PII:

Eur. Polym. J. Vol. 34, No. 8, pp. 10531060, 1998 # 1998 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0014-3057/98 $see front matter S0014-3057(97)00204-8

REVIEW ARTICLE ADVANCES IN CONDUCTIVE POLYMERS

D. KUMAR* and R. C. SHARMA
Department of Applied Chemistry, Delhi College of Engineering, University of Delhi, Delhi-110006, India (Received 12 August 1996; accepted in nal form 30 April 1997) AbstractConductive polymers are a new class of materials which exhibit highly reversible redox behaviour and the unusual combination of properties of metal and plastics. The prospective utility of conductive polymers with a potent application in number of growing technologies in biomolecular electronics, telecommunication, display devices and electrochemical storage systems, etc. has further enhanced the interest of researchers in this novel area. An eort has been made in this article to present an updated review on the various aspects of conductive polymers, viz. synthesis of conductive polymers, doping, structure analysis and proposed utility for further study of the future scientic and technological developments in the eld of conductive polymers. # 1998 Elsevier Science Ltd. All rights reserved

INTRODUCTION

The discovery of conductive polymers is unique in its accomplishment as a possible substitute for metallic conductors and semiconductors. The eorts for having a tailor-made polymer in respect of its electrical, mechanical, optical and thermal properties have been pursued by several research groups. It was thus felt that a comprehensive review devoted entirely to the current understanding and state-ofthe-art, derived from the existing published experimental and theoretical data of conductive polymers including those based on aromatic systems, would be highly desirable and inspire the dedicated researchers' venture into new experiments. The development of polymers with conductivities equal to semiconductors and metals have been presented in Table 1 and their corresponding structures are shown in Fig. 1. The conductive polymers belonging to polyenes or polyaromatics such as polyacetylene, polyaniline, polypyrrole, polythiophene, poly( p-phenylene), poly(phenylene vinylene) classes have been studied extensively. Among all the above classes, the polyaniline family of conjugated polymers is of much interest worldwide because of its unique conduction mechanism and good environmental stability in the presence of oxygen and water. Polyaniline is one of the oldest conductive polymers known. It was rst prepared by Letheby in 1862 by anodic oxidation of aniline in sulphuric acid and described as existing in four dierent states, each of which was an octamer. The decade of the 1970 s witnessed the evolution of a variety of conductive polymers [14], but poor solubility in most of the common solvents and low thermoplasticity rendered the processing of conductive polymers research to prepare soluble
*To whom all correspondence should be addressed.

forms of conductive polymers. A summary of the reported literature highlighting the polymerisation techniques of conductive polymers is presented in Table 2 [526]. Bryce et al. [7] prepared the soluble form of polythiophene by substitution in the thiophene ring's 3 position of either a methoxy group or long-chain alkyl groups and Macinnes and Funt [8] prepared the polyaniline by substitution in the ortho position of benzene ring in aniline. To study the thermal behaviour, Mcghie [27] reviewed the thermal analysis of polymers, with discussion particularly on TGA, DSC and thermochemical analysis, while Gedde [28] reviewed DSC, DTA, thermogravimetry, thermal mechanical analysis and thermal optical analysis and presented the interpretation of the consequences. The development of the eld of conductive polymers has been comprehensively reviewed, as in an earlier report in compilation volumes edited by Lund and Baizer [29], Gerischer and Tobias [30], Margolis [31], Linford [32] and by Chandler and Pletcher [33]. Other reviews include those by Deronzier and Moutet [34], Heinze [35], Simonet and Rault-Berthelot [36] and Imisides et al. [37]. This review has been structured to present an overview on preparations, doping, proposed utilities and concluding remarks on conjugated polymers.
SYNTHESIS

There is no singular method for synthesising polymers that can be transformed into conductive polymers, the incorporation of extended p-electron conjugation is of foremost importance. Conductive polymers except ionomeric polymers may be synthesised using standard methods of polymerisation [3841] including conventional as well as specic routes which include Witting, Horner and Grignard reactions, polycondensation processes and metal

