POLYMERS, ELECTRICAL AND ELECTRONIC

PROPERTIES
JACEK ULANSKI, Division of Polymer Physics, Institute of Polymers, Technical University of
Lodz, hodi, Poland
MARIAN KRYSZEWSKI, Department of Polymer Physics, Centre of Molecular and Macromolecular
Studies, Polish Academy of Sciences, Lodz, Poland

Introduction 497 3.1 Theoretical Aspects 512

1. Basic Concepts of Electronic 3.1.1 Origin of Charge Carriers 512
Structure of Insulating, 3.1.2 Charge Transport 513
Semiconducting, and 3.1.3 Charge Recombination 514
Conducting Polymers 498 3.2 Experimental Techniques 514
2. Dielectric Polymers 499 3.3 Materials 515
2.1 Theoretical Aspects 499 3.3.1 Polymers with Polyconjugated
2.1.1 Conductivity in dc and ac Multiple Bonds 515
Electrical Fields 499 3.3.2 Polymers with Aromatic
2.1.2 Dielectric Polarization in dc Amine Groups 516
and ac Electrical Fields: 3.3.3 Polymers with Large
Dielectric Relaxations 500 Polynuclear Aromatic
2.1.3 Dielectric Relaxations in Groups 516
Polymer Solutions 503 3.3.4 Inorganic Semiconducting
2.2 Experimental Techniques 504 Polymers 516
2.3 Materials 505 3.3.5 Molecularly Doped Polymers . 517
2.3.1 General Characteristics of 3.4 Applications 518
Polymer Dielectrics 505
4. Conducting Polymers 518
2.3.2 Dielectric Thin Films 506
2.3.3 Electrets; Piezoelectric and 4.1 Theoretical Aspects 518
Pyroelectric Polymers 506 4.1.1 Basic Concepts 518
2.3.4 Liquid-Crystalline 4.1.2 Doping and Charge
Polymers 508 Transport 519
2.4 Electric Breakdown 508 4.2 Experimental Techniques 520
2.4.1 Types of Breakdown and 4.3 Materials 521
Factors Influencing the 4.3.1 Synthesis 521
Electric Breakdown 508 4.3.2 Characteristics 522
2.4.2 Electrical Treeing 509 4.3.3 Processable Conducting
2.4.3 Measurement Techniques 509 Polymers 524
2.5 Surface Charging 510 4.3.4 Heterogeneous Conducting
2.5.1 Origin of Surface Polymer Composites 524
Electrification 510 4.3.5 Superconducting Polymers .... 526
2.5.2 Antistatic Agents 510 4.4 Applications 526
2.6 Applications 510 Glossary 527
3. Semiconducting and
Photoconducting Works Cited 528
Polymers 511 Further Reading 529

INTRODUCTION applied field. No polymers are completely

Polymers in an electric field exhibit a re- free of charges. However, in most polymeric
distribution of charges that are mobile materials, the number of free charge carriers
enough to respond in the time scale of the is very small, and their mobility is very low,
498 Polymers, Electrical and Electronic Properties
so that polymers are essentially insulating
materials. Low dc conductivity a may often
be attributed to impurities (ions) and a small
concentration of electrons or holes that may
be injected from electrodes, particularly at
high fields. At very high fields, the injected
carriers will lead to a variety of breakdown
phenomena.
If the concentration of intrinsic thermally
generated or photogenerated mobile carriers
and their mobility is higher, polymeric ma-
terials exhibit semiconducting properties.
Usually the conductivity of polymeric insula-
tors and semiconductors varies exponentially
with temperature. Because the mobility and
concentration of charge carries are thermally
activated, the properties of polymeric semi-
conductors cannot be described using classi-
cal models elaborated for covalent semicon-
ductors.
If the diffusion of mobile charges is spa-
tially limited, the dc conductance is absent,
but ac conductivity can be observed. If the
limitation of carrier mobility is important,
e.g., at the phase boundary, interfacial polar-
ization occurs. The polarization may also be
induced by the redistribution or partial ori-
entation of dipoles bound to the polymer
chains in the direction of electrical field. The
polarization effects are related to dielectric
properties characterized by the dielectric
permittivity, which is frequency dependent.
Low concentrations of charges and dipoles
in polymeric materials are responsible for
their good dielectric properties, which can
be modified by the chemical constitution and
structure of the polymeric system.
Polymeric materials can exhibit high con-
ductivity when the chemical structure of the
polymer chain is such that a large number of
delocalized charge carriers can be thermally
generated (low ionization potential of the
macromolecular chain) or enhanced by
molecular doping using donor or acceptor
molecules. These systems are polymeric con-
ductors; however, the charge transport
mechanism differs from that of metals.
1. BASIC CONCEPTS OF ELECTRONIC
STRUCTURE OF INSULATING,
SEMICONDUCTING, AND
CONDUCTING POLYMERS
All materials when subjected to an electri-
cal field show electronic and atomic polari-
zations. They depend on the frequency and
are active at co = 10~12 to 10~15 s"1. These
phenomena are responsible for optical prop-
erties. The most important for polymeric di-
electrics is the polarization connected with
the presence of dipoles bound to the back-
bone or with the pendant groups. Under an
electric field, they undergo orientation that is
frequency and temperature dependent. When
the electric field is removed, this polarization
disappears with time and with temperature
increase, and it is called relaxation polariza-
tion. It defines the dielectric permittivity er,
the value of which is in consequence fre-
quency and temperature dependent. For a
good insulating material, the concentration
of mobile dipoles must be low, and er values
are low. Usually, nonpolar saturated poly-
mers are oxidized to some extent, and the
presence of C=O groups is responsible for
an increase of er values. High values of er are
suitable for capacitor materials, but they ex-
hibit dielectric losses at certain frequencies,
which is an important drawback. The chem-
ical composition and structure of the poly-
meric material must be designed to the
needs of particular applications (McCrum et
al., 1967).
In the solid state, organic molecules, in-
cluding macromolecular systems, retain their
identity and interact weakly through van der
Waals or electrostatic forces. The electron-
electron interactions within a macromolecu-
lar chain are stronger then those between
chains. The electrons are moving in a non-
periodic potential, which varies with time
within an isolated molecule because of the
existence of many possible conformations.
Most polymers are amorphous or partially
crystalline solids. The lack of periodic long-
range order distinguishes polymers from co-
valent semiconductors. This fact implies that
physical phenomena in an electric field are
different in polymers than in covalent semi-
conductors and dielectrics.
When a charge carrier is injected into a
polymer, it changes the electronic charge
density at the molecular site that it occupies
and at the neighboring molecular sites. This
results in intramolecular and intermolecular
relaxations, which lower the energy of the
system by the relaxation energy Er (Duke et
al, 1978). The intermolecular and intramo-
lecular contributions to relaxation energies
can be large. For polymers, usually Er(intra)
= £ r (mter) = i_2 eV; therefore, molecular
 Polymers, Electrical and Electronic Properties 499
anions or cations are stable and contribute
in polymeric insulators to conductivity and
surface charging. The intramolecular con-
tributions depend on the local molecular
structure near the injected charge. Local var-
iations in composition and chemical consti-
tution cause spatial fluctuations in the site
energies of charge in these materials. Such
fluctuations are important because they cre-
ate localized molecular-ion states in poly-
mers, which are involved in contact charge
exchange (i.e., contact charging of pendant
group polymers, e.g., polystyrene), and ex-
trinsic localized molecular-ion states that
control the transport properties of molecu-
larly doped polymers. The average value of
intermolecular contributions to the relaxa-
tion energy depends on the dielectric re-
sponse of the medium and may be deter-
mined from the measurements of electronic
motion in the system (photoemission, UV ab-
sorption, electron transfer).
Polymeric solids consisting of molecular
units characterized by low ionization poten-
tial or high electronic affinity exhibit
semiconducting properties. To this class of
polymers belong unsaturated polymers, mac-
romolecular systems containing aromatic or
heterocyclic moieties, etc. The most impor-
tant is the extent of electron delocalization
and the energy needed to transfer an elec-
tron from the highest occupied to the lowest
unoccupied molecular orbit. The "energy
gap" is usually above 1 eV, and the genera-
tion of mobile carriers as well as their mo-
bility is thermally activated. To the large
class of semiconducting polymers belong
such systems as show an ability to form
charge transfer complexes (CT complexes)
usually with low-molecular-weight additives
of low ionization potential or high electron
affinity and polarizability. Conductivities of
semiconducting polymers of the order of
10~6 to 10~3 S/cm are related to hopping
transport on localized states (Stolka, 1988).
Electronic motion can occur along a one-
dimensional molecule. Reduced dimension-
ality implies that the electronic states are
governed by collective ground states called
Fermi-surface instabilities. In a one-dimen-
sional coupled electron-phonon system, be-
cause of the Peierls instability, distortion of
the backbone lattice occurs, which creates a
bond alternation and a gap at the Fermi sur-
face. Electronic states are also localized as a
result of the inherent disorder in polymers.
This fact results in low conductivity and
thermally activated charge mobilities, in con-
trast to energy-band semiconductors for
which carrier mobility decreases with in-
creasing temperature as T~n (n > 0). Poly-
meric materials characterized by high extent
of delocalization of electronic states in the
main chain and the ability to undergo redox
reactions (formations of molecular ions and/
or radicals) due to molecular doping agents
are conductors and show high conductivity,
on the order of 10"1 to 105 S/cm (Ku and
Liepins, 1987).
2. DIELECTRIC POLYMERS
The basic theoretical concepts and theo-
ries for the dielectric properties are similar
for low- and high-molecular-weight materi-
als in crystalline or amorphous phases (more
difficult interpretation in the last case).
These basic concepts are presented in the ar-
ticle DIELECTRIC PROPERTIES OF INSULATORS,
where the problems of local fields and the
continuous-medium approximation are dis-
cussed.
Dielectrics are used in capacitors and as
electrical insulation. The dielectric constant
or dielectric permittivity of a material varies
with temperature, frequency, its phase con-
stitution, and structural defects. These fac-
tors influence the behavior of induced or
permanent electrical dipoles in the polymer
exposed to a steady or alternating electrical
field. When the polarization lags the external
field strength, it results in an electrical en-
ergy loss that appears as dissipated heat. It
is proportional to the product of the relative
permittivity and the tangent of the lag
angle 0.
Energy loss in polymers arises also from
ion and electron migration. Generally, over-
heating or cyclic heating results in degrada-
tion of a dielectric polymer and breakdown.
2.1 Theoretical Aspects
2.1.1 Conductivity in dc and ac Electri-
cal Fields The relative permittivity of a
polymer dielectric er is defined as a ratio of
the permittivity e to the permittivity of
empty space e0:
500 Polymers, Electrical and Electronic Properties
er = e/e0. (1)
Inserting of a dielectric into a parallel-plate
capacitor whose plate area A is very large
and plate spacing d is small would increase
the capacity from Co = (A/d)eQ to
C = (A/d)e = (A/d)(eoer) = C o e, (2)
For dc, we have
V - § - J f and/ = cf. (3)
If the dielectric contains free charges (elec-
trons, holes, or ions), a dc field leads to a
conductance of the material. Potential differ-
ence is connected with current density ac-
cording to
Je = E / A = (4)
where E is the electrical field [V/m] and pe is
called resistivity, and its reciprocal cre is elec-
trical conductivity. Usually, volume resistiv-
ity pe is given as a volume resistance reduced
to a cubical unit volume and expressed in fl
m although the unit Q, cm is used frequently.
Similarly, volume conductivity ae = \lpe is
used and expressed in (Q cm)" 1 or S/cm.
If the sinusoidal voltage is used,
V = VQ sincot (5)
where Vo is the maximum voltage and o) =
lirf, where f is the frequency and t is time
then / = CVQ cosatf; i.e., the current is TT/2
out of phase. This equation applies only to
an ideal case, i.e., when a loss-free dielectric
of ae = 0 is in the capacitor. For a real di-
electric, the current lags voltage by TT/2 - 8,
where 8 is a measure of power loss:
W = irfVler tanS, (6)
where W is expressed in watts (W).
Small values of power loss, or loss factor,
which is the product er tanS, are characteris-
tic of a good dielectric. The dissipation fac-
tor is tanS = exle2 where ex and e2 are given
by the complex electrical permittivity func-
tion
ie2 (7)
where ex is the real part (the dielectric per-
mittivity or electric inductive capacity) and e2
is the imaginary part (the dielectric absorp-
tion). Their dependence on frequency, tem-
perature, and polymer structure will be dis-
cussed in Sec. 2.2.1.
A very important factor of major signifi-
cance in judging the usefulness of an insula-
tor is called dielectric strength. It will be dis-
cussed in Sec. 2.4.
Usually, for low-conductivity plastics—di-
electrics—the values of resistivity p and con-
ductivity a are time dependent, and the ap-
parent volume resistivity increases with
increasing time. This effect is related to com-
plex polarization phenomena that occur
when an electrical field is applied. When a
step voltage is applied to an insulator, its re-
sistance and capacitance changes can be rep-
resented by known equivalent circuits: series
circuit and parallel circuit. They can be used
for elucidation of the above-mentioned time
dependence of the current. A simple relation
between current and voltage like Ohm's law
is usually valid only for low fields. At higher
electrical fields, super-Ohmic behavior is ob-
served and related to the space charge (elec-
tronic or ionic charges trapped in various de-
fects of the material under study). The
theories of space-charge-limited currents
(SCLC) and of the conductivity dependence
on temperature and field for disordered di-
electric materials are advanced and make
possible the basic understanding of the dc
conductance (Kao and Hwang, 1981).
2.1.2 Dielectric Polarization in dc and
ac Electrical Fields: Dielectric Relaxations
When a dielectric is inserted between the
charged plates of a capacitor, dielectric di-
poles are formed whose electric moment is
given by
(8)
where q is a positive charge separated from
a negative charge of the same value by the
distance r. The origin of the vector (JL is at
the negative charge. The total dipole mo-
ment per unit of volume is called the polari-
zation P, which is
P = e0E(er - 1). (9)
The field at a molecule in the interior of a
 Polymers, Electrical and Electronic Properties 501
dielectric between the plates of a charged ca-
pacitor is larger than the applied field E. Be-
cause of polarization that occurs within and
on the surfaces of the dielectric, the dipole
moment induced in the molecule depends on
local field Eloc, thus:
= o:Eloc. (10)
The variable a is called the polarizability of
the molecule. For N molecules per unit of
volume, the total polarization is
P = NaE]oc, (ID
and
er - 1 = P/e0E = NaEloj€0E. (12)
The value of Eloc depends on the model ac-
cepted for its calculation. The simplest is the
Clausius-Mossotti model from which it fol-
lows that
P = (Na/3)(er + 2)E, (13)
or
Na/3e0 = (M/d)(e - 2); (14)
here, M is molecular weight and d is the
density. Debye (1945) derived the relation
between the permanent dipole moment |x
and dipolar polarizability:
a0 = fjL2/3kT. (15)
The polarization can be divided into two
parts: distortion polarization, which is inde-
pendent of temperature (electronic polariza-
tion and atomic polarization), and dipole po-
larization. Thus we can write the following:
er - 1 N This phenomenon is called dielectric relaxa-
(16)
2 d 3e0
where e^ is dielectric permittivity at very
high frequency, related to electronic polari-
zation.
