Beruflich Dokumente
Kultur Dokumente
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
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 thin, polymer films can be obtained by extru-
increases. sion and/or blowing of one-component or
These insulation properties can be dis- multicomponent layered systems.
cussed from the viewpoint of dc and ac Chemical vapor deposition and plasma
terms (McCrum et al, 1967). Voltage gradi- polymerization have been recently applied
ents across insulating systems depend pri- for obtaining high-quality dielectric films,
marily on the leakage rather than on the ca- mostly organosilicon materials. Preparation
pacitance. For this reason, insulators for conditions will decide the quality of the ob-
high-voltage application must be formulated tained materials, which in many cases are
in such a way that they show low conductiv- transparent, well adhering to the support,
ity. In the case of high-voltage insulation, and insoluble.
trapped charges have been taken into consid- Very thin films are prepared by polymeri-
eration, which can be troublesome when a zation of di-p-xylylene. The substrate is ex-
sudden polarity reversal is required. posed to a controlled atmosphere of a pure
Specific requirements are to be fulfilled monomer, and coating occurs as vapor-dep-
for low-electric-loss polymers, e.g., used in osition polymerization (Beach, 1978). If the
the insulation of transoceanic cables. They di-p-xylylene is used in plasma polymeriza-
are met in general by polyolefins, e.g., poly- tion, it forms plasma polymers that contain
ethylene, which combines very low dielectric a minor amount of branched and cross-
loss with moldability, toughness, and flexibil- linked chains, and its solubility suggests a
ity. High-performance thin polypropylene material of low molecular weight. This pro-
films have also been developed for various cess has certain similarities to vacuum me-
types of power capacitors. Extremely low- tallization.
conductivity materials such as those used in
electret microphones are required for various 2.3.3 Electrets; Piezoelectric and Pyro-
types of high-power capacitors. High-purity, electiic Polymers Electrets are dielectrics
pinhole-free, chemically inert poly(p-xyly- that create for a long time a strong external
lene) (Szwarc, 1976) and its chlorine-substi- electric field. The phenomenon is connected
tuted ultrathin film have been developed as with dipoles oriented during polarization
insulation barrier coatings for semiconductor treatment or with the presence of incompen-
surfaces. High-temperature resistant poly- sated, stable charge (Sessler, 1982). Perma-
mers like various types of polyimides are of- nent polarization is usually obtained by heat-
ten used as thin insulating layers in micro- ing or melting and solidifying a polar
electronics. polymer in an external electric field (ther-
moelectrets) or by photoexcitation (photo-
2.3.2 Dielectric Thin Films Dielectric electrets). There is the possibility to induce
polymer thin films are rarely prepared by charges in a polarized dielectric by y irradi-
thermal evaporation, electron-beam evapora- ation (radioelectrets) or by ion implantation.
tion, or slip casting (melting of the powder) Electrets may be obtained from natural di-
on metallic or semiconductor surfaces; how- electrics—e.g., waxes—or various polymeric
ever, these techniques have created more dielectrics with low dielectric constant and/
and more interest in the fabrication of mi- or of high Tg.
croelectronic devices. Mostly used is spin Most frequently, electrets are obtained by
coating from dilute solutions of polymers polarization of polar dielectrics in high elec-
characterized by appropriate dielectric prop- tric fields. The charge at the surface of an
erties. Care must be taken (rotation speed, electret is due to the orientation of dipoles;
temperature, vapor pressure of the solvent, thus, heterocharge is formed. There are also
etc.) in order to obtain pinhole-free films. injected charge carriers (homocharge) that
Recently, the spin-coating technique has disappear much more slowly with time. The
been used to obtain thin insulating films by resulting charge and the lifetime of an elec-
spin coating of a dispersion of polymer tret depend on the material used and on po-
spheres of low diameter on a metallic or larization conditions. There are electrets that
semiconducting surface and melting the ob- can be obtained from nonpolar dielectrics as
tained monosphere-thick layer (e.g., polysty- a result of charge carriers injected from the
rene monodisperse lattices). Thicker, but still electrodes or induced by irradiation. Most
Polymers, Electrical and Electronic Properties 507
important are thin-film electrets, which are 7.0 X 10-30 C m) and C-CN (^0 = 12 X
obtained from good dielectrics by electron- 10~30 C m)—may also lead to useful piezo-
beam irradiation whereby the charge is ac- electric macromolecular materials. Poly(vi-
cumulated at a known distance from the sur- nylidene chloride) chains, because of the
face of the film. Electrets of high density of presence of bulky chlorine atoms, are pre-
charges are also prepared by corona charg- vented from adopting the highly polar all-
ing and by using controlled breakdown on trans conformation. The poly(vinylidene cya-
large surfaces. There is a method of electret nide-vinyl acetate) alternating copolymer
preparation by the so-called "wet technique." exhibits a piezoelectric constant similar to
This consists in contacting the dielectric with PVDF.
a liquid characterized by high conductivity The very important structural feature of
in electric fields. The liquid layer is removed PVDF is high crystallinity (40-60%). It can
later on. crystallize in three major crystalline forms—
Electrets are subject to an aging process, a, (3, and y. The a form is obtained when the
but by careful treatment, one can obtain polymer crystallizes from the melt below 150
charged materials lasting a long time and °C. The structure of the a crystals is mono-
creating high electric fields. There are al- clinic with the chains having trans-gauche-
ready known techniques that are useful for trans-gauche conformation and a dipole mo-
determination of the charge distribution in ment that has components normal and
the poled material. Important information parallel to the chain axis. The dipole mo-
about the relaxation parameters of oriented ments of two chains in the unit cell are an-
dipoles and trapped charges are obtained by tiparallel, and the crystal shows no sponta-
well-elaborated, thermally stimulated depo- neous polarization. Drawing the PVDF film
larization techniques (van Turnhout, 1987; below 130 °C to several times its original
see also Sec. 3.2). It makes possible more de- length results in a new crystal form, the /3
tailed understanding of electret formation form. This crystal has the orthorhombic unit
and its aging. Principal applications are elec- cell in which the chains have all-trans con-
trostatic filters and electroacoustic transduc- formation. These chains have a large dipole
ers. moment (/JL0 = 7.06 X 10~30 C m) per mono-
Piezoelectricity is a phenomenon related meric unit, and they are packed in such a
to the appearance of resultant electric mo- way that the crystal exhibits spontaneous po-
ment connected with charges on the surface larization Pc (for the ideal crystal Pc = 0.3 C/
of a material under compression or exten- m2). In real /3-form crystals, Pc is smaller be-
sion (spontaneous polarization). This effect cause of defects. The stable /3-form crystals
was first observed in crystals with polar axes should, however, have more than 3% of de-
and without a symmetry center. Pyroelectric fects (head-to-head and tail-to-tail defects).
effects are similar to piezoelectric in the ap- The conversion from the a to the /3 form de-
pearance of opposite charges on the surfaces pends on draw ratio and draw temperature.
of a material but under homogeneous heat- The j8 form of PVDF crystals is characterized
ing. by the highest molecular packing. The y
Most piezoelectric polymers are also poly- form is obtained by crystallization under at-
mer electrets. Maximum piezoelectricity is mospheric pressure, just below the melting
roughly related to the dielectric permittivity; temperature, or by melt crystallization under
thus, it is determined basically by the chem- high pressure. The y-form crystals can be
ical structure of the polymer. The chain con- transformed into the (3 form by mechanical
figuration and bulk morphology are equally deformation of the crystal.
important for piezoelectricity. Poly(vinyl- The PVDF electrets are prepared by an-
idene fluoride) (PVDF), because of its highly nealing and poling c-axis oriented films con-
polar C-F bonds and high dipole moment taining /3-form crystals. Typical poling tem-
(fi0 = 6.4 X 10"30 C m), has the highest di- perature is Tp = 80-120 °C, and the
electric constant (e = 8.0) and shows the electrical poling field is Ep = 50-150 MV/m.