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D. Kumar and R. C. Sharma

Table 1. Conductivities of conductive polymers with selected dopants Polymer Polyacetylene Polypyrrole Polythiophene Poly(3-alkylthiophene) Polyphenylenesulphide Polyphenylene-vinylene Polythienylene-vinylene Polyphenylene Polyisothi-anaphthene Polyazulene Polyfuran Polyaniline Doping materials I2, Br2Li, Na, AsF5 BF 4 , ClO4 , tosylate BF4 , ClO 4 , tosylate, FeCl4 BF 4 , ClO4 , FeCl4 AsF5 AsF5 AsF5 AsF5 Li, K BF 4 , ClO4 BF 4 , ClO4 BF 4 , ClO4 HCl Conductivity (s/cm) 104 500 7.5 103 103 103104 500 104 2.7 103 103 50 1 100 200

catalysed polymerisation techniques. Oxidative coupling with oxidising Lewis acid catalysts generally leads to polymers with aromatic or heterocyclic building blocks. Conductive polymers may be synthesised by any one of the following techniques: 1. Chemical polymerisation 2. Electrochemical polymerisation 3. Photochemical polymerisation 4. Metathesis polymerisation 5. Concentrated emulsion polymerisation 6. Inclusion polymerisation 7. Solid-state polymerisation 8. Plasma polymerisation 9. Pyrolysis 10. Soluble precursor polymer preparation.

Among all the above categories, chemical polymerisation [4245] is the most useful method for preparing large amounts of conductive polymers, since it is performed without electrodes [10, 11]. Chemical polymerisation (oxidative coupling) is followed by the oxidation of monomers to a cation radical and their coupling to form dications and the repetition of this process generates a polymer. All the classes of conjugated polymers may be synthesised by this technique. Electrochemical polymerisation is normally carried out in a single- or dual-compartment cell by adopting a standard three-electrode conguration in a supporting electrolyte, both dissolved in an appropriate solvent. Electrochemical polymerisation [4548] can be carried out potentiometrically by using a suitable power supply (potentiogalvanostat).

Fig. 1. Conductivity of some conjugated polymers.

Advances in conductive polymers

Table 2. List of synthesis techniques of conductive polymers Polymer Polyacetylene Polythiophene Polyaniline Polyisoprene Polybutadiene Poly(2, 3-dimethyl-butadiene) Polypyrrole Poly(p-phenylene-terephthalamide) Polypyrrole-polymide composites PVC Polystyrene Poly(p-phenylene) Poly(a-naphthylamine) 3-Octylthiophene-3-methylthiophene Poly(1,4-phenylene) Poly(aniline-co-o-anisidine) polymn., polymerisation Method used Chemical polymn. Chemical Polymn. Electrochemical polymn. Chemical polymn. Electrochemical polymn. Inclusion polymn. Inclusion polymn. Inclusion polymn. Chemical polymn. Electrochemical polymn. Electrochemical polymn. Electrochemical polymn. Chemical polymn. Concentrated emulsion polymn. Chemical polymn. Electrochemical polymn. Electrochemical polymn. Electrochemical polymn. Chemical polymn. References 1 57 13, 16, 22 8 13 9 9, 17 9 10 1315, 25 14 12 18 19 20 21 23 24 26

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Generally, potentiostatic conditions are recommended to obtain thin lms, while galvanostatic conditions are recommended to obtain thick lms. The electrochemical technique has received wider attention both because of the simplicity and the added advantage of obtaining a conductive polymer being simultaneously doped. Besides this, a wider choice of cations and anions for use as ``dopant ions'' is available in the electrochemical polymerisation process. Free-standing as well as self-supporting conductive polymer lms of desired thickness or geometry can be obtained. Using this novel technique, a variety of conductive polymers like polypyrrole, polythiophene, polyaniline, polyphenylene oxide pyrrole and polyaniline/polymeric acid composite have been generated. Pyrrole in aqueous acetontrile solvent containing tetraethyl ammonium tetrauoroborate was electropolymerised in a twoelectrode electrochemical cell. Polypyrrole containing the BF 4 ion (dopant) was obtained as a lm deposited on the platinum electrode surface [49]. This method has also been used to polymerise acetylene. In an electrolytic cell, consisting of Pt as cathode and a Ni strip as anode, acetylene gas is passed over a solution comprising NiBr2 dissolved in CH3CN. On application of voltage varying from 5 to 40 V for about 50 min, polyacetylene lms can be easily grown on a Pt electrode. The degree of doping depends on the dopant concentration, voltage applied and the amount of charge passed. Photochemical polymerisation [50] takes place in the presence of sunlight. This technique utilises photons to initiate a polymerisation reaction in the presence of photosensitisers. Recently, pyrrole has been photopolymerised using a ruthenium(ll) complex as photosensitiser. Under photoirradiation, RU(ll) is oxidised to Ru(lll) and the polymerisation is initiated by a one-electron transfer oxidation process. Polypyrrole (PPy) lms may be obtained by photosensitised polymerisation of pyrrole using a copper complex as the photosensitiser. Photopolymerisation of benzo(C)thiophene has been carried out in acetonitrile using CCl4 and tetrabutylammoniumbromide.

