Structure-directed growth of high conductivity PEDOT from liquid-like oxidant layers during vacuum vapor phase polymerization

Vapor phase polymerization (VPP) is at the forefront for synthesizing high conductivity poly(3,4-ethylenedioxythiophene) (PEDOT) as an alternative to indium tin oxide (ITO). Little attention, however, has been directed to the oxidant layer used in the polymerization process. In this study the observation of an oxidant layer (oxidant + PEG-PPG-PEG) possessing liquid-like properties during the vacuum synthesis of PEDOT is reported. This is in contrast to the other oxidant layer variants studied which are observed as solid (pristine oxidant) or gel-like (oxidant + pyridine). Tailoring of the liquid-like properties leads to confluent PEDOT films with a conductivity of 2500 S cm(-1), placing this PEDOT within the conductivity range of commercially available ITO. Building on the liquid-like observation, XPS and ToF-SIMS experiments reveal that PEDOT growth is via a bottom-up mechanism with transportation of new oxidant up to the forming PEDOT layer.