Simultaneous Surface Modification and Defect Passivation on Tin Oxide–Perovskite Interfaces using Pseudohalide Salt of Sodium Tetrafluoroborate

Passivating electron‐transporting layers (ETLs) with alkali salts have demonstrated a facial approach that is essential in healing defective surfaces, consequently improving the functionality and stability of perovskite‐based solar cells (PSCs). Herein, the pseudohalide salt of sodium tetrafluoroborate, whose anions have a higher electronegativity than other halide salts (i.e., iodide and chloride), with the potential to passivate the surface of tin oxide while enhancing the optoelectronic properties of a perovskite film, is presented. Meanwhile, the density functional theory calculations show that BF 4 − /F − ions exhibit a robust ionic interaction with an uncoordinated Sn 4+ site. In contrast, the Na ion is bound to an oxygen atom of the OH − group, which helps reduce surface defect states and improves charge transfer properties. Thus, the best PSC exhibits a current density of 23.51 mA cm −2 , an open‐circuit voltage of 1.10 V, and an excellent fill factor of 80.48, providing an efficiency of 20.82%, which exceeds that of a control device (18.38%). Importantly, the retention of the power conversion efficiency on NaBF 4 ‐based PSCs without encapsulation is 18.44% after 1000 h of aging under ambient conditions, whereas the retention of a control device is only 16.08%.