Organic Materials For Electronic and Optoelectronic Devices (

View Article Online / Journal Homepage / Table of Contents for this issue
JOURNAL OF
Yasuhiko Shirota
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Yamadaoka,
Suita, Osaka, 565-0871, Japan. E-mail: shirota@ap.chem.eng.osaka-u.ac.jp
Materials
Organic materials for electronic and optoelectronic devices{
CHEMISTRY
Received 11th October 1999, Accepted 2nd November 1999
Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.
This article concentrates on our recent results on several classes of photo- and electro-active organic materials
that permit thin lm formation and discusses their synthesis, properties, functions and potential applications for
electronic and optoelectronic devices. The materials studied include amorphous molecular materials, titanyl
phthalocyanine, oligothiophenes with well-dened structures, and non-conjugated polymers containing pendant
oligothiophenes or other p-electron systems. The thin lms of these materials nd potential applications for use
in organic electroluminescent, photovoltaic, electrochromic, and other devices.
1 Introduction
Recent extensive studies have shown that organic materials
exhibit a variety of interesting optical, electrical, photoelectric,
and magnetic properties in the solid state. Photo- and electroactive organic materials have been the subject of recent
attention, including organic semiconductors, organic metals
including superconductors, organic photoconductors, organic
photoactive materials for solar cells, organic non-linear optical
materials, organic ferromagnets, photo- and electrochromic
organic materials, resist materials, liquid crystals, and others.
Among them, organic photoconductors, liquid crystals, and
resist materials have been put to practical use for photoreceptors in electrophotography, display devices, and lithographic processes for the production of semiconductor devices.
In addition, organic materials have found a number of
potential applications for use in electronic and optoelectronic
devices such as sensors, plastic batteries, solar cells, eld-effect
transistors, optical data storage, organic electroluminescent
devices, switching devices, frequency doublers, and many
others.
In contrast to inorganic materials that consist of covalent or
ionic bonds of atoms over the entire expanse of solids, organic
materials are based on independent molecules and characterised by weak intermolecular interactions. Therefore, designs
of organic materials can be readily performed on the molecular
level. In particular, organic p-electron systems have received
attention as potential photo- and electro-active materials.
When these organic materials are used in electronic and
optoelectronic devices, they are normally in the form of thin
lms. Organic thin lms are prepared by various techniques,
e.g., solvent cast from solution, spin coating, vacuum vapor
deposition, electrochemical deposition, LangmuirBlodgett
and monolayer self-assembly techniques. Both ordered and
disordered lms can be generated, depending on the technique
of thin lm fabrication.
We have performed studies of the creation of novel photoand electro-active organic materials and their structures,
reactions, properties, functions and applications for electronic
and optoelectronic devices. This article concentrates on our
recent results on several classes of organic materials that permit
thin lm formation, e.g., amorphous molecular materials,
titanyl phthalocyanines, oligothiophenes with well-dened
structures, and non-conjugated polymers containing pendant
oligothiophenes or other p-electron systems, and discusses their
{Basis of a presentation given at Materials Chemistry Discussion
No. 2, 1315 September 1999, University of Nottingham, UK.
synthesis, structures, reactions, properties, functions, and

potential applications for electronic and optoelectronic devices.
Amorphous molecular materials have found successful application for use in organic electroluminescent (EL) devices and
are expected to nd further potential applications as photovoltaic, photochromic and resist materials. Photovoltaic
devices using titanyl phthalocyanine, oligothiophenes with
well-dened structures, and pendant polymers and electrochromic devices using a novel family of polymers containing
pendant oligothiophenes have been studied. General aspects of
these devices are briey described here.
Organic electroluminescent (EL) devices
Organic EL devices have recently received a great deal of
attention for their application as full-colour, at-panel displays
as well as from the standpoint of scientic interest. They are
attractive because of low voltage driving, high brightness,
capability of multicolour emission by the selection of emitting
materials and easy fabrication of large-area and thin-lm
devices. Following the reports on organic EL devices using
single crystals of anthracene,1 recent pioneering works on
organic EL devices using low molecular-weight organic
materials2 and a conjugated polymer3 have triggered extensive
research and development of this eld.
The structure of organic EL devices consists of single or
multiple layers of organic thin lms sandwiched normally
between the transparent indium-tin-oxide (ITO) coated glass
and vacuum-evaporated metals with low work function such as
magnesium (Mg) and aluminium (Al). The operation of
organic EL devices involves injection of holes and electrons
from the ITO and Mg or Al electrodes, respectively, transport
of injected charge carriers, recombination of holes and
electrons in the emission layer to generate an electronically
excited state molecule, followed by luminescence emission. In
order to achieve high performance in organic EL devices, it is
necessary to attain charge balance. Generally, layered devices
consisting of charge-transport and emitting layers can more
readily achieve charge balance than single-layer devices using
an emitting material alone. This is because a suitable
combination of charge-transporting and emitting materials in
layered devices reduces the energy barrier for the injection of
charge carriers from the electrodes and because the chargetransport layer acts as a blocking layer against the injection of
either holes or electrons from the adjoining layer and their
subsequent escape from the device.
For the fabrication of high-performance organic EL devices,
not only emitting materials but also charge-transporting
J. Mater. Chem., 2000, 10, 125
This journal is # The Royal Society of Chemistry 2000
View Article Online
materials are required. Both polymers and small molecules are

candidates for materials in organic EL devices. The materials
for organic EL devices should meet the following requirements:
(1) to possess a suitable ionisation potential and electron
afnity for energy level matching for the injection of charge
carriers at the interfaces between the electrode/organic material
and organic material/organic material, (2) to permit the
formation of a uniform lm without pinholes, (3) to be
morphologically stable, (4) to be thermally stable, (5) to be
electrochemically stable, and (6) to be highly luminescent for
emitting materials. In addition, doping of luminescent
compounds has been shown to be an effective method for
attaining high brightness and desirable emission colour.4
For the fabrication of high-performance organic EL devices,
development of new materials with high performance and
judicious choice of the combination of emitting and chargetransporting materials and the combination of emitting and
luminescent dopant molecules as well as an understanding of
basic processes, such as charge injection from the electrodes,
charge transport, recombination of charge carriers to generate
the electronically excited-state molecule, are of vital importance.
Recent years have witnessed signicant progress with regard
to brightness, multi- or full-colour emission, and durability and
thermal stability of organic EL devices.
Organic photovoltaic devices
Devices for photoelectric conversion using organic materials,
which nd potential applications as solar cells and photosensors, are mainly classied into photoelectrochemical and
photovoltaic devices. Photoelectrochemical cells consist of
inorganic semiconductors and organic dyes as a sensitiser
immersed in an ionically conductive electrolyte containing a
redox couple, where light is absorbed by the organic dye.5,6
Photovoltaic devices consist of thin lms of organic materials
sandwiched between two metal electrodes. A built-in electric
eld, formed in the semiconductor in contact with the
electrolyte in the photoelectrochemical cell and in the organic
layer at the interface with the metal electrode or with the other
organic layer in the photovoltaic device, is responsible for the
photogeneration of charge carriers.
Organic solid-state photovoltaic devices have attracted
attention because of their light weight, potentially low cost,
and ready fabrication of large-area, thin-lm devices. Both
Schottky-type and pn heterojunction cells using low molecular-weight organic materials and polymers have been
fabricated, and their performance characteristics investigated.
In Schottky-type cells, a single-layer organic material is
sandwiched between two dissimilar electrodes to form a
Schottky barrier in the organic layer at the interface with the
metal electrode. On the other hand, pn heterojunction cells are
typically based on a double-layer structure of organic thin
lms, where the organic/organic interface plays an important
role in the performance, the electrodes simply providing ohmic
contacts to the organic layers. pn Heterojunction devices have
advantages over Schottky-type devices in that they do not
necessarily need the use of low work-function metals that
readily undergo air oxidation as electrode materials. It is also
expected that a higher quantum yield for photogeneration of
charge carriers is attained due to electron donoracceptor
interactions of the two dyes.
The conversion efciency of organic photovoltaic devices is
still lower than that of inorganic photovoltaic devices. The
reason for this may be attributed to low photogeneration
efciency of charge carriers and to high electrical resistivity of
organic materials which stems from the low mobility and low
density of free carriers. The basic processes of the operation of
organic photovoltaic devices have been understood in terms of
the energy band model for inorganic semiconductors; however,
2
J. Mater. Chem., 2000, 10, 125
many organic materials do not form energy bands. It is

therefore necessary to understand the mechanism of photoelectric conversion in organic photovoltaic devices on the
molecular level. It is important to understand what impurity
species are involved in the formation of the built-in potential at
the interface between the organic material and electrode and
two kinds of organic materials as well as the mechanism for the
photogeneration of charge carriers in organic materials.
Improving the quantum efciency of the photogeneration of
charge carriers is a key issue for the development of organic
photovoltaic devices with high conversion efciency.
Recent signicant progress in solid-state solar cells using the
combination of organic dyes and inorganic semiconductors7
and using interpenetrating polymer networks810 has attracted
renewed interest in this eld.
Electrochromic devices
Organic electrochromic devices, which are characterised by
low-voltage operation, good optical contrast, and wide viewing
angle, can be potentially used as smart windows that control
the sun radiation in buildings and cars, rear-view mirrors for
cars, and display devices.11 Low molecular-weight organic
compounds, e.g., viologen derivatives and metallophthalocyanines, and polymers including both p-conjugated and pendant
polymers have been studied for electrochromic materials. Such
organic materials have the potential capability of multi-colour
display and in particular, polymer thin lms are attractive
because they may exhibit a memory effect and have a good
cycle life. Improvement in the cyclability of the colouration and
decolouration and the design and synthesis of new redox
systems are important issues.12,13 All solid-state devices using
polymer electrolytes or polymer gel electrolytes14,15 as well as
electrochromic devices using thin lms of organic materials
immersed in an electrolyte solution have been studied.
Photoinduced electrochromic devices have also been studied.16
2 Amorphous molecular materials

Low molecular-weight organic compounds generally tend
to crystallise readily, and hence they usually exist as crystals
below their melting points, except for certain solvents, e.g.,
2-methyltetrahydrofuran, which readily form glasses at
77 K. Although it had been reported that amorphous or
quasi-amorphous lms of polycyclic aromatic hydrocarbons
are formed by vacuum deposition at low temperature17 and a
few organic compounds form amorphous glasses at ambient
temperatures,18,19 little attention had been paid to amorphous
glasses of low molecular-weight organic compounds until the
late 1980s.
Since then, we have performed systematic studies of the
creation of low molecular-weight organic compounds that
readily form stable amorphous glasses above room temperature, which we refer to as ``amorphous molecular materials'' or
``molecular glasses'', and their structures, reactions, properties,
functions and applications. We considered that such work may
open up a new eld of organic materials science that deals with
molecular glasses as distinct from covalently-bonded inorganic
glasses and that such amorphous molecular materials may
constitute a new class of organic functional materials.
Amorphous molecular materials or molecular glasses are of
interest because of the following aspects. They are in a
thermodynamically nonequilibrium state and hence may
exhibit glass-transition phenomena usually associated with
amorphous polymers. It is thought that they assume a variety
of states such as the amorphous glass, supercooled liquid, and
crystal. They may be characterised by the presence of free
volume and by the disorder of both intermolecular distance and
orientation. They may form uniform, transparent amorphous
thin lms by vapor deposition and spin-coating methods. In
View Article Online
contrast to single crystals and liquid crystals which show

anisotropic properties, amorphous molecular materials may
exhibit isotropic properties as well as homogeneous properties
due to the absence of grain boundaries. In contrast to
polymers, they are pure materials with well-dened molecular
structures and denite molecular weights without any distribution. We have been interested in elucidating the correlation
between molecular structure and glass-forming properties,
structures of molecular glasses, relaxation processes of
molecular glasses, reactions in molecular glasses as a new
medium, properties of molecular glasses, dynamic control of
properties and functions, and applications of amorphous
molecular materials for electronic and optoelectronic devices.
In this section, amorphous molecular materials are discussed
from the following three standpoints: (1) design and synthesis
of amorphous molecular materials, (2) characteristic features
of their structures, reactions, and properties, and (3) functions
and applications of amorphous molecular materials.
2.1 Design and synthesis of amorphous molecular materials

