal structure of rubrene
Rubrene T = 100 K
Chemical formula
Formula weight
Cell setting
Space group
a (
A)
b (
A)
c (
A)
V (
A3 )
Z
calc (g cm3 )
No. of reflections for cell param.
Crystal size (mm)
C42 H28
532.68
Orthorhombic
Cmca
26.789(4)
7.170(1)
14.211(2)
2729.6(7)
4
1.296
4621
Platelet, orange
0.51 0.45 0.03
Table B.1: Crystal data and details of the structure determination of rubrene at 100 K
Diffractometer
Radiation type
Monochromator
range ( )
Tmin
Tmax
Total data
Unique data
Rint
max ( )
Range of h, k, l
Bruker Smart Apex;

CCD area detector
Mo K
Graphite
and scans
2.9 29.3
0.952
0.998
10125
1424
1201
0.035
26.4
31 h 33
8 k 8
17 l 17
Table B.2: Data collection for rubrene at 100 K
121
122
Appendix B. Crystal structure of rubrene
No. of reflections
R[F 2 > 4(F 2 )],
wR(F 2 ),
Goodness of Fit (S)
min
max
1424
124
0.037
0.099
1.06
0.21 (e
A3 )
0.26 (e
A3 )
Table B.3: Refinement for rubrene at 100 K
Atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
H4
H5
H7
H8
H9
H10
H11
x
0.02737(6)
0.05314(5)
0.02678(5)
0.05191(5)
0.02646(5)
0.10760(5)
0.14292(5)
0.19199(5)
0.20685(5)
0.17219(5)
0.12302(5)
0.0883(5)
0.0438(5)
0.1328(5)
0.2167(5)
0.2413(6)
0.1825(6)
0.0978(5)
y
0.00000(-)
-0.14464(16)
-0.29578(16)
-0.44754(17)
-0.58934(17)
-0.13448(16)
-0.24817(18)
-0.25089(19)
-0.1389(2)
-0.0251(2)
-0.02362(18)
-0.447(2)
-0.689(2)
-0.327(2)
-0.332(2)
-0.140(2)
0.054(2)
0.054(2)
z
0.00000(-)
0.04914(8)
0.08755(8)
0.13412(9)
0.17534(9)
0.07274(8)
0.02881(9)
0.05979(10)
0.13448(10)
0.17857(10)
0.14816(9)
0.1357(10)
0.2065(10)
-0.0256(10)
0.0279(11)
0.1546(10)
0.2311(12)
0.1804(11)
Ueq (
A2 )
0.0135(5)
0.0141(3)
0.0142(4)
0.0170(4)
0.0186(4)
0.0148(3)
0.0185(4)
0.0225(4)
0.0244(4)
0.0233(4)
0.0189(4)
0.016(4)
0.020(4)
0.021(4)
0.028(4)
0.025(4)
0.032(4)
0.021(4)
Table B.4: Fractional atomic coordinates of rubrene at 100 K
123
Rubrene T = 125 K
Chemical formula
Formula weight
Cell setting
Space group
a (
A)
A)
b (
c (
A)
V (
A3 )
Z
calc (g cm3 )
Crystal size (mm)
C42 H28
532.68
Orthorhombic
Cmca
26.789(4)
7.173(1)
14.246(2)
2737.5(7)
4
1.292
4800
Platelet, orange
0.51 0.45 0.03
Atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
H4
H5
H7
H8
H9
H10
H11
x
0.02723(7)
0.05315(5)
0.02670(5)
0.05192(6)
0.02634(6)
0.10755(5)
0.14287(5)
0.19178(6)
0.20663(6)
0.17202(6)
0.12299(6)
0.0882(6)
0.0442(5)
0.1324(6)
0.2170(6)
0.2416(7)
0.1817(6)
0.0976(6)
y
0.00000(-)
-0.14435(18)
-0.29541(18)
-0.44699(19)
-0.58862(18)
-0.13436(18)
-0.2473(2)
-0.2505(2)
-0.1387(2)
-0.0252(2)
-0.0236(2)
-0.445(2)
-0.688(2)
-0.325(2)
-0.330(2)
-0.141(2)
0.056(2)
0.053(2)
z
0.00000(-)
0.04909(9)
0.08757(8)
0.13405(9)
0.17511(9)
0.07266(9)
0.02915(10)
0.05983(11)
0.13433(11)
0.17824(11)
0.14796(9)
0.1358(10)
0.2072(11)
-0.0251(11)
0.0266(11)
0.1545(11)
0.2302(13)
0.1789(10)
Ueq (
A2 )
0.0156(5)
0.0160(4)
0.0162(4)
0.0193(4)
0.0213(4)
0.0168(4)
0.0214(4)
0.0265(5)
0.0285(5)
0.0281(5)
0.0218(4)
0.022(4)
0.027(4)
0.023(4)
0.034(5)
0.033(4)
0.043(5)
0.019(4)
124
Rubrene T = 150 K
Chemical formula
Formula weight
Cell setting
Space group
a (
A)
A)
b (
c (
A)
V (
A3 )
Z
calc (g cm3 )
Crystal size (mm)
C42 H28
532.68
Orthorhombic
Cmca
26.775(4)
7.1680(10)
14.258(2)
2736.4(7)
4
1.293
4648
Platelet, orange
0.51 0.45 0.03
Atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
H4
H5
H7
H8
H9
H10
H11
x
0.02727(7)
0.05307(5)
0.02670(5)
0.05186(6)
0.02630(6)
0.10744(5)
0.14283(5)
0.19169(6)
0.20647(6)
0.17191(6)
0.12289(6)
0.0877(6)
0.0447(6)
0.1328(6)
0.2163(6)
0.2412(7)
0.1813(7)
0.0976(6)
y
0.00000(-)
-0.14417(18)
-0.29515(18)
-0.44662(19)
-0.58805(19)
-0.13413(18)
-0.2470(2)
-0.2498(2)
-0.1379(2)
-0.0249(2)
-0.0237(2)
-0.448(2)
-0.688(2)
-0.324(2)
-0.330(2)
-0.142(2)
0.055(3)
0.053(2)
z
0.00000(-)
0.04907(9)
0.08757(8)
0.13409(9)
0.17505(10)
0.07267(9)
0.02912(10)
0.06004(12)
0.13425(11)
0.17798(11)
0.14788(10)
0.1341(11)
