Moreover, polymer films are successfully prepared by convenient blade coating, which lead to ordered films and enables large-area flexible devices application. Owning to better backbone conjugation and bilateral side chains arrangement, PTTE-TVT obtains preferable stacking with a high hole mobility of 0.54 cm2 V−1 s−1 (6 times of that of PTE-TVT) and excellent doping efficiency, ultimately achieves a conductivity of 302 Scm-1 and PFmax of 189.9 μW m−1 K−2. The difference of conformational lock pattern and spatial geometry induced by the subtle regulation of spacer results in quite difference in backbone conjugation, intermolecular stacking, carrier mobility and final OTE performance. Herein, two new polymers PTTE-TVT and PTE-TVT are developed by combining conformationally locked ester-substituted thiophenes with thienothiophene (or thiophene) spacer and highly coplanar thienylenevinylene (TVT). Thiophene-based simple polymers are the most investigated p-type organic thermoelectric (OTE) materials for their readily tunable structure and low-cost synthesis, whereas it is difficult for them to achieve high mobility and power factor (PF) through common film fabrication.

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