Plasma polymerisation is a technique for prepar ) that ing ultrathin uniform layers (50100 A strongly adhere to an appropriate substrate. Electric glow discharge is used to create low-temperature ``cold'' plasma. The advantage of this technique is that it eliminates various steps needed for the conventional coating process. Metathesis polymerisation is unique, diering from all other polymerisations in that all the double bonds in the monomer remain in the polymer. It was a natural outgrowth of ZieglerNatta polymerisation in that the catalysts used are similar, and often identical, i.e. a transition metal compound plus usually an organometallic alkylating agent. Metathesis polymerisation is further divided into three classes: ring-opening metathesis of cyclo-olens (ROMP); metathesis of alkynes, acyclic or cyclic; and metathesis of diolens. By far the greatest amount of work has been done on ROMP. Pyrolysis is probably one of the oldest approach utilised to synthesise conductive polymers by eliminating heteroatoms from the polymer by heating it to form extended aromatic structures. The product of polymer hydrolysis can be a lm, powder or a bre depending on the form and nature of the standing polymer including the pyrolysis condition. Nevertheless, conductive polymers have also been synthesised by other techniques such as chain polymerisation, step-growth polymerisation, chemical vapour deposition, solid-state polymerisation, soluble precursor polymer preparation, concentrated emulsion polymerisation, etc. However, most of these techniques are time-consuming and involve the use of costly chemicals.

FABRICATION OF FILMS

It is known that conductive polymer lms have a very large surface to volume ratio, which consequently inuences the lm properties over bulk materials. Keeping a precise control over the various parameters on conductive polymer lms, a number

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D. Kumar and R. C. Sharma

of techniques have been introduced for fabrication of thin to thick lms. These techniques are 1. 2. 3. 4. Solution cast Spin cast Vacuum deposition LangmuirBlodgett (LB) lm fabrication.

3. 4. 5. 6.

electrochemical doping self doping radiation-induced doping and ion-exchange doping.

The solution cast method can be used for the fabrication of ordered lms. The solution cast method and spin cast technique depend upon the solubility of the conductive polymers, previously synthesised by the chemical polymerisation technique. The LB lm deposition technique has been applied to organic thin lms fabrication arranged in ordered states. Precise thickness control coupled with the degree of control over the molecular architecture has rmly established a role for LB lms in thinlm technology. The feasibility of locating functional parts at the molecular level along with control of the thickness of the resultant lm are the novel features of this technique.
DOPING

Of these, the rst three techniques are widely used because of convenience and low cost. In the gaseous doping process, polymers are exposed to the vapours of the dopant under vacuum. Solution doping involves the use of a solvent in which all the products of doping are soluble. 1,4-Poly(butadiene) polymers having a non-conjugated backbone have been doped with halogen to form semiconductors [9]. Eective doping of polymer anions during chemical polymerisation of pyrrole using Fe3+ based oxidants and electrolytes increases the conductivity several-fold [10]. Vadera and Kumar have demonstrated that certain dopants could give rise to magnetic ordering in these polymers along with the electron acceptor (e.g. iodine, FeCl3, AsF5, etc.) or electron donor (e.g. Na, Li, etc.) to the polymer which is considered to generate positive carriers (holes) or negative carriers (electrons) in the p-conjugated system.
NATURE OF DOPANT

