LAUSR

A novel n‐type copolymer dopant polystyrene–poly(4‐vinyl‐N‐hexylpyridinium fluoride) (PSpF) with fluoride anions is designed and synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. This is thought to be the first polymeric fluoride dopant. Electrical conductivity of 4.2 S cm–1 and high power factor of 67 µW m–1 K–2 are achieved for PSpF‐doped polymer films, with a corresponding decrease in thermal conductivity as the PSpF concentration is increased, giving the highest ZT of 0.1. An especially high electrical conductivity of 58 S cm–1 at 88 °C and outstanding thermal stability are recorded. Further, organic transistors of PSpF‐doped thin films exhibit high electron mobility and Hall mobility of 0.86 and 1.70 cm2 V–1 s–1, respectively. The results suggest that polystyrene–poly(vinylpyridinium) salt copolymers with fluoride anions are promising for high‐performance n‐type all‐polymer thermoelectrics. This work provides a new way to realize organic thermoelectrics with high conductivity relative to the Seebeck coefficient, high power factor, thermal stability, and broad processing window.