Management of Donor and Acceptor Building Blocks in Dopant‐Free Polymer Hole Transport Materials for High‐Performance Perovskite Solar Cells

Abstract The dominant hole transport material (HTM) in state‐of‐the‐art perovskite solar cells (PSCs) is Spiro‐OMeTAD, which needs to be doped using hydrophilic dopants to improve its hole mobility and conductivity, resulting in inferior device stability. Here, we propose an effective molecular design strategy to construct dopant‐free polymer HTMs by selecting four structurally related polymers and investigating their structure–property relationship. It is found that the donor and acceptor units with longitudinal conjugate extension, such as BDT‐T and BDD, could not only enhance the planarity of the conjugated polymer backbone and tune the energy levels but also promote the face‐on orientation, resulting in superior charge extraction and transport. The optimized device utilizing dopant‐free polymer HTM shows a high open‐circuit voltage of 1.19 V and a champion efficiency of 24.04 % with greatly improved operational stability, making it among the best performance PSCs based on dopant‐free HTMs.