highest piezoelectric constant (Wada, 1982). The induced surface charge is opposite to
Fluoropolymers and copolymers with vi- the poling field (heterocharge). There is a
nylidene fluoride are good piezoelectric poly- small part of irreversible polarization; the re-
mers. Other polar groups—e.g., C-Cl (/z,0 = maining part is stable below Tp. The mecha-
508 Polymers, Electrical and Electronic Properties
nism of the polarization is still a subject of gated. They show two different collective
discussion. It is accepted that the piezoelec- modes. Some main-chain/side-group LCPs
tricity and pyroelectricity of PVDF and its have ferroelectric smectic phases as well.
large polarization depend on the number of They appear when these system are oriented
crystallites in the /3 form and on its ability to as a result of surface effects and/or for low
align during polarization. It is correlated also magnetic fields. This allows for the combi-
with the dipole residues from amorphous nation of typical polymeric features with the
regions and their incorporation into crystal- properties of the ferroelectric smectic
lites at grain boundaries. Thus, both chemi- phases. Thus, in addition to their conven-
cal structure and physical factors play im- tional use in displays, a wide field of new ap-
portant roles. plications may be expected, e.g., as piezoele-
ments made from cross-linked elastomers or
2.3.4 Liquid-Crystalline Polymers Liq- as pressure sensors.
uid-crystalline polymers (LCPs) are of partic-
ular interest because of their very interesting
mechanical properties in the oriented state 2.4 Electric Breakdown
and their nonlinear optical behavior. Liquid-
crystalline side-group polymers contain di- 2.4.1 Types of Breakdown and Factors
pole moments related to the pendant group Influencing the Electric Breakdown
(some LCPs also have a dipole moment in Electric breakdown occurs when the current
the backbone chain). The dipole character of flowing through the sample increases, lead-
LCPs makes it possible to study the molecu- ing to its failure, and the applied voltage
lar dynamics of those systems using broad- cannot be stable (Fisher, 1982). The applied
band dielectric spectroscopy covering the voltage leading to material disruption is
frequency range 10~4 up to 1010 Hz (Kremer called breakdown voltage, and the corre-
et ah, 1990). Thus, it is possible to study sponding voltage gradient at failure is elec-
both fast processes (e.g., rotation of meso- tric strength in kV/mm. The knowledge of
genic groups around their long molecular the breakdown mechanism is not complete,
axis) and slow relaxations (e.g., relaxation but one can distinguish the following:
close to Tg). 1. Intrinsic breakdown, which is related to
For LCPs with side groups, five different pure and defect-free material and occurs
dielectric relaxations have been found. For at the highest possible voltage. It is due to
combined main-chain/side-group systems, the increased random motion of elec-
the systematic chemical modification of di- trons, which at the electric breakdown
poles revealed three relaxation processes. gain higher energy than they lose to the
The a relaxation corresponds to the dynamic system.
glass transition. The rotation of the main- 2. Thermal breakdown, which is related to
chain mesogen around its long molecular heat emission. If the rate of heating un-
axis is called /3m relaxation, whereas j85 relax- der voltage exceeds the rate of cooling by
ation is correlated with the rotation of the thermal transfer, thermal breakdown may
side-group mesogen around its long molecu- occur at a limited section of the material.
lar axis. It is worth noting that for These restricted paths of breakdown are
side-group LCPs, a collective relaxation pro- called Wagner breakdowns.
cess (5 process) was found and ascribed to 3. Gas-discharge-dependent breakdown is
the hindered rotation of side groups around related to electric discharges in gas,
the polymeric main chain. Similar behavior which may occur on the surface or voids
was found for combined main-chain/side- and on various discontinuities of electri-
group liquid crystalline polymers as well as cal insulation. It can be due to ionization-
for some copolymers, in which it is sup- induced surface flashover or arcing.
pressed at the smectic-crystalline transition. 4. Physical-defect-dependent breakdown is
The dielectric relaxation studies also give affected by all types of cracks, voids, for-
valuable information on the mobilities in eign inclusions, and factors that introduce
various smectic phases depending on tem- physical deterioration of plastics.
perature. Recently, low-molecular-mass fer-
roelectric liquid crystals have been investi- Actual electrical breakdown may involve
Polymers, Electrical and Electronic Properties 509
two or more types simultaneously or sequen- tern, which may finally bridge the gap be-
tially. The true intrinsic breakdown can tween electrodes and cause the failures. The
never be achieved experimentally, but exper- practical importance of treeing has been em-
iments carried out at low temperature with phasized in many cases, particularly for
dc voltage applied for very short times are polyethylene cables. Some insulations con-
taken as the intrinsic value. taining stress concentration or even some
If the thermal breakdown tests are made kinds of trees do not fail in short periods. In
at high frequencies (above 1 MHz), failure fact, reports of long lifetimes of solid insula-
occurs at relatively low voltages. Usually, tion suggest that well-designed and well-con-
tanS increases with increasing temperature, structed insulating systems operate within
and the rate of heating rises rapidly. Many the limits of electrical, mechanical, and ther-
factors influence the thermal breakdown mal stresses for a long time.
voltage: geometry (particularly the thickness
of the sample), thermal conductivity, dielec- 2.4.3 Measurement Techniques Mea-
tric permittivity, absorbed moisture, etc. It surements of the electric breakdown strength
depends also on the general tendency for are standardized, and the equipment and
physical degradation of the plastic under procedures for electric breakdown test are
study. clearly described in ASTM D 149. The im-
Surface discharges are a source of ioniza- portant features that have to be fulfilled by
tion and may cause slow degradation of the each equipment are an appropriate device to
polymeric material at its surface or within measure the test voltage at the specimen and
cracks and voids. Progressive surface degra- not only the primary voltage of the testing
dation (tracking) is particularly important in transformer, a device for increasing the test
the presence of surface contaminations. Co- voltage at uniform rate, strictly sine wave,
rona and partial discharge are local effects and a device for removing the voltage at
occurring in gas where the voltage locally ex- breakdown.
ceeds the gas-breakdown potential. Usually, the corona test and the arc resis-
Breakdown connected with physical de- tance test are made in connection with elec-
fects depends also on mechanical stress and tric breakdown test. Standardized proce-
vibrations. This type of failure depends on dures are difficult to be developed, especially
the nature of defects, the time under electri- for volume corona, i.e., for corona dis-
cal stress, contaminations, and chemical charges in voids at conducting inclusions.
constitution of the polymers. There is a cer- ASTM D 2275 is applied to measure the co-
tain similarity between electrical strength rona resistance. For dry arc resistance,
and mechanical strength because electrical ASTM D 495 is used. A 12.5-kV voltage
breakdown involves physical destruction. In (open circuit), which produces an arc be-
the same temperature regions, both modulus tween chisel-shaped tungsten electrodes, is
and dielectric strength show significant re- applied.
ductions in magnitude. A number of works have been carried out
to elaborate various methods of treeing test
2.4.2 Electrical Treeing Treeing is re- (electrical and water treeing test), each of
lated to sporadic discharges that are inter- them having its advantages. ASTM D 3756
mittent and not steady like corona dis- describes a test for electrical treeing between
charges (Ku and Liepins, 1987). The a sharply pointed needle and a rounded nee-
mechanism of treeing is very similar to elec- dle. The only quite well-standardized test for
tric breakdown. Treeing breakdown starts in wet-treeing of cables is that of the Associa-
the regions of the highest and most divergent tion of Edison Illuminating Companies [IC
electrical stresses. The insulation system con- CS5-79].
