An Efficient One‐Arrow‐Two‐Hawks Strategy Achieves High Efficiency and Stable Batch Variance for Benzodifuran‐based Polymer Solar Cells

Abstract With the development of organic solar cells (OSCs), the high‐performance and stable batch variance are becoming a new challenge for designing polymer donors. To obtain high photovoltaic performance, adopting polymers with high molecular weight as donors is an ordinary strategy. However, the high molecular weight need to subtly control the reaction time and state, inevitably caused batch‐to‐batch variations. Herein, a strategy of steric effect is applied to benzodifuran (BDF)‐based polymer by introducing different positions of Cl atom, producing two polymers PBDFCl‐1 and PBDFCl‐2. The more twisted side chains conformation not only achieve the control of moderate molecular weight for PBDFCl‐2, but also easily form molecular stacking through adopting BDF unit and maintain sufficient polymeric crystallinity. Due to the optimized stacking mode and good blend miscibility, PBDFCl‐2‐based device exhibitsa more elegant power conversion efficiency (PCE) of 17.00% compared to PBDFCl‐1‐based device. This is the highest efficiency record for BDF‐based binary OSCs. Meanwhile, the PCE device variation of the different molecular weights for PBDFCl‐2 is little, indicating the reduction of the batch variation. Therefore, smartly using steric effect of Cl atom in strong crystalline BDF unit can form efficient molecular stacking regulations and realize the coordination of high‐performance and stable batch variance.