Abstract
Molecular doping plays a crucial role in modulating the performance of polymeric semiconductor (PSC) materials and devices. Despite the development of numerous molecular dopants and doping methods over the past few decades, achieving highly efficient doping of PSCs remains challenging, primarily because of the inadequate matching of frontier energy levels between the host polymers and the dopants, which is critical for facilitating charge transfer. In this work, we introduce a novel doping method termed photoexcitation-assisted molecular doping (PE-MD), capable of transcending limitations imposed by energy level disparities through the mediation of efficient photoinduced electron transfer between polymers and dopants. This approach significantly amplifies the electrical conductivity of the PDPP4T polymer, increasing it by more than 4 orders of magnitude to a maximum value of 349.67 S cm(-1). Given that only the irradiated region experiences a substantial increase in doping level, the PE-MD process facilitates the photoresist-free and precise patterning of doped polymers at a resolution down to 1 μm. Furthermore, the enhanced electrical conductivity of the photoexcitation-assisted molecularly doped PDPP4T film promotes efficient thermoelectric conversion, yielding an impressive initial power factor of 226.1 μW m(-1) K(-2) and a figure-of-merit (ZT) of 0.18, accompanied by improved thermal and ambient stability. The PE-MD strategy not only remarkably elevates the doping level of PSCs toward efficient thermoelectric conversion but also preserves the easy processability of flexible and integrated devices.