sists always of non-absolutely smooth elec- Tracking tests have been standardized in
trodes, imperfect electrode-insulation inter- the United States. There are four types of
face, and not perfectly isotropic material, as tracking test:
well as there being contaminant particles or
cavities. These defects influence the appear- 1. Dust-and-Fog Tracking and Erosion
ance of treeing phenomenon. Small channels (ASTM D 2132),
of degradation develop into a treelike pat- 2. Differential Wet Tracking (ASTM D 2302),
510 Polymers, Electrical and Electronic Properties
3. Inclined plane Tracking and Erosion ing with the basic polymer, but above all, the
ASTM D 2303, and polymer surface must be treated to optimize
4. Comparative Tracking Index (ASTM D the performance of the system. The tendency
3638). of polymers to store electric charge was
overcome in the past by addition of carbon
black or acetylene black to rubber, by addi-
2.5 Surface Charging
tion of metallic powders to plastics, and by
2.5.1 Origin of Surface Electrification blending of metallic or metal-coated fibers
The presence of electrostatic charge is rec- with synthetic fibers. At present, conducting
ognized by mutual attraction or repulsion polymers, thin vacuum-deposited metal lay-
with other surfaces, possibly with small dis- ers, or formation of charge-transfer com-
charges (sparks), and by the dust attraction plexes at the surface are of interest for vari-
effect. When brought into intimate contact ous applications.
with a neutral material, e.g., by rubbing,
polymers become positively or negatively 2.6 Applications
charged on separation. The one that be-
comes positively charged acts as an electron Polymers are used in many electrical ap-
donor, while the other, which becomes neg- plications as primary electrical insulation, or
ative, acts as an electron acceptor (Ritsko, they may have a structural function, inde-
1982; see also TRIBOLOGY). pendent of an electrical function; thus,
The sequence of polymers according to choice of an appropriate polymer as an in-
their charging behavior is called the tribo- sulator depends on its particular application.
electric series. It is a general rule that if two An interesting survey of various basic electri-
substances become charged by mutual con- cal properties of polymers with regard to
tact, the substance with higher dielectric their applications is given by Ku and Liepins
constant will get the positive charge. The tri- (1987).
boelectric series can be established by con- Useful dielectrics are usually divided into
tact potential differences. three principal classes: those with er < 12,
The microscopic nature of electronic those with er > 12, and ferroelectrics. The
states involved in triboelectricity is still un- last class is represented among polymeric
der study (Lowell and Rose-Innes, 1980). The materials by some ferroelectric liquid-crystal-
molecular-ion model of bulk intrinsic states line polymers. The first category may be di-
provides an acceptable microscopic descrip- vided into subcategories based on operating
tion of the charge-transfer process, but fur- temperature; however, this division is yet not
ther advances in the understanding of this fully justified because polymeric materials
phenomenon are needed. Very important is depending on their chemical constitution
the rate of charge decay. It depends on the and structure can be used as insulators and
side groups that constitute the polymer dielectrics up to 400 °C (depending on time
chain. When side-chain substituents are in- of application of severity of temperature con-
volved in charging the surface, charge decay ditions).
is faster. The ability of the polymer to bind Polymers fulfill generally well the typical
ions is also a very important factor. A small requirements of an insulator:
amount of impurity can alter the surface
charging to a high extent. Surface charging 1. they usually have high enough dielectric
is of importance for the flow behavior of strength to withstand an electrical field
polymer powders and is a key process in all between the conductors (e.g., in capaci-
xerographic techniques. tors);
2. they show high insulation resistance to
2.5.2 Antistatic Agents The electro- prevent the leakage of the current;
static charge can be reduced by use of anti- 3. they exhibit a good arc resistance to pre-
static agents. Even a small surface charge vent damage in the case of arcing;
density can give rise to an electric field 4. they show appropriate mechanical prop-
strong enough to cause arcing in air (electri- erties to resist shock, vibrations, etc.; and
cal charge in carpets in dry air). Antistatic 5. they usually maintain their integrity un-
agents can be used in formulations by mix- der a wide variety of environmental haz-
Polymers, Electrical and Electronic Properties 511
ards such as humidity, temperature feasible and patterning can be achieved in
changes, and radiation. lithography.
For domestic wiring insulation, the best All these features make it possible for this
electrical properties are not necessary; thus type of polymer to be applied in microelec-
plasticized PVC is firmly established. Ester tronics as microresists and printed circuit
plasticizers also change the nonflammability boards (Saone and Martynenko, 1989).
of PVC, but some appropriately chosen com- Evidently, polymers are used as molded
positions may compensate this insufficiency. components for chip encapsulation. The en-
High-quality polyethylene is used for tele- capsulant must be very pure material with
communication cables while polypropylene an excellent barrier to moisture and contam-
(biaxially oriented) and poly(ethylenether- inant ions, independently of superior electri-
ephtalate) films are used in capacitor manu- cal, physical, and manufacturing properties.
facturing. Many organic polymers fulfill these condi-
Among some relatively new developments tions, both thermosetting and thermoplastic
in thermoplastics, the polymer blends (e.g., materials.
polycarbonate/ABS blends, where ABS In addition to good dielectric and insulat-
stands for a mixture of acrylonitrile-styrene ing properties, the polymers are widely used
and butadiene-styrene copolymers) are cho- because of good processing characteristics
sen for connectors and switch casings, where (small and intricate shapes can be readily
high impact strength, good surface quality, and economically manufactured), good me-
and low mould shrinkage are required. The chanical properties (resistance to impact
low resistivity and high dielectric strength of loads and stiffness, even at elevated temper-
these materials are relatively unaffected by atures), dimensional stability, and retention
external moisture, and so they are suitable of many properties in hot and/or moist envi-
for waterproof switches. ronment over long periods of time.
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 3. SEMICONDUCTING AND
long-term charge-storage capability because PHOTOCONDUCTING POLYMERS
of the low conductivity and low carrier mo-
The conductivity of every material can be
bility. Typical examples of polymers that can
enhanced when charge carriers are generated
store real charges and polarization charges
or injected by appropriate radiation. If UV,
are polyolefins and poly(ethyleneterephthal-
visible, or near-IR radiation is used, we deal
ate). Poly(tetrafluoroethylene) (Teflon™) and
with photoconductivity. In the case of x-ray,
its fluoro-ethylene-propylene copolymers are
gamma-ray, or other, e.g., electron, irradia-
examples of materials with good insulating
tion, the term radiation-induced conductivity
properties, and poly(vinylidene fluoride) is
is usually used. High-energy irradiation in-
characteristic of small dipolar relaxation.
evitably results in chemical degradation of
Applications of polymers in the electronic
the polymer, and these problems are outside
industry are continuously increasing. Poly-
of the scope of this article. An ideal, elec-
mer piezoelectrets are used in microphones
tronically photoconductive polymer should
and small loudspeakers. Polymer dielectrics
have no free charge carriers (thus, it should
are rapidly gaining importance as substitutes
show very low conductivity in the dark) and
for inorganic (ceramic-based) insulators.
high quantum efficiency of charge-carrier
These applications are dominated by poly-
photogeneration, and it should allow fast
imide films, which offer particularly useful
transportation of the photogenerated
characteristics:
charges.