0.2071(11)
-0.0250(11)
0.0272(12)
0.1537(12)
0.2297(14)
0.1778(11)
Ueq (
A2 )
0.0172(5)
0.0177(4)
0.0181(4)
0.0220(4)
0.0242(4)
0.0191(4)
0.0242(4)
0.0306(5)
0.0335(5)
0.0324(5)
0.0252(4)
0.023(4)
0.031(4)
0.031(4)
0.038(5)
0.043(5)
0.048(5)
0.026(4)
125
Rubrene T = 175 K
Chemical formula
Formula weight
Cell setting
Space group
a (
A)
A)
b (
c (
A)
V (
A3 )
Z
calc (g cm3 )
Crystal size (mm)
C42 H28
532.68
Orthorhombic
Cmca
26.828(4)
7.181(1)
14.306(2)
2756.1(7)
4
1.284
4431
Platelet, orange
0.51 0.45 0.03
Atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
H4
H5
H7
H8
H9
H10
H11
x
0.02718(7)
0.05303(5)
0.02673(5)
0.05186(6)
0.02622(6)
0.10736(5)
0.14277(5)
0.19159(6)
0.20620(6)
0.17173(6)
0.12281(6)
0.0886(6)
0.0443(5)
0.1330(6)
0.2168(6)
0.2406(7)
0.1809(6)
0.0975(5)
y
0.00000(-)
-0.14399(17)
-0.29472(17)
-0.44615(18)
-0.58729(19)
-0.13391(18)
-0.24639(19)
-0.2491(2)
-0.1376(2)
-0.0245(2)
-0.0235(2)
-0.447(2)
-0.686(2)
-0.324(2)
-0.328(2)
-0.139(2)
0.056(2)
0.053(2)
z
0.00000(-)
0.04909(8)
0.08762(8)
0.13392(9)
0.17496(9)
0.07267(9)
0.02938(10)
0.06005(11)
0.13407(11)
0.17770(11)
0.14762(9)
0.1352(10)
0.2063(10)
-0.0237(11)
0.0272(11)
0.1527(11)
0.2295(13)
0.178(1)
Ueq (
A2 )
0.0197(5)
0.0206(4)
0.0206(4)
0.0251(4)
0.0282(4)
0.0216(4)
0.0278(4)
0.0353(5)
0.0388(5)
0.0379(5)
0.0290(5)
0.031(4)
0.034(4)
0.035(4)
0.048(5)
0.043(5)
0.054(5)
0.027(4)
126
Rubrene T = 200 K
Chemical formula
Formula weight
Cell setting
Space group
a (
A)
A)
b (
c (
A)
V (
A3 )
Z
calc (g cm3 )
Crystal size (mm)
C42 H28
532.68
Orthorhombic
Cmca
26.838(4)
7.181(1)
14.332(2)
2762.1(7)
4
1.281
4251
Platelet, orange
0.51 0.45 0.03
Table B.11: Crystal data and details of the structure determination of rubrene at 200
K
Atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
H4
H5
H7
H8
H9
H10
H11
x
0.02718(7)
0.05301(5)
0.02666(5)
0.05171(6)
0.02627(6)
0.10730(5)
0.14271(6)
0.19149(6)
0.20606(7)
0.17164(7)
0.12264(6)
0.0880(7)
0.0447(6)
0.1325(6)
0.2169(7)
0.2407(8)
0.1809(8)
0.0971(6)
y
0.00000(-)
-0.14396(19)
-0.29437(19)
-0.4456(2)
-0.5864(2)
-0.13351(19)
-0.2461(2)
-0.2484(3)
-0.1373(3)
-0.0244(3)
-0.0233(2)
-0.443(2)
-0.686(2)
-0.324(2)
-0.328(3)
-0.139(2)
0.057(3)
0.052(2)
z
0.00000(-)
0.04907(9)
0.08762(9)
0.13397(10)
0.17497(10)
0.07261(9)
0.02964(11)
0.06023(13)
0.13390(13)
0.17747(12)
0.1473(1)
0.1341(12)
0.2055(12)
-0.0239(11)
0.0280(13)
0.1536(12)
0.2298(16)
0.1789(12)
Ueq (
A2 )
0.0215(6)
0.0221(4)
0.0224(4)
0.0275(5)
0.0315(5)
0.0236(4)
0.0310(5)
0.0401(6)
0.0442(6)
0.0430(6)
0.0320(5)
0.034(5)
0.038(5)
0.032(4)
0.055(6)
0.053(5)
0.068(6)
0.035(4)
127
Rubrene T = 235 K
Chemical formula
Formula weight
Cell setting
Space group
a (
A)
A)
b (
c (
A)
V (
A3 )
Z
calc (g cm3 )
Crystal size (mm)
C42 H28
532.68
Orthorhombic
Cmca
26.818(5)
7.174(1)
14.348(3)
2760.5(9)
4
1.282
3849
Platelet, orange
0.51 0.45 0.03
K
Atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
H4
H5
H7
H8
H9
H10
H11
x
0.02725(7)
0.05282(5)
0.02673(5)
0.05163(6)
0.02624(7)
0.10725(6)
0.14260(6)
0.19131(6)
0.20583(7)
0.17143(7)
0.12234(7)
0.0880(6)
0.0443(6)
0.1326(6)
0.2163(7)
0.2410(8)
0.1796(7)
0.0971(7)
y
0.00000(-)
-0.1437(2)
-0.2940(2)
-0.4448(2)
-0.5852(2)
-0.1332(2)
-0.2455(3)
-0.2471(3)
-0.1364(3)
-0.0242(3)
-0.0230(3)
-0.443(2)
-0.682(3)
-0.324(2)
-0.325(3)
-0.137(3)
0.052(3)
0.054(3)
z
0.00000(-)
0.04905(11)
0.08752(10)
0.13381(12)
0.17462(12)
0.07259(11)
0.02974(13)
0.06057(15)
0.13366(15)
0.17699(14)
0.14690(12)
0.1359(12)
0.2055(12)
-0.0238(12)
0.0277(13)
0.1527(13)
0.2290(15)
0.1768(13)
Ueq (
A2 )
0.0237(7)
0.0246(5)
0.0247(5)
0.0311(5)
0.0355(6)
0.0265(5)
0.0342(6)
0.0459(7)
0.0505(7)
0.0497(7)
0.0364(6)
0.033(5)
0.042(5)
0.032(5)
0.055(6)
0.060(6)
0.060(6)
0.041(5)
128
Rubrene T = 275 K
Chemical formula
Formula weight
Cell setting
Space group
a (
A)
A)
b (
c (
A)
V (
A3 )
Z
calc (g cm3 )
Crystal size (mm)
