Novel Dithienopyrrole‐Based Conjugated Copolymers: Importance of Backbone Planarity in Achieving High Electrical Conductivity and Thermoelectric Performance

The development of conjugated polymers with structures that are suitable for efficient molecular doping and charge transport is a key challenge in the construction of high‐performance conjugated polymer‐based thermoelectric devices. In this study, three novel conjugated polymers based on dithienopyrrole (DTP) are synthesized and their thermoelectric properties are compared. When doped with p‐dopant, a donor–acceptor type copolymer, DPP‐MeDTP, exhibits higher electrical conductivity and thermoelectric power factor compared to the other donor–donor type copolymers. The high electrical conductivity of DPP‐MeDTP compared to the other polymers originates from the high degree of backbone planarity and molecular order, which contributes to its high charge carrier mobility. In addition, the highly crystalline structure of DPP‐MeDTP is well maintained upon doping, while the crystalline order of the other polymers decreases significantly upon doping. The findings of this work not only provide insights into the design of DTP‐based conjugated polymers for thermoelectric use but also demonstrate the significance of a high degree of molecular order and structural robustness upon doping to achieve high thermoelectric performance. Novel conjugated copolymers based on dithienopyrrole (DTP) unit are synthesized and compared to provide insights into the effect of the combination of DTP units with other chemical moieties on the thermoelectric properties of the resulting polymers. The results demonstrate the importance of high backbone planarity and crystallinity of conjugated copolymers for achieving high thermoelectric performance.