Structurally‐tuned benzo[1,2‐b:4,5:b']dithiophene‐based polymer as a dopant‐free hole transport material for perovskite solar cells

Abstract For highly efficient and stable perovskite solar cells (PSCs), hole transport material (HTM) should be designed and synthesized to afford suitable energy levels, high charge transport, efficient passivation ability, and high device stability. Here, we systematically modulated benzo[1,2‐b:4,5:b']dithiophene‐based polymer by finely controlling the thienyl and pyridyl contents within the conjugated backbone in order to develop a high performance dopant‐free HTM for PSCs. We found that the optimized copolymer with 25% of pyridine content exhibits improved energy level, charge transport, and morphology compared with control homopolymers. As a result, remarkably high power conversion efficiencies up to 21.1% were achieved by employing the optimized polymer as a dopant‐free HTM in PSCs.