Glass formation. In order to create amorphous molecular
materials, it is of importance to establish guidelines for the
design of amorphous molecular materials through the study of
the relationship between molecular structure and glass-forming
property. Based on the simple idea that nonplanar molecular
structure might prevent easy packing of molecules and hence
ready crystallisation, we have proposed a new concept, the pelectron starburst molecule, for the design of amorphous
molecular materials and synthesized several novel families
of organic p-electron systems, e.g., 4,4',4@-tris(diphenylamino)triphenylamine (TDATA),20 1,3,5-tris(diphenylamino)
benzene (TDAB),21 2,4,6-tris(diphenylamino)-1,3,5-triazine
(TDATz),22 and 1,3,5-tris(4-diphenylaminophenyl)benzene
(TDAPB),23 and various derivatives of each family.2437
Whereas triphenylamine and 1,3,5-triphenylbenzene instantly
crystallise instead of forming amorphous glasses despite being
nonplanar molecules,38,39 these new families of pelectron
systems have been found to readily form amorphous glasses
above room temperature, except for the parent compounds
TDAB, TDATz, and 2,4,6-tris[4-methylphenyl(phenyl)amino]1,3,5-triazine (p-MTDATz), either by rapidly cooling with
liquid nitrogen or by slowly cooling on standing in air.
Formation of the glassy state was conrmed by differential
scanning calorimetry (DSC), X-ray diffraction (XRD), and
polarising microscopy. Fig. 1 shows the DSC curves of m-
Fig. 1 DSC curves of m-MTDATA.
MTDATA as an example. When a polycrystalline sample of mMTDATA obtained by recrystallisation from THFethanol
was heated, an endothermic peak due to melting was observed
at 203 C. When the isotropic liquid was cooled down on
standing in air, a transparent glass was spontaneously formed
via a supercooled liquid. When the amorphous glass sample
was again heated, a glass-transition phenomenon was observed
at 75 C. On further heating above the glass-transition
temperature (Tg), an exothermic peak due to crystallisation
was observed at ca. 160 C to give the same crystal as obtained
by recrystallisation from solution, which melted at 203 C.20
The same DSC curves were reproduced repeatedly.
Relationship between molecular structure and glass-forming
property, glass-transition temperature (Tg), and stability of the
glassy state. We have studied the correlation between molecular structure and the glass-forming property, Tg, and stability
of the glassy state. X-Ray crystal structure analysis of the single
crystals of amorphous molecular materials grown from
solution or from melt have shown that the molecular structures
of all the compounds studied are nonplanar.35,40,41 Figs. 2 and
3 show the molecular structures of TDATA and a-TPTAB.28,37
With regard to TDATA, four triphenylamine moieties have
propeller-like structures, where the four nitrogen atoms deviate
from the plane consisting of the three carbon atoms bonded to
the nitrogen atom. The distances between the plane and the
and the dihedral angles between
nitrogen atom are 0.010.04 A
the plane consisting of the three carbon atoms bonded to the
nitrogen atom and the least square planes of the phenyl rings
bonded to the nitrogen atom are 3255. In the case of aTPTAB, the three thienyl groups in the nonplanar molecule are
disordered, each taking two positions by approximately 180
rotation along the single bond connecting the thiophene ring
and the nitrogen atom. The case is the same for b-TPTAB.
The nonplanar molecular structure is responsible for the
glass formation, but not all compounds with nonplanar
molecular structures necessarily show glass formation, as
exemplied by TDAB, TDATz, and p-MTDATz, which
instantly crystallise instead of forming glasses even when the
melt samples are rapidly cooled with liquid nitrogen. However,
incorporation of substituents exerts a great inuence on the
ease of glass formation. That is, introduction of alkyl or
halogen substituents into TDAB and TDATz or the replacement of three phenyl groups in TDAB by three thienyl groups
permitted the formation of glasses by cooling the melt samples
either with liquid nitrogen (for p-MTDAB, a- and b-TPTAB)
or on standing in air (for o- and m-MTDAB, o- and mMTDATz).21,28 It should also be noted that whereas TDATA
requires rapid cooling with liquid nitrogen for the formation
of a glass, its methyl-substituted derivatives, o-, m-, and pMTDATA, spontaneously form amorphous glasses when the
Fig. 2 Molecular structure of TDATA.
J. Mater. Chem., 2000, 10, 125
View Article Online
melt samples are cooled on standing in air.20 It is suggested that

the incorporation of the methyl or halogen substituents or the
replacement of the phenyl group by the thienyl group increases
the number of conformers and the mode of packing of
molecules, preventing crystallisation and facilitating glass
formation. The result of X-ray crystal structure analysis of
a- and b-TPTAB that the thienyl group is disordered is also in
support of the idea that a- and b-TPTAB can take on different
conformations with almost equal conformational energies.28,35
The kind of halogen substituent at the o-, m-, or p-position
of XTDABs (X~F, Cl, Br) strikingly affects the ease of
glass formation, Tg, and stability of the glassy state.30 The
ease of glass formation and the stability of the resulting
glass have been found to be enhanced in the order
FTDAB%ClTDABvBrTDAB. The Tg is also affected by
the type of halogen atom, increasing in the order
FTDABvClTDABvBrTDAB. The easier glass formation
and enhanced stability of the resulting glass in the order
F%ClvBr are understood in terms of the bulkiness and weight
of the halogen atom. That is, the more bulky and heavier
halogen atom will prevent the easy packing of molecules and
diffusion of molecules in the process of crystal growth, and
hence prevent crystallisation. The incorporation of a heavier
halogen atom will tend to hinder translational, rotational, and
4
J. Mater. Chem., 2000, 10, 125
vibrational motions of the molecule, leading to an increase in

Tg.
The stability of the glassy state is enhanced with increasing
molecular size. Tri(biphenyl-4-yl)amine (TBA) forms a
glass;40,42 however, it tends to crystallise in several days at
room temperature. On the other hand, the glassy state of mMTDATA is very stable at room temperature without any
crystallisation for more than 10 years. Whereas the glass of pMTDAB tends to crystallise in several months on standing
in air at room temperature, the amorphous glasses of 1,3,5tris[4-diphenylaminophenyl(phenyl)amino]benzene (p-DPATDAB)26 and 1,3,5-tris{N-[4-bis(4-methylphenyl)aminophenyl]-N-(4-diphenylaminophenyl)amino}benzene (MTBDAB)34
are very stable without any crystallisation even on heating
above their Tgs.
The Tg of molecular glasses is understood as the temperature
at which molecular motions of a group of molecules, which are
caused by intramolecular bond rotations, start to take place,
resulting in a change in the position of the gravity of molecules.
In applying amorphous molecular materials for electronic and
optoelectronic devices, thermal stability is often required. It is
thus necessary to develop amorphous molecular materials with
high Tgs. We have shown that Tg can be increased by the
incorporation of a structurally rigid moiety, that is, by
View Article Online
Fig. 3 Molecular structure of a-TPTAB. The population ratios of the

disordered thienyl groups A and B are 0.73 : 0.27, and 0.32 : 0.18,
respectively (see text).
decreasing the exibility of nonplanar molecules.24,27,3133 For

example, when the diphenylamino group in the TDAB,
TDATA, and TDAPB families is replaced by a rigid carbazolyl
group, the Tg increases by approximately 70 C. In addition, Tg
increases with increasing molecular size and weight,26,34 and by
the introduction of heavy substituents. Introduction of
intermolecular interactions such as hydrogen bonding or
dipolar interactions also provides an approach for increasing
Tg.
Guidelines for molecular design and synthesis of novel families
of amorphous molecular materials based on p-electron systems.
Studies of the relationship between the molecular structure and
the glass-forming property, Tg and stability of the glassy state
have provided several guidelines for the design of amorphous
molecular materials. An increase in the number of conformers
together with nonplanar molecular structure is the requirement
for the formation of amorphous glasses. Introduction of bulky
and heavy substituents and enlargement of molecular size are
the important factors for attaining the stability of the glassy
state. Tg can be increased by the incorporation of a rigid moiety
or an intermolecular hydrogen bonding site into nonplanar
molecules, by the enlargement of molecular size and by
increasing the molecular weight. Based on these guidelines, we
have created a variety of novel amorphous molecular materials,
which include a number of p-electron starburst molecules,2037
tris(oligophenylenyl)amines,4043 p-electron systems containing
an oligothiophene moiety,4447 p-electron systems containing
an azobenzene moiety,4851 and others.5257 Table 1 summarises Tg, crystallisation temperatures (Tc), and melting
points (Tm) of some amorphous molecular materials.
Very recently, a number of new amorphous molecular
materials, e.g., p-electron starburst molecules containing
oxadiazole and quinoxaline moieties,5860 spiro-linked compounds based on p-electron systems,61,62 dendrite macromolecules,63,64 and others,65 have been developed. Some of them
function as materials for organic EL devices.
to show well-dened glass-transition phenomena. In addition,

many of them have been found to exhibit polymorphism,
assuming different crystalline forms depending upon the
history of heat treatment.
For example, p-MTDAB, a-TPTAB, and b-TPTAB take on
three different crystal forms.21,28,35,66 Fig. 4 shows DSC curves
of a-TPTAB. When a crystalline sample of a-TPTAB obtained
by recrystallisation from benzenehexane or cyclohexane
(crystal A) was heated, an endothermic peak due to a solid
solid phase transition was observed at 169 C, where the crystal
A was transformed into a different crystal form (crystal B). On
further heating, the crystal B melted at 187 C to give an
isotropic liquid. When the isotropic liquid was rapidly cooled
with liquid nitrogen, a transparent glass was formed. When the
amorphous glass was again heated, a glass-transition phenomenon was observed at 38 C, and then an exothermic peak due
to crystallisation to form another crystal (crystal C) was
observed around 70 C. Thereafter, an exothermic peak due to
a solidsolid phase transition from the crystal C to the crystal B
was observed around 133 C, followed by the melting of the
crystal B at 187 C. It is of interest to note that the mode of
phase transformation is different between a-TPTAB and bTPTAB. While a-TPTAB undergoes solidsolid phase transitions from the crystal C to the crystal B, b-TPTAB undergoes
phase transitions involving melting and crystallisation. In the
case of p-MTDAB, phase transition involves melting followed
by crystallisation.66 The morphological changes of a-TPTAB
are summarized in Scheme 1.
As described above, it has been demonstrated that the
2.2 Characteristic features of amorphous molecular materials

morphological changes, structures, reactions, and properties
Some characteristic features of amorphous molecular materials
with regard to relaxation phenomena, structures, reactions,
and solid-state properties are described here.
Relaxation phenomena of amorphous molecular materials.
Since the glassy state is a state of thermodynamic nonequilibrium, it tends to be transformed into the state of
thermodynamic equilibrium. Elucidating the relaxation phenomena of amorphous molecular materials is a subject of
importance. Amorphous molecular materials have been found
J. Mater. Chem., 2000, 10, 125
View Article Online
relaxation of the molecular glass is characterised by welldened glass transition, followed by either solidsolid or
meltingcrystallisation phase transformations, nally leading
to the formation of the crystal with the highest melting point.
The phenomena of polymorphism observed for many amorphous molecular materials suggest the existence of different
conformers, which is responsible for the ready formation of the
glassy state.
Structures of molecular glasses. The positron annihilation
lifetime (PAL) technique has recently been used for characterising the free volume of amorphous polymers.67 We have
6
J. Mater. Chem., 2000, 10, 125
estimated the average size of free volume hole in a few

molecular glasses, e.g., m-MTDATA, m-MTDAB, p-DPATDAB, and MTBDAB, in comparison with that of polystyrene, using the PAL technique.68,69 The PAL spectra were
analyzed into three lifetime components and the long-lived
component was attributed to the pick-off annihilation of opositronium (o-Ps) in the free volume. The radius of the free
volume hole was calculated from the semiempirical equation. It
was found that the average size of the free volume of the
molecular glasses was smaller than that of a polystyrene glass
3, m-MTDAPB: 87 A
3, polystyrat 30 C (m-MTDATA: 80 A
3) and that the average size of the free volume hole of
ene: 120 A
molecular glasses increases with increasing molecular size. The
temperature dependence of PAL showed that the temperature
at which the slope of the plot of the lifetime of o-Ps versus
temperature increased steeply corresponds to the glasstransition temperature. The size of free volume may affect
reactions in the molecular glass and its properties.
Reactions in molecular glasses. Molecular glasses are
expected to serve as novel reaction media as well as novel
host matrices for embedding functional materials such as
photochromic materials. We have studied photochromic
View Article Online
Table 1 Glass-transition temperatures (Tg), crystallisation temperatures (Tc), and melting points (Tm) of some amorphous molecular
materials
Compound
Tg/C
Tc/C
Tm/C
TDATAa
o-MTDATAa
m-MTDATA
p-MTDATAa
TCTAa
89
76
75
80
150
134
153
160
130
190
275b
200b
203
265b
296b
o-MTDAB
m-MTDAB
p-MTDAB
p-FTDAB
p-ClTDAB
p-BrTDAB
a-TPTABa
b-TPTABa
TCBa
p-DPA-TDAB
MTBDAB
42
47
55
54
64
72
38
46
126
107
134
121
85
81
66
112
c
70
76
164
c
c
161
183
210
228
181
165
187b
210b
330b
240
d
o-MTDATz
m-MTDATza
TDAPB
o-MTDAPB
m-MTDAPB
p-MTDAPB
TCPBa
55
42
121
109
105
110
172
85
67
196
154
167
c
215
175
175b
269
279
231
243
356b
Fig. 4 DSC curves of a-TPTAB.
a
Exhibits polymorphism. bTm of the crystal with the highest melting
point. cNo crystallization on heating from the glass. dObtained as an
amorphous glass.
reactions of 4-dimethylaminoazobenzene (DAAB) dispersed in

the lm of m-MTDATA and TCTA in the solid lm state in
order to elucidate the properties of molecular glasses as host
matrices and to gain information on the microstructures of the
molecular glasses.7072
It was found that DAAB dispersed in the lm of mMTDATA or TCTA amorphous glass undergoes reversible
photoisomerisation. The cis-fractions of DAAB at the photostationary state at 30 C were estimated to be ca. 0.26 and 0.27
for the m-MTDATA and TCTA lms containing a 0.01 molar
ratio of DAAB. These values are smaller than those (0.85) in
solution and in a polystyrene glass.
It is also notable that the apparent rate constant at the initial
stage of the backward thermal cistrans isomerisation of
DAAB in these molecular glasses was larger than those in the
polystyrene matrix and benzene solution, as shown in Fig. 5. In
contrast to the reaction in benzene solution which followed
rst-order kinetics, the backward thermal cistrans isomerisation of DAAB in the lms of molecular glass and polystyrene
did not follow rst-order kinetics, being analyzed by the rstorder kinetics of two components. The rate constant of the
slower component obtained for the m-MTDATA, TCTA, and
polystyrene lms was equal to that of the benzene solution. The
fractions of the faster component were considerably larger for
the m-MTDATA and TCTA lms than for the polystyrene
matrix lm; this leads to the faster apparent rate constant at the
initial stage for the m-MTDATA and TCTA amorphous lms
than for the polystyrene matrix lm. Table 2 lists the kinetic
parameters obtained for the reactions in the m-MTDATA and
TCTA glasses, the polystyrene matrix, and the benzene
solution. The slower component is attributed to the reaction
of the photogenerated, structurally relaxed cis-isomer and the
faster component is thought to be attributable to the reaction
of the photogenerated cis-isomer with a strained conformation
due to the presence of the surrounding matrix which restricts
the molecular motion of DAAB.
These results suggest that the size of local free volume in the
m-MTDATA and TCTA host matrices is smaller than that in
Scheme 1 Morphological changes of a-TPTAB.
the polystyrene glass. Therefore, a large number of transDAAB molecules remain unchanged in these molecular glass
matrices at the photostationary state and the proportion of
strained cis-isomer relative to the relaxed one is large in these
molecular glasses. The result of the reaction in molecular
glasses is in agreement with the result of the free volume size
estimated by the PAL technique.
Charge transport properties in molecular glasses. Charge
transport is involved in the operation processes of photoreceptors in electrophotography, organic EL devices and eldeffect transistors. Charge transport in organic disordered
systems has been studied extensively with regard to polymers
and molecularly-doped polymer systems, where low molecular-
Fig. 5 First-order plots for the thermal cistrans isomerisation of