1. stability up to temperatures as high as Three classes of polymers are known to
450 °C; exhibit semiconducting and photoconducting
2. high electrical resistivity and breakdown properties: polymers with 7r-polyconjugated
strength, and low dielectric loss; multiple bonds (like polyacetylene), polymers
3. excellent chemical resistance; and with (7-bonded silicon or germanium atoms
4. coating of substrates with thin films is in the main chain (like polysilanes), and
512 Polymers, Electrical and Electronic Properties
polymers with saturated backbones and pen- In polymers, the thermal generation is
dant aromatic groups [like poly(N-vinylcar- usually negligible, even in undoped polymers
bazole)(PVK)]. Another class of polymeric with polyconjugated multiple bonds, because
semiconductors comprises molecularly of the large band gap. Photogeneration is in-
doped polymers consisting of an electrically trinsic, when it occurs by photoexcitation of
insulating and inactive polymer matrix the polymer molecule, or extrinsic, when the
doped with charge-transfer (CT) complexes light is absorbed by pigments or dyes dis-
forming additives. persed in a polymer matrix and the genera-
In polymers with extended 7r-electron sys- tion process occurs within the dopant mole-
tems in the backbone, the molecular p orbi- cules. Intrinsic photogeneration is confined
tals broaden into filled and empty bands, to the UV range (i.e., the range of the poly-
and the polymer should be an intrinsic mer absorption spectrum), but its efficiency
metal. However, because of bond alternation can be increased and action spectrum shifted
(Peierls distortion), there is a finite gap (e.g., into the visible range by doping with a suit-
around 1.4 eV for polyacetylene) between able electron acceptor that forms a charge
these bands. transfer complex with, usually donorlike,
In silicon-backbone polymers, significant polymer.
delocalization of electrons occurs along the It is generally accepted that the charge-
chain, and their electronic behavior is very carrier photogeneration occurring within a
different from analogous cr-bonded carbon- polymer is a multistep process that can be
backbone polymers; the band gap in polysi- divided into two main phases, as shown in
lanes is of the order of 4 eV, while in carbon the scheme in Fig. 2 (Okamoto and Itaya,
analogs it is close to 8 eV. 1984). The first phase, the efficiency of
Pendant-group polymers have electronic which is field independent, is the absorption
states similar to thosfe of the pendant aro- of a quantum by a molecule or a CT com-
matic molecules, and so their properties are plex and its photoionization (most probably
similar to those of the polymers molecularly via unrelaxed exciplex states), followed by
doped with chromophores, where the charge formation of the hole-electron pair, which is
transport occurs via hopping among local- separated at some characteristic thermaliza-
ized sites associated with pendant groups or tion length. The efficiency of this first phase
dopant molecules. is called the primary quantum yield. The sec-
4.3.2 Characteristics Among numer- more stable trans form occurs upon doping
ous conducting polymers, three, polyacetyl- or heating. When doped with alkali metals,
ene, polypyrrole, and polyaniline (Fig. 4), PA shows n-type conductivity and is highly
seem to be the most representative. environmentally unstable. Doping with oxi-
Polyacetylene is the simplest polyconju- dative agents, like iodine, bromine, SbF6, or
gated polymer. It was obtained in a highly AsF5 results in p-type conductivity. The value
conducting state for the first time by Shira- of conductivity of doped PA depends both on
kawa et al (1977), and this disclosure marks the synthesis method and on the doping and
the beginning of intensive studies on con- may reach 105 S/cm (Naarmann and Theo-
ducting polymers. Its role as a model, quasi philou, 1987); however, typically it ranges
1-D conductor with soliton-type excitations is from 102 to 103 S/cm. The differences in con-
emphasized in Sec. 4.1. ductivity arise from differences in morphol-
As obtained, PA is usually a mixture of ogy, influencing the hopping conductivity be-
trans and cis forms; isomerization to the tween the polyacetylene chains, and from
Polymers, Electrical and Electronic Properties 523
differences in conjugation length, influencing 100 S/cm, and the temperature dependence
the charge transport along the PA chain. of dc conductivity (adc) is described usually
Only the so-called "high-cr" PA, obtained by the Mott law developed for variable-range
by the Naarmann method, stretched, and hopping (VRH) (Mott and Davis, 1979) in
highly doped, shows metal-like temperature disordered materials:
dependence of conductivity at high tempera-
tures, and it remains high also in the zero- a-dc = cr0exp[-(7y7T-25], (25)
temperature limit. The thermopower of
"high-cr" PA is linearly proportional to where a0 and To are constants (this equation
temperature, as for the ideal metallic diffu- holds essentially only in the low-temperature
sion, indicating that it is dominated by quasi regime). However, the density of states at the
1-D metallic conduction in highly conducting Fermi level calculated from the fit to the
regions. The macroscopic conductivity shows VRH model is unacceptably higher than that
largely nonmetallic behavior because it in- obtained from independent ESR studies; also
volves also charge transport through some the metal-like behavior of the thermopower
kind of barriers, e.g., sp3 defects. is in contradiction to the VRH model. The
The conductivity of unstretched PA, for present understanding of the charge-carrier
example, the Shirakawa-type PA consisting transport in PPy involves the concept of per-
of randomly oriented fibrils of diameter typ- colation on a fractal network. The measure-
ically about 200 A, is not only much smaller ments of spin dynamics by NMR at various
but also it tends to zero in the zero-temper- temperatures indicate an anomalous diffu-
ature limit, showing the absence of continu- sion in fractal structures of effective dimen-
ous metallic paths. The temperature depend- sion 8 = 1 at low temperatures; the 8 in-
ence can be fitted by an equation describing creases with increasing temperature. It is in
tunneling between small metallic islands agreement with the frequency dependence of
controlled by the charging energy of the is- the ac conductivity (aac) following the equa-
lands: tion
where a0 and To are constants (Kaiser, 1993). with 5 = 1 — 6/3. At elevated temperatures,
Polypyrrole was the first electrochemically the effective dimension increases, indicating
synthesized conducting polymer (Diaz et at, an increasing role of the interchain hopping.
1979), and it receives considerable interest For three-dimensional hopping at high tem-
due to the combination of relatively high peratures, the dc conductivity is given by
conductivity with environmental stability,
good mechanical properties, and simplicity crdc = cr0 exp(-2oR) expi-EJkT), (27)
of preparation. The PPy films are obtained
from the monomer directly in the conduct- where R is the distance between the neigh-
ing (oxidized) state because the oxidation po- boring hopping sites, EA is the energy barrier
tential of PPY polymer is lower than that of between the sites, and a is the inverse local-
the monomer; doping occurs simultaneously ization length. The investigations of 3,4-cy-
with the electropolymerization because the cloalkyl-substituted PPy fully support this
counterions incorporate into the polymer in mechanism, showing direct correlation of R
order to maintain the electrical neutrality of with the size of the substituent (Ruhe et at,
the film. The electrolyte consists of a solvent 1989).
(usually acetonitrile or water), pyrrole, and Polyaniline (PANI), known for many years
various ions, so that PPY can be easily as so-called "aniline black," has attracted
doped with a variety of counterions. The considerable research interest only recently,
doping (oxidation) is reversible, and PPy can when its unusual electrochemical and optical
be electrochemically transformed into neu- properties were uncovered (MacDiarmid and
tral, nonconducting form. Epstein, 1989). Polyaniline is unique among
The PPy films are amorphous and flexible, conducting polymers because its electronic
but with very low ultimate elongation. Their properties can be altered both by redox pro-
conductivities range in most cases from 1 to cesses involving electron transfer and by
524 Polymers, Electrical and Electronic Properties
acid-base chemistry involving protonation. and investigated are polythiophenes (Fig. 4)
PANI exists in five forms very different in substituted with alkyl chains, like poly(3-oc-
electrical and magnetic properties. An insu- tylthiophene) (Elsenbaumer et at., 1986).
lator-conductor transition, like for other con- They are soluble in several common organic
ducting polymers, occurs upon charge-trans- solvents and are melt processable at temper-
fer doping, and the conducting PANI form, atures below 200 °C, so that they can be
emeraldine salt, can be obtained directly blended with thermoplastics and elastomers
from the leucoemeraldine, which is a large- using standard techniques and then doped in
band-gap insulator. Additionally, protonation order to transform the poly(3-alkylthiophene)
of the semiconducting PANI form, the emer- into the conducting state.
