An Ellipsometric Study of the Nucleation and Growth of Polythiophene Films

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Abstract
The electrodeposition of polythiophene films has been monitored ellipsometrically. The species that are generated immediately after application of the polymerization potential form in solution near the electrode. Deposition of material on the electrode commences a short time later, in agreement with the point at which current‐time data indicate nucleation of growth sites. Previous analysis of current‐time data suggested three‐dimensional growth, but calculation of film thickness as a function of time from ellipsometric data shows that the process is more complex. Films formed at different potentials require different thicknesses of polymer to be deposited before the film properties approach those characteristic of the bulk film. There is, furthermore, a marked distinction between the optical properties of films as grown at potentials above and below approximately 2.0V. The presence of excess water in the polymerization solution results in the production of a film about 1.5 nm thick which is optically dissimilar from that produced in the absence of water.

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