Synergistic Temperature Regulation and Interface Engineering of Magnetron‐Sputtered NiO x for Inverted Perovskite Solar Cells

Magnetron‐sputtered nickel oxide (NiO x ) has emerged as a stable and efficient hole transport layer (HTL) for high‐performance inverted perovskite solar cells (PSCs) due to its high carrier mobility, excellent stability, and compatibility with large‐scale manufacturing. However, the limited crystallinity of sputtered NiO x films and interfacial mismatch with perovskites still restrict device efficiency. Here, we present a synergistic strategy that integrates sputtering temperature optimization with bilayer molecular modification (Me‐4PACz/PEACl) for interfacial passivation. By tuning the substrate temperature during NiO x sputtering, its optoelectronic properties were effectively enhanced, while sequential deposition of Me‐4PACz and phenethylammonium chloride (PEACl) layers further regulated the buried perovskite interface and passivated defects. As a result, the optimized PSCs achieved a champion power conversion efficiency (PCE) of 23.37%. The unencapsulated devices retained over 90% of their initial PCE after 1500 h of storage under an inert N 2 atmosphere, highlighting their excellent operational stability. Importantly, benefiting from the compatibility of magnetron sputtering with scalable screen‐printing processes, large‐area devices (1 cm 2 ) were successfully fabricated, underscoring the scalability and industrial potential of this integrated approach.