C42 H28
532.68
Orthorhombic
Cmca
26.938(5)
7.211(1)
14.461(3)
2809.1(9)
4
1.259
3697
Platelet, orange
0.51 0.45 0.03
K
Atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
H4
H5
H7
H8
H9
H10
H11
x
0.02714(7)
0.05290(5)
0.02661(5)
0.05169(7)
0.02612(7)
0.10704(6)
0.14248(6)
0.19109(7)
0.20544(8)
0.17115(8)
0.12231(7)
0.0890(7)
0.0450(6)
0.1322(6)
0.2160(7)
0.2404(9)
0.1794(8)
0.0964(7)
y
0.00000(-)
-0.14318(18)
-0.29299(18)
-0.4439(2)
-0.5841(2)
-0.13275(19)
-0.2446(2)
-0.2464(3)
-0.1361(3)
-0.0238(3)
-0.0226(2)
-0.441(2)
-0.684(2)
-0.324(2)
-0.324(3)
-0.138(3)
0.057(3)
0.050(2)
z
0.00000(-)
0.04901(9)
0.08757(9)
0.13369(10)
0.17468(11)
0.07255(10)
0.03009(12)
0.06060(15)
0.13363(15)
0.17662(14)
0.14648(11)
0.1366(12)
0.2061(12)
-0.0219(12)
0.0268(14)
0.1536(15)
0.2296(16)
0.1780(13)
Ueq (
A2 )
0.0294(6)
0.0301(4)
0.0310(4)
0.0387(5)
0.0433(5)
0.0329(4)
0.0425(6)
0.0560(7)
0.0626(8)
0.0599(7)
0.0449(6)
0.053(5)
0.053(5)
0.048(5)
0.078(6)
0.083(7)
0.085(7)
0.054(5)
129
Rubrene T = 293 K
Chemical formula
Formula weight
Cell setting
Space group
a (
A)
A)
b (
c (
A)
V (
A3 )
Z
calc (g cm3 )
Crystal size (mm)
C42 H28
532.68
Orthorhombic
Cmca
26.86(1)
7.193(3)
14.433(5)
2788.5(18)
4
1.269
1924
Platelet, orange
0.51 0.45 0.03
K
Atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
H4
H5
H7
H8
H9
H10
H11
x
0.02705(7)
0.05294(5)
0.02658(5)
0.05147(7)
0.02589(7)
0.10704(6)
0.14252(6)
0.19095(7)
0.20534(8)
0.17085(8)
0.12213(7)
0.0875(6)
0.0444(5)
0.1318(6)
0.2165(7)
0.2409(8)
0.1794(8)
0.0955(6)
y
0.00(-)
-0.1429(2)
-0.2928(2)
-0.4433(2)
-0.5831(2)
-0.1325(2)
-0.2440(2)
-0.2455(3)
-0.1351(3)
-0.0241(3)
-0.0226(3)
-0.441(2)
-0.680(2)
-0.324(2)
-0.321(3)
-0.133(2)
0.060(3)
0.055(2)
z
0.00(-)
0.04897(10)
0.08756(10)
0.13347(11)
0.17451(12)
0.07249(11)
0.03033(13)
0.06085(16)
0.13354(16)
0.17627(15)
0.14638(12)
0.1339(10)
0.2050(12)
-0.0213(12)
0.0286(14)
0.1504(12)
0.2267(16)
0.1763(12)
Ueq (
A2 )
0.0327(7)
0.0335(5)
0.0341(5)
0.0424(6)
0.0475(6)
0.0369(5)
0.0467(6)
0.0623(8)
0.0694(9)
0.0659(8)
0.0499(6)
0.036(4)
0.055(5)
0.053(5)
0.085(7)
0.072(6)
0.091(7)
0.054(5)
Summary
Organic materials are targeted to be implemented as new semiconductors in plastic electronic components for commercial devices. They offer advantages with
respect to traditional inorganic semiconductors regarding processability (they require simple techniques such as spin coating, printing) and functionality (modification of the molecules offers enormous variety in functionalization). Rapid
progress is being made in the development of organic electronic devices. The
use of organic field-effect devices for large scale applications requires high performance, reliability and stability, long lifetimes, good control and reproducibility.
One measure of the performance of a semiconductor is the electronic mobility. This is a benchmark for the success of the different organic semiconductors.
The achievement of good transport properties is associated with high mobilities.
The work presented in this thesis aims to take a step forward towards the understanding of the microscopic processes that determine the electronic mobility in
molecular crystals: the orientation of the molecules, intermolecular interactions,
defect densities and charge transport. This thesis incorporates the study of the
properties of organic molecular crystals at the materials level (Chapters 2, 4, 5,
6), as well as in devices (Chapter 3). The primary goals of our work are to be
able to relate the molecular stacking, defect density and device geometry with
the electronic properties and further to apply that knowledge in the design of
electronic devices with enhanced performance.
Past investigations have been hampered by low reproducibility of the exper131
132
Summary
imental results, and by structural defects that prevented measurements of the