aldine base, yields the emeraldine salt by a Counterion-induced processability of con-
conversion of the quinoid ring to the ben- ducting PANI was achieved by using a suita-
zoid structure with an associated spin un- ble functionalized acid to protonate the base
pairing resulting in conductivity changes by form of PANI (Cao et at, 1993). Polyaniline
10 orders of magnitude. The conducting soluble in common organic solvents was syn-
PANI form, emeraldine salt, shows good thesized by introducing counterions of large
chemical stability. PANI was categorized ini- size, which reduce the interchain interac-
tially as an intractable polymer; then several tions. Using sulfonic acids, like dodecylben-
methods were reported to dissolve this poly- zene sulfonic acid, soluble polyanilines in the
mer, for example, in strong acids, but an conducting state were obtained. Diesters of
important advance was the elaboration of phosphoric acid with alkyl substituents, be-
the counterion-induced processability of con- ing protonating agents for the emeraldine
ducting PANI (see Sec. 4.3.3.). base, cause also plastification and solubiliza-
tion of the protonated, conducting emeral-
4.3.3 Processable Conducting Polymers dine salt; conducting films can be obtained
Practically all initially obtained conducting by casting as well as by hot pressing (Laska
polymers were not processable (insoluble et at, 1993). Various other protonic acids
and nonmelting). Insolubility causes serious acting as surfactants can be used. The con-
problems in characterization of the molecu- ductivity obtained in PANI films cast from
lar structure of conducting polymers since solutions is quite high, usually in the range
many investigation techniques can be ap- 1-400 S/cm.
plied only for polymer solutions. For com-
mercial applications, it is also necessary to 4.3.4 Heterogeneous Conducting Poly-
have materials processable with conventional mer Composites Making polymer com-
plastic technologies. posites is one of the most effective and flexi-
The insolubility of conjugated polymers in ble methods in getting speciality materials.
the conducting state was related to side re- Great progress has been made in obtaining
actions, like cross-linking, caused by free fully organic, heterogeneous, electrically con-
radicals, radical ions, and ions present in the ducting systems (Kryszewski, 1991). One can
doped polymers. For these reasons, the first distinguish several main groups in terms of
approaches to processing conducting poly- their composition, morphology, and conduc-
mers were limited to systems obtained via tivity.
tractable precursor polymers. Nonconducting Conducting colloid composites. Stable col-
precursors can be dissolved in order to pro- loids can be made of different conducting
duce films or fibers; these films or fibers can polymers in aqueous and nonaqueous media
be further processed, e.g., oriented by allowing one to cast films or to press pellets
stretching, and then converted into a con- of the dried dispersions. In these systems,
ducting, but no longer processable, state. conducting grains are surrounded by an in-
Highly oriented, anisotropic PA films are ob- sulating steric stabilizer. Colloidal polypyr-
tained in this way, using the so-called Dur- role (PPy) can be obtained in the form of
ham route (Edwards and Feast, 1980). spherical particles of diameter in the range
Further progress in processing of con- 50-500 nm, depending on the preparation
ducting polymers was achieved by solubili- conditions, and yields films with conductivity
zation of polyconjugated polymers by substi- in the range 0.1-2 S/cm. In the case of poly-
tuting side groups in them. The most known aniline (PANI) colloids, the grain size can be
Polymers, Electrical and Electronic Properties 525
smaller; the cast films of PANI with PPy, the conductivity is ca. 2 S/cm (Rector et
poly(vinyl acetate) stabilizer show a conduc- al., 1991). Another route for manufacturing
tivity of ca. 6 S/cm (Aronson et al, 1991). conducting fibers consists in polymerization
Blends of processable conducting polymers of acetylene in gel fibers containing 2 wt %
with inert polymers. In most of these com- of ultrahigh-molecular-weight PE (Chiang et
posites, the conducting phase is made of al, 1988). The fibers comprise up to 80 wt %
poly(3-alkylthiophene)s (P3AT), because of PA, and after doping with iodine, their
these polymers are soluble in common or- conductivity is 1200 S/cm; fibers drawn 2-3
ganic solvents and also can be melt-blended times show after doping a conductivity
without decomposition (Laakso et al, 1989). around 6000 S/cm.
Further progress in such composites is ex- Conducting polymer salts with polymeric
pected as a result of works on the counter- counterions. Very specific PPy composites
ion-induced processability of PANI (see Sec. can be produced in one step by electrochem-
4.3.3). Very high effectiveness of the con- ical synthesis using polymeric counterions,
ducting phase formation has been achieved like poly(p-styrenesulfonate) (PSS) or other
by so-called gel decoration. Conducting gels anionically derivatized polymers, including
of ultrahigh-molecular-weight PE and poly(3- elastomers. In such materials, the insulating
octylthiophene) (P3OT) were prepared by ge- phase, i.e., polycounterions, is an intrinsic
lation from solutions in decalin followed by part of the conducting phase. It has been
doping with iodine. No percolation threshold demonstrated that the conductivity behavior
was found down to 0.0005 vol fraction of of such composites is controlled by the poly-
P3OT, and already above 0.02 vol fraction, counterion conformation (Glatzhofer et al,
the conductivity saturates reaching values in 1987). Choosing proper sulfated polymers,
the range 10~3 to 10~2 S/cm. The conducting one can get thermoplastic and elastic PPy
network is formed of conjugated chains ei- composites (Wernet, 1991).
ther absorbed or entangled within the PE Reticulate doped polymers consisting of a
network (Heeger et al, 1991). crystalline network of "organic metals" pene-
Mixtures of insulating polymer matrices trating a polymer matrix. Reticulate doped
and fillers made of conducting polymers. polymers (RDP) are obtained by crystalliza-
From the point of view of preparation, these tion of conducting charge-transfer (CT) com-
mixtures can be most readily related to poly- plexes or salts in situ in a polymer matrix
mer-carbon-black composites. The particles (Jeszka et al, 1981). When conditions are op-
of insoluble and/or infusible polymers, e.g., timized, a continuous network consisting of
PPy or PANI powders, play the role of con- microcrystals penetrates the polymer matrix
ducting filler. Utilizing the high thermal sta- allowing one to obtain conducting materials
bility of polyaniline tosylate (up to 250 °C for with extremely low loading, below 0.003 vol
short intervals in nitrogen) it is possible to fraction. A great number of various systems
prepare blends with a variety of conventional have been elaborated (Ulanski, 1990). The
thermoplastics (Kulkarni et al., 1991). CT complexes and salts used as the dopants
Composites obtained by polymerization of include organic semiconductors, organic
conjugated polymers within an insulating metals, and organic superconductors. The
matrix. Some monomers, like pyrrole, can best systems exhibit conductivities above 1
penetrate insulating polymeric matrices and, S/cm at merely 1 wt % of the dopant; the
after subsequent polymerization, form con- films are transparent, flexible, and environ-
ducting networks. This can be easily done mentally stable. A modified reticulate doping
with porous materials, such as paper, for method, the so-called zone-casting technique,
which conductivity as high as 10"l S/cm has allows production of anisotropic composites
been reported. Often used is the electro- with conducting crystals forming parallel
chemical method in which pyrrole penetrates paths, showing very high anisotropy of con-
an insulating substrate on a precoated elec- ductivity, 106 or more; another modification
trode and electropolymerizes in situ. Con- yields films that are only surface conduct-
ducting fibers have been obtained by chemi- ing.
cal polymerization of pyrrole within the While the number of polymeric conduct-
voids of never-dried poly(p-phenylene tere- ing composites is quickly growing, the con-
phthalamide) fibers. At 0.57 vol fraction of ductivity mechanism in such systems is not
526 Polymers, Electrical and Electronic Properties
fully understood. Most of the models consid- ducting polymer composites were obtained
ered are oversimplified, related to polymer/ recently by reticulate doping of polycarbon-
conducting filler (e.g., carbon black) ate with (BEDT-TTF)2I3 (Laukhina et at,
mixtures. In general, in heterogeneous sys- 1995). The highest superconductivity transi-
tems, different mechanisms can contribute tion temperature reported so far for organic
to the charge-carrier transport: high-mobility systems, approaching 33 K, was found for
motion in ordered regions (e.g., within crys- fullerenes, C60, intercalated with alkali metals
talline inclusions or along nondefected, ori- M, of general formula M3C60 (Fischer and
ented polymer chains); hopping among local- Bernier, 1993) (see FULLERENES).
ized states in disordered regions; tunneling
between highly conducting islands—all con-
trolled by, generally speaking, the percola- 4.4 Applications
tion process.
