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Electrochemical polymerization of 3-methylthiophene on highly oriented poly(vinylidene fluoride) (PVDF) film was achieved by cyclic voltammetry to yield well-ordered poly(3-methylthiophene) (P3MT) thin films with anisotropic structural and conductivity properties. The conductivity of P3MT along the direction perpendicular to the chain direction of PVDF, after electrochemical dedoping, is 59 ± 3 S cm−1, while that along the PVDF chain direction is 1.2 ± 0.4 S cm−1. The high conductivity of the P3MT is attributed to the well-ordered structure with its flat-on single crystals as confirmed by electron diffraction and Reflection Absorption Infra-red Spectroscopy (RAIRS). The data are consistent with P3MT chains aligned with π–π stacking perpendicular to the chain direction of the PVDF substrate. Epitaxial electropolymerization is an unusual method of preparing highly ordered thin films of organic semiconductors

Anisotropic highly-conductive films of poly(3-methylthiophene) from epitaxial electropolymerization on oriented poly(vinylidene fluoride)