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Conjugated polymers with narrower bandgaps usually induce higher carrier mobility, which is vital for the improved thermoelectric performance of polymeric materials. Herein, two indacenodithiophene (IDT) based donor–acceptor (D-A) conjugated polymers (PIDT-BBT and PIDTT-BBT) were designed and synthesized, both of which exhibited low-bandgaps. PIDTT-BBT showed a more planar backbone and carrier mobility that was two orders of magnitude higher (2.74 × 10 −2  cm 2 V −1 s −1 ) than that of PIDT-BBT (4.52 × 10 −4  cm 2 V −1 s −1 ). Both exhibited excellent thermoelectric performance after doping with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, where PIDTT-BBT exhibited a larger conductivity (0.181 S cm −1 ) and a higher power factor (1.861 μW m −1  K −2 ) due to its higher carrier mobility. The maximum power factor of PIDTT-BBT reached 4.04 μW m −1  K −2  at 382 K. It is believed that conjugated polymers with a low bandgap are promising in the field of organic thermoelectric materials.

Backbone Effects on the Thermoelectric Properties of Ultra-Small Bandgap Conjugated Polymers