The reexamination of the problem of the
internal field by Onsager (1936) leads to a re-
lation that takes into consideration interac-
tions between the molecule and the field.
When er is large compared with ex (which is
always small), the Onsager equation can be
expressed as
2eJ(er + 2)2 - Ntf/lkT. (17)
It implies many important correlations:
1. The dielectric constant is directly propor-
tional to the number of polar molecules
per unit volume.
2. The dielectric constant is proportional to
the square of permanent dipole moment.
3. The dielectric constant is proportional to
the reciprocal of the absolute tempera-
ture.
This equation is true for not very strong
polar liquids. For polar liquids with hindered
rotation of dipoles and for solids, Kirkwood
(1939) generalized the treatment of the inter-
nal field. The use of the Kirkwood equation
for polymers is not straightforward because
of the mutual influence between segments of
the chain so that the effective dipole mo-
ment decreases.
Orientation polarization occurs when the
applied field interacts with the permanent
electric dipoles that arise from the asymme-
try of the molecule. For most materials, tan5
varies with frequency; the frequency of tanS
maximum is known as the relaxation fre-
quency. The number and amplitudes of indi-
vidual loss processes depend on the number
of dipolar species and on their possible sep-
arate or cooperative motions (McCrum et ah,
1967). The dipole polarization is connected
with reorientation of molecules or molecular
segments; thus, the process is interfered with
by the "friction" from the surrounding mole-
cules. The reorientation of dipoles involves
motion in viscous media, and the polariza-
tion process is delayed, reaching an equilib-
rium only after a relatively long time. When
the electric field is removed, a long time is
also needed for the polarization to disappear.
tion. The time needed for the polarization to
decay by lie of the original equilibrium value
is called the relaxation time, being the recip-
rocal of the relaxation frequency.
Relaxation processes are evidently ther-
mally activated, but no simple Arrhenius-
type formula can be used for determination
of the thermal activation energy and of the
shift of the tan6 maximum with temperature.
It is usual to plot the dielectric permittivity
502 Polymers, Electrical and Electronic Properties
ex or e2 as a function of temperature or fre-
quency as is shown in Fig. 1.
The identification and localization of loss
peaks in different polymers is usually carried
out using the nomenclature first suggested
by Deutsch et al (1954). The relaxations ob-
served at the highest temperature (constant
frequency) or at the lowest frequency (con-
stant temperature) are called the a relaxa-
tions, and the others are called j8, y, etc. in
order of decreasing temperature (or increas-
ing frequency).
The broadening of relaxation spectra is
still a subject of many experimental and the-
oretical studies. It is known that the simple
Debye relation does not fit the experimental
data for polymers, particularly for a and ft
relaxations. Semiempirical equations describ-
ing the broadening of the relaxation spectra
[tanS = f(T) or tanS = f(f)] have been sug-
gested by many authors, e.g., Havriliak and
Negami (1967). More advanced theories de-
scribing the temperature dependence of tan5
= f(T) [or e, = fx(T) and e2 = f2(T)l includ-
ing extended exponential relations as well as
mode-coupling theory, make it possible to
separate individual peaks of which the di-
electric relaxation spectrum consists and to
correlate the observed maxima with specific
motion of particular polar groups or polar
segments.
Molecular interpretations of the various
loss regions should also take into account
the physical structure of polymeric materials.
In amorphous polymers, the loss region as-
sociated with the glass-rubber transition ob-
served above the glass transition temperature
Tg is called the a relaxation. It is related to
the hindered rotation of the main chain. Be-
tan cf
-40 0 40 80 120
• °C
FIG. 1 . Dispersion curves of e and of tanS for
poly(vinyl acetate) (Wurstlin, 1951).
low Tg, this backbone segmental motion is
frozen in, and only local movements of small
portions of the main chains as well as mo-
tions of pendant polar groups occur. Usually,
there is a mixture of these effects, which are
not easy to separate.
In crystalline polymers, the interpretation
of the loss peaks is complicated (McCrum et
al, 1967). At high temperature, low-fre-
quency losses are often called a relaxations,
but they are usually associated with the crys-
talline regions. There are further /3, y, etc. re-
laxations within disordered or amorphous
phases. The highest amorphous peak is at-
tributed to large segments of the main chain
(associated with Tg) in amorphous phase,
and the lower temperature peaks have a sim-
ilar meaning as mentioned earlier.
The conformation and position of side
groups play an important role in the mobil-
ity of the polymer chains, since they deter-
mine both the steric hindrance and chain
packing. The chain conformation may, in a
specific case, facilitate the formation of in-
termolecular or intramolecular hydrogen
bonds leading to lowering of the mobility of
main-chain segments and/or side groups.
Bulky groups attached to the main chain
with lower mobility increase the activation
energy and relaxation time of the relaxation.
It is interesting to note that large groups at-
tached to side chains will increase partially
the main-chain mobility; they still increase
the hindrance, but the adjacent polymer
chains are farther away. Those two effects
will define the magnitude of the main-chain
relaxations. The addition of low-molecular-
weight material (e.g., plasticizer) to a poly-
mer results in an increased separation of the
chains, and the main-chain segment mobility
increases. Addition of the plasticizer has only
a small effect on side-chain relaxation be-
cause the side groups themselves act as plas-
ticizer (internal plasticization). When the
added molecules are able to form charge-
transfer complexes with groups of main or
side chains, an antiplasticization effect is ob-
served to decreased molecular mobility.
Dielectric materials contain—as was men-
tioned before—freely migrating charges as
free ions and/or electrons or holes. The mi-
gration of these charges in a dc field causes
negative or positive ions to be accumulated
on the positive or negative electrode, respec-
tively. Polarization caused by charge migra-
 Polymers, Electrical and Electronic Properties
tion is called space-charge polarization or
ion polarization depending on the nature of
the migrating charges. These polarization ef-
fects occur simultaneously with the polariza-
tion connected with dipole reorientation. Dif-
ferentiation between the two processes,
which show similar behavior, is often diffi-
cult. Much effort has been devoted to sepa-
rating these two phenomena in experiments
and theory, but this problem remains still
actual.
Similarly to dc resistance, both dielectric
permittivity and tan£ are related to the pres-
ence of moisture; ac properties are sensitive
to the presence of moisture even in the ab-
sence of a continuous, low-resistance path.
Thus, ac measurements respond precisely
and quickly to moisture penetration (poly-
mers with fillers, laminates, etc.). The ac
properties are also sensitive to thermal ag-
ing, particularly to dielectric discontinuities
such as voids, delaminations, etc.
Since e^ e2, and tan 5 are determined by
molecular structure, it is obvious that me-
chanical losses and electrical losses are
closely related. One should, however, say
that the mechanical and dielectric loss peaks
do not always coincide because nonidentical
motions are involved, e.g., nonpolar groups
do not contribute to dielectric properties.
If a polymeric dielectric consists of chains
built up of bulky, highly polar subunits
whose orientation may not be random, the
dielectric permittivity e is dependent on di-
rection and described by a third-rank tensor.
The anisotropy of dielectric permittivity is
important for discussion of nonlinear optical
properties of polymers at high electric fields.
In characterization of dielectric properties of
polymers, the anisotropy of e is usually ne-
glected.
When the dielectric consists of two phases
(two components) and one of them with di-
electric permittivity e' or conductivity a' is
dispersed in the second phase (matrix) (with
e" or o"), interfacial polarization occurs and
energy is dissipated. This phenomenon was
first discussed by Maxwell in 1883 and Wag-
ner in 1914 (van Beek, 1967). The average
bulk dielectric permittivity e can be easily
calculated, and it depends on the volume
fraction of the dispersed phase. The separa-
tion of the expression that describes the di-
electric permittivity e of the dispersion into
real and imaginary parts leads to formulas
503
that contain the conductivity of the better
conducting phase. The frequency dependence
of the interfacial polarization is identical
with that of simple (Debye-type) relaxation.
This treatment is applicable for spherical
particles without interactions. In polymeric
materials, these conditions are rarely ful-
filled, and particle shape is important in de-
termining the magnitude of the effect; there-
fore, the effects of the shape of conducting
dispersed particles (ellipsoids) and their ori-
entation parallel or perpendicular to the field
has been considered. Interfacial polarization
occurs at frequencies below 1 MHz. Dielec-
tric loss in an ac field and its maximum fre-
quency depends on electrical properties of
the components and on their distribution.
2.1.3 Dielectric Relaxations in Polymer
Solutions The studies of dilute polymer
solutions, where intermolecular effects are
minimized, lead to much important infor-
mation on the influence of chain structure
on the dielectric behavior of polymers
(Stockmayer, 1967). Dipole geometry defines
the possible reorientations in electrical field.
The dipoles can be connected with
a. flexible side chains (e.g., polyarylates),
b. rigid groups or atoms bound to the back-
bone [e.g., poly(vinyl chloride)], or
c. rigid groups in the backbone (e.g., poly-
esters).
Macromolecular dipoles arise from the
vectorially summed contributions of individ-
ual chain dipoles (Volkenstein, 1963). The
determination of dipole moment is a valua-
ble pointer to polymer chain configuration
and to polymer sequencing. The rotational
isomeric-state model is often applied for cal-
culation of the mean square dipole moment
(|JL2). One has to take into consideration the
above-mentioned dipole contributions. If
there are flexible side-chain dipoles, it is dif-
ficult to quantify how those dipoles contrib-
ute to the total polarization via backbone
reorientation. The perpendicular dipoles are
most common and represent the only dipoles
present in poly(vinylhalides), unbranched
polyoxides, polyimines, and polysulfones.
The chemical structure of many monomers
results in a long-chain dipole per residue;
thus, they may make no contribution to (|x2)
because of sequences of plane reflections.
Perpendicular dipoles sum over all chain
504 Polymers, Electrical and Electronic Properties
configurations regardless of long-range inter-
actions, whereas parallel dipoles are sub-
jected to some constraints such as skeletal
bonds, leading to excluded volume. The
knowledge of <|x2) can be useful information
concerning the relative equilibrium popula-
tion of gauche and trans configurations in
the system when reliable experimental data
are available.
The rotational isomeric-state model is ap-
plicable to isolated macromolecules and to
the assembly averaged total dipole. This
model takes no account of internal field
problems (the external field is usually modi-
fied by neighboring dipoles). The study of in-
finite dilute solutions and solutions in sol-
vents of low dielectric permittivity relying on
Debye's equation cannot lead to satisfactory
results, particularly for macromolecules. The
Onsager model with modifications (non-
spherical cavities and elimination of discon-
tinuity at the cavity edge) is more useful. It
must be pointed out that the polymeric di-
pole moment is time dependent as a result of
micro-Brownian movement of the chains
and entanglements that must be correlated.
The solution of the problem is the use of the
correlation function approach. The theories
of Kirkwood and Frohlich provide a satisfac-
tory basis for interpretation of the experi-
mental results (Block and Walker, 1982).
The frequency dependences of e^ and e2
provide kinetic parameters for the relaxation
process, and thermal activation parameters
are accessible from variable temperature
measurements. One should avoid charge mi-
gration, which is common in polyelectrolyte
solutions or when macromolecular and sol-
vent phase have different conductivities (the
interfacial relaxations disturb the correct
evaluation of dipole relaxations).
In semidilute solutions, detailed molecular
motions or the interactions between mole-
cules are not clarified as yet. The interpreta-
tion of the experimental data is usually done
in terms of normal-mode process and seg-
mental-mode processes.
2.2 Experimental Techniques
Electrical property measurements can be
divided into low-stress phenomena, which
are not particularly dependent on the electri-
cal stress level (these measurement tech-
niques will be described below), and high-
stress phenomena, which will be analyzed in
the discussion of electrical breakdown (Sec.
2.4.3).
Electrical test procedures often used for
plastics materials include measurements of
conductivity (resistivity) and measurements
of dielectric properties. Techniques for the
measurements of all important electrical
properties of polymers are described in de-
tail by Bartnikas (1987). Techniques for the
measurement of resistivity (or conductivity)
are described in ASTMD 257. There are
three commonly used methods, which are
based on the use of
1. a bridge (e.g., Wheatstone) comparison
method;
2. a comparison method using a sensitive
current-indicating device; or
3. the voltammeter method.
With the best available equipment, values
of resistance as high as 1017 Q, can be mea-
sured. Insulation resistance is a combination
of volume and surface resistance; that is why
it is important to preserve correct measure-
ment conditions. The leakage current from
the guard to the measuring electrode is
shunted in such a way that it is not mea-
sured. However, errors are introduced if the
resistance between the guard and measuring
electrode is less than about 100 times the in-
ternal resistance of the current-measuring
device. When very high resistances have to
be measured, the internal resistance, the
time constant of the measurement, and the
problem of guarding are increased. The sur-
face of the dielectric measured and of the
contacting electrodes must be very clean, be-
cause contamination strongly affects both
the volume and the surface resistances. Elec-
trode design is very important in the mea-
surement of electrical resistance. It is some-
times specified in the test methods for
specific materials. Round rather than square
electrodes are most common. Thin coatings
of conducting paints are useful, but the ef-
fect of dispersant or solvent on the plastic
should be taken into consideration. Evapo-
rated metal or thin metal foil electrodes are
often applied; in the last case, a minimum of
the adhesive (e.g., silicone grease) should be
used, preserving good contact with the test
specimen.
For resistance measurements to determine
changes caused by moisture or elevated tern-
 Polymers, Electrical and Electronic Properties
peratures, gold electrodes are most suitable
at very high temperature or under corrosive
condition. Resistance measurement must be
made in the desired surroundings and not
after removal from the conditioning cham-
ber. Usually, shield leads with high leakage
resistance are used through the walls of con-
ditioning chambers, and the shield is con-
nected to the guard circuit during measure-
ments.
For the tanS or ex and e2 measurements,
an oscillating electrical field is applied to a
specimen between two electrodes. In view of
the importance of dielectric permittivity and
tan6 and their dependence on frequency and
temperature, there are many developments
of instruments and methodology to measure
these quantities. Usually, the measuring sys-
tems can be divided into dielectric spectrom-
eter and dielectric thermal analyzer. A di-
electric spectrometer scans the frequency
response of permittivity and tanS at a series
of temperatures, often by Fourier transform
of the "current vs time" response to a step
change in the voltage. The dielectric thermal
analyzer monitors tanS at a constant fre-
quency as the temperature is increased with
time. The dc step response technique covers
10- 4 to 106 Hz.