intrinsic properties of organic materials. In recent years, an unprecedented control of the structural properties at the molecular level and of the charge density
distribution has been achieved by better understanding the properties of the organic semiconductor material, and by careful design of device structures.
In this general context, we study single crystals of pentacene and rubrene,
molecular conductors with the highest reported mobilities. Although in single
crystal form they may never match the general requirements for incorporation in
large scale applications, they provide unique tool for the investigation of intrinsic
properties and model systems. For the materials that we focus on, we perform the
crystal growth and crystal structure determination by X-ray diffraction. For pentacene we also investigate the chemical properties using IR spectroscopy, UV-Vis
and mass spectroscopy combined with high performance liquid chromatography
(HPLC). We use space charge limited current (SCLC) and field-effect transistor
(FET) measurements to study the charge transport properties.
In Chapter 2 we demonstrate that the purity of the material is critical for highperformance electronic devices. Impurities can form electrically active states in
the band gap of semiconductors, or distort the charge distribution in the surrounding crystal introducing states in the gap. Thus, they strongly influence the
electronic properties of organic crystals. We perform a quantitative analysis of
the pentacenequinone content, the major impurity in pentacene single crystals.
Furthermore, we show that the reduction of its concentration by a factor of five
(from 0.11% to 0.028%) leads to a decrease of the number of electronically active traps by two orders of magnitude (from Nt = 1013 cm3 to Nt = 1011 cm3 )
and a high mobility ( = 35 cm2 /Vs). In the analysis, we incorporate corrections for the effective thickness of the crystal that result from the anisotropic
resistivity and from the distribution of the electric field inside the material. A
detailed description of the algorithm is incorporated in Chapter 4. In Chapter 3
we demonstrate that the pentacenequinone impurity is located preferentially at
the surface of the crystal and strongly affects the conduction in FET devices by
scattering the charges. We overcame this limitation by converting the impurity
scattering centers into the gate dielectric. The transistors built in this way are
characterized by on/off ratios of 106 and mobilities that reproduce the values
determined for the bulk.
Organic electronic devices need to operate exposed to air. Thus, the influence
of moisture and oxygen are critical in their behavior. Our work concentrates on
improving the performance and reliability of organic based devices. We investigate the physical processes that govern the electrical conduction in these materials
Summary
133
in the presence of air. We demonstrate in Chapter 5 that oxygen/water vapor

