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The paper critically reviews some recent developments in the field of electrically conducting polymers which have
grown very rapidly since the discovery that there is a very sharp increase in conductivity when intrinsically insulating
organic conjugated polymers such as, polyacetylene are doped with oxidizing or reducing agents. These polymers, also
called synthetic metals, combine the electrical properties of polymers with the advantages of polymers and have such a vast
scope of diverse applications that these are being perceived as the materials of the twentyfirst century. Doped organic
conducting polymers, though conducting, suffer from two disadvantages of chemical instability and poor processibility. One
of the fundamental challenges in the field of conducting polymers, therefore, is to design low band gap intrinsically
conducting polymers so that there is no need to dope them. Various strategies presently used for designing polymers with
tailor-made conduction properties and some recent results obtained using these strategies are discussed. Lastly, some of the
important applications of electrically conducting polymers are also discussed with a view to highlight the great potential of
these materials.
Keywords: Electrically conducting polymers, Synthetic metals, Band-gap, Electronic structure, Donor-acceptor polymers,
Copolymers, Band structure engineering
Introduction
Polymers have always been considered as insulators of electricity. No one would have believed 30 y ago that
polymers could conduct as good as metals. But now such feats have been achieved and that through simple
modification of ordinary organic conjugated polymers. Called electrically conducting polymers or synthetic
metals, these materials combine the electrical properties of metals with the advantages of polymers such as,
lighter weight, greater workability, resistance to corrosion and chemical attack and the lower cost and have
infiltrated our day-to-day life with a wide range of products, extending from most common consumer goods to
highly specialized applications in space, aeronautics, electronics, and non-linear optics. It is, therefore, no
wonder that these polymers are called the Materials of the twentyfirst century.
The first major breakthrough in the field of electrically conducting polymers took place around 1978 when it
was demonstrated by Shirakawa et al.1,2 that polyacetylene (PA), an intrinsically insulating organic conjugated
polymer, exhibits dramatic increase in electrical conductivity3 on treatment with oxidizing (electron-accepting)
or reducing (electron-donating) agents. These oxidation and reduction reactions, which induce high conductivity
in PA are termed as p-doping and n-doping, respectively.
The discovery of highly conducting PA led to a sudden spurt in research activity directed towards the study of
new conducting polymeric systems. The instability of PA in air4 further intensified this research (on exposure to
air, covalent bonds are formed between oxygen and carbon atoms and these bonds lower the conductivity of PA
because of their interruption of conjugated double bonds). The result is that at present many novel conducting
systems are known and these include polypyrrole (PPY), poly (phenylacetylene) (PPA), poly (p-phenylene
sulphide) (PPS), poly (p-phenylene) (PPP), polythiophene (PTP), polyfuran (PFU), polyaniline (PAN),
polyisothianaphthene (PIN) and, their derivatives. These polymers, though they share many structural features
such as a conjugated backbone, planarity and large anisotropy ratio (i.e. the intrachain conductivity is much
larger than the inter-chain conductivity), however have a wide range of conductivity depending upon; (i) The
doping per cent, (ii) The alignment of polymer chains, (iii) The conjugation length, and (iv) The purity of the
sample.
Some Special Features of Conducting Polymers
716 J SCI IND RES VOL 63 SEPTEMBER 2004
Polymer + X ( Polymer) n + + X n
in the case of an oxidation (p-doping) process and
Polymer + M ( Polymer) n + M n +
for a reduction (n-doping) process
X = I2, Br2, AsF5,.... and M= Na, Li
The above reactions most likely occur in the case of unsaturated polymers with -electrons as they can be
easily removed or added to the polymeric chains to form polyions and, therefore, these are the types of polymers
which assume high conductivity on doping.
