Enhanced Efficiency and Intrinsic Stability of Wide‐Bandgap Perovskite Solar Cells through Dimethylamine‐Based Cation Engineering

High efficiency and stable wide‐bandgap perovskite solar cells (PSCs) are important for perovskite‐based tandem solar cells. However, the efficiency and stability of wide‐bandgap PSCs suffers from severe phase segregation and surface defects. In this study, we propose a cation engineering strategy for wide‐bandgap perovskite deposited by a two‐step sequential method through the incorporation of dimethylamine hydroiodide (DMAI) into the lead halide complex in the first step. The DMAI additive modifies the crystal structure and grain growth of perovskite film, resulting in enhancing crystal quality, suppressing photo‐induced halide segregation, reducing defect density, and improving charge carrier mobility. As a result, we achieved a champion photoelectric conversion efficiency (PCE) of 21.9% for 1.68 eV wide‐bandgap PSCs. Additionally, the stability of PSCs based on DMA doped perovskite was strongly enhanced, after being exposed to ambient air for 1500 hours, the unencapsulated device maintained an impressive 80.6% of their initial efficiency, demonstrating great potential for stable and efficient wide‐bandgap PSCs.