Various methods covering the range 10~3
to 1010 Hz are mentioned here:
1. Schering-type bridge (capacitance bridge)
(10- 1 to 106 Hz);
505
2. transformer ratio-arms bridge in which
the ratio arms are closely coupled trans-
formers; and
3. microwave bridges (10-70 GHz) or trans-
mission lines (0.3-40 GHz).
Selection from these methods allows mea-
surements to be made to the desired levels of
accuracy and the frequency required. Resis-
tance measurements are used to measure in-
directly the influence of other factors, such
as moisture, that may affect electrical
strength and are useful in studying resin
cure. Recently, ionic conductivity has been
applied successfully to this purpose too. Di-
electric thermal analysis instruments are
used to investigate rheological properties, the
glass transition, and other transition phe-
nomena.
2.3 Materials
2.3.1 General Characteristics of Poly-
mer Dielectrics Various degrees of molec-
ular freedom are possible in polar polymers.
If the crystalline lattice is highly imperfect
and the shape of molecules is symmetrical so
that there is considerable molecular free-
dom, the dipoles in a crystal may be able to
make a substantial contribution to polariza-
tion effects. It is evident from Table 1 that
dielectric permittivity eu dielectric loss
(tan8), and electrical conductivity a = Up
are interrelated and increase in about the

Table 1. Electrical properties of some polymers at room temperature (Ku and Liepins, 1987).
Dielectric Dielectric Volume
permittivity ex loss tan 8 resistivity
Polymer (at 100 Hz) (at 100 Hz) p [S" 1 cm]
Cz'5-polybutadiene 2.05 0.00051 3.1 X 1015
Low-density polyethylene 2.22 0.0039 2.5 X 1015
Czs-polyisoprene 2.26 0.0094 7.1 X 1016
7rarcs-polyisoprene 2.27 0.00038 7.8 X 1016
High-density polyethylene 2.30 0.00011 2.2 X 1016
Polystyrene 2.31 0.00029 2.5 X 1016
Polycarbonate 2.72 0.00115 2.2 X 1013
Poly(dimethylsiloxane) 2.86 0.00025 5.3 X 1014
Poly(phenylmethyl, dimethyl)siloxane 2.87 0.00010 3.0 X 1014
Poly(diphenyl, dimethyl)siloxane 2.90 0.00041 9.8 X 1014
Poly(methylmethacrylate) 3.03 0.057 1.2 X 1013
Chlorosulfonyl polyethylene 5.63 0.138 2.6 X 1013
Poly(ethylacrylate) 5.56 0.013 1.4 X 1013
Poly(trifluoropropyl, methyl)siloxane 6.85 0.109 2.7 X 1011
Poly(chloroprene) 7.83 0.639 8.2 X 109
Viton (copolymer of vinylidene) fluoride and
hexafluoropropylene 8.55 0.0403 4.1 X 1011
506 Polymers, Electrical and Electronic Properties
same fashion as the polarity of the polymer
increases.
These insulation properties can be dis-
cussed from the viewpoint of dc and ac
terms (McCrum et al, 1967). Voltage gradi-
ents across insulating systems depend pri-
marily on the leakage rather than on the ca-
pacitance. For this reason, insulators for
high-voltage application must be formulated
in such a way that they show low conductiv-
ity. In the case of high-voltage insulation,
trapped charges have been taken into consid-
eration, which can be troublesome when a
sudden polarity reversal is required.
Specific requirements are to be fulfilled
for low-electric-loss polymers, e.g., used in
the insulation of transoceanic cables. They
are met in general by polyolefins, e.g., poly-
ethylene, which combines very low dielectric
loss with moldability, toughness, and flexibil-
ity. High-performance thin polypropylene
films have also been developed for various
types of power capacitors. Extremely low-
conductivity materials such as those used in
electret microphones are required for various
types of high-power capacitors. High-purity,
pinhole-free, chemically inert poly(p-xyly-
lene) (Szwarc, 1976) and its chlorine-substi-
tuted ultrathin film have been developed as
insulation barrier coatings for semiconductor
surfaces. High-temperature resistant poly-
mers like various types of polyimides are of-
ten used as thin insulating layers in micro-
electronics.
2.3.2 Dielectric Thin Films Dielectric
polymer thin films are rarely prepared by
thermal evaporation, electron-beam evapora-
tion, or slip casting (melting of the powder)
on metallic or semiconductor surfaces; how-
ever, these techniques have created more
and more interest in the fabrication of mi-
croelectronic devices. Mostly used is spin
coating from dilute solutions of polymers
characterized by appropriate dielectric prop-
erties. Care must be taken (rotation speed,
temperature, vapor pressure of the solvent,
etc.) in order to obtain pinhole-free films.
Recently, the spin-coating technique has
been used to obtain thin insulating films by
spin coating of a dispersion of polymer
spheres of low diameter on a metallic or
semiconducting surface and melting the ob-
tained monosphere-thick layer (e.g., polysty-
rene monodisperse lattices). Thicker, but still
thin, polymer films can be obtained by extru-
sion and/or blowing of one-component or
multicomponent layered systems.
Chemical vapor deposition and plasma
polymerization have been recently applied
for obtaining high-quality dielectric films,
mostly organosilicon materials. Preparation
conditions will decide the quality of the ob-
tained materials, which in many cases are
transparent, well adhering to the support,
and insoluble.
Very thin films are prepared by polymeri-
zation of di-p-xylylene. The substrate is ex-
posed to a controlled atmosphere of a pure
monomer, and coating occurs as vapor-dep-
osition polymerization (Beach, 1978). If the
di-p-xylylene is used in plasma polymeriza-
tion, it forms plasma polymers that contain
a minor amount of branched and cross-
linked chains, and its solubility suggests a
material of low molecular weight. This pro-
cess has certain similarities to vacuum me-
tallization.
2.3.3 Electrets; Piezoelectric and Pyro-
electiic Polymers Electrets are dielectrics
that create for a long time a strong external
electric field. The phenomenon is connected
with dipoles oriented during polarization
treatment or with the presence of incompen-
sated, stable charge (Sessler, 1982). Perma-
nent polarization is usually obtained by heat-
ing or melting and solidifying a polar
polymer in an external electric field (ther-
moelectrets) or by photoexcitation (photo-
electrets). There is the possibility to induce
charges in a polarized dielectric by y irradi-
ation (radioelectrets) or by ion implantation.
Electrets may be obtained from natural di-
electrics—e.g., waxes—or various polymeric
dielectrics with low dielectric constant and/
or of high Tg.
Most frequently, electrets are obtained by
polarization of polar dielectrics in high elec-
tric fields. The charge at the surface of an
electret is due to the orientation of dipoles;
thus, heterocharge is formed. There are also
injected charge carriers (homocharge) that
disappear much more slowly with time. The
resulting charge and the lifetime of an elec-
tret depend on the material used and on po-
larization conditions. There are electrets that
can be obtained from nonpolar dielectrics as
a result of charge carriers injected from the
electrodes or induced by irradiation. Most
 Polymers, Electrical and Electronic Properties 507
important are thin-film electrets, which are
obtained from good dielectrics by electron-
beam irradiation whereby the charge is ac-
cumulated at a known distance from the sur-
face of the film. Electrets of high density of
charges are also prepared by corona charg-
ing and by using controlled breakdown on
large surfaces. There is a method of electret
preparation by the so-called "wet technique."
This consists in contacting the dielectric with
a liquid characterized by high conductivity
in electric fields. The liquid layer is removed
later on.
Electrets are subject to an aging process,
but by careful treatment, one can obtain
charged materials lasting a long time and
creating high electric fields. There are al-
ready known techniques that are useful for
determination of the charge distribution in
the poled material. Important information
about the relaxation parameters of oriented
dipoles and trapped charges are obtained by
well-elaborated, thermally stimulated depo-
larization techniques (van Turnhout, 1987;
see also Sec. 3.2). It makes possible more de-
tailed understanding of electret formation
and its aging. Principal applications are elec-
trostatic filters and electroacoustic transduc-
ers.
Piezoelectricity is a phenomenon related
to the appearance of resultant electric mo-
ment connected with charges on the surface
of a material under compression or exten-
sion (spontaneous polarization). This effect
was first observed in crystals with polar axes
and without a symmetry center. Pyroelectric
effects are similar to piezoelectric in the ap-
pearance of opposite charges on the surfaces
of a material but under homogeneous heat-
ing.
Most piezoelectric polymers are also poly-
mer electrets. Maximum piezoelectricity is
roughly related to the dielectric permittivity;
thus, it is determined basically by the chem-
ical structure of the polymer. The chain con-
figuration and bulk morphology are equally
important for piezoelectricity. Poly(vinyl-
idene fluoride) (PVDF), because of its highly
polar C-F bonds and high dipole moment
(fi0 = 6.4 X 10"30 C m), has the highest di-
electric constant (e = 8.0) and shows the
highest piezoelectric constant (Wada, 1982).
Fluoropolymers and copolymers with vi-
nylidene fluoride are good piezoelectric poly-
mers. Other polar groups—e.g., C-Cl (/z,0 =
7.0 X 10-30 C m) and C-CN (^0 = 12 X
10~30 C m)—may also lead to useful piezo-
electric macromolecular materials. Poly(vi-
nylidene chloride) chains, because of the
presence of bulky chlorine atoms, are pre-
vented from adopting the highly polar all-
trans conformation. The poly(vinylidene cya-
nide-vinyl acetate) alternating copolymer
exhibits a piezoelectric constant similar to
PVDF.
The very important structural feature of
PVDF is high crystallinity (40-60%). It can
crystallize in three major crystalline forms—
a, (3, and y. The a form is obtained when the
polymer crystallizes from the melt below 150
°C. The structure of the a crystals is mono-
clinic with the chains having trans-gauche-
trans-gauche conformation and a dipole mo-
ment that has components normal and
parallel to the chain axis. The dipole mo-
ments of two chains in the unit cell are an-
tiparallel, and the crystal shows no sponta-
neous polarization. Drawing the PVDF film
below 130 °C to several times its original
length results in a new crystal form, the /3
form. This crystal has the orthorhombic unit
cell in which the chains have all-trans con-
formation. These chains have a large dipole
moment (/JL0 = 7.06 X 10~30 C m) per mono-
meric unit, and they are packed in such a
way that the crystal exhibits spontaneous po-
larization Pc (for the ideal crystal Pc = 0.3 C/
m2). In real /3-form crystals, Pc is smaller be-
cause of defects. The stable /3-form crystals
should, however, have more than 3% of de-
fects (head-to-head and tail-to-tail defects).
The conversion from the a to the /3 form de-
pends on draw ratio and draw temperature.
The j8 form of PVDF crystals is characterized
by the highest molecular packing. The y
form is obtained by crystallization under at-
mospheric pressure, just below the melting
temperature, or by melt crystallization under
high pressure. The y-form crystals can be
transformed into the (3 form by mechanical
deformation of the crystal.
The PVDF electrets are prepared by an-
nealing and poling c-axis oriented films con-
taining /3-form crystals. Typical poling tem-
perature is Tp = 80-120 °C, and the
electrical poling field is Ep = 50-150 MV/m.
The induced surface charge is opposite to
the poling field (heterocharge). There is a
small part of irreversible polarization; the re-
maining part is stable below Tp. The mecha-
508 Polymers, Electrical and Electronic Properties
nism of the polarization is still a subject of
discussion. It is accepted that the piezoelec-
tricity and pyroelectricity of PVDF and its
large polarization depend on the number of
crystallites in the /3 form and on its ability to
align during polarization. It is correlated also
with the dipole residues from amorphous
regions and their incorporation into crystal-
lites at grain boundaries. Thus, both chemi-
cal structure and physical factors play im-
portant roles.
2.3.4 Liquid-Crystalline Polymers Liq-
uid-crystalline polymers (LCPs) are of partic-
ular interest because of their very interesting
mechanical properties in the oriented state
and their nonlinear optical behavior. Liquid-
crystalline side-group polymers contain di-
pole moments related to the pendant group
(some LCPs also have a dipole moment in
the backbone chain). The dipole character of
LCPs makes it possible to study the molecu-
lar dynamics of those systems using broad-
band dielectric spectroscopy covering the
frequency range 10~4 up to 1010 Hz (Kremer
et ah, 1990). Thus, it is possible to study
both fast processes (e.g., rotation of meso-
genic groups around their long molecular
axis) and slow relaxations (e.g., relaxation
close to Tg).
For LCPs with side groups, five different
dielectric relaxations have been found. For
combined main-chain/side-group systems,
the systematic chemical modification of di-
poles revealed three relaxation processes.
The a relaxation corresponds to the dynamic
glass transition. The rotation of the main-
chain mesogen around its long molecular
axis is called /3m relaxation, whereas j85 relax-
ation is correlated with the rotation of the
side-group mesogen around its long molecu-
lar axis. It is worth noting that for
side-group LCPs, a collective relaxation pro-
cess (5 process) was found and ascribed to
the hindered rotation of side groups around
the polymeric main chain. Similar behavior
was found for combined main-chain/side-
group liquid crystalline polymers as well as
for some copolymers, in which it is sup-
pressed at the smectic-crystalline transition.
The dielectric relaxation studies also give
valuable information on the mobilities in
various smectic phases depending on tem-
perature. Recently, low-molecular-mass fer-
roelectric liquid crystals have been investi-
gated. They show two different collective
modes. Some main-chain/side-group LCPs
have ferroelectric smectic phases as well.
They appear when these system are oriented
as a result of surface effects and/or for low
magnetic fields. This allows for the combi-
nation of typical polymeric features with the
properties of the ferroelectric smectic
phases. Thus, in addition to their conven-
tional use in displays, a wide field of new ap-
plications may be expected, e.g., as piezoele-
ments made from cross-linked elastomers or
as pressure sensors.
2.4 Electric Breakdown
2.4.1 Types of Breakdown and Factors
Influencing the Electric Breakdown
Electric breakdown occurs when the current
flowing through the sample increases, lead-
ing to its failure, and the applied voltage
cannot be stable (Fisher, 1982). The applied
voltage leading to material disruption is
called breakdown voltage, and the corre-
sponding voltage gradient at failure is elec-
tric strength in kV/mm. The knowledge of
the breakdown mechanism is not complete,
but one can distinguish the following:
1. Intrinsic breakdown, which is related to
pure and defect-free material and occurs
at the highest possible voltage. It is due to
the increased random motion of elec-
trons, which at the electric breakdown
gain higher energy than they lose to the
system.
2. Thermal breakdown, which is related to
heat emission. If the rate of heating un-
der voltage exceeds the rate of cooling by
thermal transfer, thermal breakdown may
occur at a limited section of the material.
These restricted paths of breakdown are
called Wagner breakdowns.
3. Gas-discharge-dependent breakdown is
related to electric discharges in gas,
which may occur on the surface or voids
and on various discontinuities of electri-
cal insulation. It can be due to ionization-
induced surface flashover or arcing.
4. Physical-defect-dependent breakdown is
affected by all types of cracks, voids, for-
eign inclusions, and factors that introduce
physical deterioration of plastics.