present in air diffuses into the crystal. This process generates holes/traps, leading
to enhancement/decrease of the conductivity. The two effects are opposite, they
appear together, and they can have comparable magnitudes. By combining electrical and gravimetric measurements, we obtain quantitative information about
these effects. We find that on average two O2 molecules are needed in the presence
of light to create one hole, compared with four molecules in the dark.
For rubrene single crystals, in Chapter 6 we relate the dramatic changes in
electronic mobility at 175 K to modifications in the crystal structure via the transfer integrals between neighboring molecules. DSC measurements show evidence
for a phase transition at 175 K, but this is not detected by our X-ray diffraction
experiments.
We have obtained high electronic mobilities in organic crystals by careful control of the material degree of purity. Furthermore, we have successfully fabricated
and measured organic FETs in which we are able to reproduce the high mobilities
evaluated from the experiments that describe the bulk properties. Our interests
involve a broad area of research, and combine crystal growth, crystal structure
determination and charge transport measurements. The work presented in this
thesis gives insight into physical processes such as the generation and migration
of defects in organic crystals, environmental effects and device geometry effects
that influence the electrical conduction in molecular crystals.
Samenvatting
Organische materialen komen in aanmerking voor nieuwe halfgeleidertoepassingen

in plastic elektronica componenten in commerciele apparatuur. Deze materialen
bieden voordelen ten opzichte van de gangbare anorganische halfgeleiders als
het gaat om verwerking (er zijn slechts relatief simpele technieken zoals spin
coaten en printen nodig) en functionaliteit (modificatie van de moleculen biedt
een rijke varieteit in functie). Veel vooruitgang is reeds geboekt in de ontwikkeling
van organische elektronische devices. Grootschalig gebruik van organische
Veldeffecttransistoren houdt in dat hoge eisen moeten worden gesteld aan
hun prestaties, betrouwbaarheid, stabiliteit, levensduur, beheersbaarheid en
reproduceerbaarheid.
Een maat voor de prestatie van een halfgeleider is de beweeglijkheid van zijn
ladingsdragers. Dit is een graadmeter voor het succes van verschillende organische
halfgeleiders. Het tot stand brengen van goede transporteigenschappen is inherent
aan het bereiken van hoge mobiliteiten. Het onderzoek dat in dit proefschrift
aan de orde komt, stelt zich ten doel om te komen tot een beter begrip van de
microscopische processen die ten grondslag liggen aan de elektrische geleiding in
moleculaire kristallen: het verband tussen moleculen, intermoleculaire interacties,
defect dichtheden en ladingstransport. Dit proefschrift omvat naast onderzoek
naar eigenschappen van organische moleculaire kristallen op het gebied van
materialen (Hoofdstukken 2, 4, 5, 6), tevens onderzoek naar hun eigenschappen
wanneer zij zijn ingebouwd in devices (Hoofdstuk 3). De kerndoelen van
135
136
Samenvatting
ons onderzoek zijn enerzijds het in staat zijn om moleculaire stapeling, defect
dichtheid en device opbouw in verband te brengen met elektronische eigenschappen
en anderzijds om die kennis toe te passen in het ontwerp van elektronische
devices met verbeterde prestaties. Onderzoek in het verleden werd bemoeilijkt
door de slechte reproduceerbaarheid van meetresultaten en de aanwezigheid van
structuurdefecten, zodat de metingen aan intrinsieke eigenschappen ontoegankelijk
waren. In de laatste jaren is een ongekende beheersing mogelijk van zowel de
structuureigenschappen op moleculaire schaal als van de ladingsdichtheidsverdeling
door een beter begrip van materiaaleigenschappen van organische halfgeleiders en
een zorgvuldig ontwerp van de device opbouw.
Binnen deze algemene context bestuderen we in het bijzonder eenkristallen
van pentaceen en rubreen, moleculaire geleiders met de tot dusver hoogst
gerapporteerde mobiliteiten. Hoewel dergelijke materialen in de hoedanigheid van
eenkristal nooit aan de algemeen geldende eisen voor toepassing op grote schaal
kunnen voldoen, verschaffen deze eenkristallen ons toch een uniek instrumentarium
voor onderzoek naar intrinsieke eigenschappen en bieden zij ons tevens model
systemen. Van de materialen waar wij ons op richten, groeien we eenkristallen
en bepalen hun kristalstructuur door middel van Rontgendiffractie. Verder doen
wij onderzoek naar de chemische en fysische eigenschappen van pentaceen. De
bepaling van dergelijke eigenschappen berust op het gebruik van infrarood-, UVVis- en massaspectroscopie in combinatie met vloeistofchromatografie met hoog
oplossend vermogen. We maken gebruik van ruimteladingsbegrensde stroom- en
veldeffecttransistor metingen om de ladingstransporteigenschappen te bestuderen.
In hoofdstuk 2 tonen we aan dat de zuiverheid van het materiaal een sterke
invloed heeft op de prestaties van de elektronische devices. Onzuiverheden kunnen
elektrisch actieve toestanden in de band gap van halfgeleiders introduceren, of de
ladingsverdeling in het aangrenzende kristalvolume verstoren. Op die manier
benvloeden zij in sterke mate de elektronische eigenschappen van organische
kristallen. We verrichten een kwantitatieve analyse op pentaceenchinon, de
belangrijkste onzuiverheid in pentaceen eenkristallen. Bovendien tonen we aan
dat het terugbrengen van de concentratie van deze onzuiverheid met een factor
vijf (van 0.11% naar 0.028%) resulteert in een afname met twee ordes van grootte
van het aantal afgevangen ladingsdragers (van Nt = 1013 cm3 naar Nt = 1011
cm3 ) en ook de mobiliteit hoger wordt ( = 35 cm2 /Vs).
In de analyse corrigeren we voor de effectieve kristaldikte die wordt veroorzaakt
door de anisotrope weerstand en de verdeling van het elektrische veld binnen het
materiaal. Een gedetailleerde beschrijving van het algoritme wordt behandeld in
hoofdstuk 4. In hoofdstuk 3 komt aan bod dat pentaceenchinon onzuiverheden
Samenvatting
137
zich bij voorkeur aan het kristaloppervlak bevinden en bovendien daar de

