Vapour phase polymerized (VPP) PEDOT obtained using triblock copolymer PEG–PPG–PEG:Fe(III) tosylate polymeric oxidative layers has shown record-high conductivity and unique thermoelectric properties. These properties are related to the molecular weight, morphology and doping of PEDOT. Here we show that in its unwashed condition, the PEDOT chain adopts a neutral benzenoid conformation. The polymer chain converts into the charged quinoid structure after the removal of oxidizers with solvent washing. X-ray diffraction results suggest that the dopant is also incorporated into the packed polymer after the washing process. The changes in the chain structure and doping lead to the characteristic polaron and bipolaron absorption in the 800 and 1200 nm range. We observed a large contraction of the film after washing that is likely due to these changes, along with the removal of excessive polymer:oxidizer trapped in the PEDOT matrix. The contraction of films can be completely suppressed by mechanical clamping. PEDOT films without contraction show both a higher conductivity and higher optical transparency.

中文翻译：

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在大分子液体状表面上形成的PEDOT膜的收缩†

使用三嵌段共聚物PEG–PPG–PEG：Fe（III）获得的气相聚合（VPP）PEDOT）甲苯磺酸盐聚合的氧化层已显示出创纪录的高电导率和独特的热电性能。这些性质与PEDOT的分子量，形态和掺杂有关。在这里，我们表明，在未清洗的情况下，PEDOT链采用了中性的苯并合物构象。用溶剂洗涤除去氧化剂后，聚合物链转化为带电荷的醌型结构。X射线衍射结果表明，在洗涤过程之后，掺杂剂也被掺入填充的聚合物中。链结构和掺杂的变化导致在800和1200 nm范围内特征极化子和双极化子吸收。我们观察到清洗后薄膜的大收缩可能是由于这些变化，以及去除了残留在PEDOT基质中的过多的聚合物：氧化剂。膜的收缩可以通过机械夹紧完全抑制。没有收缩的PEDOT膜显示出更高的电导率和更高的光学透明度。