Moreover, the conductivity of a polymer can be increased several-fold by doping it with an oxidative/reductive substituents or by donor/acceptor radicals. Shirakawa and Ikeda [1] discovered that doping of polyacetylene (PA) with metallic regimes increases its conductivity by 913 orders of magnitude. Doping is accomplished by chemical methods of direct exposure of the conjugated polymer to a charge transfer agent (dopant) in the gas or solution phase, or by electrochemical oxidation or reduction. The doping is usually quantitative and the carrier concentration is directly proportional to the dopant concentration. Doping of conductive polymers involves random dispersion or aggregation of dopants in molar concentrations in the disordered structure of entangled chain and brils. Polymer doping leads to the formation of conjugational defects, viz. solitons, polarons or bipolarons in the polymer chain. An x-ray diraction study on iodine-doped polyacetylene shows that the C0C bond length of the polyacetylene chain increases with donor doping but decreases on acceptor doping. The presence of localised electronic states of energies less than the band-gap arising from changes in local bond order, including the formation of solitons, polarons and bipolarons have led to the possibility of new types of charge conduction present in these polymer systems. Chart 1 gives the charge and spin characteristics of these defects.
Chart 1 Typical properties of solitons, polarons and bipolarons Defect Spin Charge Soliton Soliton Polaron Bipolaron neutral charged charged charged 1/2 0 1/2 0 0 +e 0r e +e or e +2e or 2e

Doping agents or dopants are either strong reducing agents or strong oxidising agents. They may be neutral molecules and compounds or inorganic salts which can easily form ions, organic dopants and polymeric dopants. The nature of dopants play an important role in the stability of conductive polymers. For example, perchloric acid doped polyacetylene is not sensitive to water and oxygen. Similarly, electrochemical doping of polyacetylene with sodium uoride makes it more resistant to oxygen. When poly(3-methylthiophene) is doped with SO3CF 3 it develops stability in atmospheric air. Stabilisation of the conductive polymers has been tried by two routes, viz. incorporation of antioxidants, such as benzoquinone and hindered phenols or by using radical traps such as azobisisobutylonitrile. Another method is ion implantation.
CONDUCTIVITY IMPROVEMENT TECHNIQUES

Conductivity of the polymers may be improved by the modication of polymerisation conditions. The important conductive polymers synthesised in the modied polymerisation conditions are described in the following paragraph. 1. Polyacetylene (PA) polymerisation in silicon oila room temperature process: The production of PA determines the direct relationship between conductivity and crystallinity and the indirect relationship with the number of sp3 orbitals. If the polymerisation conditions are modied, e.g. by silicon oil, a new N(CH)x polyacetylene can be obtained at room temperature. Its quality is equally good as the standard S(CH)x prepared by the Shirakawa technique at 788C. Ageing of the standard catalyst also improves the properties of PA.

Polymers may be doped by the following techniques: 1. gaseous doping 2. solution doping

Advances in conductive polymers

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2. Polyacetylene (PA) polymerisation via olen metathesis: The synthesis of PA and substituted PA by the ring opening metathesis polymerisation (ROMP) of cyclo-octatraene (COT) and substituted COT have been reported [51] recently. 3. Phenylene-based conductive polymers: The conductive poly( p-phenylene) was rst prepared by the reaction of dihalobenzene with sodium by the Ullmann reaction. Many substituted polyphenylenes were also prepared using the same reaction. Poly(phenylene vinylene) is a composite polymer of polyphenylene and polyacetylene. It was shown to become conductive upon doping with AsF5 with a conductivity of 3.0 S/cm [52]. 4. Conductive polymer with condensed aromatic units: Polynaphthalene prepared by oxidative polymerisation from naphthalene by the action of CuCl2 has an electrical conductivity of 1.2 103 S/cm and polyphthalene [53] was synthesised by oxidative polymerisation with Polyphenanthrylene PdCl2=1.4 1014 S/cm. was prepared by the polycondensation of phenanthrene with CuCl2 at 1008C having a conductivity of 6 107 S/cm. 5. Polymer with heteroaromatic units: Conductive polymers with heteroaromatic units have been synthesised from pyrrole, indole, carbazole, imidazole, pyridine, quinaldine and thiophene. Armour et al. [54] prepared polymers from furan, pyrrole and thiophene using trichloro and triuoro acetic acid. The resulting products are of dark colours and have short conjugated pelectrons and low electrical conductivity. 6. Conductive polymers with aromatic and heteroaromatic and conjugated aliphatic units: Polymers with aromatic, substituted aromatic and heteroaromatic systems blended to conjugated aliphatic units like vinylenes, substituted vinylene and 1,4-dibutadienediyl to form longchain polyconjugated molecules have coplanar structures. Polymeric vinylenes (R0CH1CH0)x were prepared by the Witting reaction. The dialdehyde of aromatics or heteroaromatics and its Witting salts reacted with two types of vinylenes: cis and trans. Donoracceptor complexes of oligomeric and polymeric vinylenes have higher conductivity than the starting materials. Conductive polymers with tetracyano-pquinodimethane (TCNQ) of oligomeric stibine, tetramethoxystibine and 1,2-di-2-thienylethylenes have higher conductivities than single monomers. 7. Azomethines are conjugated molecules with aromatic and heteroaromatic units: These can be easily prepared by the reaction of dialdehyde with diamines in solution or a melt.
APPLICATIONS