interaction between the charge on the chain (electron or hole) acquired as a result of doping and the molecular
structure are the direct consequence of the strong electron-phonon interaction present in these quasi-one-
dimensional polymers. Thus, charge-carrying species in doped organic conjugated polymers are not free
electrons or holes as in the case with inorganic semiconductors but quasi-particles such as, solitons, polarons and
bipolarons which may move relatively freely through the material. It is now very well established that in
polymers with degenerate ground state such as, trans-polyacetylene, charged solitons (positively charged or the
negatively charged depending upon whether p-doping or n-doping) are the charge carriers, whereas in polymers
with non-degenerate ground state such as, cis polyacetylene, polypyrrole, polythiophene or poly (p-
phenylene), initially polarons (positively charged or negatively charged) are formed on doping. These polarons
then combine to form spinless bipolarons which act as the charge carriers. The formation of bipolaron is also
supported by calculations which show that the formation of one bipolaron is thermodynamically more stable
than that of two separated polarons despite the Coulomb repulsion between two similar charges.
(a) Substitution/Fusion,
(b) Ladder Polymerization,
(c) Topological methods,
(d) Copolymerization, and
(e) Donor-Acceptor polymerization
Substitution / Fusion
In this method, one starts with small band-gap polymers and tries to modify their electronic properties by
substitution provided their chemical nature and experimental conditions allow these substitution reactions. The
following two guidelines are of great help in the strategy of substitution:
(a) In polymers with degenerate ground state such as, trans-PA, it is now well established that the band-gap
decreases as a function of decreasing bond length alternation along the chain. Thus, if a substituent
decreases the bond length alternation along the backbone the band-gap of the resulting polymer shall
decrease and vice-versa.
(b) On the other hand, in polymers with non-degenerate ground state such as, poly (p-phenylene) (PPP),
polypyrrole (PPY), etc., it has been found that the band-gap decreases as a function of increasing quinoid
character of the polymer backbone.
Using the above guidelines, the effect of substituents on the band structure of PA has been investigated in few
cases like, fluorinated polyacetylenes18, halogen and cyano substituted polyacetylenes19 and alkoxy-substituted
poly (p-phenylenevinylene)s20. Polymers having azobenzene substituents in the main chain have been studied by
Izumi et al.21. The azobenzene units in the conjugated polymer backbone make the polymers thermally stable
polymer.
Recently, a new low band-gap polymer (1.16 eV), namely poly (5,6-dithiooctyl isothianaphthene) has been
718 J SCI IND RES VOL 63 SEPTEMBER 2004
synthesized22. This polymer has been found as a useful active material in construction of solar cells in
combination with PCBM (6,6 phenyl C61-butyric acid). Highly conductive new aniline copolymers containing
butylthio substituent have also been successfully prepared23 with conductivity of the
order of 1 S cm-1. All these new butylthioaniline copolymers are highly soluble in common organic solvents
despite the presence of large amount of bulky butythio substituent. Although in some cases, substitution may
decrease the conductivity of the polymer but the resulting polymer has higher electron affinity and can,
therefore, be used in LEDs. A series of cyano-substituted distyryl benzenes24 have also been synthesized. It has
been observed that by properly adjusting copolymer compositions, a combined high electron affinity and
transport was achieved in a statistic copolymer, namely poly (fluorenebenzothiadiazsole-
cyanophenylenevinylene) (PFB-CNPV)24.
Thus, all these various kinds of substituents are in use for improving solubility, decreasing band-gaps,
increasing polarizabilities and conductivity, and finally optimizing luminescence efficiencies.
