Complementary study on the electrical and structural properties of poly(3-alkylthiophene) and its copolymers synthesized on ITO by electrochemical impedance and Raman spectroscopy

Targeting the use of organic conjugated polymers in organic solar cells, this study looks at the electrochemical properties of poly(3-alkylthiophene) films: poly(3-methylthiophene), poly(3-hexylthiophene), poly(3-octylthiophene) and its copolymers electrochemically synthesized on a tin-doped indium oxide (ITO) substrate. Electrochemical impedance spectroscopy (EIS) was used to monitor the change in the electrochemical behavior of these films on the ITO and the charge transfer resistance (R_CT) values were determined in open circuit potential (OCP) and at different overpotentials. Together with the EIS, the ex situ and in situ Raman spectroscopy was used to characterize the influence of aromatic radical cation and dication species, present in the polymer matrix of homo and copolymers, in the management processes seen in the Nyquist and Bode-phase diagrams for different systems obtained on ITO. The EIS results in OCP showed an decrease in resistance demonstrating increased conductivity with the copolymerization, and through the Bode-phase diagram and the ex situ Raman spectra, these changes were related to the oscillation of the radical cation and dication along the polymer matrix. By studying Nyquist and Bode-phase diagrams in the overpotentials, an increase in R_CT values in higher potentials was seen that could be related to the bipolaronic process, which after the deconvolution of the in situ Raman spectra, was possible to relate these results to the stabilization of the dication species in the homo and copolymers matrix when subjected to high potential.