DAAB in (a) m-MTDATA lm, (b) polystyrene lm, (c) benzene
solution (3.361024 mol dm23) at 30 C after the reaction system has
reached the photostationary state upon irradiation with 400 nm light.
J. Mater. Chem., 2000, 10, 125
View Article Online
Table 2 Kinetic parameters of the thermal cistrans isomerisation of DAAB at 30 C in the molecular glasses, polystyrene, and benzene solutiona
Reaction medium
k1/min21
f1
k2/min21
f2
m-MTDATA lmb
TCTA lmb
Polystyrene lm
Benzene solutionc
0.083
0.032
0.062
0.54
0.35
0.12
0.003
0.003
0.003
0.003
0.46
0.65
0.88
1.00
Analyzed by the rst-order kinetics of two components: [cis]t/[cis]0~f1 exp(2k1t)zf2 exp(2k2t). b0.01 molar ratio of DAAB. cSingle component.
weight organic materials are dispersed in binder polymers. It is

known that charge transport in organic disordered systems
such as amorphous polymers and molecularly-doped polymer
systems generally shows the following characteristic features:
(a) the drift mobility of charge carriers is very small, being in
the order from ca. 10281024 cm2 V21 s21, (b) the drift
mobility is electric-eld dependent, and (c) charge transport
is a thermally activated process. It has generally been
understood that charge transport in organic disordered systems
takes place by a hopping process. A few models have been
proposed to explain temperature and electric-eld dependencies of the drift mobilities of disordered systems, which include
the PooleFrenkel model,73 the small-polaron model,74,75 and
the disorder formalism.76,77
It has recently been shown that charge transport in
molecularly-doped polymer systems is greatly dependent
upon the binder polymer. In fact, the hole drift mobility of
molecularly-doped polymer systems has been reported to vary
by two orders of magnitude depending upon the binder
polymer.7880 Chargedipole interactions between a charge on
the transport molecule and the binder polymer are thought to
cause the uctuation of both the hopping site energy and the
overlap integral. In order to clarify intrinsic charge-transport
properties of low molecular-weight organic materials in the
disordered system, charge transport in the amorphous glassy
state of low molecular-weight organic materials in the absence
of a binder polymer should be investigated.
Creation of amorphous molecular materials has made it
possible to investigate charge transport in the glassy state. We
have measured charge-carrier drift mobilities of a variety of
molecular glasses.23,4044,57,8191 Table 3 lists the hole drift
mobilities of some molecular glasses. It is shown that the hole
drift mobilities of molecular glasses are in the order from 1026
to 1022 cm2 V21 s21 at an electric eld of 1.06105 V cm21 at
room temperature. o-MTDAB, p-BPD, and tris[4-(2-thienyl)phenyl]amine exhibit high hole drift mobilities exceeding
1.061023 cm2 V21 s21 and tris[4-(5-phenyl-2-thienyl)phenyl]amine the highest mobility of 1.06102 cm2 V21 s21 at an
electric eld of 16105 V cm21 at 293 K.81,90 Although the
values of hole drift mobilities vary greatly depending upon
molecular structure, higher drift mobilities of amorphous
Table 3 Hole drift mobilities of molecular glasses
Material
mh/cm2 V21 s21
m-MTDATA
o-MTDAB
p-DPA-TDAB
MTBDAB
m-MTDAPB
o-TTA
m-TTA
p-TTA
o-BPD
m-BPD
p-BPD
BMA-3T
BMA-4T
3.061025 a
3.061023 b
1.461024 b
2.561025 b
1.661025 b
7.961024 a
2.361025 a
8.861024 a
6.561024 a
5.361025 a
1.061023 a
2.861025 a
1.061025 a
Measured at an electric
b
2.06105 V cm21 at 293 K.
eld
of
J. Mater. Chem., 2000, 10, 125
1.06105 V cm21
and
molecular materials relative to those of polymers and

molecularly-doped polymer systems may be attributed to the
absence of dilution effects of hopping sites and to the absence
of chargedipole interactions between charge carriers and the
binder polymer.
We have studied the relationship between molecular
structure and charge-transport properties in order to gain
information on the guidelines for the molecular design of
amorphous molecular materials with high drift mobility.81 A
few examples are given here. The charge-carrier drift mobility
greatly varies depending upon the position of the phenyl group
in the biphenyl moiety. Hole drift mobilities of the o- and pisomers of TTA and BPD have been found to be more than one
order of magnitude larger than those of the m-isomers of TTA
and BPD (Table 3). The analysis of the electric-eld and
temperature dependencies of the drift mobilities of these
materials in terms of the disorder formalism showed that the
difference in the energetic disorder s is responsible for the
difference in the hole drift mobility among o-, m-, and pisomers: the s value signicantly increases in the order o-TTA
(0.059 eV)vp-TTA (0.071 eV)vm-TTA (0.093 eV) and o-BPD
(0.071 eV)vp-BPD (0.075 eV)vm-BPD (0.105 eV).57
It is thought that the degree of the variation of the molecular
geometry caused by the rotation along the CC and CN bonds
is responsible for the difference in the s value among the o-, m-,
and p-isomers; the smaller variation of the molecular geometry
results in the smaller energetic disorder s. The variation of the
molecular geometry may be much smaller for o- and p-isomers
than that for the m-isomer due to the restricted internal
rotation in the o-terphenyl moiety for the o-isomers and to the
smaller number of conformers resulting from the bond rotation
for the symmetrical p-isomer. Thus, decreasing the variation of
molecular geometry by restricting internal rotation or by
increasing the symmetry of the molecule is suggested to be a
guiding principle for the molecular design for high mobility.
The effect of molecular size on the charge-carrier drift
mobility was studied using a novel family of molecular glasses
having a similar molecular skeleton but a varying molecular
size, o-MTDAB, p-DPA-TDAB, and MTBDAB. It was found
that the hole drift mobilities of these molecular glasses vary by
two orders of magnitude depending on the molecular size: the
hole drift mobility increased with decreasing molecular size
in the order MTBDABvp-DPA-TDABvo-MTDAB. oMTDAB exhibited a high mobility of 361023 cm2 V21 s21
at an electric eld of 2.06105 V cm21 at 293 K.91
The drift mobility (m) of charge carriers generally increases
with increasing electric eld (E), following the relation
ln m3exp(SE1/2), where S is a coefcient. We have found for
the rst time the negative electric-eld dependence of chargecarrier drift mobility with regard to molecular glasses.43 As
Fig. 6 shows, the molecular glass of o-TTA exhibited the
negative electric-eld dependence of hole drift mobility. The
hole drift mobility of the o-TTA glass increased with increasing
electric eld in a temperature range below 285 K, following the
electric-eld dependence of exp(SE1/2); however, the hole drift
mobility started to decrease with increasing electric eld above
285 K. The negative electric-eld dependence of charge-carrier
drift mobility is understood as arising from the contribution of
the diffusion process of charge carriers against the direction of
View Article Online
electric eld due to the presence of positional disorder S caused

by the disorder of the intermolecular p-electron overlap. That
is, faster detour routes against the electric eld exist due to the
presence of the positional disorder S. The rate of the diffusion
of charge carriers through the detour routes increases with
rising temperature because of the growing mean energy of
charge carriers. However, the diffusion rate gradually decreases
with increasing electric eld; this results in the negative electriceld dependence of charge-carrier drift mobility. The analysis
of the electric-eld and temperature dependencies of drift
mobilities in the temperature range below 285 K in terms of the

disorder formalism gave the following hole-transport parameters for the molecular glass of o-TTA: m0~9.761023 cm2
V1 s21, s~0.059 eV, S~2.4, and C~4.461024 (cm V21)1/2.
The small s value as well as the presence of the positional
disorder S is responsible for the negative electric-eld
dependence of the drift mobility of the o-TTA glass. The
negative electric-eld dependence of drift mobility was also
observed for m-MTDATA.88,89
Studies of charge transport and in particular, the observation
J. Mater. Chem., 2000, 10, 125
View Article Online
Fig. 6 Electric-eld dependence of the hole drift mobilities of the

o-TTA glass at various temperatures.
of the negative electric-eld dependence of charge-carrier drift

mobility have veried the presence of the disorder of
intermolecular distance and orientation in amorphous molecular materials.
Very recently, charge transport in vacuum deposited
amorphous lms has also been studied. The values of hole
and electron drift mobilities are mostly in the range from 1025
to 103 cm2 V1 s1.9297
2.3 Functions and applications of amorphous molecular
materials
We have created several novel classes of functional amorphous
molecular materials, e.g., electrically conducting amorphous
molecular materials, photochromic amorphous molecular
materials, molecular resists, amorphous molecular materials
for photovoltaic and organic EL devices.
Electrically conducting amorphous molecular materials. Low
molecular-weight organic electrical conductors hitherto studied
are either single crystals or polycrystals of charge-transfer
complexes, ion-radical salts, and partially oxidised metal
complexes. With the aim of developing electrically conducting
amorphous molecular materials which might serve as molecular solder, we have studied the chemical doping of a TPTTA
glass with iodine.24
A transparent amorphous lm of TPTTA formed by cooling
the melt sample or by solvent cast was exposed to iodine vapor
for three days in a glass tube to give a black, lustrous lm. It
was proved to be an amorphous glass, as characterised by DSC
and XRD. The chemically-doped amorphous lm was
identied as a TPTTA radical-cation salt with I32 and I52 as
dopants, as characterised by IR, Raman, and electronic
absorption spectroscopy. The iodine-doped amorphous glass,
(TPTTA)I2.6, exhibited a room-temperature conductivity of
161025 S cm21 with an activation energy of 0.36 eV.
Photochromic amorphous molecular materials. Photochromic materials are candidates for potential technological
applications for optical recording, storage of information,
optical switching, etc. In applying photochromic materials for
such devices, they may be used in the form of a solid lm.
Extensive studies have been made of photochromism of
polymers containing photochromic chromophores and composite polymer systems, where low molecular-weight photo10
J. Mater. Chem., 2000, 10, 125
chromic compounds are dispersed in polymer binders.98 We

have studied the creation of amorphous molecular materials
with photochromic function, which we refer to as ``photochromic amorphous molecular materials'' or ``photochromic
molecular glasses''. They may constitute a novel class of
photochromic compounds that exhibit a glass-transition
phenomenon usually associated with polymers, forming uniform amorphous lms by themselves in the absence of polymer
binders. They have the advantage that there is no dilution of
photochromic chromophores relative to photochromic polymers and composite polymer systems.
Based on this concept, we have created a novel family of
photochromic amorphous molecular materials containing an
azobenzene chromophore.4851 It includes 4-[bis(4-methylphenyl)amino]azobenzene
(BMAB),
4-[bis(4-methylphenyl)amino]-4'-methoxyazobenzene (MeO-BMAB), 4-[di(biphenyl4-yl)amino]azobenzene (DBAB), 4,4'-bis[bis(4-methylphenyl)
amino]azobenzene (BBMAB), and 4,4'-bis[bis(4'-tert-butylbiphenyl-4-yl)amino]azobenzene (t-BuBBAB). These compounds
were found to readily form amorphous glasses with Tgs of 27,
33, 68, 79, and 177 C, respectively, and to exhibit photochromism in their amorphous lms. Photoisomerisations from
trans- to cis- and cis- to trans-isomers took place repeatedly
under alternating irradiation with 450 and 550 nm light each
for one minute (Fig. 7). The fractions of cis-isomer at the
photostationary state in the amorphous lm were 0.54, 0.29,
0.53, 0.17, and 0.15 for BMAB, MeO-BMAB, DBAB,
BBMAB, t-BuBBAB, respectively. The photogenerated cisform undergoes thermal isomerisation to the trans-form.
Stabilisation of the photogenerated cis-form at ambient
temperature was attained by the incorporation of a bulky
group. More than 80% of the photogenerated cis-form of tBuBBAB remained unchanged after ve days at room
temperature; however, the cis-form was completely transformed into the trans-form by heating the sample to
Fig. 7 Change of absorbance at 430 nm for amorphous BMAB lm

under alternating irradiation with 450 nm and 550 nm light at 20 C.
View Article Online
140 C. Thus, the backward cistrans thermal isomerisation can

be controlled by temperature.50
Molecular resists. The minimum feature size in semiconductor devices has constantly been becoming signicantly smaller,
and 64 Mbit dynamic random access memories (DRAMs)
requiring 0.35 mm resolution are now in commercial production. Nanolithography is a future important technique for the
fabrication of metal-oxide-semiconductor (MOS) and quantum
devices. Electron-beam lithography has been used for the
fabrication of advanced devices, e.g. 1 Gbit or 4 Gbit DRAMs
with 180 and 150 nm patterns. Resist materials with a high
resolution and a high sensitivity are required for electron-beam
lithography. Organic polymers or composite polymer systems,
where photosensitive low molecular-weight organic compounds
are dispersed in polymers, have been used as resist materials
owing to their excellent lm-forming properties.99 However, it is
thought that the molecular size of resist materials limits the