Actual electrical breakdown may involve
 Polymers, Electrical and Electronic Properties 509
two or more types simultaneously or sequen-
tially. The true intrinsic breakdown can
never be achieved experimentally, but exper-
iments carried out at low temperature with
dc voltage applied for very short times are
taken as the intrinsic value.
If the thermal breakdown tests are made
at high frequencies (above 1 MHz), failure
occurs at relatively low voltages. Usually,
tanS increases with increasing temperature,
and the rate of heating rises rapidly. Many
factors influence the thermal breakdown
voltage: geometry (particularly the thickness
of the sample), thermal conductivity, dielec-
tric permittivity, absorbed moisture, etc. It
depends also on the general tendency for
physical degradation of the plastic under
study.
Surface discharges are a source of ioniza-
tion and may cause slow degradation of the
polymeric material at its surface or within
cracks and voids. Progressive surface degra-
dation (tracking) is particularly important in
the presence of surface contaminations. Co-
rona and partial discharge are local effects
occurring in gas where the voltage locally ex-
ceeds the gas-breakdown potential.
Breakdown connected with physical de-
fects depends also on mechanical stress and
vibrations. This type of failure depends on
the nature of defects, the time under electri-
cal stress, contaminations, and chemical
constitution of the polymers. There is a cer-
tain similarity between electrical strength
and mechanical strength because electrical
breakdown involves physical destruction. In
the same temperature regions, both modulus
and dielectric strength show significant re-
ductions in magnitude.
2.4.2 Electrical Treeing Treeing is re-
lated to sporadic discharges that are inter-
mittent and not steady like corona dis-
charges (Ku and Liepins, 1987). The
mechanism of treeing is very similar to elec-
tric breakdown. Treeing breakdown starts in
the regions of the highest and most divergent
electrical stresses. The insulation system con-
sists always of non-absolutely smooth elec-
trodes, imperfect electrode-insulation inter-
face, and not perfectly isotropic material, as
well as there being contaminant particles or
cavities. These defects influence the appear-
ance of treeing phenomenon. Small channels
of degradation develop into a treelike pat-
tern, which may finally bridge the gap be-
tween electrodes and cause the failures. The
practical importance of treeing has been em-
phasized in many cases, particularly for
polyethylene cables. Some insulations con-
taining stress concentration or even some
kinds of trees do not fail in short periods. In
fact, reports of long lifetimes of solid insula-
tion suggest that well-designed and well-con-
structed insulating systems operate within
the limits of electrical, mechanical, and ther-
mal stresses for a long time.
2.4.3 Measurement Techniques Mea-
surements of the electric breakdown strength
are standardized, and the equipment and
procedures for electric breakdown test are
clearly described in ASTM D 149. The im-
portant features that have to be fulfilled by
each equipment are an appropriate device to
measure the test voltage at the specimen and
not only the primary voltage of the testing
transformer, a device for increasing the test
voltage at uniform rate, strictly sine wave,
and a device for removing the voltage at
breakdown.
Usually, the corona test and the arc resis-
tance test are made in connection with elec-
tric breakdown test. Standardized proce-
dures are difficult to be developed, especially
for volume corona, i.e., for corona dis-
charges in voids at conducting inclusions.
ASTM D 2275 is applied to measure the co-
rona resistance. For dry arc resistance,
ASTM D 495 is used. A 12.5-kV voltage
(open circuit), which produces an arc be-
tween chisel-shaped tungsten electrodes, is
applied.
A number of works have been carried out
to elaborate various methods of treeing test
(electrical and water treeing test), each of
them having its advantages. ASTM D 3756
describes a test for electrical treeing between
a sharply pointed needle and a rounded nee-
dle. The only quite well-standardized test for
wet-treeing of cables is that of the Associa-
tion of Edison Illuminating Companies [IC
CS5-79].
Tracking tests have been standardized in
the United States. There are four types of
tracking test:
1. Dust-and-Fog Tracking and Erosion
(ASTM D 2132),
2. Differential Wet Tracking (ASTM D 2302),
510 Polymers, Electrical and Electronic Properties
3. Inclined plane Tracking and Erosion
ASTM D 2303, and
4. Comparative Tracking Index (ASTM D
3638).
2.5 Surface Charging
2.5.1 Origin of Surface Electrification
The presence of electrostatic charge is rec-
ognized by mutual attraction or repulsion
with other surfaces, possibly with small dis-
charges (sparks), and by the dust attraction
effect. When brought into intimate contact
with a neutral material, e.g., by rubbing,
polymers become positively or negatively
charged on separation. The one that be-
comes positively charged acts as an electron
donor, while the other, which becomes neg-
ative, acts as an electron acceptor (Ritsko,
1982; see also TRIBOLOGY).
The sequence of polymers according to
their charging behavior is called the tribo-
electric series. It is a general rule that if two
substances become charged by mutual con-
tact, the substance with higher dielectric
constant will get the positive charge. The tri-
boelectric series can be established by con-
tact potential differences.
The microscopic nature of electronic
states involved in triboelectricity is still un-
der study (Lowell and Rose-Innes, 1980). The
molecular-ion model of bulk intrinsic states
provides an acceptable microscopic descrip-
tion of the charge-transfer process, but fur-
ther advances in the understanding of this
phenomenon are needed. Very important is
the rate of charge decay. It depends on the
side groups that constitute the polymer
chain. When side-chain substituents are in-
volved in charging the surface, charge decay
is faster. The ability of the polymer to bind
ions is also a very important factor. A small
amount of impurity can alter the surface
charging to a high extent. Surface charging
is of importance for the flow behavior of
polymer powders and is a key process in all
xerographic techniques.
2.5.2 Antistatic Agents The electro-
static charge can be reduced by use of anti-
static agents. Even a small surface charge
density can give rise to an electric field
strong enough to cause arcing in air (electri-
cal charge in carpets in dry air). Antistatic
agents can be used in formulations by mix-
ing with the basic polymer, but above all, the
polymer surface must be treated to optimize
the performance of the system. The tendency
of polymers to store electric charge was
overcome in the past by addition of carbon
black or acetylene black to rubber, by addi-
tion of metallic powders to plastics, and by
blending of metallic or metal-coated fibers
with synthetic fibers. At present, conducting
polymers, thin vacuum-deposited metal lay-
ers, or formation of charge-transfer com-
plexes at the surface are of interest for vari-
ous applications.
2.6 Applications
Polymers are used in many electrical ap-
plications as primary electrical insulation, or
they may have a structural function, inde-
pendent of an electrical function; thus,
choice of an appropriate polymer as an in-
sulator depends on its particular application.
An interesting survey of various basic electri-
cal properties of polymers with regard to
their applications is given by Ku and Liepins
(1987).
Useful dielectrics are usually divided into
three principal classes: those with er < 12,
those with er > 12, and ferroelectrics. The
last class is represented among polymeric
materials by some ferroelectric liquid-crystal-
line polymers. The first category may be di-
vided into subcategories based on operating
temperature; however, this division is yet not
fully justified because polymeric materials
depending on their chemical constitution
and structure can be used as insulators and
dielectrics up to 400 °C (depending on time
of application of severity of temperature con-
ditions).
Polymers fulfill generally well the typical
requirements of an insulator:
1. they usually have high enough dielectric
strength to withstand an electrical field
between the conductors (e.g., in capaci-
tors);
2. they show high insulation resistance to
prevent the leakage of the current;
3. they exhibit a good arc resistance to pre-
vent damage in the case of arcing;
4. they show appropriate mechanical prop-
erties to resist shock, vibrations, etc.; and
5. they usually maintain their integrity un-
der a wide variety of environmental haz-
 Polymers, Electrical and Electronic Properties 511
ards such as humidity, temperature
changes, and radiation.
For domestic wiring insulation, the best
electrical properties are not necessary; thus
plasticized PVC is firmly established. Ester
plasticizers also change the nonflammability
of PVC, but some appropriately chosen com-
positions may compensate this insufficiency.
High-quality polyethylene is used for tele-
communication cables while polypropylene
(biaxially oriented) and poly(ethylenether-
ephtalate) films are used in capacitor manu-
facturing.
Among some relatively new developments
in thermoplastics, the polymer blends (e.g.,
polycarbonate/ABS blends, where ABS
stands for a mixture of acrylonitrile-styrene
and butadiene-styrene copolymers) are cho-
sen for connectors and switch casings, where
high impact strength, good surface quality,
and low mould shrinkage are required. The
low resistivity and high dielectric strength of
these materials are relatively unaffected by
external moisture, and so they are suitable
for waterproof switches.
The permanency of storage of real and
polarization charges depends on conductiv-
ity, carrier mobility, and dipolar relaxation.
Insulating polymers may show a very good
long-term charge-storage capability because
of the low conductivity and low carrier mo-
bility. Typical examples of polymers that can
store real charges and polarization charges
are polyolefins and poly(ethyleneterephthal-
ate). Poly(tetrafluoroethylene) (Teflon™) and
its fluoro-ethylene-propylene copolymers are
examples of materials with good insulating
properties, and poly(vinylidene fluoride) is
characteristic of small dipolar relaxation.
Applications of polymers in the electronic
industry are continuously increasing. Poly-
mer piezoelectrets are used in microphones
and small loudspeakers. Polymer dielectrics
are rapidly gaining importance as substitutes
for inorganic (ceramic-based) insulators.
These applications are dominated by poly-
imide films, which offer particularly useful
characteristics:
1. stability up to temperatures as high as
450 °C;
2. high electrical resistivity and breakdown
strength, and low dielectric loss;
3. excellent chemical resistance; and
4. coating of substrates with thin films is
feasible and patterning can be achieved in
lithography.
All these features make it possible for this
type of polymer to be applied in microelec-
tronics as microresists and printed circuit
boards (Saone and Martynenko, 1989).
Evidently, polymers are used as molded
components for chip encapsulation. The en-
capsulant must be very pure material with
an excellent barrier to moisture and contam-
inant ions, independently of superior electri-
cal, physical, and manufacturing properties.
Many organic polymers fulfill these condi-
tions, both thermosetting and thermoplastic
materials.
In addition to good dielectric and insulat-
ing properties, the polymers are widely used
because of good processing characteristics
(small and intricate shapes can be readily
and economically manufactured), good me-
chanical properties (resistance to impact
loads and stiffness, even at elevated temper-
atures), dimensional stability, and retention
of many properties in hot and/or moist envi-
ronment over long periods of time.
3. SEMICONDUCTING AND
PHOTOCONDUCTING POLYMERS
The conductivity of every material can be
enhanced when charge carriers are generated
or injected by appropriate radiation. If UV,
visible, or near-IR radiation is used, we deal
with photoconductivity. In the case of x-ray,
gamma-ray, or other, e.g., electron, irradia-
tion, the term radiation-induced conductivity
is usually used. High-energy irradiation in-
evitably results in chemical degradation of
the polymer, and these problems are outside
of the scope of this article. An ideal, elec-
tronically photoconductive polymer should
have no free charge carriers (thus, it should
show very low conductivity in the dark) and
high quantum efficiency of charge-carrier
photogeneration, and it should allow fast
transportation of the photogenerated
charges.
Three classes of polymers are known to
exhibit semiconducting and photoconducting
properties: polymers with 7r-polyconjugated
multiple bonds (like polyacetylene), polymers
with (7-bonded silicon or germanium atoms
in the main chain (like polysilanes), and
512 Polymers, Electrical and Electronic Properties
polymers with saturated backbones and pen-
dant aromatic groups [like poly(N-vinylcar-
bazole)(PVK)]. Another class of polymeric
semiconductors comprises molecularly
doped polymers consisting of an electrically
insulating and inactive polymer matrix
doped with charge-transfer (CT) complexes
forming additives.
In polymers with extended 7r-electron sys-
tems in the backbone, the molecular p orbi-
tals broaden into filled and empty bands,
and the polymer should be an intrinsic
metal. However, because of bond alternation
(Peierls distortion), there is a finite gap (e.g.,
around 1.4 eV for polyacetylene) between
these bands.
In silicon-backbone polymers, significant
delocalization of electrons occurs along the
chain, and their electronic behavior is very
different from analogous cr-bonded carbon-
backbone polymers; the band gap in polysi-
lanes is of the order of 4 eV, while in carbon
analogs it is close to 8 eV.
Pendant-group polymers have electronic
states similar to thosfe of the pendant aro-
matic molecules, and so their properties are
similar to those of the polymers molecularly
doped with chromophores, where the charge
transport occurs via hopping among local-
ized sites associated with pendant groups or
dopant molecules.
3.1 Theoretical Aspects
3.1.1 Origin of Charge Carriers The
charge carriers necessary to transmit the
electrical charge through a material can orig-
inate from four basic processes: thermal gen-
eration, photogeneration, injection, or pho-
toinjection from electrodes. In general,
polymers can be p-type or n-type transport-
ing materials. Practically all photoconductive
polymers are p type, and only holes are mo-
bile. Although some potentially electron-
transporting polymers have been synthesized
[e.g., polymers with acceptor-type trinitroflu-
orenone (TNF) pendant groups], they exhibit
poor mechanical properties because of low
molecular weight, and they have insufficient
electron mobility. Polymeric systems with
mobile electrons or bipolar systems can be
obtained by doping of the hole-transporting
or inert polymers with low-molecular-weight
acceptors, for example PVK-TNF.
In polymers, the thermal generation is
usually negligible, even in undoped polymers
with polyconjugated multiple bonds, because
of the large band gap. Photogeneration is in-
trinsic, when it occurs by photoexcitation of
the polymer molecule, or extrinsic, when the
light is absorbed by pigments or dyes dis-
persed in a polymer matrix and the genera-
tion process occurs within the dopant mole-
cules. Intrinsic photogeneration is confined
to the UV range (i.e., the range of the poly-
mer absorption spectrum), but its efficiency
can be increased and action spectrum shifted
into the visible range by doping with a suit-
able electron acceptor that forms a charge
transfer complex with, usually donorlike,
polymer.
It is generally accepted that the charge-
carrier photogeneration occurring within a
polymer is a multistep process that can be
divided into two main phases, as shown in
the scheme in Fig. 2 (Okamoto and Itaya,
1984). The first phase, the efficiency of
which is field independent, is the absorption
of a quantum by a molecule or a CT com-
plex and its photoionization (most probably
via unrelaxed exciplex states), followed by
formation of the hole-electron pair, which is
separated at some characteristic thermaliza-
tion length. The efficiency of this first phase
is called the primary quantum yield. The sec-
hv
'D + A
[•D. ..A] Encounter complex
A"] Nonrelaxed exciplex
1
\
D+ .. .A~] Bound hole-electron pair
ro —
Electric Separation Geminate
field to free carriers recombination
a + - H b" [D + A ~] Relaxed exciplex
-hu.A
D+ A
FIG. 2. A scheme of photogeneration of charge car-
riers; D, electron donor; A, electron acceptor (Oka-
moto and Itaya, 1984).