geleiding in sterke mate benvloeden door ladingsdragers te verstrooien. Door
onzuiverheden die fungeren als strooicentra om te vormen tot gate dielectricum,
kan deze belemmering worden verholpen. De transistoren die op deze manier
vervaardigd zijn, hebben een aan/uit verhouding van 106 en mobiliteiten die
overeenstemmen met de waarden die zijn gevonden voor het bulk materiaal.
Organische elektronische devices moeten hun taak kunnen blijven vervullen
wanneer ze worden blootgesteld aan de lucht. Daarom is de invloed van vocht en
zuurstof van belang voor hun gedrag. Ons werk richt zich op het verbeteren van
de prestaties en betrouwbaarheid van organische devices. Hiertoe onderzoeken
we de fysische processen die de elektrische eigenschappen van deze materialen
bepalen in de aanwezigheid van lucht. We tonen aan in hoofdstuk 5 dat de
zuurstof/waterdamp die aanwezig is in de lucht diffundeert in het kristal. Dit
diffusieproces genereert gaten/vallen, wat leidt tot verbetering/verslechtering van
de geleiding. De twee effecten zijn in competitie, treden gezamenlijk op en kunnen
van vergelijkbare orde van grootte zijn. Door elektrische en thermogravische
metingen te combineren verschaffen we ons een kwantitatief beeld van deze
effecten. We hebben vastgesteld dat er in de aanwezigheid van licht gemiddeld
twee O2 moleculen nodig om een gat te creeren, vergeleken met vier moleculen
in het donker. Hoofdstuk 6 behandelt rubreen eenkristallen. We brengen
de enorme verandering in mobiliteit bij 175 K in verband met veranderingen
in kristalstructuur met behulp van overdrachtsmatrixelement tussen naburige
moleculen. DSC metingen duiden op een fase overgang bij 175 K, maar hiervoor
zijn geen aanwijzingen gevonden in een R
ontgendiffractie studie.
We hebben hoge mobiliteiten bereikt door een uitgebalanceerde beheersing van
de zuiverheidsgraad van de gebruikte materialen. Verder hebben we op succesvolle
wijze devices vervaardigd en organische FETs gemeten die in staat waren de hoge
mobiliteiten te reproduceren zoals die gevonden waren in experimenten die de
bulk eigenschappen in kaart plegen te brengen. Onze belangstelling gaat uit naar
een breed onderzoeksgebied en combineert kristalgroei, kristal structuurbepaling
en ladingstransport metingen. Het werk dat in dit proefschrift aan de aan de orde
komt, geeft inzicht in de fysische processen zoals het ontstaan en de migratie van
defecten in organische kristallen, omgevingseffecten en effecten op de electrische
geleiding van moleculaire kristallen die gerelateerd zijn aan de device opbouw.
List of Publications
B. B. Van Aken, O. D. Jurchescu, A. Meetsma, Y. Tomioka, Y. Tokura,

