Electrochemical polymerization of 2,2'-bithiophene (BTh) in a tetrabutylammonium tetrafluoroborate (TBABF₄)/acetonitrile solution on a single-walled carbon nanotubes (SWNTs) film has been studied by cyclic voltammetry and Raman scattering. Two composites result from the electrochemical synthesis: i) poly(bithiophene) (PBTh) doped with carbon nanotubes and ii) PBTh functionalized SWNTs. In the case of PBTh doped SWNTs, a charge transfer process is argued by change of the position of Raman lines associated with the radial breathing modes (RBM) of SWNTs and the C=C stretching vibration of PBTh. For the latter composite, an analysis of the Raman band with the maximum situated to 1595 cm^-1 associated with the tangential mode of SWNTs reveals a functionalization of side-walls of nanotubes with polymer. A post chemical treatment of the PBTh functionalized SWNTs composite with a basic solution induces the increase in the intensity of the Raman band at 178 cm^-1 associated with radial breathing modes of SWNTs bundles, which suggests an additional nanotubes roping with PBTh as a binding agent. For a better understanding of the above results, Raman studies concerning the oxidation-reduction process at the interface SWNTs films/the TBABF₄ solution in the absence of BTh are shown, too.

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