 Polymers, Electrical and Electronic Properties
ond phase is further separation of the carri-
ers, which contribute to the current if they
avoid geminate recombination. This phase is
field dependent, its mechanism is similar to
the process of ion-pair dissociation in weak
electrolytes (Brownian motion in the super-
imposed field of the gemine carrier and ex-
ternal field), and it has been successfully de-
scribed by the Onsager theory.
3.1.2 Charge Transport In molecular,
disordered solids, the overlapping of elec-
tronic orbitals is small, any excess charge is
localized on the host molecule, and the exis-
tence of extended states ranging over more
than several molecules is unlikely; thus, band
theory cannot be applied.
In intrinsically photoconducting polymers
and in molecularly doped polymers without
polyconjugated multiple bonds, the charge-
carrier transport occurs via thermally acti-
vated hopping (Bottger and Bryksin, 1986)
among the chromophore groups or among
the dopant molecules. Because all these ma-
terials are mostly amorphous and the hop-
ping sites are randomly oriented in space
and randomly distributed, there is a fluctua-
tion of wave-function overlap between adja-
cent hopping sites, so-called off-diagonal dis-
order. The variations of the polarization
energy due to positional disorder result also
in the fluctuation of site energies, so-called
diagonal disorder. Consequently, there is a
very broad distribution of hopping probabil-
ities. This is a reason for the relatively low
mobility of charge carriers, in most cases
much lower than 10~3 cmW s.
If one considers a narrow sheet of charge
carriers injected into the sample (like in the
time-of-flight measurements; see Sec. 3.2),
the distribution of hopping times will cause
a spreading of the carrier packet as it prop-
agates through the sample. For a Gaussian
distribution of the site energies, the carriers
will reach the substrate electrode as a coher-
ent packet (although of increasing width)
drifting with time-independent average veloc-
ity; the transient time is well defined, and
the transport is termed nondispersive.
In many polymer photoconductors, espe-
cially at low temperatures, the motion of
charge carriers is an incoherent process in-
volving time-dependent hopping frequency,
and the transport is dispersive. The current
pulse in the time-of-flight experiment is a
513
featureless trace because of the very wide,
non-Gaussian spread of the carrier packet. In
the pioneering work of Sher and Montroll
(1975), the dispersive transport of carriers
hopping among a random set of localized
isoenergetic sites was described by means of
the formalism of continuous-time random
walk, with the assumption of off-diagonal
(positional) disorder only. At present, it is
commonly accepted that the dispersion is
mainly due to diagonal disorder. The width
of the Gaussian distribution of site energies
determines the possibility that carriers attain
dynamic equilibrium during a transit, the
criterion for nondispersive transport (Bass-
ler, 1984). Monte Carlo simulations for a sys-
tem with a Gaussian energy distribution in
addition to off-diagonal disorder predict all
the characteristics of the dispersive transport
in polymers: Poole-Frenkiel type field de-
pendence of the carrier mobility, tempera-
ture dependence of the mobility, narrowing
of the dispersion with increasing tempera-
ture leading to a transition from dispersive
to nondispersive transport at high tempera-
tures, and changes of the transport proper-
ties at the polymer glass transition tempera-
ture (Pautmeier et al, 1990). Alternative
models based on conventional multiple-trap-
ping transport predict also non-Gaussian dis-
persive transport, but they are not applicable
to polymers with hopping transport.
In spite of the very high concentration of
impurities and defects present in polymers,
trapping phenomena usually do not affect
significantly the hopping transport in photo-
conducting polymers (Scott et al, 1993). This
is because the hole transport sites (chromo-
phore groups or additives) have very low ox-
idation potential, and it is unlikely that other
molecules present in the material (e.g., im-
purities) can have still lower oxidation po-
tential, unless proper molecules are inten-
tionally chosen and introduced. In terms of
solid-state chemistry, the hole hopping trans-
port can be described as a reversible oxida-
tion-reduction process; the localized hole
forms a cation radical and can accept an
electron from the next neutral molecule, and
so the hole ("cation radical") performs a ran-
dom walk generally in the direction of the
applied electric field (Mort and Pfister, 1982).
In polymers with o--bonded arrays of sili-
con or germanium atoms in the backbone,
the hole transport occurs by hopping via the
 514 Polymers, Electrical and Electronic Properties
cr-derived states rather than via side-chain
groups (Stolka et ah, 1990). As a result of
considerable delocalization of charge carriers
along the chain, the transport is nondisper-
sive, and the mobility is around 10~4 cm2/
Vs.
3.1.3 Charge Recombination Most of
the photogenerated charge carriers undergo
geminate recombination, and only a small
part of the carriers are separated from their
initial counter charges. Then, because in
semiconducting polymers usually only posi-
tive charges are mobile, recombination of
carriers occurs when a moving hole meets
the immobile electron. The electrons are lo-
calized at the photogeneration groups or are
trapped in their vicinity. The recombination
rate constants in polymers are relatively
high, comparable to those found in semicon-
ductors. For materials where both holes and
electrons are mobile, like in PVK heavily
doped with TNF, the rate of recombination
depends on the combination of carrier mo-
bilities fi and concentration n and can be ex-
pressed by the equation
dn Aire
/jun2,
dt
where e is the dielectric permittivity (Pear-
son and Stolka, 1981).
3.2 Experimental Techniques
The photoconductivity upon steady illu-
mination is given by the equation
where g0 is the number of photogenerated
carriers in unit volume per second, r is the
lifetime of carriers before recombination, e is
the electron charge, and fi is the drift mobil-
ity.
Often-used steady-state photoconductivity
measurements with sandwich-type samples
provided with semitransparent electrodes
yield information about the photoconductiv-
ity of the investigated material only if the
electrode-sample contacts are Ohmic, which
is not easily achievable. The measured pho-
tocurrent density is equal to
jph = <JdE + aphE = (TdE + {(j>IJd)reixE,
where ad is the dark conductivity, E is the
electric field, <>
/ is the quantum efficiency of
photogeneration, d is the sample thickness,
and 70 is the total absorbed light (photon/cm2
s). The dark current can be measured and
subtracted, but the fundamental photocon-
ductivity parameters, 0, r, and \x (in the sec-
ond term), cannot be separated. For this rea-
son, the steady-state measurements can
provide only a comparison of photoconduc-
tivity and dark conductivity and the relative
action spectra of photoconductivity.
Quantum efficiency and mobility are de-
termined from dynamic measurements by
means of time-of-flight (TOF) technique or
xerographic discharge (Mort and Pfister,
1982). The TOF method consists of generat-
ing a narrow sheet of charges by the use of a
short pulse of strongly absorbed light or of
an electron beam, and monitoring the cur-
rent when the carriers drift across the sam-
ple in order to determine the transit time rT
and then the mobility: JJL = (dlrT){\IE). For
nondispersive transport, the transit time is
indicated by a sharp drop of the current; for
dispersive transport, the current monotoni-
cally decreases, and only in the log-log plot
(18) of the current vs time can some characteris-
tic point (kink) be distinguished, which is in-
terpreted as the transit time.
In the xerographic discharge technique,
the sample is provided only with a bottom
electrode. The free surface of the sample is
charged to a high potential Vo by corona dis-
charge, and then the decay of the surface po-
tential, V(t), is monitored after a short pulse
of light. If the total charge generated in the
(19) sample is small, as compared with the co-
rona-deposited charge, CV0 (where C is the
capacitance of the sample), and if the pho-
toinjection from the deposited charge layer
and the charge trapping can be neglected,
the quantum efficiency is given by
(21)
dt
When the xerographic discharge experi-
ments are performed under space-charge-
limited conditions, which means when the
intensity of the light source is high enough
to generate in a short time a charge compa-
rable to CV0, the initial potential decay rate
(20) is related to the transit time by the equation
 Polymers, Electrical and Electronic Properties
dV
(22)
dt
Consequently, the mobility can be deter-
mined from the initial potential decay rate.
This method of determination of /JL is re-
commended for materials with dispersive
transport, where the TOF technique yields
ambiguous results. Space-charge-limited
conditions can be easily fulfilled in a two-
layer configuration of the sample, when the
investigated transport polymer film is pro-
vided with highly effective thin photogenera-
tion layer, e.g., evaporated a-Se.
Trapping and recombination phenomena
can be investigated using thermally stimu-
lated current (TSC) and thermoluminescence
(TL) techniques (Braunlich, 1979). TSC con-
sists in measuring a current flowing as a re-
sult of thermal release of trapped carriers in
the sample heated with a constant heating
rate; TL consists in measuring the light emit-
ted through recombination of the detrapped
carriers. The traps in the sample are popu-
lated at low temperature by photoexcitation,
y irradiation, or electron-beam or corona
discharge. The obtained TSC and TL spectra
exhibit maxima that can be attributed to the
detrapping from trap levels. The analysis of
the shapes, positions, and intensities of the
maxima and their dependence on experimen-
tal conditions (mainly on heating rate and
on electric field) yields information on the
trapping parameters and mechanism. Inter-
pretation of the TSC maxima can be ambig-
uous for low-mobility materials when the
shape and position of the maximum can be
controlled by the transport process (the so-
called transport peak); for these reasons, si-
multaneous measurements of TSC and TL
are recommended.
3.3 Materials
Photoconductivity is exhibited by many
different types of polymers prepared by vari-
ous methods of synthesis, like free-radical
polymerization, ionic polymerization, poly-
condensation, ring-opening polymerization,
Ziegler-Natta polymerization, electrochemi-
cal polymerization, and photopolymeriza-
tion. Taking into account their structure,
they can be divided into several main
groups.
515
3.3.1 Polymers with Polyconjugated
Multiple Bonds Polymers with unsatu-
rated backbone show low-energy optical
transitions. The most studied polymer with
conjugated 7r-electron backbone is polyacet-
ylene (CH)^ (PA), which has two possible
forms: cis and trans (Fig. 3; see also Sees.
4.1.1, 4.1.2, and 4.3.2). Pristine cis-?A is al-
most an insulator, with conductivity below
10~10 S/cm; it displays photoconductivity
only in the UV range. Trans-?A has conduc-
tivity around 10~6 S/cm, is photoconducting,
and shows the transport properties of a
semiconductor. A large positive value of the
thermopower coefficient indicates p-type
conduction.
Perfectly conjugated polymer single crys-
tals of macroscopic dimensions (even several
centimeters) can be prepared by solid-state
polymerization of diacetylene monomers. Be-
cause of the deficiency of free charge carri-
ers, polydiacetylenes are essentially insula-
tors, with conductivities of the order of 10"10
S/cm or less, but they show relatively high
photoconductivity in the visible range. Poly-
diacetylene single crystals exhibit interesting
nonlinear optical properties with high third-
order susceptibility.
Many other polymers with polyconjugated
multiple bonds show photoconductivity, even
in the visible and in the near-IR ranges, but
their dark conductivities are usually also
high (Stolka, 1988).
(a) H H H
I I
H H H
H H H H H
/
= c
\ \
H H H
FIG. 3. Schematic structures of polyacetylene in two
possible forms: (a) trans, (b) cis.
516 Polymers, Electrical and Electronic Properties
3.3.2 Polymers with Aromatic Amine
Groups Many polymers containing an
aromatic amine group show substantial pho-
toconductivity, among them the most impor-
tant photoconducting polymer, poly(N-vinyl-
carbazole) (PVK), this being the first
practically applied and commercialized or-
ganic photoconductor (Mort and Pfister,
1982).
Pristine, purified PVK shows photocon-
ductivity only in the UV range; the photogen-
eration spectrum has several steps in coinci-
dence with the PVK absorption spectrum,
which means with the excitation into subse-
quent higher singlet states. The primary
quantum yield for PVK is around 0.14, and
the thermalization length is in the range 22.5
A (for excitation into the first singlet state) to
30 A (for excitation into the third singlet
state). The absolute quantum yield for pho-
togeneration of holes is around 10~3 at a
field of 105 V/cm and approaches the value
0.05 at 106 V/cm. The hole mobility at a field
of 105 V/cm is around 10"6 cmW s.
PVK has been doped with numerous CT
complexes forming additives like tetracyano-
ethylene, tetracyanoquinedimethane, chlor-
anil, or Lewis acids; the most intensively in-
vestigated and practically used is the system
PVK-TNF. It is photoconducting also in visi-
ble light because the CT band of this com-
plex extends through the visible range. For
the system with 1:1 molar ratio TNF to PVK
monomer, the primary quantum yield in the
visible range (A = 550 nm) is 0.23, the ther-
malization length is 35 A, and the absolute
quantum yield is around 10~2 at 105 V/cm
and approaches 10"1 at 106 V/cm, being
the same for holes and electrons. The PVK-
TNF system is bipolar; with increasing TNF
concentration, the hole mobility decreases
below 10~8 cmW s for the 1:1 molar ratio,
while the electron mobility increases up to
around 10"6 cmW s at the field 5 X 105 V/
cm.
PVK has rather unfavorable mechanical
properties. Its brittleness creates considera-
ble technical problems, especially if it is to
be used in the form of thin film. For this
reason, several attempts have been made to
obtain polymers with carbazole, or other ar-
omatic amine pendant groups, having better
application properties: various vinyl back-
bone polymers, polyacrylates, polymethaciy-
lates, and copolymers of vinyl carbazole with
different comonomers (including acceptor-
type comonomers). Some of these polymers
were sensitized with TNF and other electron
acceptors. In a few cases, their mechanical
and film-forming properties are improved,
but usually at the expense of the photocon-
ducting properties. Even if some of these
materials exhibit higher hole mobility than
PVK, their photogeneration efficiencies are
lower.
3.3.3 Polymers with Large Polynuclear
Aromatic Groups A variety of polymers
with pendant-condensed aromatic groups
have been synthesized and their photocon-
ducting properties have been investigated
(Stolka and Pai, 1978). Polymers with naph-
thalene, pyrene, chiysene, or acridine as pen-
dant groups show usually low photoconduc-
tivity, constrained to the UV range only. In
some cases (for example in polymers with
anthracene groups, like polyvinylphenylan-
thracene), their photoconductivity is compa-
rable to that of PVK, but because of oxida-
tive instability, poor mechanical properties
(brittleness), and difficult synthesis, these
polymers have no practical importance.
3.3.4 Inorganic Semiconducting Poly-
mers Polymers with silicon and germa-
nium backbones are insulators in the pure
state, but the band gap in some cases is only
around 4 eV, i.e., two times smaller than in
saturated polymers with a carbon backbone.
In some sense, they resemble polyconjugated
polymers; the absorption spectra display a
red shift effect with increasing molecular
weight, typical for polymers with electrons
delocalized along the chain. The conductivity
of polysilane derivatives can be considerably
enhanced, up to around 0.1 S/cm, by suitable
doping with a strong electron acceptor, e.g.,
polysilastyrene becomes a semiconductor
when doped with arsenic pentafluoride
(Miller and Michl, 1989).