and T. T. M. Palstra, Orbital-order-induced metal-insulator transition in
La1x Cax MnO3 , Phys. Rev. Lett. 90, 066403 (2003).
O. D. Jurchescu, J. Baas, and T. T. M. Palstra, Effect of impurities on the
mobility of single crystal pentacene, Appl. Phys. Lett. 84, 3061 (2004).
O. D. Jurchescu, J. Baas, and T. T. M. Palstra, Electronic transport

properties of pentacene single crystals upon exposure to air, Appl. Phys.
Lett. 87, 052102 (2005).
A. Vollmer, O. D. Jurchescu, I. Arfaoui, I. Salzmann, T. T. M. Palstra, P.

Rudolf, J. Niemax, J. Pflaum, J. P. Rabe, and N. Koch, The effect of oxygen
exposure on pentacene electronic structure, Eur. Phys. J. E 17, 339 (2005).
O. D. Jurchescu, and T. T. M. Palstra, Crossover from one- to twodimensional space-charge-limited conduction in pentacene single crystals,
Appl. Phys. Lett. 88, 122101 (2006).
139
140
List of publications
O. D. Jurchescu, A. Meetsma, and T. T. M. Palstra, Low-temperature

structure of rubrene single crystals grown by vapor transport, Acta Cryst.
B 62, 330 (2006).
O. Ostroverkhova, D. G. Cooke, F. A. Hegmann, J. E. Anthony, V.

Podzorov, M. E. Gershenson, O. D. Jurchescu, and T. T. M. Palstra,
Ultrafast carrier dynamics in pentacene, functionalized pentacene, tetracene,
and rubrene single crystals, Appl. Phys. Lett. 88, 162101 (2006).
O. D. Jurchescu, M. Popinciuc, B. J. van Wees, and T. T. M. Palstra,

Interface controlled high-mobility organic transistors, submitted.
A. J. C. Buurma, I. Shokaryev, O. D. Jurchescu, A. Meetsma, R. A. de

Groot, and T. T. M. Palstra, Crystal growth, structure and electronic band
structure of Tetracene-TCNQ, submitted.
I. Shokaryev, A. J. C. Buurma, O. D. Jurchescu , G. A. de Wijs, T. T. M.

