ESR and Transport Studies in Electrochemically Doped Polythiophene Film

Electron spin resonance (ESR), electrical conductivity and thermoelectric power are studied in electrochemically prepared and doped polythiophene films. The ESR spin density increases by two orders of magnitude up to dopant concentration of ca. 3 mol%, then decreases, while the conductivity increases drastically by more than ten orders of magnitude until this doping level, followed by a rather mild increase. The ESR linewidth decreases sharply from 9 G to 0.4 G upon slight doping with shape change from Gaussian to Lorenzian. The contribution of Pauli-paramagnetism to the spin succeptibility and the positive thermoelectric power of ca. 20 µV/K which depends linearly on the temperature are observed at heavily doped region. These results are discussed in terms of shallow and deep polarons, and formation of bipolaron up to intermediate doping levels and the hole conduction at the metallic regime.