Donor–acceptor conjugated polymers as high-mobility semiconductors: prospects for organic thermoelectrics

Abstract

Donor–acceptor conjugated polymers are emerging as a new class of organic semiconductors, where the donor and acceptor moieties function as hole and electron transporters, respectively. The potential of being doped as both p-type and n-type makes them attractive for scalable manufacturing, and they have been widely explored for organic photovoltaics. They can be particularly appealing for organic thermoelectrics, primarily due to their high interchain mobility alongside intrachain mobility. The high intrinsic mobility, resulting from the push–pull effect of the donor–acceptor moieties, ensures high electrical conductivity with minimal doping, which is crucial for maintaining a high Seebeck coefficient in thermoelectric materials. In this review, we explain the molecular structure and energetics, as well as their relationship to the electronic structure of donor–acceptor polymers. We also review the existing literature on how structural and energetic modifications can be implemented to modulate interchain transport, intrachain transport, and doping efficiencies. Based on these, we propose that improvements in molecular design, characterization methods, and the integration of data science and machine learning can accelerate research on donor–acceptor polymers for thermoelectrics and beyond.