Practical use of the basic property of con-
4.3.5 Superconducting Polymers The ducting polymers, the electrical conductivity,
search for superconducting polymers was was limited for a long time by problems with
motivated by Little's hypothesis (1964) that a processing and stability. The first commer-
quasi one-dimensional polyconjugated chain cialized conducting, fully organic polymeric
with side groups in which oscillations of systems were the transparent, flexible, and
electronic charge can be induced may exhibit stable films obtained by the reticulate doping
high-temperature exciton-type superconduc- technique (see Sec. 4.3.4). Conductive and
tivity. No such polymer was found; more- transparent films are produced also by dis-
over, there are theoretical arguments that persing particles of an intrinsically conduct-
such a 1-D chain, isolated because of bulky ing polymer (e.g., polypyrrole or polyaniline)
side groups, cannot sustain long-range order. in an inactive polymer matrix (Roth and
The first discovered superconducting ma- Graupner, 1993).
terial without metallic elements was crystal- Remarkable progress in the application of
line poly(sulfur nitride), (SN)X. The (SN), conducting polymers as antistatic materials,
crystals are obtained by solid-state polymeri- electromagnetic shielding, sheathing for elec-
zation of S2N2 crystals, obtained by pyrolitic tric power cables, and conducting fibers and
conversion of S4N4 in the presence of silver textiles can be expected as a result of the
wool as a catalyst. The superconductivity discovery of processable (from solution or
transition temperature depends on crystal from melt) conducting polymers with im-
perfection and ranges from 0.26 to 0.35 K. proved environmental stability. Conducting
Several experimental observations, like the films or fibers made of composites of con-
specific heat anomaly and, first of all, the ducting polymers with high-performance
Meissner effect, show that (SN)X is a bulk polymers yields conductivity materials of
type-II superconductor in which electron- outstanding mechanical properties. The tech-
electron Umklapp scattering between elec- nique of decoration of a preexisting gel net-
tron and hole pockets of the Fermi surface work by a conducting polymer should be a
occurs rather than the usual electron-pho- useful technique for producing conducting
non-electron interactions (Gill et at, 1982- composites with very low content of con-
83). ducting polymers (Heeger, 1993).
Recent works on organic superconductors Numerous attempts have been made in
are concentrated on other synthetic metals— order to exploit practically unusual electrical
molecular CT complexes. The first such sys- and optical phenomena induced by the injec-
tem, tetramethyltetraselenafulvalene phos- tion of carriers into the 7r-electron system of
phorus hexafluoride, exhibits superconduc- conducting polymers. Reversibility of the
tivity below 0.9 K under pressure of 12 kbar. electrochemical doping of PA has allowed
Other systems are superconducting also at construction of light-weight, high-power-
ambient pressure: /ns-ethylenedithiolotetra- density rechargeable batteries. Doped PA
thiafulvalene with iodine, (BEDT-TTF)2I3, forms a Schottky-type contact to various
when transformed into the so-called fi* substrates, making possible construction of
phase, shows a superconductivity transition photovoltaic devices, and because the band
at around 7 K (Yagubskii, 1993). Supercon- gap of PA matches perfectly the solar energy
Polymers, Electrical and Electronic Properties 527
spectrum, PA-based solar cells have been Bipolaron: A correlated pair of ions, be-
built. ing the effect of interaction of two polarons.
At present, various polymer batteries have Bipolarons carry double charge and no spin.
already been commercialized. Typically, they Charge-Transfer Complex: Product of
contain a polymer anode (e.g., with PPy or molecular interaction between electron do-
PANI as the electrochemically active mate- nor and electron acceptor.
rial), an electrolyte based on lithium salt so- Conductor: A material in which carriers
lution, and a lithium or lithium alloy coun- are plentiful; either the valence band is only
terelectrode. The high charge-storage partially filled or the valence and conduction
capacity of conducting polymers has been bands overlap.
utilized also in the construction of capacitors Dispersive Transport: A hopping trans-
with anode and cathode made of polypyrrole port in which Gaussian statistic is not appli-
showing energy-storage density values two cable because of the very broad spread of
orders of magnitude bigger than conven-
the hopping times extending into the time
tional capacitors.
range of the experiment.
Doping/dedoping-induced changes in the Electrophotography: A technique of im-
absorption spectra of conducting polymers
age copying consisting in exposing of a co-
are utilized for electrochromic devices. The
rona-charged layered photoconductor to the
undoped polymer, if its energy gap is greater
then 3 eV, is transparent in visible light; af- image reflected from the original so that
ter doping, it has a high absorption coeffi- dark areas remain charged. Then the latent
cient (105 cm" 1 ), and thus thin films are suf- image is developed by electrostatic attraction
ficient for effective attenuation of the of the toner particles to the charged areas
transmitted light. Displays made of electro- and is transferred to a sheet of paper.
chromic polymers exhibit a broad viewing Ferroelectric: A material that exhibits
angle and high stability of the image without spontaneous polarization and electric hyster-
the need of a permanently applied electric esis.
field, in contrast to the displays made of liq- Hopping Transport: A conduction mech-
uid crystals. anism in which charge carriers hop among
The very high third-order nonlinear opti- localized sites of dimensions smaller than
cal susceptibility of conjugated polymers the average intersite distance.
with subpicosecond response times and high Insulator: A material with few carriers of
damage thresholds are the reasons for great low mobility, characterized by a wide energy
interest in these polymers as nonlinear opti- gap in terms of the band structure model.
cal materials for photonics. Peierls Transition: A metal-insulator
Many other potential applications of con- transition in one-dimensional systems in-
jugated polymers are reported: chemical sen- duced by a symmetry-reducing distortion
sors, making use of changes of conductivity (e.g., dimerization in frans-polyacetylene).
of these polymers due to redox reactions; Photoconductor: A semiconductor whose
separation membranes, utilizing drastic conductivity is sensitive to light because of
changes of permeability of conducting poly- the creation of electron-hole pairs by absorp-
mers upon oxidation; electronic devices, us- tion of photons.
ing the ability of these materials to form rec- Piezoelectric: A material that becomes
tifying junctions, Schottky barriers, etc.; polarized when stressed.
LEDs built of polymers like poly(p-phenylene Polaron: A defect formed by ionization of
vinylene) showing electroluminescence; and a polyconjugated polymer, consisting of a
drug release devices, where the drug mole- radical ion associated with a distortion of
cules, incorporated as counterion into the the lattice around the charge.
conducting polymer, can be released during Polyconjugated Polymer: Polymer with
the reduction (Salaneck et al, 1991).
an extended 7r-electron system in the back-
bone (with unsaturated backbone).
GLOSSARY Relaxation Time: The time required for a
Aromatic Amine Group: A group often disturbed system to reach lie of the final
present in pendant groups of photoconduct- equilibrium configuration.
ing polymers, consisting of a nitrogen atom Relaxation Frequency: The reciprocal of
with adjacent aromatic group(s). the relaxation time.
