Abstract
The morphologies of PEDOTh films deposited on platinum electrodes, using different electrochemical modes but conditions selected to obtain layers with similar electroactivities, have been analysed by atomic force microscopy (AFM). Ex situ AFM showed a fibber-like topography for the potentiodynamically synthesised films, contrasting to the granular character of those formed at constant potential. In situ contact mode AFM, used to examine the initial stages of the polymer growth and the surface morphology evolution, disclosed the development of long segments with the number of potential cycles, and the formation of identical globular nodules, which diameter increases with the growth charge. The morphological changes imparted by the switching process revealed to be more marked in films grown at constant potential. Thickness measurements performed on oxidised and reduced films unveiled the swelling/shrinking of the polymers during the ingress/egress of the perchlorate anions, with film volume changes of ca. 20% upon oxidation.
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