An n‐Type Conjugated Polymer with Low Crystallinity for High‐Performance Organic Thermoelectrics

Abstract Conjugated polymers (CPs) with low crystallinity are promising candidates for application in organic thermoelectrics (OTEs), particularly in flexible devices, because the disordered structures of these CPs can effectively accommodate dopants and ensure robust resistance to bending. However, n‐doped CPs usually exhibit poor thermoelectric performance, which hinders the development of high‐performance thermoelectric generators. Herein, we report an n‐type CP (ThDPP‐CNBTz) comprising two acceptor units: a thiophene‐flanked diketopyrrolopyrrole and a cyano‐functionalized benzothiadiazole. ThDPP‐CNBTz shows a low LUMO energy level of below −4.20 eV and features low crystallinity, enabling high doping efficiency. Moreover, the dual‐acceptor design enhances polaron delocalization, resulting in good thermoelectric performance. After n‐doping, ThDPP‐CNBTz exhibits an average electrical conductivity ( σ ) of 50.6 S cm −1 and a maximum power factor (PF) of 126.8 μW m −1 K −2 , which is among the highest values reported for solution‐processed n‐type CPs to date. Additionally, a solution‐processed flexible OTE device based on doped ThDPP‐CNBTz exhibits a maximum PF of 70 μW m −1 K −2 ; the flexible device also shows remarkable resistance to bending strain, with only a marginal change in σ after 600 bending cycles. The findings presented in this work will advance the development of n‐type CPs for OTE devices, and flexible devices in particular.