Dopant‐induced Morphology of Organic Semiconductors Resulting in High Doping Performance

Abstract Doping plays a crucial role in modulating and enhancing the performance of organic semiconductor (OSC) devices. In this study, the critical role of dopants is underscored in shaping the morphology and structure of OSC films, which in turn profoundly influences their properties. Two dopants, trityl tetrakis(pentafluorophenyl) (TrTPFB) and N , N ‐dimethylanilinium tetrakis(pentafluorophenyl)borate (DMA‐TPFB), are examined for their doping effects on poly(3‐hexylthiophene) (P3HT) and PBBT‐2T host OSCs. It is found that although TrTPFB exhibits higher doping efficiency, OSCs doped with DMA‐TPFB achieve comparable or even enhanced electrical conductivity. Indeed, the electrical conductivity of DMA‐TPFB‐doped P3HT reaches over 67 S cm −1 , which is a record‐high value for mixed‐solution‐doped P3HT. This can be attributed to DMA‐TPFB inducing a higher degree of crystallinity and reduced structural disorder. Moreover, the beneficial impact of DMA‐TPFB on the OSC films' morphology and structure results in superior thermoelectric performance in the doped OSCs. These findings highlight the significance of dopant‐induced morphological and structural considerations in enhancing the film characteristics of OSCs, opening up a new avenue for optimization of dopant performance.