528 Polymers, Electrical and Electronic Properties
Soliton: A defect in £ran5-polyacetylene, sko, J. J., Thomas, H. R., Paton, A. (1978), Phys.
being the domain wall across which the Rev. B 18, 5717-5739.
bond alternation on the chain is reversed. Edwards, J. H., Feast, W. J. (1980), Polymer 21,
The neutral soliton is the radical defect; the 595-596.
charged solitons are the anion or cation de- Ehinger, K., Roth, S. (1985), in: H. Kuzmany,
M. Mehring, S. Roth (Eds.), Electronic Properties of
fects carrying charge but no spin. Polymers and Related Compounds, Springer Series
Synthetic Metals: A class of conducting in Solid-State Science Vol. 63, Berlin: Springer,
materials generally not containing metal at- pp. 67-74.
oms and usually consisting of organic mole- Elsenbaumer, D. L. E., Jen, K. Y., Oboodi, R.
cules or macromolecules. Synthetic metals (1986), Synth. Met. 15, 169-174.
have low-dimensional structures and exhibit Fischer, J. E., Bernier, P. (1993), La Recherche
high electrical conductivity, in the best cases 250, 46.
metal-like, with respect to the value of the Fisher, P. (1982), in: D. A. Seanor (Ed.), Electri-
conductivity and temperature dependences cal Properties of Polymers, New York: Academic
of conductivity and of thermopower. Some Press, p. 319.
of these materials also exhibit superconduc- Frommer, J. E., Chance, R. R. (1988), in: J. I.
tivity at low temperatures. Kroschwitz (Ed.), Electrical and Electronic Proper-
ties of Polymers, New York: J. Wiley and Sons, p.
Time-of-Flight Technique: A method of 301.
determination of charge-carrier mobility con- Gill, W. D., Clarke, T. C, Street, G. B. (1982-
sisting in measurement of the transit time of 83), Appl. Phys. Comm. 2, 211-282.
a packet of charges across the sample. Glatzhofer, D. T., Ulanski, J., Wegner, G.
Xerographic Discharge Technique: A (1987), Polymer 28, 449-453.
method of determination of quantum effi- Havriliak, S., Negami, S. (1967), Polymer 8,
ciency of photogeneration and of charge-car- 161-172.
rier mobility, consisting in monitoring of the Heeger, A., Smith, P., Fizazi, A., Moulton, J.,
decay of the surface potential of the corona- Pakbaz, K., Rughooputh, S. (1991), Synth. Met. 41,
charged sample after a short pulse of light. 1027-1032.
Heeger, A. (1993), Synth. Met. 57, 3471-3482.
Jeszka, J. K., Ulanski, J., Kryszewski, M.
Works Cited (1981), Nature 298, 390-391.
Kaiser, A. B. (1993), Mater. Sci. Forum 122, 13-
Aronson, M. C, Aldissi, M., Armes, S. P., 24.
Thompson, J. D. (1991), Synth. Met. 41, 837-842.
Kao, K. C, Hwang, W. (1981), Electrical Trans-
Bartnikas, R. (Ed.) (1987), Engineering Dielec- port in Solids, Oxford: Pergamon Press.
trics, Vol. IIB, Special Technical Publication 926,
Philadelphia: ASTM. Kirkwood, J. G. (1939), J. Chem. Phys. 7, 911-
919.
Bassler, H. (1984), Philos. Mag. 50, 347-362.
Kivelson, S. (1981), Phys. Rev. Lett. 46, 1344-
Beach, W. F. (1978), Macromolecules 11, 72-76. 1348.
Block, H., Walker, S. M. (1982), in: J. V. Dawk- Kremer, F., Vallerian, S. U., Zentel, R. (1990),
ins (Ed.), Developments in Polymer Characteriza- Adv. Mater. 2, 145-146.
tion-3, London: Applied Science Publishers, p. 75.
Kryszewski, M. (1991), Synth. Met. 45, 289-296.
Bottger, H., Bryksin, V. V. (1986), Hopping
Conduction in Solids, Weinheim: VCH Publishers. Ku, C. C, Liepins, R. (1987), Electrical Proper-
ties of Polymers, Munich: Hanser Publishers.
Braunlich, P. (Ed.) (1979), Thermally Stimulated
Relaxation in Solids, Berlin: Springer Verlag. Kulkarni, G. V., Mathew, W. R., Wessling, B.,
Merkle, H., Blaettner, S. (1991), Synth. Met. 41,
Cao, Y., Smith, P., Heeger, A. J. (1993), Synth. 1009-1012.
Met. 57, 3514-3519.
Laakso, J., Osterholm, J.-E., Nyholm, P., Stubb,
Chiang, J. C, Smith, P., Heeger, A. J., Wudl, F. H., Punkka, E. (1989), Synth. Met. 37, 145-150.
(1988), Polym. Commun. 29, 161-165.
Laska, J., Trznadel, M., Proh, A. (1993), Mater.
Debye, P. (1945), Polar Molecules, New York: Sci. Forum 122, 177-184.
Dover Publications Inc.
Laukhina, E. E., Merzhanov, V. A., Pesotskii, S.
Diaz, A. F., Kanazawa, K. K., Gardini, G. I., Khomenko, A. G., Yagubskii, E. B., Ulanski, J.,
(1979), /. Chem. Soc. Chem. Commun. 635. Kryszewski, M., Jeszka, J. K. (1995), Synth. Met.
Deutsch, K., Hoff, E. A. W., Reddish, W. 70, 797-800.
(1954), /. Polym. Sci. 13, 565-582. Little, W. A. (1964), Phys. Rev. 134, A1416-
Duke, C. B., Salaneck, W. R., Fabish, T. J., Rit- A1424.
Polymers, Electrical and Electronic Properties 529
Lowell, L., Rose-Innes, A. C. (1980), Adv. Phys. Weagley, R. J., McGrane, K. M. (1990), Synth. Met.
29, 947-1023. 37, 295-303.
MacDiarmid, A. G., Epstein, A. J. (1989), Fara- Stolka, M., Abkowitz, M. A. (1993), Synth. Met.
day Discuss. Chem. Soc. 88, 317-332. 54, 417-425.
McCrum, N. G., Read, B. E., Williams, G. Stolka, M. (1988), in: J. I. Kroschwitz (Ed.),
(1967), Anelastic and Dielectric Effects in Polymeric Electrical and Electronic Properties of Polymers,
Solids, New York: J. Wiley and Sons. New York: J. Wiley and Sons, p. 301.
Miller, R. D., Michl, J. (1989), Chem. Rev. 89, Stolka, M., Pai, D. M. (1978), Adv. Polymer Sci.
1359-1410. 29, 1-45.
Mort, J., Pfister, G. (1982), in: J. Mort and G. Szwarc, M. (1976), Polym. Eng. Sci. 16, 473-
Pfister (Eds.), Electronic Properties of Polymers, 479.
New York: J. Wiley and Sons, p. 215.
Ulariski, J. (1990), Synth. Met. 39, 13-42.
Mott, N. F., Davis, E. A. (1979), Electronic Pro-
cesses in Non-Crystalline Materials, Oxford: Claren- Ulahski, J., Jeszka, J. K., Kryszewski, M.
don Press. (1981), Polym.-Plast. Technol. Eng. 17, 139-191.
Naarmann, H., Theophilou, N. (1987), Synth. van Beek, L. K. H. (1967), in: J. B. Birks (Ed.),
Met. 22, 1-8. Progress in Dielectrics, Vol. 7, London: Heywood
Books, p. 69.
Okamoto, K., Itaya, A. (1984), Bull. Chem. Soc.
Jpn. 57, 1626-1630. van Turnhout, J. (1987), in: G. M. Sessler (Ed.),
Electrets, Berlin: Springer Verlag, p. 81.
