High‐Performance Perovskite Solar Cells Achieved through Synchronous Regulation of Crystallization and Carrier Dynamics via Amidoxime Additives

Abstract Synchronously regulating perovskite crystallization and managing charge carrier dynamics played significant role in pursuing high‐performance perovskite solar cells (PSCs). Herein, a series of amidoxime‐based isomerization additives are developed by bonding amidoxime at ortho‐ (2‐PyA), meta‐ (3‐PyA), and para‐ (4‐PyA) position of pyridine unit, respectively, to investigate their comprehensive influences on the perovskite crystallization and carrier dynamics. The comprehensive computational and experimental analyses reveal that amine (‐NH 2 ), hydroxyl (─OH) and imine (─C═N) of amidoxime synergistically coordinate with Pb 2+ to modulate crystallization, while the pyridine unit effectively bonds with molecule iodine (I 2 ) through halogen‐nitrogen (halogen–N) coordination to suppress the I‐related defects. These interactions are more pronounced for meta‐positioned 3‐PyA due to the reduced steric hindrance effect and weaker electron‐withdrawing capability, compared to 2‐PyA and 4‐PyA analogues. Consequently, 3‐PyA‐treated perovskite films exhibit enhanced crystallinity, reduced bulk‐defects and non‐radiative recombination, and prolonged lifetime, thereby enabling n‐i‐p PSC to achieve an efficiency of 26.31% with an exceptional operational stability, maintaining 92.0% and 85.0% of their initial efficiencies after aging in air atmosphere for 2100 h and continuously tracking at the maximum power‐point under one‐sun illumination (100 mW cm −2 ) for 1200 h, respectively.