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In this contribution, doping of oriented thin films is investigated for three PBTTT polymers bearing different side chains including linear alkyl ─(CH)─H, single ether ─(CH)─O─(CH)─H and alkyl-siloxane ─(CH)─(Si(CH)O)─Si(CH) A combination of transmission electron microscopy, polarized UV-vis-NIR spectroscopy and transport measurements helps uncover the essential role of the chemical nature of side chains on the efficacy of the doping and on the resulting thermoelectric performances in oriented PBTTT films. Siloxane side chains help to reach record alignment level of PBTTT with dichroic ratio beyond 50 for an optimized rubbing temperature but they impede effective doping of PBTTT crystals with FTCNNQ, resulting in very poor TE properties. By contrast, doping the amorphous phase of all three PBTTTs with magic blue (MB) results in excellent TE performances.

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