resolution of the pattern in nanometre-size lithography. It is
therefore desirable to reduce the molecular size of resist
materials in order to obtain nanometre-size lithographic
patterns. Creation of low molecular-weight organic resist
materials, which we refer to as ``molecular resist materials'', is
expected to be one of the breakthroughs.
Based on this idea, we have designed and synthesized several
novel classes of molecular resist materials that form uniform
amorphous lms, 1,3,5-tris[4-(4-tolylsulfonyloxy)phenyl]benzene (TsOTPB), 1,3,5-tris[2-(tert-butoxycarbonyloxy)phenyl]benzene (o-BCOTPB), 1,3,5-tris[4-(tert-butoxycarbonyloxy)phenyl]benzene (p-BCOTPB), 4,4',4@-tris(allylsuccinimido)triphenylamine (ASITPA), and 1,3,5-tris[4-(4-vinylphenylcarbonyloxy)phenyl]benzene (VCTPB). TsOTPB, o- and p-BCOTPB
have been found to function as positive resists and ASITPA and
VCTPB as negative resists with high resolution capability on
J. Mater. Chem., 2000, 10, 125
11
View Article Online
exposure to an electron beam.5356 Related to this work, an

oligomer of a calixarene derivative has been reported to function
as a negative electron-beam resist with high resolution.100
Line patterns of 150, 70, and 40 nm could be fabricated for
the TsOTPB positive resist, ASITPA negative resist, and pBCOTPB positive resist, respectively. p-BCOTPB showed a
high sensitivity of 4.4 mC cm22. Fig. 8 shows the SEM images
of negative-tone line and space patterns for the ASITPA lm
and positive-tone line and space patterns for the p-BCOTPB
lm. Molecular resist materials are expected to be promising
candidates for the future nanometre lithography.
Organic photovoltaic devices. With the aim of creating
visible light-sensitive amorphous molecular materials for
photovoltaic devices, new p-electron starburst molecules
involving intramolecular charge transfer, 4,4',4@-tris[4-methylphenyl(4-nitrophenyl)amino]triphenylamine
(MNTDATA)
and 4,4',4@-tris[5-(dimesitylboryl)thiophen-2-yl]triphenylamine
(MB-TPA), were designed and synthesized. It was found that
MNTDATA and MB-TPA readily form amorphous glasses
with Tgs of 134 and 161 C, respectively, and that the
absorption bands of these compounds extend to the wavelength
12
J. Mater. Chem., 2000, 10, 125
range of visible light. pn Heterojunction devices using

MNTDATA or MB-TPA as a p-type material and
anthra[2@,1@,9@ : 4,5,6; 6@,5@,10@ : 4',5',6']diisoquino[2,1-a : 2',1'a']dibenzimidazole-10,21-dione (PV) as an n-type material were
found to respond to visible light, exhibiting conversion
efciencies of 0.4 and 0.1%, respectively, when irradiated
with monochromatic light of 440 nm which MNTDATA and
MB-TPA mainly absorb.101,102
Organic electroluminescent (EL) devices. Amorphous molecular materials are promising candidates for use in organic EL
devices. They permit the formation of smooth, uniform
amorphous thin lms by vacuum deposition or by coating
from solution. We have performed a series of studies of the
creation of novel families of hole-transporting, electrontransporting, and emitting amorphous molecular materials
for organic EL devices and the fabrication and performances of organic EL devices using amorphous molecular
materials.103,104
(a) Hole-transporting amorphous molecular materials. With
regard to low molecular-weight hole-transporting materials for
View Article Online
Fig. 8 (a) SEM image of negative-tone line and space patterns for the
ASITPA resist lm on exposure to 50 keV electron beam at
12 mC cm22. (b) SEM image of positive-tone line and space patterns
for the p-BCOTPB resist lm on exposure to 50 keV electron beam at
200 mC cm22.
organic EL devices, N,N'-bis(3-methylphenyl)-N,N'-diphenyl[1,1'-biphenyl]-4,4'-diamine (TPD) has been widely used;

however, TPD lacks thermal and morphological stability. It
is desirable that the materials should have high Tgs for
attaining thermal stability of organic EL devices. We have
created several novel families of hole-transporting amorphous
molecular materials with higher Tgs, which include the
TDATA family, e.g., m-MTDATA,20 the naphthyl- or
biphenyl-substituted derivatives of TDATA, 1-TNATA,33 2TNATA,33 o-PTDATA,36 m-PTDATA,36 p-PMTDATA,36
and TCTA,27 and the TDAB and TDAPB families, e.g., pDPA-TDAB,26 MTBDAB,34 and the o-, m-, and p-methyl
substituted derivatives of TDAPB (o-, m-, and p-MTDAPB).23
Very recently, new TPD derivatives with Tgs higher than that
of TPD have been developed. They are the naphthyl-,
phenanthryl-, and biphenyl-substituted derivatives, N,N'-di(1-naphthyl)-N,N'-diphenyl-[1,1'-biphenyl]-4,4'-diamine
(a-NPD),105
N,N'-di(9-phenanthryl)-N,N'-diphenyl-[1,1'biphenyl]-4,4'-diamine,106 o-BPD,57 m-BPD,57 and p-BPD.57
In 1994, we reported for the rst time the thermal stability of an
organic EL device using TCTA as the hole-transporting layer
and tris(quinolin-8-olato)aluminum (Alq3) as the emitting
layer, showing that the device operates at 150 C, whereas
the double-layer device using TPD and Alq3 ceased emission
when the temperature rose to 65 C.27 Thermally stable organic
EL devices have been developed using hole-transporting
amorphous molecular materials with high Tgs in combination
with Alq3 as an emitting material.32,36,107
We reported in 1994 that a multilayer organic EL device
consisting of an emitting layer of Alq3 and double holetransporting layers of m-MTDATA and TPD, ITO/mMTDATA/TPD/Alq3/MgAg, exhibits higher luminous efciency and signicantly enhanced operational stability than
double-layer devices consisting only of an emitting layer of
Alq3 and a single hole-transport layer of TPD,108 paving the
way for durable organic EL devices. While the double-layer
device consisting of a single hole-transport layer of TPD and an
emitting layer of Alq3 generates a leak current in a short time
during operation, multilayer devices using the m-MTDATA or
1-TNATA layer in contact with the ITO electrode operate
safely without generating a leak current. The ITO/m-MTDA )/TPD(100 A
)/Alq3(500 A
)/MgAg device exhibited a
TA(600 A
maximum luminescence of 24 000 cd m22 at an applied voltage
of 15 V and a luminous efciency of 2.4 lm W21. The
multilayer structure as shown in Fig. 9 has since been widely
employed for fabricating organic EL devices with high
operational stability, where HTL1 acts as a hole-injection
layer. The materials of the TDATA family, e.g., m-MTDATA,
1-TNATA, 2-TNATA, o-, m-PTDATA and p-PMTDATA,
which are characterised by very low ionisation potentials and
the good quality of their amorphous lms, function as an
excellent hole injection layer in contact with the ITO electrode.
The materials with higher ionisation potentials such as TPD, aNPD, o-, m-, and p-BPD, TCTA, p-DPA-TDAB, and o-, m-,
and p-MTDAPB function as materials for HTL2. The halfdecay time of the initial luminescence of 300 cd m22 was 2000 h
at room temperature for the multilayer device, ITO/mMTDATA/a-NPD/Alq3/MgAg. The device consisting of
double hole-transport layers of p-PMTDATA and p-BPD
and an Alq3 emitting layer exhibited high performance and
signicant thermal stability: the device operated at 150 C,
retaining a luminance of 80% of the initial value measured at
20 C (Fig. 10).36 It has been shown that doping of an intense
uorescent molecule in the emitting material Alq3 improves not
only the luminous efciency but also the thermal and
operational stability of organic EL devices using 1-TNATA
as HTL1.109
(b) Electron-transporting amorphous molecular materials.
Electron-transporting materials can be used in combination
with emitting materials either with weaker electron-accepting
properties or with hole-transporting properties. As compared
with hole-transporting materials, there have been few examples
of electron-transporting materials, which include Alq3, oxadiazole derivatives,33,58,110 3-(biphenyl-4-yl)-4-phenyl-5-(4-tertbutylphenyl)-1,2,4-triazole,111 and 1,1'-dimethyl-2,5-di(2-pyridyl)silole.112
We have created novel families of thermally stable, electrontransporting amorphous molecular materials, 1,3,5-tris(4-tertbutylphenyl-1,3,4-oxadiazolyl)benzene (TPOB),33,58 1,3,5tris[5-(dimesitylboryl)-2-thienyl]benzene (TMB-TB),113 5,5'bis(dimesitylboryl)-2,2'-bithiophene (BMB-2T),46 and 5,5@bis(dimesitylboryl)-2,2' : 5',2@-terthiophene (BMB-3T).46 These
compounds readily form stable amorphous glasses with Tgs of
137, 160, 107, and 115 C, respectively.
Both BMB-2T and BMB-3T function as excellent electrontransporting materials in combination with an emitting material
Alq3 to enhance the performance of the organic EL devices.46
Multilayer organic EL devices using BMB-2T or BMB-3T as an
electron-transporting material, Alq3 as an emitting material,
and m-MTDATA and a-NPD as hole-transporting materials,
)/a-NPD(200 A
)/Alq3(300 A
)/BMBITO/m-MTDATA(300 A
)/MgAg, emitted bright green light
nT (n~2 or 3)(200 A
originating from the electronically excited singlet state of
Alq3, exhibiting approximately 10 to 20% higher luminous and
quantum efciencies and 1.6 to 1.8 times higher maximum
luminance than the organic EL device without the BMB-nT
)/a-NPD(200 A
)/Alq3(500 A
)/
layer, ITO/m-MTDATA(300 A
J. Mater. Chem., 2000, 10, 125
13
View Article Online
MgAg. In multilayer organic EL devices using BMB-nT as an

electron-transport layer, electron injection takes place more
readily by a stepwise process through the BMB-nT layer.
(c) Emitting amorphous molecular materials. Organic EL
devices permit multi-colour or full-colour emission by the
selection of emitting materials. With regard to low molecularweight organic emitting materials, Alq3 has been used most
extensively as a green-emitting material with electron-transporting properties. In order to achieve full-colour emission,
red, green, and blue emissions are needed.
Blue-emitting low molecular-weight organic materials which
have been reported include 1,3-bis[4-(N,N-dimethylamino)phenyl-1,3,4-oxadiazolyl]benzene,110 4,4'-bis(2,2-diphenylethenyl)biphenyl,114 3-(biphenyl-4-yl)-5-(4-dimethylamino)-4-(4-ethylphenyl)-1,2,4-triazole,115 and 2,2',7,7'-tetra(biphenyl-4-yl)-9,9'spirobiuorene.61 Organic EL devices using these blue-emitting
materials have been reported to exhibit brightness of
approximately 1000 cd m22 except for 4,4'-bis(2,2-diphenylethenyl)biphenyl, which exhibits much higher luminance.
We have created novel blue-emitting amorphous molecular
materials, tri(p-terphenyl-4-yl)amine (p-TTA),42 tri(o-terphenyl-4-yl)amine (o-TTA)43 and BMB-2T.46 o- and p-TTA have
hole-transporting properties and BMB-2T has electron-transporting properties. They display intense blue uorescence with
quantum efciencies of 0.48, 0.68 and 0.86 in THF solution.
p-TTA functions not only as a blue-emitting material but
also as a good host material for uorescent dopants, e.g.,
perylene. A bilayer organic EL device using p-TTA as a blueemitting material and p-DPA-TDAB as a hole-transporting
material emitted blue light resulting from p-TTA116 and a
bilayer device using perylene-doped TTA, ITO/p-DPA-TDAB
)/perylene (5 mol%) doped p-TTA (600 A
)/MgAg,
(600 A
emitted bright blue light resulting from perylene instead of p14
J. Mater. Chem., 2000, 10, 125
TTA.117 Whereas the EL spectrum of the undoped device was

in accordance with the PL spectrum of p-TTA, that of the
perylene-doped device was in good agreement with the
uorescence spectrum of perylene in a dilute solution. Fig. 11
shows the EL spectra of the perylene-doped and undoped
organic EL devices. The device exhibited a maximum
luminance of 2400 cd m22 at a driving voltage of 17 V and a
luminous efciency of 0.5 lm W21 at a luminance of
100 cd m22. The emission started at an applied voltage of
approximately 5 V. The external quantum efciency was
estimated to be 0.8%.
BMB-2T functions not only as an excellent electrontransporting material but also as a novel blue-emitting material
for organic EL devices. Blue-emitting BMB-2T was found to
form exciplexes with hole-transporting materials such as TPD;
however, the exciplex formation was prevented by the insertion
of a thin layer of a new amorphous molecular material, 1,3,5tri(biphenyl-4-yl)benzene (TBB) (Tg~88 C), in between the
hole-transport layer of TPD and the emitting layer of BMB2T.118 The multilayer device consisting of m-MTDATA, TPD,
TBB, and BMB-2T exhibited blue emission from BMB-2T with
a maximum luminescence of 1100 cd m2.
The combination of two kinds of blue-emitting materials
with electron-transporting and hole-transporting properties,
BMB-2T and o- or p-TTA, resulted in the blue-emission mainly
from BMB-2T.119 A triple-layer organic EL device using mMTDATA as a hole-injection layer, o-TTA or p-TTA as a
hole-transport layer, and BMB-2T as an emitting layer,
ITO/m-MTDATA(300 A )/TTA(200 A )/BMB-2T(300 A )/
), emitted blue light resulting mainly from BMBMgAg(1000 A
2T and partly from o- or p-TTA. Fig. 12 shows the EL
spectrum of the device together with the PL spectrum of the
amorphous thin lm of BMB-2T. The EL spectrum with lmax
at 446 and 472 nm is in accordance with the PL spectrum of
View Article Online
the lm of BMB-2T. A very weak emission with lmax at

