Synergistic Passivation of Pyridinium Tetrafluoroborate (PyBF₄) in Inverted (CsPbI₃)_0.05((FAPbI₃)_1−<i>x</i>(MAPbBr₃)_<i>x</i>)_0.95 Solar Cells with Atomic Layer De

Nickel oxide (NiO) is a promising hole transport layer (HTL) that can be used to fabricate efficient, large‐scale inverted‐type perovskite solar cells (PSCs). However, depositing a high‐quality perovskite layer on NiO substrates comparable to those realized in the normal structure still presents a challenge. Herein, a pyridinium tetrafluoroborate (PyBF 4 ) additive is introduced to passivate the intrinsic defects in the bulk perovskite films. The nitrogen Lewis base in the PyBF 4 molecule interacts well with uncoordinated Pb 2+ cations, leading to high‐quality perovskite films with minimized defects. Meanwhile, the pseudohalide BF 4 − can fill halogen vacancies in the perovskite films to enable defect passivation. As a result, the perovskite precursor solution with PyBF 4 shows better reproducibility for high‐efficiency devices. The optimal PSC based on PyBF 4 modification yields a champion power conversion efficiency of 22.7% with atomic layer deposited NiO as the HTL.