It has been found recently that many
polysilane derivatives are excellent photocon-
ductors. In the pure state, they are photo-
conducting only in the UV range; long chain
segments of trans conformation are the low-
est-energy chromophores. These polymers
can be made photoconducting in the visible
range by suitable doping, for example with
TNF. In poly(methylphenylsilane) (PMPS),
the quantum yield of hole generation is elec-
 Polymers, Electrical and Electronic Properties
trie-field dependent, and for high fields, it
approaches 1%.
Similarly as in many amorphous organic
and inorganic solids, charge transport occurs
via thermally assisted hopping and is con-
trolled by the distribution of the energies of
the transport sites and their average separa-
tion. Insensitivity of the hole mobility to the
nature of side groups shows that the hop-
ping sites are associated with a electronic
states of the backbone. Because of delocali-
zation of the charge along the chain, in poly-
silanes the transport sites are not localized
states (like carbazole pendant groups in
PVK) but domains of trans conformers sepa-
rated by conformation irregularities.
In silicon- and germanium-backbone lin-
ear polymers, holes are the majority carriers,
transport is nondispersive, and mobility
around 10~4 cmW s is usually reported at
room temperature. Carrier mobility is tem-
perature and field dependent and sensitive to
the glass transition temperature Tg. Below Tg,
the mobility exhibits a single activation en-
ergy over a broad temperature range; for
PMPS, it is 0.24 eV at 2.5 X 105 V/cm and
decreases below 0.2 eV at 6 X 105 V/cm. At
high fields and temperatures, the hole mobil-
ity may approach 10~2 cmW s. The activa-
tion energy of mobility decreases strongly
above Tg, and in some cases, the mobility be-
comes practically temperature independent
(e.g., for polysilane derivatives with aliphatic
side groups). The field dependence of the
mobility and of its activation energy in these
polymers indicates the Poole-Frenkel effect
of barrier lowering by a factor /3PF£05; how-
ever, the experimentally obtained value of
j8PF is about two times lower than the theo-
retical Poole-Frenkel coefficient /3PF = (e3/
7ree0)05 (Stolka et at, 1990).
In PMPS, the trap-free, nondispersive
transport results in a nearly rectangular TOF
pulse, with hole mobility independent of
sample thickness. The hole mobility can be
reduced by doping with molecules with
lower oxidation potential, creating traps for
holes and resulting in trap-controlled hop-
ping. However, when the energy level of the
dopant site is close to the energy level of the
transport site in the polymer, dopant mole-
cules are transport active, and heavy doping
may result in a substantial increase of the
mobility. In PMPS doped with Af,Af'-bis(4-
methylphenyD-MAT -bis(4-ethylphenyl)- [1,1' -
517
(3,3'-dimethyl)biphenyl]-4,4'-diamine, the
hole mobility at E = 2.5 X 105V/cm in-
creases by ca. three orders of magnitude up
to the unusually high value 10"1 cmW s
(Stolka and Abkowitz, 1993).
3.3.5 Molecularly Doped Polymers
The molecularly doped polymers have gained
a lot of interest as photoconducting materi-
als for two reasons. First, in these materials,
one can combine good mechanical properties
of a chosen polymer matrix with appropriate
electronic properties of dopant molecules
(Ulanski et al, 1981). In particular, it is pos-
sible to introduce different types of dopants,
e.g., dye molecules in order to extend the
photoconductivity action spectrum (sensiti-
zation) and transport molecules to enhance
the carrier mobility. However, to gain high
mobility, up to 50 wt % of dopant (donor or
acceptor type) is added to the polymer (Scott
et al, 1993), and so the mechanical proper-
ties of the polymer matrix are changed to a
great extent.
Second, solid solutions of various dopants
in an inactive polymer matrix are model sys-
tems for the investigation of charge genera-
tion and transport in photoconducting poly-
mers. Investigations of polycarbonate (PC)
doped molecularly with N-isopropylocarba-
zole (NIPC) have allowed for direct determi-
nation of the influence of concentration of
generation and transport sites (i.e., carbazole
groups) on the basic photoconduction pa-
rameters in PVK. It was shown that the vinyl
chain of PVK plays no active role in the pho-
toconduction process. Photogeneration effi-
ciency increases with increasing NIPC con-
centration because of an increase of primary
quantum yield. This results from an increase
of the thermalization length due to higher
carrier mobility at higher concentration of
hopping sites (i.e., dopant molecules). The
hole mobility exhibits exponential depend-
ence on the average separation between
NIPC molecules. The mobility increases with
temperature, and the determined activation
energy rises with decreasing dopant content;
both the mobility and its activation energy
are field dependent. An addition to the PC-
NIPC system of a second donor-type dopant,
triphenyl amine (TPA), with ionization po-
tential lower than NIPC introduces effective
traps for holes, resulting in trap-controlled
hopping. The hole mobility first decreases
518 Polymers, Electrical and Electronic Properties
with increasing TPA concentration. However,
when the decreasing separation between the
TPA molecules allows overlapping of elec-
tronic orbitals, another effective channel for
hole hopping among TPA molecules is
formed, and the hole mobility starts to in-
crease again (Mort and Pfister, 1982).
3.4 Applications
Photoconducting polymers were the first
electroactive polymers, and in general the
first electroactive organic materials, to be
practically used on a commercial scale.
Polymer photoconductors, first of all the
PVK-TNF system, compete successfully with
inorganic materials in application in electro-
photography as a result of sufficiently good
electrical properties (almost trap-free trans-
port) and the ease of production of large-
area, homogeneous films at low price. In
practical electrophotographic devices, the or-
ganic photoconductors are often used in the
two-layer configuration, with separated pho-
togeneration layer and transporting layer. In
such a configuration, the problem of remov-
ing immobile electrons from the bulk of p-
type photoconductors is avoided (this prob-
lem does not exist in bipolar PVK-TNF).
Large-area solar cells are another poten-
tial and much-wanted application of photo-
conducting polymers. Such devices have not
yet been realized because of low conversion
efficiency. The low costs of producing are
frustrated by poor stability against solar UV
light (Stolka, 1988).
4. CONDUCTING POLYMERS
Polymers with extended 7r-electron sys-
tems in the backbone exhibit electronic
properties very different from common poly-
mers; they have low ionization potentials
and high electron affinities. As a result of
these properties, they can be easily reversibly
oxidized or reduced by suitable dopants,
and, when doped, they can show very high
conductivity, in the best cases comparable
with the conductivity of metals. For this rea-
son, they are called synthetic metals.
The conducting polymers belong to the
class of synthetic metals together with other
molecular conductors: charge-transfer com-
plexes made of segregated stacks of acceptor
and donor molecules, like tetrathiafulvalene-
tetracyanoquinodimethane, and the so-called
Krogman salts containing stacks of PtX4 or
lrX4 (X = CN or C2O4), like potassium cy-
anoplatinate oxidized by bromine. All these
systems have in common the quasi 1-D char-
acter of the charge-carrier transport, because
the charge delocalization is confined to quasi
1-D structures: the polymer chains or the
stacks of molecules (Ku and Liepins, 1987).
4.1 Theoretical Aspects
4.1.1 Basic Concepts Conducting poly-
mers are in general disordered systems, and
band theory elaborated for crystalline semi-
conductors should not be directly used; how-
ever, periodicity of the 7r-conjugated back-
bone makes possible a description of
electronic structure in terms of energy
bands. An idealized picture of polyacetylene
shows a planar trans-(CR)x chain with all the
bonds of equal length. Each carbon atom in
the chain has in an addition to three a elec-
trons also one IT electron. Molecular-orbital
theory predicts that with increasing chain
length, the energy gap between valence and
conduction bands vanishes, and for high mo-
lecular weight, the p orbitals of the TT elec-
trons would form a half-filled energy band
with the Fermi level in the middle. The poly-
mer should be an intrinsic metal. However,
the linear-combination-of-atomic-orbitals the-
ory shows that the polyene chain is stable
only if it undergoes dimerization, i.e., if al-
ternation of bond lengths occurs. In general,
a one-dimensional metal cannot be stable,
because all linear chains of atoms undergo
distortion and lower their symmetry leading
to the creation of collective electronic
ground states of reduced symmetry called
Fermi-surface instabilities (charge-density
waves, spin-density waves, or bond-order-al-
ternation waves).
The self-induced metal-insulator transi-
tion, called Peierls transition, is in trans-
(CHX a consequence of the dimerization ac-
companied by a distortion of the electronic
charge density creating a band gap of
around 1.4 eV. Perfectly dimerized trans-
(CH)X has two equivalent structures, which
differ only in the sequence of bond alterna-
tions: single/double or double/single. If both
structures are present on one chain, they are
 Polymers, Electrical and Electronic Properties
separated by a topological defect. This radi-
cal defect can move by bond flipping along
the chain, not changing its energy because
these two structures have the same energy
(the system is degenerate in energy). At the
defect, the 7r-wave functions change phases,
and their amplitudes approach zero; the rad-
ical defect is described as a neutral soliton. A
solitary wave travels without changing shape
or speed on collision with another soliton. A
soliton is not a point defect, but it extends
over about 15 carbon-carbon bonds. The
neutral soliton creates a new state in the
band gap; it is a species without charge, but
it has spin \ and can be detected by EPR.
The charged soliton is an anion or cation de-
fect, which carries charge but no spin (Lu,
1988).
Spinless transport was observed in PA but
also in other polyconjugated polymers that
are not degenerate in energy. In such poly-
mers, like polypyrrole, polythiophene, poly(p-
phenylene), or poly(p-phenylene sulfide), the
two structures of different sequences of bond
alternation have different energies: the aro-
matic structure has lower energy than the
quinoid one. Therefore a mobile soliton can-
not exist because it would migrate immedi-
ately to reduce the length of the quinoid
structure. In these polymer chains, in order
to restore the initial aromatic structure on
the other side of the defect, the defect has to
contain both a soliton and an antisoliton.
Such a pair constitutes a polaron, which is a
species carrying a charge and a spin \. In
other words, the polaron is a radical ion
(cation or anion) associated with distortion
of the lattice around the charge. If two such
coupled electron-photon states are present
on the same chain, they react exothermically
and form a bipolaron, a spinless double-
charge carrier. The direct evidence of for-
mation of solitons, polarons, and bipolarons
comes from optical spectroscopy. Photoexci-
tation of an electron-hole pair, followed by
charge-pair separation, results in the forma-
tion of a localized defect characteristic of the
given polymer: £ran5-polyacetylene shows a
photoinduced absorption band associated
with the soliton level, and other polyconju-
gated polymers, able to form bipolaron
states, show two photoinduced absorption
bands corresponding to the optical transi-
tions between the band edges and the two
519
polaron levels in the gap (Frommer and
Chance, 1988).
4.1.2 Doping and Charge Transport
The fundamental effect of doping in terms of
semiconductor physics is to generate free
carriers, and only in this respect can the
term "doping" be used for the description of
the processes of oxidation or reduction of
the polyconjugated polymers by electron ac-
ceptors or donors. The mechanism of doping
of conducting polymers is, however, very dif-
ferent from that for crystalline semiconduc-
tors. One of the main sources of this dif-
ference is a large deformability of the
macromolecules. The dopant molecules are
introduced between polymer chains, so that
morphological changes occur on doping. Be-
cause the dopant molecules are not built into
the rigid crystal lattice, they can be removed,
and so the doping is reversible. The concen-
tration of dopants in highly conducting poly-
mers may approach 50 wt %, and so the
terms "polymer salt" or "charge-transfer
complex" are often preferred over the term
"doped polymer" (Wegner, 1981).
Because of the charge transfer between
the polymer chain and the dopant, the poly-
mer chain is electrically charged; injected
charges distort the charge-density waves on
the chain and through electron-phonon cou-
pling can alter the macromolecular geome-
try. In consequence, a defect is formed on
the chain, and a new level is created in the
band gap. The type of defect formed depends
on the structure and state of the polymer. In
the case of trans-(CH)x, the interaction of the
dopant with an existing neutral soliton yields
a positive soliton for acceptor dopant (p dop-
ing) or a negative soliton for donor dopant
(n doping). Direct oxidation (reduction) of
trans-(CH)x by an acceptor (a donor) dopant
yields a positive (negative) polaron, introduc-
ing two new levels in the band gap. At low
doping and at low temperatures, the charged
defect on the chain is localized by the Cou-
lombic binding energy to the ionized dopant.
With increasing doping, on some chains two
polarons will be formed; on collision, they
will convert into two uncorrelated charged
solitons. The conductivity increases accom-
panied by a decrease of EPR signal intensity.
In bipolaron-supporting polymers, introduc-
tion of the dopant yields also an ionized
polymer chain, and polarons (radical ions)
520 Polymers, Electrical and Electronic Properties
are formed. With increasing concentration,
the polarons interact, eliminating radicals
and producing correlated pairs of ions, i.e.,
bipolarons. The spinless conductivity in
these polymers is attributed to bipolaron mi-
gration (Frommer and Chance, 1988).
The doping of polyconjugated polymers
results in dramatic changes in absorption
spectra. In trans-(CH)x, upon oxidation by
electrochemical doping, a new absorption
band emerges associated with the polaron
(radical cation); with increasing dopant con-
centration, this band evolves to the absorp-
tion band of the charged soliton (cation). In
bipolaron-supporting polymers, the polaron
absorption bands emerging at low dopant
concentration convert to bipolaron absorp-
tion at high doping. The growth of the new
absorption bands with increasing dopant
concentration is accompanied by a decrease
of the absorption band of the neutral poly-
mer.
An unusual property of conducting poly-
mers—spinless conductivity—was observed
for the first time for trans-(CH)x with low
dopant concentration, and it was related to
charge transport by charged soli tons. How-
ever, an isolated charged soliton cannot
jump to the next, defect-free chain because it
would require high energy to rearrange the
bond alternation. According to the Kivelson
model (1981), such a jump is possible if a
neutral soliton is present on the next chain.
Because the neutral soliton is more readily
ionized than the defect-free chain, it is un-
likely that enough neutral solitons would re-
main to support the increasing conductivity
with increasing doping. Therefore, Kivelson's
model cannot explain the spinless conductiv-
ity in trans-(CR)x at higher dopant concen-
tration; evidently, it cannot explain also the
spinless conductivity in other polyconjugated
polymers that are not soliton supporting. A
more general model of spinless transport as-
sumes that it is executed by bipolarons [in
trans-(CR)x, the bipolaron would be formed
by a pair of uncorrelated charged solitons],
which can jump between chains with rela-
tively low activation energy (Frommer and
Chance, 1988). However, also this model
lacks generality to the polymers with the
highest doping level, where the conductivity
can be described by conventional electronic
mechanisms involving hopping or tunneling
(Schimmel et al, 1990).
The macroscopic conductivity of a con-
ducting polymer is a function of intrachain
conductivity and interchain conductivity.