approximately 410 nm resulting from o-TTA was also
observed. Neither exciplex emission in the longer wavelength
was observed nor was the EL spectrum affected by the
magnitude of the applied voltage. As suggested from Tables 4a
and b, the energy barrier for electron injection from the BMB2T layer into the o-TTA layer is thought to be higher than that
for the hole injection from the o-TTA layer into the BMB-2T
layer, and hence the recombination of holes and electrons
takes place mainly in the layer of BMB-2T to generate

the electronically excited singlet state of BMB-2T.
The multilayer organic EL device, ITO/m-MTDATA )/o- or p-TTA(200 A
)/BMB-2T(300 A
)/MgAg(1000 A
),
(300 A
exhibited high performances with maximum luminances of
2400 and 1700 cd m2 at a driving voltage of 17 V and luminous
and external quantum efciencies of 0.11 and 0.08 lm W21 and
0.33 and 0.24% for p- and o-TTA, respectively, at a luminance
of 300 cd m22.119 These values are much higher than those
J. Mater. Chem., 2000, 10, 125
15
View Article Online
Fig. 9 Multilayer organic EL device consisting of the double holetransport layers and the emitting layer. EL: emitting layer, HTL: hole
transport layer.
reported for blue-emitting organic EL devices using other

materials such as OXD8,110 p-EtTAZ,115 and spiro-6W61
(maximum luminance: ca. 1000 cd m2).
Oligothiophenes have been reported to function as emitting
materials in organic EL devices;120,121 however, their performances are poor. This is probably because oligothiophenes
with well-dened structures are crystalline in nature and hence
they form polycrystalline lms by vacuum deposition or spin
coating. The uorescence quantum efciencies of polycrystalline lms of oligothiophenes are signicantly reduced as
compared with those of the corresponding solutions. It was
expected that the uorescence quantum efciency may not be
signicantly reduced in the amorphous lm state.
We have created a novel family of amorphous molecular
materials containing an oligothiophene moiety, 2,5-bis{4-[bis(4-methylphenyl)amino]phenyl}thiophene (BMA-1T),
5,5'-bis{4-[bis(4-methylphenyl)amino]phenyl}-2,2'-bithiophene
(BMA-2T),
5,5@-bis{4-[bis(4-methylphenyl)amino]phenyl}2,2' : 5',2@-terthiophene (BMA-3T), and 5,5'@-bis{4-[bis(4methylphenyl)amino]phenyl}-2,2' : 5',2@ : 5@,2'@-quaterthiophene
(BMA-4T). They readily form stable amorphous glasses with
Tgs of 86, 90, 93, and 98 C, respectively,44,45,47 functioning as
colour-tunable emitting materials depending on the length of
oligothiophene moieties. It is of interest to note that the
16
J. Mater. Chem., 2000, 10, 125
Fig. 10 Temperature dependence of luminance of the multilayer device,

ITO/p-PMTDATA/p-BPD/Alq3/MgAg. Measured in a cryostat at
1023 Torr.
HOMO levels of these compounds are more or less the same

but the HOMOLUMO gap progressively decreases with
increasing conjugation length of the oligothiophene moiety.
Both single-layer devices using BMA-nT (n~14) alone
sandwiched between the ITO and MgAg electrodes and
double-layer devices consisting of the emitting layer of
BMA-nT (n~14) with hole-transporting properties and the
electron-transport layer of Alq3 (for n~24) or TPOB (for
n~1) were fabricated.45,47,122 The EL spectra of both the
single-layer and double-layer organic EL devices were in
accordance with the PL spectrum of the corresponding BMAnT (n~14). The EL colour was light blue, yellowish green,
yellow, and orange for BMA-1T, BMA-2T, BMA-3T, and
BMA-4T, respectively. The double-layer device using BMA-3T
and Alq3 exhibited a maximum luminance of 13 300 cd m22
at a driving voltage of 18 V and a luminous efciency of
1.1 lm W21 at a luminance of 300 cd m22. The double-layer
View Article Online
)/p-TTA(600 A
)/
Fig. 11 EL spectra of (a) ITO/p-DPA-TDAB(600 A
)/perylene(5 mol%) doped
MgAg and (b) ITO/p-DPA-TDAB(600 A
)/MgAg devices, and (c) PL spectrum of perylene.
p-TTA(600 A
organic EL devices showed more than one order of magnitude

higher luminous and quantum efciencies than the corresponding single-layer organic EL devices. It is suggested that in the
double-layer device, the electron injection from the MgAg
electrode into the BMA-nT (n~14) layer becomes more
efcient in the presence of the electron-transport layer of Alq3
or TPOB due to decreased energy barriers.
There is a possibility that exciplex formation takes place at
the interface between the electron-transport layer and the holetransport layer in layered organic EL devices, affecting the
emission colour. We have studied exciplex formation at the
organic solid/solid interface between electron-transporting and
hole-transporting amorphous molecular materials and its
application for colour tuning in organic EL devices.123126
The exciplex formation was evidenced by the measurements of
)/o-TTA(200 A
)/
Fig. 12 (a) EL spectrum of ITO/m-MTDATA(300 A
)/MgAg(1000 A
) device and (b) PL spectrum of
BMB-2T(300 A
BMB-2T.
the photoluminescence spectrum and its lifetime for the

mixture of an equimolar amount of the electron-transporting
and hole-transporting material.
Since the exciplex formation takes place only at the interface
between the hole-transport and electron-transport layers,
exciplex emission is strengthened for the triple-layer organic
EL device with a thin layer of an equimolar mixture of holeand electron-transporting materials in between the holetransport and electron-transport layers. The wavelength of
exciplex emission varies depending on the electron-donating
property of the electron donor and the electron-withdrawing
property of the electron acceptor. It is expected that tuning of
the emission colour in organic EL devices can be attained by
varying the ionisation potential of the hole-transporting
material for a xed electron-transporting material.
Organic EL devices using TPOB or BMB-3T as an electron-
J. Mater. Chem., 2000, 10, 125
17
View Article Online
Table 4a Oxidation potentials, absorption and emission band maxima and Tgs of hole-transporting and emitting amorphous molecular materials
Compound
E1/2ox a/Vd
lmax(abs)b/nm
Band gapc/eV
lmax(em)b/nm
Tg/C
m-MTDATA
t-Bu-TBATA
o-PTDATA
m-PTDATA
p-PMTDATA
1-TNATA
2-TNATA
0.06
0.09
0.06
0.10
0.08
0.08
0.11
342
353
346
339
341
338
325
3.20
3.12
3.15
3.19
3.14
2.97
3.02
427
465
479
490
480
521
486
75
203
93
91
110
113
110
TPD
o-TTA
m-TTA
p-TTA
o-BPD
m-BPD
p-BPD
TCTA
m-MTDAPD
p-MTDAPB
p-DPA-TDAB
0.48
0.61
0.64
0.58
0.48
0.51
0.50
0.69e
0.66e
0.64
0.23
352
338
347
361
353
351
358
326
342
343
310
3.19
3.32
3.25
3.11
3.19
3.20
3.16
3.44
3.32
3.31
3.32
399
411
409
435
396
399
406
385
408
412
410
62
81
80
132
75
81
102
150
105
110
107
BMA-1T
BMA-2T
BMA-3T
BMA-4T
0.39
0.39
0.38
0.35
397
423
440
453
2.78
2.58
2.46
2.38
456
491
516
532
86
90
93
98
Measured in dichloromethane solution containing tetrabutylammonium perchlorate. bMeasured in tetrahydrofuran solution. cEstimated from
the electronic absorption edge. dvs. Ag/Agz (0.01 mol dm23). eEp/2.
transporting material in combination with various holetransporting amorphous molecular materials with varying
ionisation potentials emitted light resulting from the exciplex
formed at the solid interface between TPOB or BMB-3T and
the hole-transporting material. Tuning of the emission colour
from greenish blue to orange was attained by varying the
ionisation potential of the hole-transporting material for the
xed electron-transporting material TPOB.123,124 Likewise,
the emission colour of the organic EL devices using BMB-3T as
the electron-transport layer changed from greenish yellow to
orange and red for the hole transport layer of TPD, p-DPATDAB, and m-MTDATA, respectively.104
Exciplex formation also takes place at the organic solid
interface between Alq3 and hole-transporting amorphous
molecular materials with very low ionisation potentials, e.g.,
m-MTDATA and TNATA (approximately 5.1 eV) to give
yellow emission. Because the exciplex emission takes place
only at the interface, the emission colour can be turned from
yellow to green by varying the magnitude of applied
voltage.125,126
3 Titanyl phthalocyanine
Phthalocyanines have found a number of potential applications
such as catalysts, charge-carrier generation materials for
layered photoreceptors in electrophotography, photosensitisers, gas sensors, liquid crystals, photodynamic cancer therapy,
nonlinear optics, photoactive materials for photovoltaic
devices, and materials for organic EL devices.127
3.1 Characterisation of ultrathin lm of TiOPc

The molecular orientation and aggregation as well as the
electronic structure of ultrathin lms of TiOPc formed by
vacuum deposition on graphite and MoS2 substrates have been
studied using Penning ionisation electron spectroscopy (PIES)
and ultraviolet photoelectron spectroscopy (UPS).128,129 It has
been found that in the monolayer partly deposited on graphite
(grafoil) at room temperature, all TiOPc molecules are oriented
at to the substrate with the oxygen atom protruding outside
the lm surface. However, molecules with the oxygen atom
directed inside increase in number with increasing coverage
with the monolayer. On the other hand, in the monolayer lm
deposited on MoS2 at room temperature, the TiOPc molecules
aggregate. Upon annealing at 370 K, a uniform monolayer
with the oxygen atom protruding outside is formed.
3.2 Photovoltaic devices using TiOPc
A two-layer device using thin lms of copper phthalocyanine
(CuPc) and a perylene pigment (PV) sandwiched between the
ITO and silver as electrodes, ITO/CuPc/PV/Ag, has been
reported to exhibit a high conversion efciency of 0.95% under
simulated AM2 illumination at 75 mW cm22.130
We have studied titanyl phthalocyanine (TiOPc) for use in
organic solar cells.131134 The use of TiOPc as a photoactive
material for photoelectric conversion is of interest from the
following viewpoints. It was expected that the judicious choice
of n-type organic semiconductors in combination with TiOPc
permits the fabrication of pn heterojunction devices that
exhibit high conversion efciencies in view of the fact that
Table 4b Reduction potentials, absorption and emission band maxima and Tgs of electron-transporting amorphous molecular materials
Compound
E1/2red a/Vd
lmax(abs)b/nm
Band gapc/eV
lmax(em)b/nm
Tg/C
BMB-2T
BMB-3T
TPOB
TMB-TB
Alq3
21.76
21.76
22.10e
22.04
22.01
402
437
298
370
395f
2.81
2.55
3.68
3.16
2.7f
440
488
364
402
520f
107
115
137
160
Measured in dichloromethane solution containing tetrabutylammonium perchlorate. bMeasured in tetrahydrofuran solution. cEstimated from
the electronic absorption edge. dvs. Ag/Agz (0.01 mol dm23). eEp/2. fValues of vapor-deposited lm.
18
J. Mater. Chem., 2000, 10, 125
View Article Online
radical, generated by photoinduced electron transfer from

TiOPc to C60 in the C60-doped TiOPc layer, to MPCI. The
triple-layer cell showed a high conversion efciency of 0.63%
for incident white light at an intensity of ca. 94 mW cm22.134
4 Oligothiophenes with well-dened structures
TiOPc is used as charge-carrier generation layer in photoreceptors and that the device responds to light over the whole
visible wavelength region. Since TiOPc is a polymorph, it is of
interest to examine the effect of the morphology of TiOPc on its
photovoltaic properties.
A polycrystalline sample of b-TiOPc prepared by the
reaction of tetrabutyl orthotitanate with 1,3-diiminoisoindoline
in quinoline at 180 C was vacuum evaporated at ca. 1025 Torr
s21 to form an amorphous thin lm.131
at a rate of 23 A
Photovoltaic devices consisting of amorphous thin lms of
TiOPc and N,N-dimethyl-3,4:9,10-perylenebis(dicarboximide)
(MPCI), sandwiched between the ITO and Au electrodes,
showed a response to light over the whole visible wavelength
region from 400 to 900 nm, as expected from their electronic
absorption spectra. It was also shown that the cell with the
)/TiOPc(500 A
)/Au exhibits a
structure of ITO/MPCI(500 A
higher conversion efciency than the cell with the structure of
)/MPCI(500 A
)/Au. It is thought that the
ITO/TiOPc(500 A
formation of a Schottky barrier at the interface between the
MPCI layer and Au in the latter cell reduces the photovoltaic
effect resulting from the pn heterojunction between TiOPc
and MPCI. The former cell exhibited a conversion efciency of
ca. 0.35% for white light at 8130 mW cm22.132
When the cell was exposed to ethanol vapor, the amorphous
lm of TiOPc was transformed into a crystalline lm of aTiOPc, as indicated from XRD.133 While the amorphous lm
of TiOPc shows an absorption band with lmax at 720 nm, the
EtOH-treated TiOPc lm shows a new absorption band with
lmax at 830 nm, which has been assigned to a charge-transfer
exciton band.135 It was found that the pn heterojunction cell
using the polycrystalline lm of a-TiOPc exhibits a much
higher conversion efciency than the cell using the amorphous
lm under irradiation with monochromatic light which TiOPc
mainly absorbs.133 This is attributed to the greater absorption
coefcient in the wavelength range longer than 800 nm and the
higher efciency of photogeneration of charge carriers for
crystalline a-TiOPc than for amorphous TiOPc.
The effect of fullerene (C60) doping on photoelectric
conversion was investigated. A new triple-layer cell, ITO/
MPCI/C60-doped TiOPc/TiOPc/Au, exhibited a higher quantum yield for charge-carrier photogeneration (w~0.34 for
720 nm monochromatic light) than the double-layer cell
without the C60-doped TiOPc layer, ITO/MPCI/TiOPc/Au,
upon irradiation with monochromatic light which TiOPc
mainly absorbs. The higher quantum yield for charge-carrier
photogeneration upon irradiation particularly with light which
TiOPc mainly absorbs may be attributed to efcient charge
separation by successive electron transfer from the C60 anion
Oligothiophenes with well-dened structures have recently

