Conductive polymers methods

Polymers. The Tt-conjugated polymers used in semiconducting appHcations are usually insulating, with semiconducting or metallic properties induced by doping (see Flectrically conductive polymers). Most of the polymers of this type can be prepared by standard methods. The increasing use of polymers in devices in the last decade has led to a great deal of study to improve the processabiUty of thin films of commonly used polymers. 

The development of polythiophenes since the early 1980s has been extensive. Processible conducting polymers are available and monomer derivathation has extended the range of electronic and electrochemical properties associated with such materials. Problem areas include the need for improved conductivity by monomer manipulation, involving more extensive research using stmcture—activity relationships, and improved synthetic methods for monomers and polymers alike, which are needed to bring the attractive properties of polythiophenes to fmition on the commercial scale. 

Because of the aqueous solubiUty of polyelectrolyte precursor polymers, another method of polymer blend formation is possible. The precursor polymer is co-dissolved with a water-soluble matrix polymer, and films of the blend are cast. With heating, the fully conjugated conducting polymer is generated to form the composite film. This technique has been used for poly(arylene vinylenes) with a variety of water-soluble matrix polymers, including polyacrjiamide, poly(ethylene oxide), polyvinylpyrroHdinone, methylceUulose, and hydroxypropylceUulose (139—141). These blends generally exhibit phase-separated morphologies. 

Electrochemical polymeriza tion of heterocycles is useful in the preparation of conducting composite materials. One technique employed involves the electro-polymerization of pyrrole into a swollen polymer previously deposited on the electrode surface (148—153). This method allows variation of the physical properties of the material by control of the amount of conducting polymer incorporated into the matrix film. If the matrix polymer is an ionomer such as Nation (154—158) it contributes the dopant ion for the oxidized conducting polymer and acts as an effective medium for ion transport during electrochemical switching of the material. 

Thus electrical conductivity is commonly measured in units of S/cm (0 cm ). Various experimental methods have been used to measure the electrical conductivity of conductive polymers, eg, 4-probe method. Van der Pauw method, etc, and are well documented in the Hterature. 

The science and technology of conducting polymers are inherently interdisciplinary they fall at the intersection of three established disciplines chemistry, physics and engineering hence the name for this volume. These macromolccular materials are synthesized by the methods of organic chemistry. Their electronic structure and electronic properties fall within the domain of condensed matter physics. Efficient processing of conjugated polymer materials into useful forms and the fabrication of electronic and opto-electronic devices require input from engineering i. e. materials science (more specifically, polymer science) and device physics. 

One more fact, important in practice, lies in that a of the compositions based on heterogeneous blends of polymers obtained by the method 3, depends considerably on mixing temperature Tm. This is bound up with a variation of the polymer viscosity with the temperature on being introduced into the polymer mixture, a filler becomes distributed mostly in the less viscous polymer and, if the viscosity of polymers is almost the same, it is distributed comparatively uniformly and a of the composition decreases. Therefore, the dependence of a of the conducting polymer composite on Tm has a minimum (by a factor of 102 to 104) in the Tm region when the viscosities of the polymer components are close. 

It is well known, that under industrial conditions a method of introducing filler into the polymer mixture is used. In this case, the filler is introduced in the form of paste containing up to 60 per cent water in order to reduce viscosity, As heating is affected by viscous friction, the temperature conditions are not stable on mixing and, therefore, conductivity of the conducting polymer composite becomes unreproducible. Up to now this factor has not been taken into consideration. 

The electrochemistry of conducting polymers has been the subject of several reviews2-8 and has been included in articles on chemically modified electrodes.9-14 The primary purpose of this chapter is to review fundamental aspects of the electrochemistry of conducting polymer films. Applications, the diversity of materials available, and synthetic methods are not covered in any detail. No attempt has been made at a comprehensive coverage of the relevant literature and the materials that have been studied. Specific examples have been selected to illustrate general principles, and so it can often be assumed that other materials will behave similarly. 

