Tuning PEDOT:PSS conductivity with iron oxidants

Controlling the electrical properties of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is crucial for its use in a wide range of energy and sensing applications. We have polymerized PEDOT:PSS using a new iron oxidant, hemin, and compared the resulting polymer to PEDOT:PSS polymerized with the iron oxidant, FeCl3. We characterize these polymers with five different techniques:visible and near IR spectroscopy, Fourier transform infrared spectroscopy, electron spin resonance spectroscopy, four point probe conductivity measurements, and X-ray photoelectron spectroscopy. Although the elemental composition of both polymers is nearly identical, hemin-oxidized PEDOT:PSS is six orders of magnitude more conductive than FeCl3-oxidized PEDOT:PSS. This difference is associated with a change in oxidation state of the polymer. In hemin-oxidized PEDOT:PSS, bipolarons are the dominant charge carrier species. In FeCl3-oxidized PEDOT:PSS, polarons dominate. These results demonstrate that the properties of PEDOT:PSS can be controlled in a single step aqueous reaction by the choice of iron oxidant used for polymerization. (C) 2014 Elsevier B.V. All rights reserved.