Quenching Detrimental Reactions and Boosting Hole Extraction via Multifunctional NiOx/Perovskite Interface Passivation for Efficient and Stable Inverted Solar Cells

Abstract Nickel oxide (NiO x ) is one of the most promising hole transport materials for inverted perovskite solar cells (PSCs). However, its application is severely restrained due to unfavorable interfacial reactions and insufficient charge carrier extraction. Herein, a multifunctional modification at the NiO x /perovskite interface is developed via introducing fluorinated ammonium salt ligand to synthetically solve the obstacles. Specifically, the interface modification can chemically convert detrimental Ni ≥3+ to lower oxidation state, resulting in the elimination of interfacial redox reactions. Meanwhile, interfacial dipole is incorporated simultaneously to tune the work function of NiO x and optimize energy level alignment, which effectively promotes the charge carrier extraction. Therefore, the modified NiO x ‐based inverted PSCs achieve a remarkable power conversion efficiency (PCE) of 22.93%. Moreover, the unencapsulated devices obtain a significantly enhanced long‐term stability, maintaining over 85% and 80% of the initial PCEs after storage in ambient air with a high relative humidity of 50–60% for 1000 h and continuous operation at maximum power point under one‐sun illumination for 700 h, respectively.