BAKHSHI & BHALLA: ELECTRICALLY CONDUCTING POLYMERS 719
Ladder Polymerization
Ladder polymers are formed by joining simple polymers into symmetrical polymeric rings. The small energy
gap in ladder polymers is a consequence of the direct interplay of electron-lattice and electron-lattice interactions
in them. Among ladder polymers, hydrocarbon polymers with fused aromatic rings have been the focus of
enormous interest. This new class of polymers, frequently referred to as one-dimensional graphite family,
includes members such as polyacene (PAc), polyacenacene (PAcA), polyphenanthrene (PPh), polyphenanthro-
phenanthrene (PPhP) and polyperinaphthalene (PPN). The electronic structure and conduction properties of the
members of 1-D graphite family (Fig. 2) have been the subject of many theoretical investigations25,26. The
ladder-type poly-p-phenylenes (LPPP) offer the opportunity to study large, rod-like chains of planarised
phenylene units. The ground-state properties and excited states of ladder-type paraphenylene oligomers have
been calculated by applying semi-empirical methods for up to eleven-phenylene rings27. A scheme to interpret
the excited states has been developed which reveals the excitonic nature of the excited state. Ladder thiophene
polymers have also been synthesized with decreased band-gap values28. It has been observed that ladder
polymers with higher molecular weight showed better thermal resistance. Ladder polymers with band-gaps as
small as 0.2 eV have already been synthesized by Kerterz and Hughbanks29. Various other ladder polymers with
improved properties have also
been synthesized. These include poly(aroylene benzimidazoles), polyepoxysiloxanes30, and ladder polymers with
thienylene units31. Recently, photoconduction study on a ladder type poly (paraphenylene) has also been done32.
The energy spectra of one-dimensional stacks consisting of large - interacting polycyclic aromatic
hydrocarbons have been investigated theoretically33, taking into account electron correlation. The band-gap of
these stacks is about 0.8 eV. These polymers are candidates for new materials with unique electronic properties
such as, electroconductivity, photoconductivity or magnetic properties. Simultaneously, they are models for
nanometers scaled graphites (nanographites).
Topological Methods
In the case of fused ring polymers the electronic properties are found to depend strongly on the particular way
the rings are fused and the recognition of this has led to the employment of topological methods based on the
concept of topomers for designing novel polymers. It means that one has to construct the corresponding
BAKHSHI & BHALLA: ELECTRICALLY CONDUCTING POLYMERS 721
oligomers of a pair of topomers as S- and T- topomers. In the S- topomer, the two bonds connect pairwise
topologically equivalent atoms. While in the T- topomer, the end points of the two bonds are interchanged in one
subunit. If, e.g., A is the T- and B the S- topomer of the same subunit, then the following relations which are the
consequences of the interlacing theorem are valid for these pairs:
(i) The ionization potential (IP) of A is smaller than the IP of B.
(ii) The electron affinity (EA) of A is smaller than the EA of B.
(iii) The fundamental band-gap (Eg) of A is smaller than the gap of B.
Point (iii) follows immediately from (i) and (ii) because Eg = I P E A. The gap of A is, therefore, located
inside the gap of B on energy scale. The above topological arguments have been used to rationalize the large
differences in the electronic properties of fused ring polymers such as, polyacene, polyphenanthrene and
polybenzanthracene34and in search for novel low band-gap conjugated polymers35. Polyisophenanthrene, a new
hypothetical polymer is predicted to have a band-gap between polyacene and polybenzanthracene.
Unique new ladder polymer (polyindenoindenes) consisting of condensed succession of six- and five-
membered conjugated carbon rings have been synthesized36. Seven topological isomers of these
polyindenoindenes are considered theoretically. The results are analysed in terms of topological band-gaps and
geometrical relaxation. Three isomers are expected to have a band-gap smaller than 0.2 eV
(ref. 29).
Copolymerization
The strategy of growing co-polymers is highly exciting and promising. Copolymers can have tailor-made
properties depending upon the choice of two semiconducting components, their relative amounts and their
arrangement in the polymer chain. The electronic properties of a copolymer (AmBn)x (where m= block size of
component A and n= block size of component B), though generally intermediate between those of its
components (A)x and (B)x, can be tuned by varying the molecular composition of the copolymer and by varying
the arrangement of components (periodic or aperiodic) in the copolymer chain.
The electronic DOS of the various periodic and aperiodic quasi-one-dimensional model and real copolymers
of the type (AmBn)x belonging to the class of Type-I and Type-II staggered have been studied in both tight
binding approximation and by considering multi-
neighbour interaction37-40. For each of these types of
copolymers, the trends in their electronic structure and
conduction properties as a function of : (i) Composition
(m/n), (ii) Block sizes m and n, and (iii) Arrangement of
blocks in the copolymer chain have been investigated.