The electrochemistry of a polymer-modified electrode is determined by a combination of thermodynamics and the kinetics of charge-transfer and transport processes. Thermodynamic aspects are highlighted by cyclic voltammetry, while kinetic aspects are best studied by other methods. These methods will be introduced here, with the emphasis on how they are used to measure the rates of electron and ion transport in conducting polymer films. Charge transport in electroactive films in general has recently been reviewed elsewhere.9,11... 

The huge literature on the electronic conductivity of dry conducting polymer samples will not be considered here because it has limited relevance to their electrochemistry. On the other hand, in situ methods, in which the polymer is immersed in an electrolyte solution under potential control, provide valuable insights into electron transport during electrochemical processes. It should be noted that in situ and dry conductivities of conducting polymers are not directly comparable, since concentration polarization can reduce the conductivity of electrolyte-wetted films considerably.139 Thus in situ conductivities reported for polypyrrole,140,141 poly thiophene,37 and poly aniline37 are orders of magnitude lower than dry conductivities.15... 

Impedance spectroscopy is best suited for the measurement of electronic conductivities in the range 10 -7to 10 2S cm 1.145 In principle, it is perhaps the best method for this range, but it is often difficult to interpret impedance data for conducting polymer films. The charge-transfer resistance can make measurements of bulk film resistances inaccurate,145 and it is often difficult to distinguish between the film s ionic and electronic resistances.144 This is even more of a problem with chronoamperometry146 and chronopotentiometry,147 so that these methods are best avoided. 

A variety of other techniques have been used to investigate ion transport in conducting polymers. The concentrations of ions in the polymer or the solution phase have been monitored by a variety of in situ and ex situ techniques,8 such as radiotracer studies,188 X-ray photoelectron spectroscopy (XPS),189 potentiometry,154 and Rutherford backscatter-ing.190 The probe-beam deflection method, in which changes in the density of the solution close to the polymer surface are monitored, provides valuable data on transient ion transport.191 Rotating-disk voltammetry, using an electroactive probe ion, provides very direct and reliable data, but its utility is very limited.156,19 193 Scanning electrochemical microscopy has also been used.194... 

Quantum chemical calculations, 172 Quantum chemical method, calculations of the adsorption of water by, 172 Quantum mechanical calculations for the metal-solution interface (Kripsonsov), 174 and water adsorption, 76 Quartz crystal micro-balance, used for electronically conducting polymer formation, 578... 

Table 1. Conducting polymers preparation methods and conductivities...

Besides synthesis, current basic research on conducting polymers is concentrated on structural analysis. Structural parameters — e.g. regularity and homogeneity of chain structures, but also chain length — play an important role in our understanding of the properties of such materials. Research on electropolymerized polymers has concentrated on polypyrrole and polythiophene in particular and, more recently, on polyaniline as well, while of the chemically produced materials polyacetylene stih attracts greatest interest. Spectroscopic methods have proved particularly suitable for characterizing structural properties These comprise surface techniques such as XPS, AES or ATR, on the one hand, and the usual methods of structural analysis, such as NMR, ESR and X-ray diffraction techniques, on the other hand. 

Another method to synthesize hollow nanocapsules involves the use of nanoparticle templates as the core, growing a shell around them, then subsequently removing the core by dissolution [30-32]. Although this approach is reminiscent of the sacrificial core method, the nanoparticles are first trapped and aligned in membrane pores by vacuum filtration rather than coated while in aqueous solution. The nanoparticles are employed as templates for polymer nucleation and growth Polymerization of a conducting polymer around the nanoparticles results in polymer-coated particles and, following dissolution of the core particles, hollow polymer nanocapsules are obtained. 

Many other opportunities exist due to the enormous flexibility of the preparative method, and the ability to incorporate many different species. Very recently, a great deal of work has been published concerning methods of producing these materials with specific physical forms, such as spheres, discs and fibres. Such possibilities will pave the way to new application areas such as molecular wires, where the silica fibre acts as an insulator, and the inside of the pore is filled with a metal or indeed a conducting polymer, such that nanoscale wires and electronic devices can be fabricated. Initial work on the production of highly porous electrodes has already been successfully carried out, and the extension to uni-directional bundles of wires will no doubt soon follow. 

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