Parameters affecting the quality of vapour phase polymerised (VPP) PEDOT and their influence on electrochromic device performance were investigated. Specifically, the role of water during synthesis was examined and a polymerisation mechanism proposed. Paradoxically, water vapour is essential for PEDOT polymerisation, however, too high a loading leads to crystallite formation in the oxidant layer, rendering the oxidant inactive. Changes in water vapour affect the doping level of the polymer, presumably due to poor conjugation along the polymer's backbone during synthesis. The addition of a surfactant, PPG-ran-PEG, was studied using XPS. The surfactant inhibited oxidant crystal growth and slowed the rate of PEDOT polymerisation, reducing film defects and improving PEDOT conductivity. Controlling and optimising the levels of water vapour and surfactant during synthesis resulted in reproducible, high conductivity, high optical switch, PEDOT films. Finally, complementary dual-polymer electrochromic devices utilising (pre- and post-process-enhanced) VPP PEDOT and PMAS (control) were fabricated and changes in switching transmission evaluated.
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