Structure and Doping Optimization of IDT-Based Copolymers for Thermoelectrics

π-conjugated backbones play a fundamental role in determining the thermoelectric (TE) properties of organic semiconductors. Understanding the relationship between the structure–property–function can help us screen valuable materials. In this study, we designed and synthesized a series of conjugated copolymers (P1, P2, and P3) based on an indacenodithiophene (IDT) building block. A copolymer (P3) with an alternating donor–acceptor (D-A) structure exhibits a narrower band gap and higher carrier mobility, which may be due to the D-A structure that helps reduce the charge carrier transport obstacles. In the end, its power factor reaches 4.91 μW m(−1) K(−2) at room temperature after doping, which is superior to those of non-D-A IDT-based copolymers (P1 and P2). These results indicate that moderate adjustment of the polymer backbone is an effective way to improve the TE properties of copolymers.