Multi‐Site Synergistic Regulation Towards Highly Efficient and Stable Perovskite Solar Cells

ABSTRACT Perovskite solar cells (PSCs) have attracted considerable scientific interest due to their remarkable power conversion efficiency (PCE) and economically viable manufacturing processes. However, the commercialization has faced obstacles such as limited operational stability and susceptibility to moisture, which usually stem from the inferior quality of perovskite film. In this study, we present Di‐p‐toluenesulfonamide (D‐pTSAD) as triple‐functional ligand featuring multi‐site synergistic coordination with the perovskite lattice. Through this mechanism, D‐pTSAD simultaneously facilitates oriented crystal growth and mitigates defect formation, achieving a top‐performing device with a PCE of 26.22%. Comprehensive analysis reveals that D‐pTSAD forms stronger coordination with both Pb 2 + and I − ions compared to bifunctional ligands, effectively passivating defects, suppressing ion migration, and reducing nonradiative recombination. After 1,000 h of continuous maximum power point tracking, PSCs with D‐pTSAD maintained 82.5% of initial PCE. This research underscores the potency of multisite coordination chemistry in elevating both performance and stability of PSCs.