The results of these studies are summarized in Table 1.
In the case of copolymers of both Type-I and Type-I
Type-II staggered, it has been found that increasing the
proportion of low band-gap component (B)x in the
copolymer chain increases the electron affinity (EA) and
hence improves the n-dopantphilicity of the copolymer
chain. Increasing the percentage of large band-gap
component (A)x in the copolymer chain decrease the
ionization potential (IP) and hence improves the p-
dopantphilicity of the copolymer chain in the case of
Type-I copolymers while in case of Type-II staggered Type-II staggered
copolymers, this has the opposite effect of increasing the
IP and hence making it less
p-dopantphilic. To have a copolymer with prospects for both p- and n- doping, as well as better intrinsic
722 J SCI IND RES VOL 63 SEPTEMBER 2004
Table 1Trends in the electronic properties of copolymers belonging to the class of type-I (trends in the
parenthesis correspond to those for type-II staggered)
System Ionization potential Electron affinity Band-gap
conductivity, increasing the block sizes m and in of the two components A and B for a given composition is the
best solution for both Type-I and Type-II staggered copolymers.
Further, it has also been found that the electronic properties of periodic copolymers cover a wider range than
those of aperiodic copolymers. It, therefore, means that the tuning the electronic properties to a particular value
is easier by synthesizing periodic copolymers. In the case of aperiodic copolymers, on the other hand the
saturation in electronic properties is reached much faster. Aperiodic copolymers are also predicted to be better
intrinsic and extrinsic conductors of electricity than the corresponding periodic copolymers. The results obtained
here are important guidelines for designing copolymers with tailor-made conduction properties.
There have also been quite interesting investigations of the various types of other copolymers recently. These
include systems such as, cyclodiborazanedithiafulvene copolymers41, copolymers of fluorine and alkoxy
substituted poly (p-phenylene vinylene)20, carbazole-quinoline, and phenothiazine-quinoline copolymers42.
Copolymers of aniline with o- or m- toluidine and o-ethyl aniline have also been reported43,44. It has been found
that these copolymers of aniline with substituted anilines show fairly good conductivity. The electronic
properties of the hypothetical thiophene copolymers: poly (thienylenecyclopentadienylene) (PThS), poly
(thienylene-oxocyclopentadienylene) (PThOPD) and poly (thienylenethiocyclypenta-dienylene) (PThTPD) have
also been theoretically investigated45.
Copolymers of aniline and pyrrole46 and copolymers having S-S links47 have recently been studied. These
copolymers with S-S links in the backbone have better solubility and are expected to find application in Li
batteries. Novel carbazole-based copolymers48 with different comonomers have been synthesized. The emission
colour can be tuned in entirely visible region by careful choice of narrow band comonomers.
DonorAcceptor Polymerization
Another very exciting possibility and successful route in designing of low bandgap electrically conducting
polymers is provided by the donor-acceptor polymers. The principal idea behind donor-acceptor polymers is that
a regular alternation of donor- and acceptor- like moieties in a conjugated chain will induce a low band-gap.
Various novel donor-acceptor polymers differing in their electron-donating and electron-accepting moieties have
been theoretically designed and investigated49. Recently, we have studied some donor-acceptor polymers based
on polysilole50 and poly (diflurosilane), respectively51, (Fig. 3) on the basis of ab-initio Hartree Fock crystal
orbital method52. These polymers have also been studied53-55 on the basis of the one-dimensional tight binding
SCF-CO method at the MNDO-AM1 level of approximation. The calculated ab-initio electronic properties of
these donor-acceptor polymers are given in Table 2. In both the classes of polymers (Table 2), the polymers with
Y= > C=C(CN)2 have the smallest band-gap while those with Y= > C=O have the largest band-gap, implying
hereby that in these donor-acceptor polymers, > C=C(CN)2 is the strongest electron-withdrawing group and >
C=O the weakest.
