Boosting Thermoelectric Performance of Semicrystalline Conducting Polymers by Simply Adding Nucleating Agent

Abstract

Abstract Controlling the microstructure of semiconducting polymers is critical for optimizing thermoelectric performance, yet remains challenging, requiring complex processing techniques like alignment. In this study, a straightforward strategy is introduced to enhance the thermoelectric properties of semi‐crystalline polymer films by incorporating minimal amounts of nucleating agents, a method widely used in traditional polymer industries. By blending less than 1 wt% of N,N′‐(1,4‐phenyl)diisonicotinamide (PDA) into poly(2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT‐C14), controlled modulation of crystallization behavior is achieved, resulting in reduced structural disorder and enhanced charge carrier mobility. Systematic investigations reveal that an optimal PDA loading of 0.9 wt% increases the crystallization degree by 45% compared to pristine PBTTT‐C14 films. Under these optimized conditions, the PDA‐modified PBTTT‐C14 films exhibit a maximum electrical conductivity of 1,894 S cm −1 and a maximum power factor of 176 µW m −1  K −2 , showing improvements of 96% and 433%, respectively, over doped pristine PBTTT‐C14 films. These gains are attributed to the synergistic effects of polymer chain extension and reduced grain boundary resistance, which collectively enhance charge transport efficiency. Additionally, ion exchange doping is found to maintain a high charge carrier concentration while preserving the crystallinity introduced by PDA, paving the way for advanced thermoelectric materials and next‐generation polymer‐based electronics.