Effect of electrode surface on the electrochromic properties of electropolymerized poly(3,4-ethylenedioxythiophene) thin films

Abstract

Electrochromism or electrochromic contrast in electropolymerized thin films of dioxythiophenes based conjugated polymers is known to be sensitive to the structure of monomer and the polymerizing conditions. However in our studies we found that it is also sensitive to the electrode surface wherein a significantly high electrochromic contrast is observed in the electropolymerized thin films of poly(3,4-ethylenedioxythiophene), PEDOT deposited on platinum (71%) as compared to that on indium tin oxide, ITO, coated glass surface (54%). This is attributed to the formation of more conjugated polymer on the metallic surfaces as confirmed by narrow and red shifted absorption peak for PEDOT on platinum compared to broad and blue shifted peak on ITO in the UV–vis absorption spectra. This difference in the electrochromic properties of electropolymerized PEDOT thin films on the two surfaces is investigated by studying their electrochemical growth using UV–vis absorption, Raman spectroscopy and atomic force microscopy techniques. These results suggest the deposition of more conjugated polymer in the initial stages of growth (≤3 mC/cm2) on both the substrates whereas it continues the same way into the intermediate stages (up to ∼15 mC/cm2) only on platinum, thereby, resulting in higher electrochromic contrast on platinum. The coloration efficiency of PEDOT thin film was also found to be improved on platinum (465 cm2/C) compared to that on ITO (230 cm2/C). Moreover, we observed that the EC contrast of electropolymerized PEDOT thin films on platinum was found to be insensitive to polymerizing solvent that is generally not the case when polymerized on ITO. The cyclic stability of PEDOT-Pt films are better compared to that of PEDOT-ITO which is attributed to the improved reversibility of these films with respect to potential switching.