Onsager, L. (1936), /. Am. Chem. Soc. 58,
1486-1492. Volkenstein, M. V. (1963), Configurational Sta-
tistics of Polymers, New York: Interscience.
Pautmeier, L., Richtert, R., and Bassler, H.
(1990), Synth. Met. 37, 271-281. Wada, Y. (1982), in: J. Mort, G. Pfister (Eds.),
Electronic Properties of Polymers, New York: J. Wi-
Pearson, J. M., Stolka, M. (1981), Poly(N-vinyl- ley and Sons, p. 109.
carbazole), New York: Gordon and Breach.
Wegner, G., Ruhe, J. (1989), Faraday Discuss.
Pukacki, W. (1993), Mater. Sci. Forum 122, Chem. Soc. 88, 333-349.
255-268.
Wegner, G. (1981), Angew. Chem. 20, 361-381.
Rector, L. P., De Groot, D. C, Schindler, J. L.,
Marks, T. J., Carr, S. H. (1991), Synth. Met. 41, Wernet, W. (1991), Synth. Met. 41, 843-848.
935-939. Wurstlin, F. (1951), Kolloid Z, 84-102.
Ritsko, J. J. (1982), in: J. Mort, G. Pfister Yagubskii, E. B. (1993), Mol Cryst. Liq. Cryst.
(Eds.), Electronic Properties of Polymers, New York: 230, 139-156.
J. Wiley and Sons, p. 13.
Lu, Yu (1988), Solitons and Polarons in Con-
Roth, S., Graupner, W. (1993), Synth. Met. 57, ducting Polymers, Singapore: World Scientific.
3623-3631.
Ruhe, J., Ezquerra, T. A., Mohammadi, M., En-
kelmann, V., Kremer, F., Wegner, G. (1989), Synth. Further Reading
Met. 28, C217-C223.
Salaneck, W. R., Clark, D. T., Sammelson, E. J. Bailey, R. T., North, A. M., Pethrick, R. A.
(Eds.) (1991), Science and Application of Conduct- (1981), Molecular Motions in Polymers, Oxford:
ing Polymers, Bristol: Adam Hilger. Clarendon Press, Chap. 5.
Saone, D. S., Martynenko, Z. (1989), Polymers Bartnikas, R., Eichhorn, M. (Eds.) (1983), En-
in Microelectronics, Fundamentals and Applications, gineering Dielectrics, Vol. IIA, Philadelphia: ASTM
Amsterdam: Elsevier. Special Technical Publication 783.
Schimmel, Th., Schwoerer, M., Naarmann, H. Block, H. (1979), Adv. Polym. Sci. 33, 93-167.
(1990), Synth. Met. 37, 1-6. Bottcher, C. J. F. (1973), Theory of Dielectric
Scott, J. C, Pautmeier, L. Th., Moerner, W. E. Polarization, Vol. I, Dielectrics in Static Fields, Am-
(1993), Synth. Met. 54, 9-19. sterdam: Elsevier.
Sessler, G. M. (1982), in: D. A. Seanor (Ed.), Bottcher, C. J. F., Bordewijk, P. (1978), Theory
Electrical Properties of Polymers, New York: Aca- of Electric Polarization, Vol. II, Dielectrics in Time
demic Press, p. 224. Dependent Fields, Amsterdam: Elsevier.
Sher, H., Montroll, E. W. (1975), Phys. Rev. B Braunlich, P. (Ed.) (1979), Thermally Stimulated
12, 2455-2477. Relaxation in Solids, Berlin: Springer Verlag.
Shirakawa, H., Louis, E. J., Mac Diarmid, A. Chien, J. C. W. (1984), Polyacetylene, Orlando:
G., Chiang, C. K., Heeger, A. J. (1977), /. Chem. Academic Press.
Soc. Chem. Commun. 578.
Hanack, M., Roth, S., Shier, H. (Eds.) (1991),
Stockmayer, W. H. (1967), Pure Appl. Chem. Proceedings of the International Conference on
15, 539-545. Science and Technology of Synthetic Metals, Tub-
Stolka, M., Abkowitz, M. A., Knier, F. E., ingen, West Germany, 1990, Synth. Met. 41-43.
530 Polymers, Electrical and Electronic Properties
Hedvig, P. (1977), Dielectric Spectroscopy of Park, Y. W., Lee, H. (Eds.) (1995), Proceedings
Polymers, Bristol: Hilger. of the International Conference on Science and
Jonscher, A. K. (1983), Dielectric Relaxation in Technology of Synthetic Metals, Seoul, 1994,
Solids, London: Chelsea Dielectric Press. Synth. Met. 69-71.
Kao, K. C, Hwang, W. (1981), Electrical Trans- Pearson, J. M., Stolka, M. (1981), Poly(N-vinyl-
port in Solids, Oxford: Pergamon Press. carbazole), New York: Gordon and Breach.
Kremer, R, Boese, D., Meier, G., Fischer, E. W. Prasad, S. V., Ulrich, D. R. (Eds.) (1988), Non-
(1983), Progr. Coll Polym. Sci. 80, 129-139. linear Optical Polymers, New York: Plenum Press.
Kroschwitz, J. I. (Ed.) (1988), Electrical and Seanor, D. A. (Ed.) (1982), Electrical Properties
Electronic Properties of Polymers: A State-of-the-Art of Polymers, New York: Academic Press.
Compendium, New York: J. Wiley and Sons. Sessler, G. M. (Ed.) (1987), Electrets, Topics in
Kryszewski, M., Ulariski, J., Bernier, P. (Eds.) Applied Physics, Vol. 33, Berlin: Springer Verlag.
(1990), Proceedings of the 21st Europhysics Con- Simon, J., Andre, J.-J. (1985), Molecular Semi-
ference on Macromolecular Physics: Electric and conductors, Berlin: Springer Verlag.
Optical Active Polymers, Lodz, Poland, 1989,
Synth. Met. 37. Skotheim, T. A. (Ed.) (1986), Handbook of Con-
ducting Polymers, Vols. 1-2, New York: Marcel
Kryszewski, M. (1980), Semiconducting Poly- Dekker, Inc.
mers, Warszawa: PWN-Polish Scientific Publish-
ers. Stafstrom, S., Salaneck, W. R., Inganas, O.,
Hjertberg, T. (Eds.), (1993), Proceedings of the In-
Ku, C. C, Liepins, R. (1987), Electrical Proper- ternational Conference on Science and Technology
ties of Polymers, Munich: Hanser Publishers. of Synthetic Metals, Goteborg, 1992, Synth. Met.
Mair, H. J., Roth, S. (Eds.) (1986), Electrisch 55-57.
Leitende Kunststoffe, Berlin: Hanser Publishers. Ulanski, J., Jeszka, J. K., Kryszewski, M.
McCrum, N. G., Read, B. E., Williams, G. (1981), Polym.-Plast Technol. Eng. 17, 139-191.
(1967), Anelastic and Dielectric Effects in Polymer van Roggen, A. (1990), IEEE Trans. Electr. In-
Solids, London: J. Wiley and Sons; reprint (1991),
Dover Publications Inc. sul. 25, 95-106.
Mort, J., Pfister, G. (Eds.) (1982), Electronic van Turnhout, J. (1975), Thermally Stimulated
Properties of Polymers, New York: J. Wiley and Discharge of Polymer Electrets, Amsterdam: Elsev-
Sons. ier.
O'Dwyer, J. J. (1964), The Theory of Electrical Williams, G. (1979), Adv. Polym. Sci. 33, 59-92.
Conduction and Breakdown in Solid Dielectrics, Ox- Wintle, H. J. (1990), IEEE Trans. Electr. Insul.
ford: Clarendon Press. 25, 27-44.