Electrochemical doping processes

These conjugated polymers can be chemically and electrochemically reduced and reoxidized in a reversible manner. In all cases the charges on the polymer backbone must be compensated by ions from the reaction medium which are then incorporated into the polymer lattice. The rate of the doping process is dependent on the mobiHty of these charge compensating ions into and out of the polymer matrix. 

Parent (unsubstituted) PF was first synthesized electrochemically by anodic oxidation of fluorene in 1985 [266] and electrochemical polymerization of various 9-substituted fluorenes was studied in detail later [220,267]. Cyclic voltammogram of fluorene ( r1ed= 1.33 V, Eox = 1.75 V vs. Ag/Ag+ in acetonitrile [267]) with repetitive scanning between 0 and 1.35 V showed the growth of electroactive PF film on the electrode with an onset of the p-doping process at 0.5 V (vs. Ag/Ag+). The unsubstituted PF was an insoluble and infusible material and was only studied as a possible material for modification of electrochemical electrodes. For this reason, it is of little interest for electronic or optical applications, limiting the discussion below to the chemically prepared 9-substituted PFs. 

A central point of research is still the analysis of the electrochemical reaction occurring during charging, which are also known under the term doping process . Even in the earhest stage of research it was clear that these processes were not comparable with the classic doping of typical semiconductors. Rather, they correspond to oxidation in the case of /7-doping or... 

A second major event in the saga of polymer conductors was the discovery that the doping processes of polyacetylene could be promoted and driven electrochemically in a reversible fashion by polarising the polymer film electrode in a suitable electrochemical cell (MacDiarmid and Maxfield, 1987). Typically, a three-electrode cell, containing the (CH) film as the working electrode, a suitable electrolyte (e.g. a non-aqueous solution of lithium perchlorate in propylene carbonate, here abbreviated to LiC104-PC) and suitable counter (e.g. lithium metal) and reference (e.g. again Li) electrodes, can be used. 

An additional important feature of this class of polymers lies in the fact that their polymerisation and doping processes may be driven by a single electrochemical operation which, starting from the monomer, first forms the polymeric chain and then induces its oxidation and deposition in the doped form as a conductive film on a suitable substrate. The polymerisation reaction may be basically described as an electrophilic substitution which retains the aromatic structure and proceeds via a radical cation intermediate ... 

For example, the p-doping process of a typical heterocyclic polymer, say polypyrrole, can be reversibly driven in an electrochemical cell by polarising the polymer electrode vs a counterelectrode (say Li) in a suitable electrolyte (say LiC104-PC). Under these circumstances the p-doping redox reaction (9.15) can be described by the scheme ... 

The evolution of the band structure - and thus of the doping process -may be conveniently monitored by detecting in situ the optical absorption during the electrochemical process, by placing the cell directly into the spectrophotometer (Danieli et al, 1985). 

Fig. 9.10 shows a typical CV of a (CH), film in a LiClO -propylene carbonate electrolyte. The voltammogram presents well-defined peaks both in the anodic (doping) and in the following cathodic (undoping) scans this confirms that the doping process of polyacetylene, as suggested by (9.10), can indeed be driven electrochemically and in a reversible way. 

Fig. 9.11 Schematic of the electrochemical p-doping process of polymer film electrodes, involving transfer of electrolyte anions A".

Considerable attention is presently devoted to heterocyclic polymers, such as polypyrrole, polythiophene and their derivatives. The kinetics of the electrochemical doping processes of these polymers has been extensively studied in electrochemical cells using non-aqueous electrolytes. 

Among the large variety of in situ experiments that have been described one can distinguish (1) those whose purpose is investigation of the electrochemical doping process itself cyclic voltammetry, quartz balance [17], mirage effect [18], and ellipsometry [19], and (2) those developed for studies of the properties of the CP UV-near-IR spectroscopy [20], IR [21], ESR [22], conductivity [23], impedence [24], and so on. 

The doping process of a single isolated chain resembles that of semiconductors. Electron acceptors or electron donors change the electron population in the valence or in the conduction band or, vice versa, electrons or holes from the polymer bands ionize the doping molecules, which are intercalated between the chains. Chemically speaking, this process equals an oxidation or reduction of the chains. The redox character of the doping process is reflected even more clearly by the fact that electrochemical oxidation and... 

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