Enhancement of the Electrical Conductivity in PEDOT:PSS Films by the Addition of Dimethyl Sulfate

A significant increase of the electrical conductivity of PEDOT:PSS films, brought about by the addition of dimethyl sulfate (DMS, (CH3)2SO4), while preserving the films' excellent flexibility and visible-light transparency, is reported. The electrical and morphological properties of the films were studied as a function of DMS concentration. At an optimal concentration of around 1:25 (DMS to PEDOT:PSS), the conductivity of the films is enhanced by a factor on the order of 1880 times that of pristine PEDOT:PSS films. Extensive spectroscopic measurements using absorbance, Raman, and FTIR techniques, as well as structural characterization by AFM microscopy, were performed. These measurements support the idea that the mechanism responsible for the conductivity enhancement is the partial replacement of the PSS− segments by SO4−2 anionic sulfates when a small amount of DMS is added to a PEDOT:PSS solution. This mechanism is associated with an increase of doping, and this doping can be understood in the following manner: due to that the SO3− ions of the PSS segment only carry one negative charge, it is more probable for them to create polaronic states, whereas the SO4−2 ions are double charged, increasing the possibility of creating bipolaron carriers in the PEDOT backbone. In this way, the partial replacement of the PSS− segments by SO4−2 ions increases the bipolaron population by an ion exchange process, and, as a consequence, the doping level is increased.