received a great deal of attention not only as model compounds
for electrically conducting polythiophenes but also as a new
class of organic p-electron systems. A number of unsubstituted
and substituted oligothiophenes have been synthesized136,137
and their molecular and crystal structures,138,139 as well as
optical,140,141 electrochemical,142,143 and electrical properties144153 have been studied.
We have investigated the synthesis and electrical and
photoelectric properties of new oligothiophenes with varying
conjugation lengths.150153 In addition, we have created novel
families of amorphous molecular materials containing the
oligothiophene moiety,4447,118,122 a novel class of gel-forming
compounds containing the oligothiophene moiety,154 and a
series of novel polymers containing pendant oligothiophenes.
4.1 Electrical conductivities of electrochemically oxidised
oligothiophenes
With regard to electrical conductivities of oligothiophenes,
both charge-transfer complexes and chemically-oxidised salts
have been reported. We have investigated electrical conductivities of a series of electrochemically oxidised oligothiophenes
with varying conjugation lengths.150153 Electrochemical oxidation is of interest in that it produces denite ion-radical salts
with one component of the supporting electrolyte as a dopant.
The compounds studied include a-ethyl-disubstituted quaterthiophene (DEt4T), quinquethiophene (DEt5T), sexithiophene with two octyl groups at the b-position (DEtDOc6T),
and septithiophene with two octyl groups at the b-position
(DEtDOc7T), and b-octyl-substituted thiophene nonamer
(6Oc9T), decamer (4Oc10T), and dodecamer (4Oc12T).
The anodic oxidations of DEt4T, DEt5T, DEtDOc6T, and
DEtDOc7T were reversible owing to the presence of the ethyl
groups at the a-position of each terminal thiophene ring, which
prevents the coupling reaction of resulting cation radicals.
Oligothiophenes with longer p-conjugation lengths, e.g.,
6Oc9T, 4Oc10T, and 4Oc12T, hardly undergo coupling
reaction of the resulting cation radicals. While the second
oxidation process of DEt4T is irreversible, those of DEt5T and
the oligothiophenes with longer p-conjugation lengths are
reversible.150 It is of interest to note that the difference between
the 1st and 2nd oxidation potentials becomes progressively
smaller with increasing conjugation length and that only one
anodic and the corresponding cathodic waves which involve
two electron oxidation and reduction are observed with regard
to 4Oc10T and 4Oc12T.152 Controlled-potential anodic oxidation of each dichloromethane solution of DEt4T and DEt6T at
the peak potential produced black powders as precipitates in
the solution. The electrochemical oxidations of DEtDOc7T,
6Oc9T, 4Oc10T, and 4Oc12T were carried out using vacuumdeposited or spin-coated lms on the ITO electrode. Table 5
summarises room-temperature conductivities of solid cation
radicals together with activation energies for electrical
conduction. It was found that electrical conductivity signicantly increases with increasing conjugation length of
oligothiophenes. The room-temperature conductivity of
electrochemically-oxidised 4Oc12T was 10 S cm21, which is
eight orders of magnitude greater than that of DEt4T
(961028 S cm-1).152
J. Mater. Chem., 2000, 10, 125
19
View Article Online
Table 5 Oxidation potentials of oligothiophenes and electrical conductivities of electrochemically oxidised oligothiophenes at 293 K
Compound
DEt4T
DEtDOc6T
DEtDOc7T
6Oc9T
4Oc10T
4Oc12T
E1/2ox/Va
0.58
0.46
0.42
0.48
0.43b
0.36b
Degree of doping (mol%)

y100
y100
y100
y100
y200
y200
Conductivity/S cm21
28 c
9610
361025 c
261022 d
461021 d
3d
10 d
Activation energy/eV
0.54
0.20
0.15
0.07
0.07
0.05
vs. Ag/Agz (0.01 mol cm23). bTwo-electron oxidation. cMeasured by a two-probe d.c. method for pellets. dMeasured by a four-probe d.c.
method for lms.
20
J. Mater. Chem., 2000, 10, 125
View Article Online
4.2 Photovoltaic properties of oligothiophenes

pn Heterojunction devices using thin lms of septithiophene
(7T) and octithiophene (8T) as p-type organic semiconductors
and PV as an n-type organic semiconductor were fabricated and
their performances examined.155 The power conversion ef )/7T(500 A
)/Au and ITO/
ciencies of the devices, ITO/PV(300 A
)/8T(300 A
)/Au, were ca. 0.2 and 0.6%, respectively,
PV(400 A
for incident white light at 10200 mW cm22. It is shown that
oligothiophenes, e.g., heptamer and octamer, constitute a new
class of promising materials that function as p-type semiconductors for use in photovoltaic devices.
5 Non-conjugated polymers containing pendant

p-electron systems
Linear p-conjugated polymers are not only known as
electrically conductive materials but also have recently been
found to function as electrochromic,14,156 photovoltaic,810 and
organic EL device materials.157,158
Non-conjugated polymers containing pendant p-electron
systems are also of interest for the following reasons; the
variety of possible pendant molecules, chemical stability, ease
of processability, photoconductivity of pendant p-electron
systems, and invariance of the standard redox potential with
the degree of doping. When these polymers are used as
electrode materials for secondary batteries, a at voltage
during discharge is expected to be maintained owing to the
invariance of the standard oxidation/reduction potentials of
these polymers with the degree of doping. Photoconductivity
coupled with semiconductivity resulting from electrochemical
doping may lead to application of doped polymers as
photoactive materials for photovoltaic devices. Non-conjugated polymers containing pendant p-electron systems may
undergo clear colour change on electrochemical doping and
dedoping.
We have studied the synthesis and electrochemical doping of
non-conjugated vinyl and methacrylate polymers containing
pendant p-electron systems, and investigated the electrical,
photovoltaic, and electrochromic properties of doped polymers.159,160 Application of non-conjugated polymers as
electrode materials for lithium secondary batteries has also
been studied.161,162 The polymers studied include poly(Nvinylcarbazole) (PVCz), poly(3,6-dibromo-N-vinylcarbazole)
(PDBrVCz), poly(2-N-carbazolylethyl vinyl ether) (PCEVE),
poly(N-glycidylcarbazole)
(PGCz),
poly(vinylferrocene),
poly[4-(diphenylamino)phenylmethyl
methacrylate]
(PDAPM), poly(1-vinylpyrene) (PVPy), poly(3-vinylperylene)
(PVPe), 1 : 1 alternating copolymers containing N-vinylcarbazole as one component,163166 and a novel class of vinyl and
methacrylate polymers containing pendant oligothiophenes
with varying conjugation length, PV3T, PV4T, PVDOc5T,
PVDOc6T, PMA3T, PMADOc4T, PMADOc5T, and PMADOc6T.167176 In particular, the novel class of polymers
containing pendant oligothiophenes are expected to have
unique properties characteristic of both the non-conjugated
backbone and the p-conjugated linear oligomers. It is of
interest to examine the correlation between the length of
pendant p-conjugated linear oligomers and electrical and
electrochromic properties of the resulting electrochemically
doped polymers.
5.1 Alternating copolymers as new electron-beam resist
materials
Certain 1 : 1 alternating copolymers, e.g., poly(olenalt-SO2), have found successful application as positive
electron-beam resists.
We have designed and synthesized a new class of 1 : 1
alternating copolymers of N-vinylcarbazole (VCz) and allyl-
glycidyl fumarate (AGF) or ethylglycidyl fumarate (EGF).

The alternating copolymers, poly(VCz-alt-AGF) and
poly(VCz-alt-EGF), which contain alternately cross-linking
epoxy or epoxy and allyl groups and a dry-etch resistant
carbazole moiety as pendant groups, function as dry-etch
resistant, negative electron-beam resists.163165
Poly(VCz-alt-AGF) and poly(VCz-alt-EGF) obtained at the
equimolar monomer feed ratio at 50 C had number-average
molecular weights of 80 000 and 60 000, molecular weight
distributions of 4.3 and 1.8, and relatively high Tgs of 130 and
140 C, respectively. They formed good lms on a silicon wafer
by spin coating.
Both copolymers were found to function as negative
electron-beam resists on exposure to a 20 keV electron beam.
Poly(VCz-alt-AGF) enabled the fabrication of ca. 0.2 mm line
width and 1 mm spacing with vertical sidewalls. The sensitivity
was as high as 2.5 mC cm22.165
5.2 Electrochemical doping of non-conjugated pendant polymers
Electrochemical doping of non-conjugated pendant polymers
was carried out by controlled-potential anodic oxidation in the
presence of tetrabutylammonium perchlorate as a supporting
electrolyte using the following methods; (1) electrolysis of
polymer lms coated on the electrode in acetonitrile, (2)
electrodeposition of doped polymer lms from dichloromethane solution of polymers, and (3) electrolytic polymerisation of vinyl monomers in dichloromethane with concurrent
deposition of doped polymer lms onto the electrode.159
The electrochemically doped polymers were identied as
partially oxidised radical cation salts containing ClO42 as a
dopant. The infrared absorption spectra and cyclic voltammograms indicate that the electrochemically doped polymers
containing pendant carbazole and triphenylamine moieties are
partially cross-linked at the 3-position of the carbazole ring and
at the para-position of the phenyl ring in the triphenylamine
moiety due to the coupling reactions of the pendant carbazole
and triphenylamine cation radicals. Polymers containing
pendant oligothiophenes, e.g., PV3T and PV4T, undergo
cross-linking at the a-position of the terminal thiophene ring.
J. Mater. Chem., 2000, 10, 125
21
View Article Online
5.3 Photovoltaic properties of doped polymers

We have studied photovoltaic properties of electrochemically
doped polymers such as PVCz and PDAPM, both of which act
as p-type semiconductors with photoconducting properties.
The use of such electrochemically doped polymers is of interest
in the following points. (1) The bulk resistivity is decreased. (2)
The species involved in the formation of the depletion layer at
the interface are clear. That is, the charge carriers, i.e., the
radical cations of the pendant molecules accept electrons at the
interface. (3) The use of doped polymerdye systems enables
both expansion of the spectral response to the visible or near
infrared region and attainment of a higher quantum efciency
for photogeneration of charge carriers.159
Schottky type devices were fabricated by sandwiching the
electrochemically doped polymer lm between the semitransparent aluminium and gold or ITO electrodes. The dyes used
are perylene or anthanthrone pigment. The cell showed
rectication behavior in the dark. A Schottky barrier is
22
J. Mater. Chem., 2000, 10, 125
formed at the interface between aluminium and the electrochemically doped polymer which act as a p-type semiconductor. The cell using 0.5 mm thick electrochemically doped
PDAPM lm doped with N,N'-bis(3,5-dimethylphenyl)3,4 : 9,10-perylenebis(dicarboximide) (XPCI) exhibited conversion efciencies of 2.8% for the transmitted monochromatic
light of 470 nm (incident photon power: 1.3 mW cm22).
5.4 Electrochromic properties of polymers containing pendant
oligothiophenes
We have synthesized novel classes of vinyl and methacrylate
polymers containing pendant oligothiophenes with varying
conjugation lengths and studied their electrical and electrochromic properties.167176 It was expected that they would
exhibit clear colour changes on electrochemical doping and
dedoping, owing to the well-dened structures of the pendant
oligothiophenes, and that the colour could be controlled by
varying the length of the oligothiophenes. These polymer lms
View Article Online
were found to undergo reversible, clear colour change on

electrochemical oxidation and reduction. For example, the
colour switches from blue to pale yellow and from green to
yellow for PV3T and PV4T, respectively. When the cycle of
doping and dedoping for each 2 s was repeated over 500 times,
reversible, clear colour change took place. The response times
for colouration and decolouration were ca. 4.8 and 0.3 s for
PVDOc6T. Novel methacrylate copolymers containing pendant terthiophene and oligo(ethylene oxide) moieties,
poly[(2,2' : 5',2@-terthiophen-5-yl)methyl
methacrylate-co-aethoxy-v-methacryloyloligo(ethylene oxide)] (poly(MA3T-coMAEO)), prepared by radical copolymerisation of the
corresponding monomers, were also found to undergo
reversible, clear colour change from yellowish orange to
purple and vice versa on electrochemical doping and dedoping.
The response time for colour change on electrochemical doping
and dedoping was found to be shorter for the copolymers than
for the corresponding methacrylate homopolymer containing
pendant terthiophene (PMA3T). Non-conjugated polymers
containing pendant oligothiophenes constitute a novel class of
electrochromic materials.
Acknowledgements
The author thanks all the coauthors of the publications cited in
this article. Financial support of the following grants is greatly
appreciated: Grant-in-Aid for Scientic Research on New
Program (05NP0301), Grant-in-Aid for Scientic Research on
Priority Area Research (04205094 and 06239243) and JSPS
Research for the Future Program (JSPS-RFTF-97P-00104)
from the Ministry of Education, Science and Culture of Japan.
References
1 M. Pope, H. P. Kallmann and P. Magnante, J. Chem. Phys.,
1963, 38, 2042.
2 C. W. Tang and S. A. Van Slyke, Appl. Phys. Lett., 1987, 51, 913.
3 J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks,
K. Mackay, R. H. Friend, P. L. Burn and A. B. Holmes, Nature,
1990, 347, 539.
4 C. W. Tang, S. A. Van Slyke and C. H. Chen, J. Appl. Phys.,

