The electrochemical bandgaps for different soluble substituted polythiophenes have been measured by cyclic voltammetry. The effect of substituents on the oxidation/reduction potentials is discussed. Bandgaps obtained by cyclic voltammetry have been found to be in general higher than optical bandgaps. Among regioregular polymers substituted with a phenyl group at position 3 of the thiophene ring, examples are found that give very symmetric voltammograms. Rationalization for this behaviour is discussed from a conformational point of view.

Synthesis and characterization of poly(quinoxaline vinylene)s and poly(pyridopyrazine vinylene)s with linear and branched aliphatic side chains are reported. The electron affinity of the polymers was measured with cyclic voltammetry (CV) and found to be highest for the pyridopyrazine vinylene polymers, Compared to CN-MEH-PPV, the pyridopyrazine vinylene polymers were easier to reduce, while the quinoxaline derivatives were harder. UV-vis absorption measurements showed that the polymers have relatively small band gaps.

The propagation speed of the front of electrochemical conversion, from semiconductor to highly doped polymer, in films of regioregular poly(3-hexylthiophene) spin cast on insulating substrates was analyzed. Propagation of the p-doped zone in polymer electrochromic devices was imaged simultaneously with recording of electrochemical data. The current is proportional to the propagation speed and has a Tafel-like behavior when taking the resistive drop in the film into account. The resistivity in the film, which gradually lowers the propagation speed, was used for determination of the conductivity of the p-doped polymer. By combining these values with the doping charge injected into the film during front migration we estimated the hole carrier mobility for different doping levels. © 2004 The Electrochemical Society.

The conductivity of chemically and electrochemically de-doped poly(3,4-ethylenedioxythiophene) (PEDOT) has been investigated in situ. We observe a decrease in the conductivity by 4-5 orders of magnitude. The change of conductivity is correlated to the change of electronic structure. We obtain the dielectric function of the polymer by spectroscopic ellipsometry and note that anisotropy is observed in both doped and neutral states. © 2002 Elsevier Science B.V. All rights reserved.