achieved with the polymers derived from acetylene, pyrrole, thiophene, aniline and their derivatives, polyphenylene, poly(phenylene vinylenes) and poly(p-heterocyclic vinylenes) have emerged as the materials to replace metals and semiconductors in the electrical and electronics industry, as well oering themselves as the materials for the optoelectronic industry. The specic engineering applications in these area are charted in Fig. 2. Some of the applications of conductive polymers are illustrated below. 1. The electronic conductivity of conductive polymers makes them suitable candidates as cathodes in rechargeable batteries. The advantages these materials oer are many, such as ease of fabrication, processability, low cost and light weight. Research ndings on a polyacetylenelithium battery [60] were published in 1981. Solid-state batteries are also possible to make using (CH)x. Several of these types of batteries have been fabricated. Conductive polymer batteries have long life, are rechargeable and can produce current density of up to 50 mA/cm2 and an energy density of 10 Watt-h/kg. Among the batteries, lithium batteries are especially important since they show a high discharging voltage (ca. 3.0 V) Li e Y Polymer
charge discharge charge discharge charge discharge

Li

p doped polymer

LiY polymer

Li p doped polymer 3

where Y =

ClO 4,

BF 4,

etc.

Similarly, the following charging reactions take place when a Znl2 solution is electrolysed by using Zn and PTh as the negative and positive electrodes, respectively. Negative electrode: Zn2 2e 4 Zn Positive electrode: 2I 4 I2 2e I2 PTh 4Iodine doped PTh 2I PTh 4Iodine doped PTh 2e ZnI2 PTh
charge discharge

4 5 6 7

Zn Iodine doped PTh 8

The recent developments toward the synthesis of new and processable polymers as well as discovering the broad range of physical phenomena and chemical exibility opens up opportunities for new technological applications [5559]. The higher environmental stability and modication of properties to suit a given end use and processability

Since the iodine doped-PTh has electrically conductive properties and stores positive charge in the polymer chain, it serves as a good polymer electrode for a battery (Fig. 3). (2) The polypyrrole conductive polymer has even higher conductivity than plastic extended with conductive ller shields. The experimental results for

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D. Kumar and R. C. Sharma

Fig. 2. Technological applications of conductive polymers.

the shielding ecacy of polypyrrole lms over a wide range of frequencies in radiation eld (1 MHz1 GHz) show an attenuation of 40 db [38]. (3) A solid electrolytic capacitor contains a dielectric oxide-coated metal foil (e.g. Al) on an electrically conductive polymer lm (e.g. polypyrrole) formed by chemical polymerisation, an electrically conductive polymer lm formed by electrolytic polymerisation and an electrically conductive coating. The capacitor has excellent thermal and moisture stability and has been used in a small video camera. (4) The polyanilines, polythiophene and polypyrrole are very useful materials for fabricating electrooptical display devices [61]. The systematic development of electro-optical polymer device structures

for optical multichip modules and related components were presented by Lytel et al. [62]. Polythiophenes show change in colour from red to blue on applying voltage. The changed colour lasts for several hours, thus showing the possibility of being used as an optical memory element. Interestingly, polythiophene can also be conveniently used as a switching element because the switching time from red to blue is 80 msec and from blue to red 300 msec. Similarly, three stable colours (yellow green, dark brown and blue) are observed in an electro-optical cell using polypyrrole. The absorbance changes in these and a few other conductive polymers such as 3-methyl thiophene [63], 3,4-dimethyl thiophene, thieno (2,3-C) pyrrole

Fig. 3. Charging and discharging of Zn/Znl2/PTh battery.

Advances in conductive polymers

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Fig. 4. Various forms of poly(aniline).