Each of these components is a function of
many factors. The intrachain conductivity
depends on conjugation length, density, and
extent of defects, and interactions with dop-
ants. The interchain conductivity in a gen-
eral sense comprises not only the charge
transfer between adjacent chains, but also
the transport between highly conducting
regions and between morphological entities,
like fibers in Shirakawa-type polyacetylene
(Ehinger and Roth, 1985). Therefore, the in-
terchain conductivity depends on various
morphological factors: chain packing and the
orientation of the chains relative to each
other, homogeneity of doping, crystallinity, if
any, and size of crystallites, and morphology
on the supramolecular scale (size and sepa-
ration of fibers, grains, etc.) (Wegner and
Ruhe, 1989). The models describing the
mechanism of conductivity in doped poly-
conjugated polymers have to take into con-
sideration both the characteristics of low-di-
mensional systems, e.g., specific charge
carriers, like solitons and bipolarons, and the
characteristics of polymeric materials, e.g.,
disorder and heterogeneity at various scales
of magnitude, molecular relaxations and
phase transitions, possible fractal structures,
and percolation phenomena.
4.2 Experimental Techniques
The simple two-electrode method for
measurements of the dc conductivity in con-
ducting polymers may yield erroneous re-
sults because of unknown contact resistance.
Also the temperature dependences of the
conductivity and current-voltage characteris-
tics can be affected by contact effects. For
these reasons, a collinear four-probe method
is preferably used. The method consists in
measuring the voltage drop V between two
inner electrodes caused by a known current /
flowing between two external electrodes; the
conductivity of the investigated material is
given by the relation
a = (I/V)(l/s), (23)
where / is the distance between the inner
(voltage) electrodes and s is the sample
cross-sectional area.
 Polymers, Electrical and Electronic Properties 521
In highly conducting materials, Joule's
heat may disturb the measurements of the
current-voltage characteristics at higher
fields and currents. Also, the conductivity
measurements at helium temperatures can
be distorted by Joule's heat because of very
small heat capacitance at low temperatures.
Heating effects can be minimized by use of
the pulse technique, consisting in measuring
the voltage signals occurring at the inner
electrodes caused by short, rectangular
pulses of the current.
The conductivity of samples of irregular
shapes (but flat and uniform in thickness)
can be measured by a modified four-probe
method, the van der Pauw technique, where
small, pointlike electrodes are placed arbi-
trarily at the periphery of the samples. Two
measurements are performed with com-
muted current and voltage electrode connec-
tions; for calculation of the conductivity
value, a correction factor, numerically calcu-
lated and published by van der Pauw, is
needed. Another modification of the four-
probe method, the Montgomery method, is
similar to the van der Pauw method but is
applied to anisotropic materials; this method
allows one to determine components of the
resistivity tensor, i.e., the anisotropy ratio.
ac conductivity measurements have
proved to be a very useful tool in investiga-
tions of the mechanism of charge transport
in conducting polymers. The frequency de-
pendences of conductivity are, together with
the temperature dependences of conductiv-
ity, characteristic of various charge transport
mechanisms. Most conducting polymers are
inhomogeneous materials, with high con-
ducting regions separated by barriers and
low-conductivity regions; these barriers dom-
inate the dc conductivity measurements. The
ac conductivity measured at sufficiently high
frequencies may give an insight into the con-
duction mechanism of highly conducting is-
lands.
In the frequency range up to 10 MHz,
conventional bridge techniques and auto-
matic impedance analyzers are used. In the
GHz microwave range, the method of the
perturbation of a resonance-cavity Q is ap-
plied. This method consists in measurement
of the frequency shift and of the broadening
of the resonance line caused by introduction
of the sample into the resonance cavity. It al-
lows for calculation of the complex dielectric
constant; the real part is related to dielectric
properties of the material, and the imaginary
part is related to ac conductivity. This
method can be applied for samples smaller
than the wavelength and the skin depth.
Thermopower measurements are widely
used for characterization of conducting poly-
mers, because the thermopower effect is not
affected by the charge transport, and so it is
less sensitive to inhomogeneities of conduct-
ing polymers than conductivity measure-
ments. The analysis of the thermopower
data, including the temperature dependence
of the Seebeck coefficient, yields information
concerning the sign of majority charge car-
riers, their density and mobility, and the
conduction mechanism. In particular, it al-
lows one to distinguish between the metallic
and semiconducting types of conductivity
(Pukacki, 1993).
4.3 Materials
4.3.1 Synthesis The number of con-
ducting polymers and synthesis techniques is
large and fast growing. One can distinguish
four major types of synthesis yielding poly-
mers with conjugated backbone: Ziegler-
Natta polymerization, electrochemical syn-
thesis, polycondensation, and pyrolysis (Ku
and Liepins, 1987).
The most frequently applied Ziegler-Natta
polymerization is the so-called Shirakawa
synthesis of polyacetylene (PA) using various
modifications of catalyst [Ti(O-n-C4H9)4-
A1(C2H5)3] system. When CH^CH is intro-
duced over the catalyst solution under ap-
propriate conditions, a (CR)X film is formed
on the surface. The choice of the kind and
concentration of the catalyst, and of the tem-
perature (typically in the range 180-450 K),
are critical. At low temperatures, the cis con-
formation dominates, yielding a reddish ma-
terial; at high temperatures, the bluish trans
conformation prevails.
Typical electrochemical polymerization
may be illustrated by the synthesis of poly-
pyrrole (PPy). A single-compartment electro-
chemical cell with two parallel electrodes
(anode made of platinum) contains an elec-
trolyte solution, for example, tetraethylam-
monium tetrafluoroborate in acetonitrile,
and pyrrole. When a current is passed
through the cell, under galvanostatic control,
522 Polymers, Electrical and Electronic Properties
electropolymerization onto the platinum H
electrode occurs, accompanied by simultane-
ous oxidation. The resulting PPy film, I
"doped" in situ with counterion (BF^ in this C
case), is black and conducting. Other poly- (a)
mers, like polythiophene and its derivatives
and polyaniline, can similarly be electropoly-
I
merized. All these polymers can be readily H
n
reversibly reduced and oxidized electrochem-
ically.
Polycondensation comprises a great num-
ber of polymerization techniques, allowing
the synthesis of various conducting poly-
mers. For example, poly(p-phenylene) can be
prepared by oxidative polymerization of ben- (b)
zene with the aid of the aluminum chloride-
cupric chloride system, or by coupling of di- n
halobenzenes with the aid of copper as the
catalyst (Ullman reaction), but also by con-
densation of aromatic nuclei in the presence
of organometallic reagents or by decomposi-
tion of diazonium salts. Other polymers, like H
poly(j?-phenylene sulfide), polyquinolines,
polyquinoxalines, or pyrrones, have also
been prepared by a variety of polycondensa- (c)
tion techniques. The precursor polymer \ //
routes constitute a special class of polycon- n
densation consisting in synthesis, as an inter-
mediate, of a "prepolymer" that can be proc-
essed (e.g., solution cast as a film and
oriented by stretching) and then converted
by some elimination reaction to the nonpro-
cessable polyconjugated polymer.
Pyrolysis, when applied to some polymers, (d)
like polyacrylonitrile or polyimides, leads to \
elimination of heteroatoms and formation of n
extended aromatic structures for which FIG. 4. Schematic structures of (a) frans-polyacety-
graphite can be a prototype. Charge carriers lene, (b) polyaniline, (c) polypyrrole, (d) polythio-
are delocalized along conjugated ladder-type phene.
chains.

4.3.2 Characteristics Among numer-
ous conducting polymers, three, polyacetyl-
ene, polypyrrole, and polyaniline (Fig. 4),
seem to be the most representative.
Polyacetylene is the simplest polyconju-
gated polymer. It was obtained in a highly
conducting state for the first time by Shira-
kawa et al (1977), and this disclosure marks
the beginning of intensive studies on con-
ducting polymers. Its role as a model, quasi
1-D conductor with soliton-type excitations is
emphasized in Sec. 4.1.
As obtained, PA is usually a mixture of
trans and cis forms; isomerization to the
more stable trans form occurs upon doping
or heating. When doped with alkali metals,
PA shows n-type conductivity and is highly
environmentally unstable. Doping with oxi-
dative agents, like iodine, bromine, SbF6, or
AsF5 results in p-type conductivity. The value
of conductivity of doped PA depends both on
the synthesis method and on the doping and
may reach 105 S/cm (Naarmann and Theo-
philou, 1987); however, typically it ranges
from 102 to 103 S/cm. The differences in con-
ductivity arise from differences in morphol-
ogy, influencing the hopping conductivity be-
tween the polyacetylene chains, and from
 Polymers, Electrical and Electronic Properties
differences in conjugation length, influencing
the charge transport along the PA chain.
Only the so-called "high-cr" PA, obtained
by the Naarmann method, stretched, and
highly doped, shows metal-like temperature
dependence of conductivity at high tempera-
tures, and it remains high also in the zero-
temperature limit. The thermopower of
"high-cr" PA is linearly proportional to
temperature, as for the ideal metallic diffu-
sion, indicating that it is dominated by quasi
1-D metallic conduction in highly conducting
regions. The macroscopic conductivity shows
largely nonmetallic behavior because it in-
volves also charge transport through some
kind of barriers, e.g., sp3 defects.
The conductivity of unstretched PA, for
example, the Shirakawa-type PA consisting
of randomly oriented fibrils of diameter typ-
ically about 200 A, is not only much smaller
but also it tends to zero in the zero-temper-
ature limit, showing the absence of continu-
ous metallic paths. The temperature depend-
ence can be fitted by an equation describing
tunneling between small metallic islands
controlled by the charging energy of the is-
lands:
(24)
where a0 and To are constants (Kaiser, 1993).
Polypyrrole was the first electrochemically
synthesized conducting polymer (Diaz et at,
1979), and it receives considerable interest
due to the combination of relatively high
conductivity with environmental stability,
good mechanical properties, and simplicity
of preparation. The PPy films are obtained
from the monomer directly in the conduct-
ing (oxidized) state because the oxidation po-
tential of PPY polymer is lower than that of
the monomer; doping occurs simultaneously
with the electropolymerization because the
counterions incorporate into the polymer in
order to maintain the electrical neutrality of
the film. The electrolyte consists of a solvent
(usually acetonitrile or water), pyrrole, and
various ions, so that PPY can be easily
doped with a variety of counterions. The
doping (oxidation) is reversible, and PPy can
be electrochemically transformed into neu-
tral, nonconducting form.
The PPy films are amorphous and flexible,
but with very low ultimate elongation. Their
conductivities range in most cases from 1 to
523
100 S/cm, and the temperature dependence
of dc conductivity (adc) is described usually
by the Mott law developed for variable-range
hopping (VRH) (Mott and Davis, 1979) in
disordered materials:
a-dc = cr0exp[-(7y7T-25], (25)
where a0 and To are constants (this equation
holds essentially only in the low-temperature
regime). However, the density of states at the
Fermi level calculated from the fit to the
VRH model is unacceptably higher than that
obtained from independent ESR studies; also
the metal-like behavior of the thermopower
is in contradiction to the VRH model. The
present understanding of the charge-carrier
transport in PPy involves the concept of per-
colation on a fractal network. The measure-
ments of spin dynamics by NMR at various
temperatures indicate an anomalous diffu-
sion in fractal structures of effective dimen-
sion 8 = 1 at low temperatures; the 8 in-
creases with increasing temperature. It is in
agreement with the frequency dependence of
the ac conductivity (aac) following the equa-
tion
crac a o)s (26)
with 5 = 1 — 6/3. At elevated temperatures,
the effective dimension increases, indicating
an increasing role of the interchain hopping.
For three-dimensional hopping at high tem-
peratures, the dc conductivity is given by
crdc = cr0 exp(-2oR) expi-EJkT), (27)
where R is the distance between the neigh-
boring hopping sites, EA is the energy barrier
between the sites, and a is the inverse local-
ization length. The investigations of 3,4-cy-
cloalkyl-substituted PPy fully support this
mechanism, showing direct correlation of R
with the size of the substituent (Ruhe et at,
1989).
Polyaniline (PANI), known for many years
as so-called "aniline black," has attracted
considerable research interest only recently,
when its unusual electrochemical and optical
properties were uncovered (MacDiarmid and
Epstein, 1989). Polyaniline is unique among
conducting polymers because its electronic
properties can be altered both by redox pro-
cesses involving electron transfer and by
524 Polymers, Electrical and Electronic Properties
acid-base chemistry involving protonation.
PANI exists in five forms very different in
electrical and magnetic properties. An insu-
lator-conductor transition, like for other con-
ducting polymers, occurs upon charge-trans-
fer doping, and the conducting PANI form,
emeraldine salt, can be obtained directly
from the leucoemeraldine, which is a large-
band-gap insulator. Additionally, protonation
of the semiconducting PANI form, the emer-
aldine base, yields the emeraldine salt by a
conversion of the quinoid ring to the ben-
zoid structure with an associated spin un-
pairing resulting in conductivity changes by
10 orders of magnitude. The conducting
PANI form, emeraldine salt, shows good
chemical stability. PANI was categorized ini-
tially as an intractable polymer; then several
methods were reported to dissolve this poly-
mer, for example, in strong acids, but an
important advance was the elaboration of
the counterion-induced processability of con-
ducting PANI (see Sec. 4.3.3.).
4.3.3 Processable Conducting Polymers
Practically all initially obtained conducting
polymers were not processable (insoluble
and nonmelting). Insolubility causes serious
problems in characterization of the molecu-
lar structure of conducting polymers since
many investigation techniques can be ap-
plied only for polymer solutions. For com-
mercial applications, it is also necessary to
have materials processable with conventional
plastic technologies.
The insolubility of conjugated polymers in
the conducting state was related to side re-
actions, like cross-linking, caused by free
radicals, radical ions, and ions present in the
doped polymers. For these reasons, the first
approaches to processing conducting poly-
mers were limited to systems obtained via
tractable precursor polymers. Nonconducting
precursors can be dissolved in order to pro-
duce films or fibers; these films or fibers can
be further processed, e.g., oriented by
stretching, and then converted into a con-
ducting, but no longer processable, state.
Highly oriented, anisotropic PA films are ob-
tained in this way, using the so-called Dur-
ham route (Edwards and Feast, 1980).
Further progress in processing of con-
ducting polymers was achieved by solubili-
zation of polyconjugated polymers by substi-
tuting side groups in them. The most known
and investigated are polythiophenes (Fig. 4)
substituted with alkyl chains, like poly(3-oc-
tylthiophene) (Elsenbaumer et at., 1986).
They are soluble in several common organic
solvents and are melt processable at temper-
atures below 200 °C, so that they can be
blended with thermoplastics and elastomers
using standard techniques and then doped in
order to transform the poly(3-alkylthiophene)
into the conducting state.
