In situ and ex situ spectroscopic study of poly(3-hexylthiophene) electrochemically synthesized

In this work, poly(3-hexylthiophene) (P3HT) film was synthesized electrochemically in non-aqueous media through the oxidation of the 3-hexylthiophene monomer using a standard three-electrode cell in acetonitrile with 0.100 mol L⁻¹ LiClO₄. The polymeric thick film was deposited on platinum plates for best quality control of the process. Cyclic voltammetry of this material showed two bands of oxidation and two bands of reduction attributed to radical cation and dication segments in the polymer chain. These were characterized by reflectance and Raman spectra, of the reduced (chemically de-doped) and oxidized (electrochemically doped) films. The generated film was subjected to anodic potentials of 1.00 and 1.45 V and characterized by an in situ Raman technique, which indicated the stabilization of the radical cation segments. In addition Raman ex situ spectra of as-prepared film was obtained. The increase in the irradiation time of the sample was enough to alter the nature of the constituent species of the oxidized film, preferably favoring the aromatic chains, together with the dication segments. Photoluminescence spectra showed a larger contribution of dication than radical cation segments for the chemically de-doped sample and under this condition showed good stability, even with variation in laser power. SEM images of P3HT film with indication of the thickness and spherical shape of the sample studied were obtained. Aided by these data it was possible to verify the Stokes shift and ionization potential (I _p), electron affinity (E.A.) and energy gap (E _g) parameters.