Potential controlled electrosynthesis of polythiophene-3 methanol: application of the two-dimensional layer-by-layer nucleation and growth model

Summary form only given. The nucleation and growth of polythiophene-3-methanol (PTM) films on platinum electrodes in 0.1 M Bu/sub 4/NclO/sub 4/ acetonitrile has been studied using potentiostatic steps (under glove box atmosphere). The data obtained from the early parts of the chronoamperogrammes fit the model of instantaneous nucleation followed by two dimensional (2D) growth. We believe that the reason for this 2D growth leading to a highly compact structure is chemical. As already demonstrated [1] the OH group easily attacks the radical cations formed during the oxidation process, as a result of which part of the monomer units couple together via ether bonds, C-O-C. These C-O-C bonds may form sites that are less favourable with respect to oxidation and the following nucleation than other parts of the electrode surface and thus drive the polymer to grow mainly in the direction parallel to the surface, the growth perpendicular to the surface being negligible.