1989, 65, 3610.
5 B. O'Regan and M. Gratzel, Nature, 1991, 353, 737.
6 M. K. Nazeeruddin, A. Kay, I. Roddicio, R. Humphry,
E. Muller, P. Liska, N. Vlachopoulos and M. Gratzel, J. Am.
Chem. Soc., 1993, 115, 6382.
7 U. Bach, D. Lupo, P. Comte, J. E. Moser, F. Weissortel,
J. Salbeck, H. Spreitzer and M. Gratzel, Nature, 1998, 395, 583.
8 G. Yu and A. J. Heeger, J. Appl. Phys., 1995, 78, 4510.
9 J. J. M. Halls, C. A. Walsh, N. C. Greenham, E. A. Marseglia,
R. H. Friend, A. C. Moratti and A. B. Holmes, Nature, 1995, 376,
498.
10 G. Yu, J. Gao, J. C. Hummelen, F. Wudl and A. J. Heeger,
Science, 1995, 270, 1789.
11 P. M. S. Monk, R. J. Mortimer and D. R. Rosseinsky,
Electrochromism: Fundamentals and Applications, VCH, Weinheim, 1995.
12 A. Kumar, D. M. Welsh, M. C. Morvant, F. Piroux,
K. A. Abboud and J. R. Reynolds, Chem. Mater., 1998, 19, 896.
13 J. D. Debad and A. J. Bard, J. Am. Chem. Soc., 1998, 120, 2476.
14 S. A. Sapp, G. A. Sotzing and J. R. Reynolds, Chem. Mater.,
1998, 10, 2101.
15 D. L. Meeker, D. S. K. Mudigonda, J. M. Osborn, D. C. Loveday
and J. P. Ferraris, Macromolecules, 1998, 31, 2943.
16 Y. Lis, J. Hagen and D. Haarer, Synth. Met., 1998, 94, 273.
17 Y. Maruyama and N. Iwasaki, Chem. Phys. Lett., 1974, 24, 26.
18 D. J. Plazek and J. H. Magill, J. Chem. Phys., 1966, 45, 3038.
19 R. J. Greet and D. Turnbull, J. Chem. Phys., 1966, 46, 1243.
20 Y. Shirota, T. Kobata and N. Noma, Chem. Lett., 1989, 1145.
21 W. Ishikawa, H. Inada, H. Nakano and Y. Shirota, Chem. Lett.,
1991, 1731.
22 T. Ohara, N. Fujii and Y. Shirota, 76th Annual Meeting of the
Chemical Society of Japan, Kanagawa, 1999, prepr. no. 1, p. 372.
23 H. Inada and Y. Shirota, J. Mater. Chem., 1993, 3, 319.
24 A. Higuchi, H. Inada, T. Kobata and Y. Shirota, Adv. Mater.,
1991, 3, 549.
25 W. Ishikawa, H. Inada, H. Nakano and Y. Shirota, Mol. Cryst.
Liq. Cryst., 1992, 211, 431.
26 W. Ishikawa, K. Noguchi, Y. Kuwabara and Y. Shirota, Adv.
Mater., 1993, 5, 559.
27 Y. Kuwabara, H. Ogawa, H. Inada, N. Noma and Y. Shirota,
Adv. Mater., 1994, 6, 677.
28 E. Ueta, H. Nakano and Y. Shirota, Chem. Lett., 1994, 2397.
29 A. Higuchi and Y. Shirota, Mol. Cryst. Liq. Cryst., 1994, 242, 127.
30 H. Kageyama, K. Itano, W. Ishikawa and Y. Shirota, J. Mater.
Chem., 1996, 6, 675.
J. Mater. Chem., 2000, 10, 125
23
View Article Online
31 A. Higuchi, K. Katsuma and Y. Shirota, Kobunshi Ronbunshu,

1996, 53, 829.
32 H. Ogawa, H. Inada and Y. Shirota, Macromol. Symp., 1997,
125, 171.
33 Y. Shirota, Y. Kuwabara, D. Okuda, R. Okuda, H. Ogawa,
H. Inada, T. Wakimoto, H. Nakada, Y. Yonemoto, S. Kawami
and K. Imai, J. Lumin., 1997, 7274, 985.
34 K. Katsuma and Y. Shirota, Adv. Mater., 1998, 10, 223.
35 H. Nakano, E. Ueta and Y. Shirota, Mol. Cryst. Liq. Cryst.,
1998, 313, 241.
36 Y. Shirota, K. Okumoto and H. Inada, Synth. Met., in the press.
37 E. Ueta, M. Nomura, W. Ishikawa, H. Nakano and Y. Shirota,
to be submitted for publication.
38 A. N. Sobolev, V. K. Belsky, J. P. Romm, N. Yu. Chernikova
and E. N. Guryanova, Acta Crystallogr., Sect. C, 1985, 41, 967.
39 Y. C. Lin and D. E. Williams, Acta. Crystallogr., Sect. B, 1975,
31, 318.
40 H. Inada, K. Ohnishi, S. Nomura, A. Higuchi, H. Nakano and
Y. Shirota, J. Mater. Chem., 1994, 4, 171.
41 J. Sakai, H. Kageyama, S. Nomura, H. Nakano and Y. Shirota,
Mol. Cryst. Liq. Cryst., 1997, 296, 445.
42 A. Higuchi, K. Ohnishi, S. Nomura, H. Inada and Y. Shirota,
J. Mater. Chem., 1992, 2, 1109.
43 H. Kageyama, K. Ohnishi, S. Nomura and Y. Shirota, Chem.
Phys. Lett., 1997, 277, 137.
44 T. Noda, I. Imae, N. Noma and Y. Shirota, Adv. Mater., 1997, 9,
239.
45 T. Noda, H. Ogawa, N. Noma and Y. Shirota, Adv. Mater., 1997,
9, 720.
46 T. Noda and Y. Shirota, J. Am. Chem. Soc., 1998, 120, 9714.
47 T. Noda, H. Ogawa, N. Noma and Y. Shirota, J. Mater. Chem.,
1999, 9, 2177.
48 S. Yoshikawa, Y. Kotani and Y. Shirota, 69th Annual Meeting of
the Chemical Society of Japan, Kyoto, 1995, prepr. no. 2, p. 641.
49 T. Ujike, K. Moriwaki, H. Nakano and Y. Shirota,
J. Photopolym. Sci. Technol., 1998, 11, 33.
50 Y. Shirota, K. Moriwaki, S. Yoshikawa, T. Ujike and H. Nakano,
J. Mater. Chem., 1998, 8, 2579.
51 D. Nagahama, T. Ujike, K. Moriwaki, S. Yoshikawa, H. Nakano
and Y. Shirota, J. Photopolym. Sci. Technol., 1999, 12, 277.
52 K. Nishimura, T. Kobata, H. Inada and Y. Shirota, J. Mater.
Chem., 1991, 1, 897.
53 M. Yoshiiwa, H. Kageyama, F. Wakaya, M. Takai, K. Gamo
and Y. Shirota, J. Photopolym. Sci. Technol., 1996, 9, 57.
54 M. Yoshiiwa, H. Kageyama, Y. Shirota, F. Wakaya, K. Gamo
and M. Takai, Appl. Phys. Lett., 1996, 69, 2605.
55 T. Kadota, H. Kageyama, F. Wakaya, K. Gamo and Y. Shirota,
56 T. Kadota, H. Kageyama, F. Wakaya, K. Gamo and Y. Shirota,
57 K. Okumoto, K. Wayaku, T. Noda, H. Kageyama and
Y. Shirota, Synth. Met., in the press.
58 J. Bettenhausen and P. Strohriegl, Adv. Mater., 1996, 8, 507.
59 J. Bettenhausen, M. Greczmiel, M. Jandle and P. Strohriegl,
Synth. Met., 1997, 91, 223.
60 M. Jandke, P. Strohriegl, S. Berleb, E. Werner and W. Brutting,
Macromolecules, 1998, 31, 6434.
61 J. Salbeck, N. Yu, J. Bauer, F. Weissortel and H. Bestgen, Synth.
Met., 1997, 91, 209.
62 J. Salbeck, F. Weissortel and J. Bauer, Macromol. Symp., 1997,
125, 121.
63 P.-W. Wang, Y.-J. Liu, C. Devadoss, P. Bharathi and J. S. Moore,
Adv. Mater., 1996, 8, 237.
64 J. Luie and J. F. Hartwig, J. Am. Chem. Soc., 1997, 119, 11 695.
65 K. Naito and A. Miura, J. Phys. Chem., 1993, 97, 6240; Chem.
Mater., 1994, 6, 2343.
66 W. Ishikawa, H. Inada, H. Nakano and Y. Shirota, J. Phys. D:
Appl. Phys., 1993, 26, B94.
67 J. Liu, Q. Deng and Y. C. Jean, Macromolecules, 1993, 26, 7149.
68 M. Kusumoto, Y. Shirota and Y. Itoh, Polym. Prep. Jpn., 1998,
47, 350.
69 M. Kusumoto, Y. Shirota and Y. Itoh, 74th Annual Meeting of
the Chemical Society of Japan, Kyoto, 1998, prepr. no. 1, p. 491.
70 H. Nakano, K. Akamatsu, K. Moriwaki and Y. Shirota, Chem.
Lett., 1996, 701.
71 M. Kusumoto, K. Moriwaki, H. Nakano and Y. Shirota,
72 K. Moriwaki, M. Kusumoto, K. Akamatsu, H. Nakano and
Y. Shirota, J. Mater. Chem., 1998, 8, 2671.
73 W. D. Gill, J. Appl. Phys., 1972, 43, 5033.
74 D. Emin, Electronic and Structural Properties of Amorphous
24
J. Mater. Chem., 2000, 10, 125
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
Semiconductors, ch. 7, ed. P. G. Le Comber and J. Mort,

Academic Press, New York, 1973.
L. B. Schein and J. X. Mack, Chem. Phys. Lett., 1988, 149, 109.
H. Bassler, Phys. Status Solidi B, 1981, 107, 9.
H. Bassler, Phys. Status Solidi B, 1993, 175, 15.
T. Sasakawa, T. Ikeda and S. Tazuke, J. Appl. Phys., 1989, 65,
2750.
P. M. Borsenberger, J. Appl. Phys., 1990, 68, 5188.
P. M. Borsenberger, E. H. Magin and J. J. Fitzgerald, J. Phys.
Chem., 1993, 97, 8250.
Y. Shirota, S. Nomura and H. Kageyama, Proc. SPIE Int. Soc.
Opt. Eng., 1998, 3476, 132 and references cited therein..
K. Nishimura, H. Inada, T. Kobata, Y. Matsui and Y. Shirota,
Mol. Cryst. Liq. Cryst., 1992, 217, 235.
S. Nomura, K. Nishimura and Y. Shirota, Mol. Cryst. Liq.
Cryst., 1994, 253, 79.
S. Nomura, K. Nishimura and Y. Shirota, Thin Solid Films, 1996,
273, 27.
S. Nomura and Y. Shirota, Chem. Phys. Lett., 1997, 268, 461.
S. Nomura, K. Nishimura and Y. Shirota, Mol. Cryst. Liq.
Cryst., 1998, 313, 247.
S. Nomura and Y. Shirota, Mol. Cryst. Liq. Cryst., 1998, 315,
217.
C. Giebeler, H. Antoniadis, D. D. C. Bradley and Y. Shirota,
Appl. Phys. Lett., 1998, 72, 2448.
C. Giebeler, H. Antoniadis, D. D. C. Bradley and Y. Shirota,
J. Appl. Phys., 1999, 85, 608.
H. Kageyama, H. Ohishi and Y. Shirota, to be submitted for
publication.
S. Nomura, H. Kageyama and Y. Shirota, 76th Annual Meeting
of the Chemical Society of Japan, Kanagawa, 1999, prepr. no. 1,
p. 402.
M. van der Auweraer, F. C. De Schryver, P. M. Borsenberger and
J. J. Fitzgerald, J. Phys. Chem., 1993, 97, 8808.
S. Heun and P. M. Borsenberger, Chem. Phys., 1995, 200, 245.
P. M. Borsenberger, E. H. Magin and J. Shi, Physica B, 1996,
217, 212.
J. A. Sinicropi, J. R. Cowdery-Corvan, E. H. Magin and
P. M. Borsenberger, Chem. Phys., 1997, 218, 331.
R. G. Kepler, P. M. Beeson, S. J. Jacobs, R. A. Anderson,
M. B. Sinclair, V. S. Valencia and P. A. Cahill, Appl. Phys. Lett.,
1995, 66, 3618.
M. Redecker, D. D. C. Bradley, M. Jandke and P. Strohriegl,
Appl. Phys. Lett., 1999, 75, 109.
(a) Photochromism, Molecules and Systems, ed. H. Durr,
H. Bouas-Laurant, Elsevier, Amsterdam, 1990; (b) G. S. Kumar
and D. C. Neckers, Chem. Rev., 1989, 89, 1915.
G. M. Wallraff and W. D. Hinsberg, Chem. Rev., 1999, 99, 1801.
J. Fujita, Y. Ohnishi, Y. Ochiai and S. Matsui, Appl. Phys. Lett.,
1996, 68, 1297.
N. Fujii, K. Katsuma and Y. Shirota, 76th Annual Meeting of the
Chemical Society of Japan, Kanagawa, 1999, prepr. no. 1, p. 373.
M. Kinoshita, T. Noda and Y. Shirota, 76th Annual Meeting of
the Chemical Society of Japan, Kanagawa, 1999, prepr. no. 1,
p. 373.
Y. Shirota, Proc. SPIE Int. Soc. Opt. Eng., 1997, 3148, 186 and
references cited therein.
Y. Shirota, T. Noda and H. Ogawa, Proc. SPIE Int. Soc. Opt.
Eng., 1999, 3797, in the press.
S. A. Van Slyke, C. H. Chen and C. W. Tang, Appl. Phys. Lett.,
1996, 69, 2160.
D. F. O'Brien, P. E. Burrows, S. R. Forrest, B. E. Koene,
D. E. Loy and M. E. Thompson, Adv. Mater., 1998, 10, 1108.
K. Itano, T. Tsuzuki, H. Ogawa, S. Appleyard, M. R. Willis and
Y. Shirota, IEEE Trans. Electron Devices, 1997, 44, 1218.
Y. Shirota, Y. Kuwabara, H. Inada, T. Wakimoto, H. Nakada,
Y. Yonemoto, S. Kawami and K. Imai, Appl. Phys. Lett., 1994,
65, 807.
H. Murata, C. D. Merrit, H. Inada, Y. Shirota and Z. Kafa,
Appl. Phys. Lett., 1999, 75, 3252.
Y. Hamada, C. Adachi, T. Tsutsui and S. Saito, Jpn. J. Appl.
Phys., 1992, 31, 1812.
J. Kido, C. Ohtaki, K. Hongawa and K. Nagai, Jpn. J. Appl.
Phys., 1993, 32, L917.
K. Tamao, M. Uchida, T. Izumizawa, K. Furukawa and
S. Yamaguchi, J. Am. Chem. Soc., 1996, 118, 11974.
M. Kinoshita and Y. Shirota, to be submitted for publication.
C. Hosokawa, H. Higashi, H. Nakamura and T. Kusumoto,
Appl. Phys. Lett., 1995, 67, 3853.
J. Kido, M. Kimura and K. Nagai, Chem. Lett., 1996, 47.
H. Ogawa, K. Ohnishi and Y. Shirota, Synth. Met., 1997, 91, 243.
View Article Online
117 H. Ogawa, T. Noda and Y. Shirota, J. Soc. Inf. Disp., in the

