Charge storage in doped poly(thiophene): Optical and electrochemical studies

We present a new method of electrochemical polymerization of poly(thiophene) using dithiophene as the starting material, from which we obtain a high-quality film with a sharp interband absorption edge. An in situ study of the absorption spectrum during the electrochemical doping process has been carried out. In the dilute regime, the results are in detailed agreement with charge storage via bipolarons; weakly confined soliton pairs with confinement parameter $\gamma \cong 0.1-0.2$. At the highest doping levels, the data are characteristic of the free-carrier absorption expected for a metal. From a parallel electrochemical voltage spectroscopy study, we find evidence of charge injection near the band edge and charge removal from the bipolaron gap states. In the dilute regime, the position of the chemical potential is consistent with charge storage in weakly confined bipolarons. The high Coulombic recovery over a charge-discharge cycle indicates that poly (thiophene) may be an excellent cathode-active material in battery applications.