Palstra, R. A. de Groot, The electronic band structure of Tetracene - TCNQ
and similar acene - TCNQ compounds, in preparation.
Propositions belonging to the thesis:

Molecular Organic Semiconductors
for Electronic Devices
1. The purity of the molecular organic semiconductor is crucial to achieve
high-performance and high-reliability electronic device operation.
Chapter 2 of this thesis
2. The greatest challenges at the present stage of the organic electronics
research, is device processability rather than new materials.
3. Oxygen diffuses reversibly into pentacene crystals and on average four O2
molecules induce the formation of one charge carrier in the dark.
4. Intentionally use of unnecessary complicated terminology does not imply
valuable scientific content.
5. Science results as well as open source software are both communal and
competitive: in both cases the property right issue is almost entirely a
matter of respecting the authorship of the original work.
6. Contrary to the expectations of some politicians, global warming is the
greatest threat to humanity during the next millennium.
7. The impact of an article in the field is more important that the impact
factor of the journal in which it is published.
8. In science lately there are more opinions than facts.
9. Your focus determines your reality.
Star Wars
10. The mistakes that are most easy to forgive are your own.

October 2006
These propositions are considered defendable and as such have been approved
by the supervisor, prof. dr. T.T.M. Palstra.

12 Thesis

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Molecular Organic Semiconductors

Oana Diana Jurchescu

MSC PhD thesis series 2006-15

Molecular Organic Semiconductors for

Oana Diana Jurchescu

Prof. Dr. T.T.M. Palstra

Prof. Dr. Y. Iwasa

2 The Effect of Impurities on the Mobility of Single Crystal Pentacene

3 Interface Controlled High-mobility Organic Transistors

4 Cross-over from 1D to 2D - Space Charge Limited Conduction

5 Electronic Transport Properties of Pentacene Single Crystals

A Crystal structure of pentacene

B Crystal structure of rubrene

Organic conductors - general aspects

Organic semiconductors are a fascinating class of materials, with a wide range

stress and pressure indication in clothes [11].

- organic light emitting diodes

1.2. Charge transport in organic semiconductors

Charge transport in organic semiconductors

Organic semiconductors are wide-band-gap and small bandwidth semiconductors.

- highest occupied molecular orbital

stands for tetramethyltetraselenafulvalene

1.2. Charge transport in organic semiconductors

Figure 1.1: Chemical formulae of organic molecules with different functionalities.

1.2. Charge transport in organic semiconductors

Scattering by defects, impurities and phonons (lattice vibrations) will decrease

where e is the elementary charge. The mobility is influenced by the scattering

- complementary metal oxide semiconductor

Organic electronic devices

1.3. Organic electronic devices

1.3. Organic electronic devices

Owing to the fragility of organic materials, processing to incorporate them in

1.3. Organic electronic devices

Reviewing the recent advances in materials, methods and emerging applications,

1.4. Organic molecular crystals

Organic molecular crystals

Characteristic of organic semiconductors are the intramolecular bonds. The

1.4. Organic molecular crystals

between neighboring sites, and, as expected, is very sensitive to orientation of the

Single crystals - model systems for investigation of intrinsic properties

Aim of the present research

1.7. Outline of the thesis

Outline of the thesis

This thesis is organized as follows:

[1] R. H. Friend, R. W. Gymer, A. B. Holmes, J. H. Burroughes, R. N. Marks,

[10] X. Guo, J. P. Small, J. E. Klare, Y. Wang, M. S. Purewal, I. W. Tam, B. H.

[13] Components fabricated on organic materials and introduced on the market

[23] D. J. Gundlach, T. N. Jackson, D. G. Schlom, and S. F. Nelson, Appl. Phys.

[39] C. W. Tang, App. Phys. Lett. 48, 183 (1986)

[58] W. Shockley, and G. L. Pearson, Phys. Rev. 74, 232 (1948)

The Effect of Impurities on the Mobility

Chapter 2. The Effect of Impurities on the Mobility

Control of the defects and impurity states in

We report a mobility of = 35 cm2 /Vs at room temperature increasing to = 58

2.2. Control of the defects and impurity states in organic crystals

Spectroscopic evidence for the presence of impurities

Figure 2.1: Molecular structure of pentacene (a) and 6,13-pentacenequinone (b).

Chapter 2. The Effect of Impurities on the Mobility

confirmed that the C=O vibration originates from a pentacenequinone molecule

Purification of the starting material

We have used vacuum sublimation under a temperature gradient as purification

2.2. Control of the defects and impurity states in organic crystals

Single crystal growth