press.
118 T. Noda, H. Ogawa and Y. Shirota, Adv. Mater., 1999, 11, 283.
119 T. Noda and Y. Shirota, J. Lumin., in the press.
120 F. Geiger, M. Stoldt, H. Schweizer, P. Bauerle and E. Umbach,
Adv. Mater., 1993, 5, 922.
121 G. Horowitz, P. Delannoy, H. Bouchriha, F. Deloffre, J.-L. Fave,
F. Garnier, R. Hajlaoui, M. Heyman, F. Kouki, P. Valat,
V. Wintgens and A. Yassar, Adv. Mater., 1994, 6, 752.
122 T. Noda, H. Ogawa, N. Noma and Y. Shirota, Appl. Phys. Lett.,
1997, 70, 699.
123 H. Ogawa, R. Okuda and Y. Shirota, Appl. Phys. A., 1998, 67,
599.
124 H. Ogawa, R. Okuda and Y. Shirota, Mol. Cryst. Liq. Cryst.,
1998, 315, 489.
125 K. Itano, H. Ogawa and Y. Shirota, Appl. Phys. Lett., 1998, 72,
636.
126 K. Okumoto and Y. Shirota, J. Lumin., in the press.
127 (a) M. Hanack, H. Heckmann and R. Polley, `Phthalocyanins
and related compounds', in Houben-Weyl, Methods Org. Chem.,
Suppl. Vol. E9d, Thieme, Stuttgart, 1997, p. 717; (b) F. H. Moser
and A. L. Thomas, The Phthalocyanines, CRC Press, Boca
Raton, 1983.
128 S. Kera, A. Abduaini, M. Aoki, K. Okudaira, N. Ueno,
Y. Harada, Y. Shirota and T. Tsuzuki, Thin Solid Films, 1998,
327329, 278.
129 S. Kera, A. Abduaini, M. Aoki, K. Okudaira, N. Ueno,
Y. Harada, Y. Shirota and T. Tsuzuki, J. Electron Spectrosc.
Relat. Phenom., 1998, 8891, 885.
130 C. W. Tang, Appl. Phys. Lett., 1986, 48, 183.
131 N. Hirota, N. Noma, Y. Shirota, K. Iuchi and H. Miyazaki,
Kobunshi Ronbunshu, 1990, 47, 839.
132 T. Tsuzuki, N. Hirota, N. Noma and Y. Shirota, Thin Solid
Films, 1996, 273, 177.
133 T. Tsuzuki, Y. Kuwabara, N. Noma, Y. Shirota and M. R. Willis,
Jpn. J. Appl. Phys., 1996, 35, L447.
134 T. Tsuzuki, Y. Shirota, J. Rostalski and D. Meissner, Solar
Energy Mater. Solar Cells, in the press.
135 T. Saito, W. Sisk, T. Kobayashi, S. Suzuki and T. Iwayanagi,
J. Phys. Chem., 1993, 97, 8026.
136 J. Nakayama, T. Konishi and M. Hoshino, Heterocycles, 1988,
27, 1731.
137 P. Bauerle, T. Fischer, B. Bidlingmeier, A. Stabel and J. P. Rabe,
Angew. Chem., Int. Ed. Engl., 1995, 34, 303.
138 S. Hotta and K. Waragai, Adv. Mater., 1993, 6, 896.
139 D. Fichou, B. Bachet, F. Demanze, I. Billy, G. Horowitz and
F. Garnier, Adv. Mater., 1996, 8, 500.
140 J. W. Sease and L. Zechmeister, J. Am. Chem. Soc., 1947, 69, 270.
141 J. M. Tour and R. Wu, Macromolecules, 1992, 25, 1901.
142 J. Guay, P. Kasai, A. Diaz, R. Wu, J. M. Tour and L. H. Dao,
Chem. Mater., 1992, 4, 1097.
143 P. Bauerle, U. Segelbaher, A. Maister and M. Mehring, J. Am.
Chem. Soc., 1993, 115, 10 217.
144 D. Fichou, G. Horowitz, B. Xu and F. Gariner, Synth. Met.,
1990, 39, 243.
145 E. E. Havinga, I. Rotte, E. W. Meijer, W. ten Hoeve and
H. Wynberg, Synth. Met., 1991, 4143, 473.
146 S. Hotta and K. Waragai, J. Mater. Chem., 1991, 1, 853.
147 A. Abderrahim, D. Didier, H. Mohamed, B. Nessak,
G. Horrowitz and F. Garnier, Adv. Mater., 1992, 4, 490.
148 Y. Matsuura, Y. Oshima, Y. Misaki, H. Fujiwara, K. Tanaka,
T. Yamabe and S. Hotta, Synth. Met., 1996, 82, 155.
149 D. D. Graf, J. P. Campbell, L. L. Miller and K. R. Mann, J. Am.

Chem. Soc., 1996, 118, 5480.
150 N. Noma, K. Kawaguchi, I. Imae, H. Nakano and Y. Shirota,
J. Mater. Chem., 1996, 6, 117.
151 N. Noma, K. Kawaguchi, I. Imae and Y. Shirota, Synth. Met.,
1997, 84, 597.
152 S. Funaoka, I. Imae, N. Noma and Y. Shirota, Synth. Met., 1999,
101, 600.
153 Y. Shirota, N. Noma, S. Funaoka, H. Yamaguchi and
H. Kawamoto, to be submitted for publication.
154 P. Liu, Y. Shirota and Y. Osada, Polym. Adv. Tech., in
contribution.
155 N. Noma, T. Tsuzuki and Y. Shirota, Adv. Mater., 1995, 7, 647.
156 F. Garnier, G. Tourillon, M. Gazard and J. C. Dubois,
J. Electrochem. Anal. Chem., 1983, 148, 299.
157 A. Kraft, A. C. Grimsdale and A. B. Holmes, Angew. Chem., Int.
Ed., 1998, 37, 402 and references cited therein.
158 R. H. Friend, R. W. Gymer, A. B. Holmes, J. H. Burroughes,
R. N. Marks, C. Taliani, D. D. C. Bradley, D. A. Dos Santos,
J. L. Bredas, M. Logdlund and W. R. Salaneck, Nature, 1999,
397, 121.
159 Y. Shirota, N. Noma, Y. Shimizu, H. Kanega, I.-R. Jeon,
K. Nawa, T. Kakuta, H. Yasui and K. Namba, Synth. Met.,
1991, 4143, 3031 and references cited therein.
160 Y. Shirota, in New Functional Materials, Vol. C, ed. T. Tsuruta,
M. Doyama and M. Seno, Elsevier Science Publishers B.V., 1993,
p. 377 and references cited therein.
161 Y. Shirota, T. Nogami, N. Noma, T. Kakuta and H. Saito, Synth.
Met., 1991, 4143, 1169.
162 I.-R. Jeon, N. Noma and Y. Shirota, Bull. Chem. Soc. Jpn., 1992,
65, 1062.
163 W. Zeng, Y. Shirota, M. Endo and Y. Tani, Chem. Lett., 1989,
1013.
164 W. Zeng, Y. Yoneda and Y. Shirota, J. Photopolym. Sci.
Technol., 1989, 2, 57.
165 Y. Shirota, Y. Yoneda, W. Zeng, H. Kawada and K. Murata,
166 Y. Shirota, Y. Matsumoto, T. Tanaka, N. Noma, K. Seki,
H. Yamamoto and H. Inokuchi, Mol. Cryst. Liq. Cryst., 1990,
183, 227.
167 K. Nawa, K. Miyawaki, I. Imae, N. Noma and Y. Shirota,
J. Mater. Chem., 1993, 3, 113.
168 K. Nawa, K. Miyawaki, I. Imae, N. Noma and Y. Shirota, Synth.
Met., 1993, 5557, 1176.
169 Y. Shirota, N. Noma, K. Namba, K. Nawa and I. Imae, Trans.
Mater. Res. Soc. Jpn., 1994, 15A, 309.
170 K. Nawa, I. Imae, N. Noma and Y. Shirota, Macromolecules,
1995, 28, 723.
171 I. Imae, K. Moriwaki, N. Noma and Y. Shirota, Synth. Met.,
1995, 69, 285.
172 Y. Ohsedo, I. Imae, N. Noma and Y. Shirota, Synth. Met., 1996,
81, 157.
173 I. Imae, K. Nawa, Y. Ohsedo, N. Noma and Y. Shirota,
Macromolecules, 1997, 30, 380.
174 I. Imae, N. Noma and Y. Shirota, Synth. Met., 1997, 85, 1385.
175 Y. Ohsedo, I. Imae and Y. Shirota, Synth. Met., 1999, 103, 969.
176 Y. Ohsedo, I. Imae and Y. Shirota, Electrochim. Acta, in the
press.
Paper a908130e
J. Mater. Chem., 2000, 10, 125
25

Organic Materials For Electronic and Optoelectronic Devices (

Enviado por

Dados do documento

Título original

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

Organic Materials For Electronic and Optoelectronic Devices (

Enviado por

Direitos autorais:

Formatos disponíveis

View Article Online / Journal Homepage / Table of Contents for this issue

Organic materials for electronic and optoelectronic devices{

Received 11th October 1999, Accepted 2nd November 1999

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.

synthesis, structures, reactions, properties, functions, and

This journal is # The Royal Society of Chemistry 2000

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.

View Article Online

materials are required. Both polymers and small molecules are

J. Mater. Chem., 2000, 10, 125

many organic materials do not form energy bands. It is

2 Amorphous molecular materials

View Article Online

contrast to single crystals and liquid crystals which show

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.

2.1 Design and synthesis of amorphous molecular materials

Fig. 1 DSC curves of m-MTDATA.

Fig. 2 Molecular structure of TDATA.

J. Mater. Chem., 2000, 10, 125

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.

View Article Online

melt samples are cooled on standing in air.20 It is suggested that

J. Mater. Chem., 2000, 10, 125

vibrational motions of the molecule, leading to an increase in

View Article Online

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.

Fig. 3 Molecular structure of a-TPTAB. The population ratios of the

decreasing the exibility of nonplanar molecules.24,27,3133 For

to show well-dened glass-transition phenomena. In addition,

2.2 Characteristic features of amorphous molecular materials

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.

View Article Online

J. Mater. Chem., 2000, 10, 125

estimated the average size of free volume hole in a few

View Article Online

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.

Fig. 4 DSC curves of a-TPTAB.

reactions of 4-dimethylaminoazobenzene (DAAB) dispersed in

Scheme 1 Morphological changes of a-TPTAB.

Fig. 5 First-order plots for the thermal cistrans isomerisation of

J. Mater. Chem., 2000, 10, 125

View Article Online

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.

weight organic materials are dispersed in binder polymers. It is

mh/cm2 V21 s21

J. Mater. Chem., 2000, 10, 125

molecular materials relative to those of polymers and

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.

View Article Online

electric eld due to the presence of positional disorder S caused

mobilities in the temperature range below 285 K in terms of the

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.

View Article Online

Fig. 6 Electric-eld dependence of the hole drift mobilities of the

of the negative electric-eld dependence of charge-carrier drift

J. Mater. Chem., 2000, 10, 125

chromic compounds are dispersed in polymer binders.98 We

Fig. 7 Change of absorbance at 430 nm for amorphous BMAB lm

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.

View Article Online

140 C. Thus, the backward cistrans thermal isomerisation can

thought that the molecular size of resist materials limits the

Published on 04 April 2000. Downloaded on 08/02/2016 19:14:28.