Hole‐Transporting Materials with Rational Combination of Pyridine and Dibenzo[a,c]phenazine as Electron Acceptor for Dopant‐Free Perovskite Solar Cells†

Comprehensive Summary Perovskite solar cells (PSCs) have been proven to be a promising option for photovoltaic conversion. With the aim to achieve efficient and stable PSCs, it is essential to explore dopant‐free hole‐transporting materials (HTMs) with high hole mobility. Herein, HTMs bearing electron donor (D)‐electron acceptor (A)‐electron donor (D) structures have been constructed with strong intramolecular charge transfer (ICT) effect, based on rational combination of dibenzo[ a , c ]phenazine and pyridine as electronic acceptors and anchoring groups to perovskite layer. Accordingly, high hole mobility (7.31 × 10 –5 cm 2 ·V –1 ·s –1 ) and photoelectric conversion efficiency (20.45%) have been achieved by dopant‐free DPyP ‐based PSC. It afforded an efficient way to design HTMs with high hole mobility by adjustment of molecular configurations and electronic property of conjugated systems.