[11] and polyaniline [64] make them quite attractive for electrochromic applications. Conductive polymers like polyaniline and polyisothionaphthene show a whole range colours as a result of their many protonation and oxidation forms (Fig. 4). The elctrochromic properties [65] of such polymers can be easily exploited to produce a number of dierent electrochromic devices, such as display and thermal ``smart windows''. The smart windows absorb some of the sunlight which changes colour in response to sunlight or temperature changes, thus saving air conditioning costs. (5) A British group has recently developed metal insulator semiconductor (MIS) structures and MIS eld-eect transistors (MISFET) by using the in situ formation of polyacetylene lms [66]. (6) A Schottky type barrier diode consisting of an electrochemically prepared copolymer of pyrrole and N-methyl pyrrole and low work function indium has been successfully utilised for the fabrication of Al/polymer/Au photovoltaic cells. The solar cells developed using semiconductor polyacetylene have a circuit developed voltage (Voc) of H0.3 V, a short circuit current (Isc) of H36 mA/cm2 and a ll factor (FF) of H0.317 and deteriorate with time because of the increasing sensitivity of (CH)x to air and humidity. (7) In order to control air pollution and to detect combustible, toxic or noxious gases at low levels, tremendous eorts are being made towards the development of simple and inexpensive semiconducting oxide gas sensors. However, the semiconducting oxide lm sensors generally operate eciently only at 3008C. In order to overcome this limitation, new materials are being developed. It is observed that vacuum deposited thin lms of polyaniline exhibit excellent gas sensing properties. The electrical conductivity, optical absorption and electrical capacitance of the metalpolymer interface is strongly inuenced by the presence of certain gas molecules. These results have led to the development of gas sensing elements for gases such as CO,

NH3, HCl and HCN. Thin-lm polyaniline-based gas sensing elements [67] are inexpensive and operate at room temperatures with satisfactory selectivity for these gases. Conductive polymers such as polyfuran and polythiophene have been seriously considered as humidity sensors, radiation detectors and gas sensors. The conductivity of perchlorate-doped polyfuran varies from 108 to 102 S/cm when exposed to humidity ranging from 10 to 80%. Similar variation in conductivity has been observed for polythiophene lms on irradiation with an electron beam in the presence of SF 6 . A signicant change in the conductivity of polypyrrole lms has also been noticed when exposed to toxic gases such as NO2 and CO [68]. Sensors [69] were also prepared from polyphenyl acetylene (PPA) doped with HCl and from polybenzyl propargylamine (PBPA) doped with iodine. (8) Medicinal use: In addition to the numerous applications discussed above, conductive polymers such as polypyrrole have been used in the past to control the release of various anions such as glutamate (Glu) and ferrocyanide, which is of interest to neuroscience.
CONCLUSIONS

To realise the advantages of conductive polymers having a rare combination of electrical, electrochemical and physical properties, it is very essential to increase their processability, environmental and thermal stabilities. From the recent studies on the polyaniline family of polymers it has been demonstrated that these polymers could be highly promising for many technological uses because of their chemical versatility, stability, processability and low cost. Another versatile area from the technological point of view is the studies on composites containing conductive polymers and an inert polymer matrix. Improving the synthesis, conductivities and optimising the catalysts pave the way for the production of highly conductive materials with reproducible quality. Moreover, there is very great potential to use conductive polymers in the virtually unexplored biochemical applications.
Acknowledgements Our thanks are, in a large measure, due to Professor P. B. Sharma, principal, Delhi College of Engineering, for his unstated help and encouragement. Financial assistance from the MHRD, Government of India, through the Delhi College of Engineering is gratefully acknowledged.
REFERENCES

1. Shirakawa, H. and Ikeda, S., Polym. J., 1971, 2, 231. 2. Frommer, J. E. and Chance, R. R., Encycl. Polym. Sci. Eng., 1986, 5, 462. 3. Roth, S. and Munstedt, H., in Electronic Properties of Polymers and Related Compounds, 63. Springer series Solid State Science, 1985. 4. Friend, R. H., in Conductive Polymers, Report from Rapra Review, Vol. 6, No. 3, Rapra Technology Ltd, Oxford, 1993, Feast, W. J., Report from Rapra Review, Vol. 1, No. 1, Pergamon Press, Oxford, 1987. 5. Jen, K. Y., Obbodi, R. and Elesnbaumer, R. L., Polym. Mater. Sci. Eng., 1985, 53, 79.

