Enhancing the n‐Type Conductivity and Thermoelectric Performance of Donor–Acceptor Copolymers through Donor Engineering

Abstract Conjugated polymers with high thermoelectric performance enable the fabrication of low‐cost, large‐area, low‐toxicity, and highly flexible thermoelectric devices. However, compared to their p‐type counterparts, n‐type polymer thermoelectric materials show much lower performance, which is largely due to inefficient doping and a much lower conductivity. Herein, it is reported that the development of a donor–acceptor (D–A) polymer with enhanced n‐doping efficiency through donor engineering of the polymer backbone. Both a high n‐type electrical conductivity of 1.30 S cm −1 and an excellent power factor ( PF ) of 4.65 µW mK −2 are obtained, which are the highest reported values among D–A polymers. The results of multiple characterization techniques indicate that electron‐withdrawing modification of the donor units enhances the electron affinity of the polymer and changes the polymer packing orientation, leading to substantially improved miscibility and n‐doping efficiency. Unlike previous studies in which improving the polymer‐dopant miscibility typically resulted in lower mobilities, the strategy maintains the mobility of the polymer. All these factors lead to prominent enhancement of three orders magnitude in both the electrical conductivity and the PF compared to those of the non‐engineered polymer. The results demonstrate that proper donor engineering can enhance the n‐doping efficiency, electrical conductivity, and thermoelectric performance of D–A copolymers.