Modeling‐Assisted Insight Into High‐Performance Perovskite Solar Cells Enabled by a Hybrid NiO x /SAM Hole Transport Layer

ABSTRACT The limited performance of inverted p‐i‐n perovskite solar cells (PSCs) with a NiO x hole transport layer (HTL) poses a significant challenge to realizing their full potential for scalable and stable photovoltaics. In order to mitigate these limitations, this study presents a combined experimental and simulation approach to systematically investigate the underlying mechanisms governing the device performance. A self‐assembled molecule Me‐4PACz, as an interfacial modifier, was introduced to form a hybrid NiO x /SAM structure. Experimental results based on space‐charge‐limited current, ultraviolet photoelectron spectroscopy, and photoluminescence/time‐resolved photoluminescence confirm that the hybrid HTL significantly reduces trap‐state density, improves energy level alignment, and suppresses non‐radiative recombination at the buried interface. These improvements lead to a remarkable enhancement in power conversion efficiency from 14.97% to 19.56%. Furthermore, by integrating experimental parameters into drift‐diffusion simulations, we developed a validated device model that reveals the critical roles of a valence band offset around 0.07 eV and a buried interface defect density on the order of 10 13 cm −3 in optimizing device performance. Our findings underscore the importance of NiO x /SAM hybrid HTLs in inverted PSCs and provide a rational strategy for achieving high‐efficiency and stable perovskite photovoltaics.