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D. Kumar and R. C. Sharma 39. Bakhshi, A. K., Bull. Electrochem., 1992, 8, 535. 40. Kulszewicz-Bajer, I., Sobezak, J., Hasik, M. and Pretula, J., Polymer, 1996, 37, 25. 41. Erdem, E., Sacak, M. and Karakisla, M. M., Polym. Int., 1996, 39, 153. 42. Chen, S. A. and Tsai, C. C., Macromolecules, 1993, 26, 2234. 43. Wei, Y., Tian, J., MacDiarmid, A. G., Masters, J. G., Smith, A. L. and Li, D., J. Chem. Soc. Chem. Commun., 1994, 7, 552. 44. Beadle, P., Armes, S. P., Gottesfeld, S., Mombourquette, C., Houlton, R., Andrews, W. D. and Agnew, S. F., Macromolecules, 1992, 25, 2526. 45. Somanathan, N. and Wegner, G., Ind. J. Chem., 1994, 33A, 572. 46. Skotheim, T. A., in Handbook of Conducting Polymers, Vols 1 and 2. Marcel Dekker, New York, 1986. 47. Malhotra, B. D., Ghosh, S. and Chandra, R., J. Appl. Polym. Sci., 1990, 40, 1049. 48. Neglur, B. R., Laxmeshwar, N. B. and Santhanam, K. S. V., Ind. J. Chem., 1994, 33A, 547. 49. Curran, D., Grimshaw, J. and Perera, S. D., Chem. Soc. Rev., 1991, 20, 1; Malli, S., Ind. J. Chem., 1994, 33A, 524. 50. Annapoorni, S., Sundaresan, N. S., Pandey, S. S. and Malhotra, B. D., J. Appl. Phys., 1993, 74, 2109. 51. Klavetter, F. L., et al., J. Am. Chem. Soc., 1988, 110, 7807; Korshsk, Y. V., Koeshak, V., Kansichka, G. and Hucker, H., Macromol. Chem. Rapid Commun., 1985, 6, 685; Gorma, C. B., Ginsburg, E. J., Marder, S. R. and Grubbs, R. H., Angew. Chem. Adv. Mater., 1989, 101. 52. Wnek, G. E., Chine, J. C. S., Karasz, F. E. and Lillya, C. P., Polymer, 1979, 20, 1441. 53. Brown, D. B., in Mixed Valence Compound Redei Dopordrechi, 1980. 54. Armour, M., Davies, A. G., Upadhayay, J. and Wassermann, A., J. Polym. Sci., part A, 1967, 5, 527. 55. Roth, S., Ind. J. Chem., 1994, 33A, 453. 56. Yano, J. and Kitani, A., Synth. Met., 1995, 69, 117. 57. Venkatachalam, S. and Krishnamurthy, V. N., Ind. J. Chem., 1994, 33A, 506. 58. Li, J., Zhang, J. Z., Geng, Y. H., Wang, L. X., Jiang, X. B. and Wang, F. S., Synth. Met., 1995, 69, 245. 59. Iida, Y., Electronic and Communications in Japan, part 2, 1996, 78, 89. 60. Negrey, P. J., Machine, D., Nainns, D. P., MacDiarmid, A. G. and Heeger, A. J., J. Electrochem. Soc., 1981, 128, 1651. 61. Ram, M. K., Sundaresan, N. S. and Malhotra, B. D., J. Phys. Chem., 1993, 97, 1580. 62. Lytel, R. et al., in Proc. SPIN Int. Soc. Opt. Eng., Vol. 1389, 1991, p. 547. 63. Garner, F., Tourillon, G., Gazzard, M. and Dubois, J. C., J. Electroanal. Chem., 1983, 148, 299. 64. Kumar, D., Sharma, R. C., Ram, M. K., Dhawan, S. K. and Chandra, S., Ind. J. Chem., 1997, 36A, 14; Kobayashi, T., Yoneyama, H. and Tamura, H., J. Electroanal. Chem., 1984, 161, 419. 65. Kanatzidis, M. G., Chem. Eng. News, 1990, Dec., 36. 66. Feast W. J. and Friend R. H., J. Mater. Sci., 1990, 25, 3796; Burroughes, J. and Friend, R., Phys. World., 1988, 24. 67. Dhawan, S. K., Kumar, D., Ram, M. K., Chandra, S. and Trivedi, D. C., Sens. Actuat. B, 1997, 40, 99. 68. MacDiarmid, A. G., in 1st International Conference on Frontiers of Polymer Research, Jan 20. New Delhi, 1991. 69. Patil, S. F., Bendekar, A. G., Patil, R. C. and Agashe, C., Ind. J. Chem., 1994, 33A, 580.