Counterion-induced processability of con-
ducting PANI was achieved by using a suita-
ble functionalized acid to protonate the base
form of PANI (Cao et at, 1993). Polyaniline
soluble in common organic solvents was syn-
thesized by introducing counterions of large
size, which reduce the interchain interac-
tions. Using sulfonic acids, like dodecylben-
zene sulfonic acid, soluble polyanilines in the
conducting state were obtained. Diesters of
phosphoric acid with alkyl substituents, be-
ing protonating agents for the emeraldine
base, cause also plastification and solubiliza-
tion of the protonated, conducting emeral-
dine salt; conducting films can be obtained
by casting as well as by hot pressing (Laska
et at, 1993). Various other protonic acids
acting as surfactants can be used. The con-
ductivity obtained in PANI films cast from
solutions is quite high, usually in the range
1-400 S/cm.
4.3.4 Heterogeneous Conducting Poly-
mer Composites Making polymer com-
posites is one of the most effective and flexi-
ble methods in getting speciality materials.
Great progress has been made in obtaining
fully organic, heterogeneous, electrically con-
ducting systems (Kryszewski, 1991). One can
distinguish several main groups in terms of
their composition, morphology, and conduc-
tivity.
Conducting colloid composites. Stable col-
loids can be made of different conducting
polymers in aqueous and nonaqueous media
allowing one to cast films or to press pellets
of the dried dispersions. In these systems,
conducting grains are surrounded by an in-
sulating steric stabilizer. Colloidal polypyr-
role (PPy) can be obtained in the form of
spherical particles of diameter in the range
50-500 nm, depending on the preparation
conditions, and yields films with conductivity
in the range 0.1-2 S/cm. In the case of poly-
aniline (PANI) colloids, the grain size can be
 Polymers, Electrical and Electronic Properties
smaller; the cast films of PANI with
poly(vinyl acetate) stabilizer show a conduc-
tivity of ca. 6 S/cm (Aronson et al, 1991).
Blends of processable conducting polymers
with inert polymers. In most of these com-
posites, the conducting phase is made of
poly(3-alkylthiophene)s (P3AT), because
these polymers are soluble in common or-
ganic solvents and also can be melt-blended
without decomposition (Laakso et al, 1989).
Further progress in such composites is ex-
pected as a result of works on the counter-
ion-induced processability of PANI (see Sec.
4.3.3). Very high effectiveness of the con-
ducting phase formation has been achieved
by so-called gel decoration. Conducting gels
of ultrahigh-molecular-weight PE and poly(3-
octylthiophene) (P3OT) were prepared by ge-
lation from solutions in decalin followed by
doping with iodine. No percolation threshold
was found down to 0.0005 vol fraction of
P3OT, and already above 0.02 vol fraction,
the conductivity saturates reaching values in
the range 10~3 to 10~2 S/cm. The conducting
network is formed of conjugated chains ei-
ther absorbed or entangled within the PE
network (Heeger et al, 1991).
Mixtures of insulating polymer matrices
and fillers made of conducting polymers.
From the point of view of preparation, these
mixtures can be most readily related to poly-
mer-carbon-black composites. The particles
of insoluble and/or infusible polymers, e.g.,
PPy or PANI powders, play the role of con-
ducting filler. Utilizing the high thermal sta-
bility of polyaniline tosylate (up to 250 °C for
short intervals in nitrogen) it is possible to
prepare blends with a variety of conventional
thermoplastics (Kulkarni et al., 1991).
Composites obtained by polymerization of
conjugated polymers within an insulating
matrix. Some monomers, like pyrrole, can
penetrate insulating polymeric matrices and,
after subsequent polymerization, form con-
ducting networks. This can be easily done
with porous materials, such as paper, for
which conductivity as high as 10"l S/cm has
been reported. Often used is the electro-
chemical method in which pyrrole penetrates
an insulating substrate on a precoated elec-
trode and electropolymerizes in situ. Con-
ducting fibers have been obtained by chemi-
cal polymerization of pyrrole within the
voids of never-dried poly(p-phenylene tere-
phthalamide) fibers. At 0.57 vol fraction of
525
PPy, the conductivity is ca. 2 S/cm (Rector et
al., 1991). Another route for manufacturing
conducting fibers consists in polymerization
of acetylene in gel fibers containing 2 wt %
of ultrahigh-molecular-weight PE (Chiang et
al, 1988). The fibers comprise up to 80 wt %
of PA, and after doping with iodine, their
conductivity is 1200 S/cm; fibers drawn 2-3
times show after doping a conductivity
around 6000 S/cm.
Conducting polymer salts with polymeric
counterions. Very specific PPy composites
can be produced in one step by electrochem-
ical synthesis using polymeric counterions,
like poly(p-styrenesulfonate) (PSS) or other
anionically derivatized polymers, including
elastomers. In such materials, the insulating
phase, i.e., polycounterions, is an intrinsic
part of the conducting phase. It has been
demonstrated that the conductivity behavior
of such composites is controlled by the poly-
counterion conformation (Glatzhofer et al,
1987). Choosing proper sulfated polymers,
one can get thermoplastic and elastic PPy
composites (Wernet, 1991).
Reticulate doped polymers consisting of a
crystalline network of "organic metals" pene-
trating a polymer matrix. Reticulate doped
polymers (RDP) are obtained by crystalliza-
tion of conducting charge-transfer (CT) com-
plexes or salts in situ in a polymer matrix
(Jeszka et al, 1981). When conditions are op-
timized, a continuous network consisting of
microcrystals penetrates the polymer matrix
allowing one to obtain conducting materials
with extremely low loading, below 0.003 vol
fraction. A great number of various systems
have been elaborated (Ulanski, 1990). The
CT complexes and salts used as the dopants
include organic semiconductors, organic
metals, and organic superconductors. The
best systems exhibit conductivities above 1
S/cm at merely 1 wt % of the dopant; the
films are transparent, flexible, and environ-
mentally stable. A modified reticulate doping
method, the so-called zone-casting technique,
allows production of anisotropic composites
with conducting crystals forming parallel
paths, showing very high anisotropy of con-
ductivity, 106 or more; another modification
yields films that are only surface conduct-
ing.
While the number of polymeric conduct-
ing composites is quickly growing, the con-
ductivity mechanism in such systems is not
526 Polymers, Electrical and Electronic Properties
fully understood. Most of the models consid-
ered are oversimplified, related to polymer/
conducting filler (e.g., carbon black)
mixtures. In general, in heterogeneous sys-
tems, different mechanisms can contribute
to the charge-carrier transport: high-mobility
motion in ordered regions (e.g., within crys-
talline inclusions or along nondefected, ori-
ented polymer chains); hopping among local-
ized states in disordered regions; tunneling
between highly conducting islands—all con-
trolled by, generally speaking, the percola-
tion process.
4.3.5 Superconducting Polymers The
search for superconducting polymers was
motivated by Little's hypothesis (1964) that a
quasi one-dimensional polyconjugated chain
with side groups in which oscillations of
electronic charge can be induced may exhibit
high-temperature exciton-type superconduc-
tivity. No such polymer was found; more-
over, there are theoretical arguments that
such a 1-D chain, isolated because of bulky
side groups, cannot sustain long-range order.
The first discovered superconducting ma-
terial without metallic elements was crystal-
line poly(sulfur nitride), (SN)X. The (SN),
crystals are obtained by solid-state polymeri-
zation of S2N2 crystals, obtained by pyrolitic
conversion of S4N4 in the presence of silver
wool as a catalyst. The superconductivity
transition temperature depends on crystal
perfection and ranges from 0.26 to 0.35 K.
Several experimental observations, like the
specific heat anomaly and, first of all, the
Meissner effect, show that (SN)X is a bulk
type-II superconductor in which electron-
electron Umklapp scattering between elec-
tron and hole pockets of the Fermi surface
occurs rather than the usual electron-pho-
non-electron interactions (Gill et at, 1982-
83).
Recent works on organic superconductors
are concentrated on other synthetic metals—
molecular CT complexes. The first such sys-
tem, tetramethyltetraselenafulvalene phos-
phorus hexafluoride, exhibits superconduc-
tivity below 0.9 K under pressure of 12 kbar.
Other systems are superconducting also at
ambient pressure: /ns-ethylenedithiolotetra-
thiafulvalene with iodine, (BEDT-TTF)2I3,
when transformed into the so-called fi*
phase, shows a superconductivity transition
at around 7 K (Yagubskii, 1993). Supercon-
ducting polymer composites were obtained
recently by reticulate doping of polycarbon-
ate with (BEDT-TTF)2I3 (Laukhina et at,
1995). The highest superconductivity transi-
tion temperature reported so far for organic
systems, approaching 33 K, was found for
fullerenes, C60, intercalated with alkali metals
M, of general formula M3C60 (Fischer and
Bernier, 1993) (see FULLERENES).
4.4 Applications
Practical use of the basic property of con-
ducting polymers, the electrical conductivity,
was limited for a long time by problems with
processing and stability. The first commer-
cialized conducting, fully organic polymeric
systems were the transparent, flexible, and
stable films obtained by the reticulate doping
technique (see Sec. 4.3.4). Conductive and
transparent films are produced also by dis-
persing particles of an intrinsically conduct-
ing polymer (e.g., polypyrrole or polyaniline)
in an inactive polymer matrix (Roth and
Graupner, 1993).
Remarkable progress in the application of
conducting polymers as antistatic materials,
electromagnetic shielding, sheathing for elec-
tric power cables, and conducting fibers and
textiles can be expected as a result of the
discovery of processable (from solution or
from melt) conducting polymers with im-
proved environmental stability. Conducting
films or fibers made of composites of con-
ducting polymers with high-performance
polymers yields conductivity materials of
outstanding mechanical properties. The tech-
nique of decoration of a preexisting gel net-
work by a conducting polymer should be a
useful technique for producing conducting
composites with very low content of con-
ducting polymers (Heeger, 1993).
Numerous attempts have been made in
order to exploit practically unusual electrical
and optical phenomena induced by the injec-
tion of carriers into the 7r-electron system of
conducting polymers. Reversibility of the
electrochemical doping of PA has allowed
construction of light-weight, high-power-
density rechargeable batteries. Doped PA
forms a Schottky-type contact to various
substrates, making possible construction of
photovoltaic devices, and because the band
gap of PA matches perfectly the solar energy
 Polymers, Electrical and Electronic Properties 527
spectrum, PA-based solar cells have been
built.
At present, various polymer batteries have
already been commercialized. Typically, they
contain a polymer anode (e.g., with PPy or
PANI as the electrochemically active mate-
rial), an electrolyte based on lithium salt so-
lution, and a lithium or lithium alloy coun-
terelectrode. The high charge-storage
capacity of conducting polymers has been
utilized also in the construction of capacitors
with anode and cathode made of polypyrrole
showing energy-storage density values two
orders of magnitude bigger than conven-
tional capacitors.
Doping/dedoping-induced changes in the
absorption spectra of conducting polymers
are utilized for electrochromic devices. The
undoped polymer, if its energy gap is greater
then 3 eV, is transparent in visible light; af-
ter doping, it has a high absorption coeffi-
cient (105 cm" 1 ), and thus thin films are suf-
ficient for effective attenuation of the
transmitted light. Displays made of electro-
chromic polymers exhibit a broad viewing
angle and high stability of the image without
the need of a permanently applied electric
field, in contrast to the displays made of liq-
uid crystals.
The very high third-order nonlinear opti-
cal susceptibility of conjugated polymers
with subpicosecond response times and high
damage thresholds are the reasons for great
interest in these polymers as nonlinear opti-
cal materials for photonics.
Many other potential applications of con-
jugated polymers are reported: chemical sen-
sors, making use of changes of conductivity
of these polymers due to redox reactions;
separation membranes, utilizing drastic
changes of permeability of conducting poly-
mers upon oxidation; electronic devices, us-
ing the ability of these materials to form rec-
tifying junctions, Schottky barriers, etc.;
LEDs built of polymers like poly(p-phenylene
vinylene) showing electroluminescence; and
drug release devices, where the drug mole-
cules, incorporated as counterion into the
conducting polymer, can be released during
the reduction (Salaneck et al, 1991).
GLOSSARY
Aromatic Amine Group: A group often
present in pendant groups of photoconduct-
ing polymers, consisting of a nitrogen atom
with adjacent aromatic group(s).
Bipolaron: A correlated pair of ions, be-
ing the effect of interaction of two polarons.
Bipolarons carry double charge and no spin.
Charge-Transfer Complex: Product of
molecular interaction between electron do-
nor and electron acceptor.
Conductor: A material in which carriers
are plentiful; either the valence band is only
partially filled or the valence and conduction
bands overlap.
Dispersive Transport: A hopping trans-
port in which Gaussian statistic is not appli-
cable because of the very broad spread of
the hopping times extending into the time
range of the experiment.
Electrophotography: A technique of im-
age copying consisting in exposing of a co-
rona-charged layered photoconductor to the
image reflected from the original so that
dark areas remain charged. Then the latent
image is developed by electrostatic attraction
of the toner particles to the charged areas
and is transferred to a sheet of paper.
Ferroelectric: A material that exhibits
spontaneous polarization and electric hyster-
esis.
Hopping Transport: A conduction mech-
anism in which charge carriers hop among
localized sites of dimensions smaller than
the average intersite distance.
Insulator: A material with few carriers of
low mobility, characterized by a wide energy
gap in terms of the band structure model.
Peierls Transition: A metal-insulator
transition in one-dimensional systems in-
duced by a symmetry-reducing distortion
(e.g., dimerization in frans-polyacetylene).
Photoconductor: A semiconductor whose
conductivity is sensitive to light because of
the creation of electron-hole pairs by absorp-
tion of photons.
Piezoelectric: A material that becomes
polarized when stressed.
Polaron: A defect formed by ionization of
a polyconjugated polymer, consisting of a
radical ion associated with a distortion of
the lattice around the charge.
Polyconjugated Polymer: Polymer with
an extended 7r-electron system in the back-
bone (with unsaturated backbone).
Relaxation Time: The time required for a
disturbed system to reach lie of the final
equilibrium configuration.
Relaxation Frequency: The reciprocal of
the relaxation time.
528 Polymers, Electrical and Electronic Properties
Soliton: A defect in £ran5-polyacetylene,
being the domain wall across which the
bond alternation on the chain is reversed.
The neutral soliton is the radical defect; the
charged solitons are the anion or cation de-
fects carrying charge but no spin.
Synthetic Metals: A class of conducting
materials generally not containing metal at-
oms and usually consisting of organic mole-
cules or macromolecules. Synthetic metals
have low-dimensional structures and exhibit
high electrical conductivity, in the best cases
metal-like, with respect to the value of the
conductivity and temperature dependences
of conductivity and of thermopower. Some
of these materials also exhibit superconduc-
tivity at low temperatures.
Time-of-Flight Technique: A method of
determination of charge-carrier mobility con-
sisting in measurement of the transit time of
a packet of charges across the sample.
Xerographic Discharge Technique: A
method of determination of quantum effi-
ciency of photogeneration and of charge-car-
rier mobility, consisting in monitoring of the
decay of the surface potential of the corona-
charged sample after a short pulse of light.
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