Synergetic Regulation of Interface Defects and Carriers Dynamics for High‐Performance Lead‐Free Perovskite Solar Cells

Abstract Severe nonradiative recombination and open‐circuit voltage loss triggered by high‐density interface defects greatly restrict the continuous improvement of Sn‐based perovskite solar cells (Sn‐PVSCs). Herein, a novel amphoteric semiconductor, O‐pivaloylhydroxylammonium trifluoromethanesulfonate (PHAAT), is developed to manage interface defects and carrier dynamics of Sn‐PVSCs. The amphiphilic ionic modulators containing multiple Lewis‐base functional groups can synergistically passivate anionic and cationic defects while coordinating with uncoordinated Sn 2+ to compensate for surface charge and alleviate the Sn 2+ oxidation. Especially, the sulfonate anions raise the energy barrier of surface oxidation, relieve lattice distortion, and inhibit nonradiative recombination by passivating Sn‐related and I‐related deep‐level defects. Furthermore, the strong coupling between PHAAT and Sn perovskite induces the transition of the surface electronic state from p‐type to n‐type, thus creating an extra back‐surface field to accelerate electron extraction. Consequently, the PHAAT‐treated device exhibits a champion efficiency of 13.94% with negligible hysteresis. The device without any encapsulation maintains 94.7% of its initial PCE after 2000 h of storage and 91.6% of its initial PCE after 1000 h of continuous illumination. This work provides a reliable strategy to passivate interface defects and construct p‐n homojunction to realize efficient and stable Sn‐based perovskite photovoltaic devices.