6. Satoh, M., Tanaka, S. and Kaeriyama, K., J. Chem. Soc. Chem. Commun., 1986, 873. 7. Bryce, M. R. et al., J. Chem. Soc. Chem. Commun., 1987, 466. 8. Macinnes, D. Jr and Funt, B. L., Synth. Met., 1988, 25, 235. 9. Thakur, M., Macromolecules, 1988, 21, 661. 10. Ohtani, A. and Shimadzu, T., Bull. Chem. Soc. Jpn, 1989, 62, 234. 11. Vadera, S. R., in 1st International Conference on Frontiers of Polymer Research, Jan 2025, New Delhi, 1991; Kumar, N., in 1st International Conference on Frontiers of Polymer Research, Jan 2025, New Delhi, 1991; Fuchen Hwa, in 1st International Conference on Frontiers of Polymer Research, Jan 2025, New Delhi, 1991. 12. Tieke, B. and Gabriel, W., Polymer, 1990, 31, 20. 13. Bidan, G., Lapkowski, M. and Travers, J. P., Synth. Met., 1989, 28, 113. 14. Koga, K., Ind, T., Ueta, S. and Takayanagi, M., Polym. J. (Tokyo), 1989, 21, 303. 15. Moss, B. K., Burford, R. P. and Skyllaskazacos, M., Mater. Forum., 1989, 13, 35. 16. Lemarire, M. et al., J. Electroanal. Chem. Interfacial Electrochem., 1990, 281, 293. 17. Shang, Q., Pramanick, S. and Hudson, B., Macromolecules, 1990, 23, 1886. 18. Hollander, A., Zimmermannq, H. and Behnisch, J., Polymer, 1990, 31, 543. 19. Ruckenstein, E. and Park, J. S., J. Appl. Polym. Sci., 1991, 42, 925. 20. Chaturvedi, V., Tanaka, S. and Kaeriyama, K., J. Chem. Soc. Chem. Commun., 1992, 22, 1658. 21. Entezami, A., Golabi, S. M. and Raof, J., Iran. J. Polym. Sci. Technol., 1992, 1, 7. 22. Entezami, A. and Arsalani, N., Iran. J. Polym. Sci. Technol., 1992, 1, 33. 23. Pei, Q., Inganas, O., Osterholm, J. E. and Laakso, J., Polymer, 1993, 34, 247. 24. Aboulkassim, A. and Chevrot, C., Polymer, 1993, 34, 401. 25. Omastova, M., Kosina, S., Skakalova, V. and Jancula, D., Synth. Met., 1993, 53, 227. 26. Pandey, S. S., Annapoorni, S. and Malhotra, B. D., Macromolecules, 1993, 26, 3190. 27. Mcghie, A. R., Electrochem. Sci. Technol. Polym., 1990, 2, 201. 28. Gedde, U. W., Drug Dev. Ind. Pharm., 1990, 16, 2465. 29. Diaz, A. F., in Organic Electrochemistry, An Introduction and Guide, 3rd edn, ed. H. Lund and M. M. Baizer, Marcel Dekker, New York, p. 1363. 30. Evans, G. P., in Advances in Electrochemical Science and Engineering, Vol. 1, ed. H. Gerischer and C. W. Tobias. VCH, Weinheim, 1990, p. 1. 31. Margolis, J. M., Conductive Polymers and Plastics. Chapman and Hall, New York, 1989. 32. MacDiarmid, A. G. and Maxeld, M., in Electrochemical Science and Technology of Polymers, Vol. 1, ed. R. G. Lingford. Elsevier, London, 1987, p. 67. 33. Chandler, G. K. and Pletcher, D., Electrochemistry, Specialist Periodical Report, Vol. 10. Royal Society of Chemistry, London, 1986, p. 117. 34. Deronzier, A. and Moutet, J. C., Acc. Chem. Res., 1989, 22, 249. 35. Heinze, J., Top. Curr. Chem., 1990, 152, 1. 36. Simonet, J. and Rault-Berthelot, J., Prog. Solid State Chem., 1991, 21, 1. 37. Imisides, M. D., John, R., Riley, P. J. and Wallace, G. G., Electroanalysis, 1991, 3, 879. 38. Naarman, H., Electronic Properties of Conjugated Polymers, 76, Springer series in Solid State Science, 1987, p. 12.