BAKHSHI & BHALLA: ELECTRICALLY CONDUCTING POLYMERS 723
Table 2Calculated electronic properties (in eV) of polysilole based donor-acceptor polymers. Values
in parenthesis are the corresponding values for donor-acceptor polymers based on poly (diflurosilane)
Y > C=CH2 > C=O > C=CF2 > C=C (CN)2
Electromagnetic Shielding
The dissipative abilities of polymers also make them ideal for electromagnetic shielding. By coating the inside
of the plastic casing with a conductive surface, this radiation can be absorbed. This can best be achieved by
using conducting plastics, which have good adhesion and thus give a good coverage and good thickness56.
Incorporated into computer cases, conducting polymers can block out electromagnetic interference in the
megahertz range.
Molecular Electronics
Molecular electronics concerns itself with the electronic structures assembled atom by atom. One proposal for
this method involves conducting polymers. A possible example is a modified PA with an electron-accepting
group at one end and an electron-withdrawing group at the other. A short section of the chain is saturated in
order to decouple the functional groups. This section is known as a spacer or a modulator barrier. This can be
used to create a logic device. There are two inputs, one light pulse which excites one end and another which
excites the modulator barrier. There is one output, a light pulse to see if the other end has become excited. To
use this, there must be lot of redundancy to compensate for switching errors61. Depending on the conducting
polymer chosen the doped and undoped states can be either colourless or intensely coloured.
Electromechanical Actuators
Polymer based actuators are a new technology. Actuators67 can function by using changes in a dimension of a
conducting polymer, changes in the relative dimensions of a conducting polymer and a counter electrode and
changes in total volume of a conducting polymer electrode, electrolyte and counter electrodes. The method of
doping and dedoping is very similar as that used in rechargeable batteries discussed earlier. What is required are
the anodic strip and the cathodic strip, changing size at different rates during charging and discharging. The
applications
of this include microtweezers, microvalves, micro-
positioners for microscopic optical elements, and actuators for micromechanical sorting68. These types of
actuators are seen as a promising technology both for existing applications and future applications in the area of
process and manufacturing automation.
polymer and a powder of the thermoplastic or thermoset to be blended in placed at the interface between two
plastic pieces to be joined. The resulting joint may be as strong as that of the pure compression molded
thermoplastic or thermoset. Depending upon the chemical composition of the conducting polymer and the
dopant used, the resulting joint may be permanent.
Conclusions
In this paper, we have given an overview of the emerging field of electrically conducting polymers with
special reference to the their special features such as molecularity and disorder, nature of doping processes and
nature of charge carriers produced on doping. One of the fundamental challenges in the field of conducting
polymers is the designing of low band-gap organic conjugated polymers. This problem has become all the more
BAKHSHI & BHALLA: ELECTRICALLY CONDUCTING POLYMERS 727
important in view of the disadvantages of poor processibility and instability associated with doped organic
conjugated polymers. Low band-gap polymers are expected to be (i) Intrinsically good electrical conductors or
semiconductors without the need of any doping; (ii) Transparent in either the intrinsic or doped state; and (iii) Of
great interest as new polymeric materials for non-linear optics (because of fewer contact problems) and other
properties. Various strategies viz., substitution/fusion, ladder polymerization, topological methods,
copolymerization and donor-acceptor polymerization currently used for designing novel low band-gap
conducting polymers and the electronic structures and conduction properties of some novel low band-gap
polymers designed using these strategies have been discussed. Lastly, we have discussed some of the
applications of these electrically conducting polymers. Significant among them are the applications in light
weight and rechargeable batteries, solid state batteries, light emitting diodes, electrochromic devices, sensors,
molecular electronics etc. Much research will be needed before many of the above applications become a reality.
The stability and processibility both need to be substantially improved if these polymers are to be used in the
market place. Regardless of the practical applications that are eventually developed for electrically conducting
polymers, they will certainly continue to challenge researchers in the years to come with new and unexpected
phenomena.
Acknowledgements
One of the authors (A K Bakshi) is thankful to DST (Department of Science and Technology) for the financial
support. Geetika Bhalla is grateful to CSIR (Council of Scientific and Industrial Research), New Delhi for the
award of fellowship.
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