Relationship between chain length, disorder, and resistivity in polypyrrole films.

The effects of the polymerization temperature and of voltammetric cycling on the chain length and the resistivity of polypyrrole films are investigated. The studies provide further proof for the existence of at least two different types of polypyrrole, the so-called PPy I and PPy II. As the electropolymerization of conjugated systems in contrast to normal polymerization reactions is a fully activated process, the generation of these different types of PPy depends on experimental parameters such as temperature or formation potentials. UV-vis measurements demonstrate that PPy II comprises significantly shorter chains than PPy I (8-12 vs 32-64 units); moreover, film conductivity is found to increase with the fraction of PPy II. This fraction is changed via the polymerization temperature as well as by cyclic voltammetry, both of which can induce a metal-insulator transition. The counter-intuitive relationship between resistivity and chain length is interpreted in terms of disorder-dominated transport, in which the shorter chains of PPy II support the formation of delocalized electronic states, thereby increasing the localization length. Thus, our results are in agreement with recent broadband reflectivity measurements.