Recent Advances in Self‐Assembled Molecules for Inverted Perovskite Photovoltaics

Self‐assembled molecules (SAMs) have emerged as a promising hole transport layer in inverted perovskite solar cells (PSCs), owing to their advantages of low cost, tunable energy level alignment, ultrathin nature, and excellent interface passivation properties. This review systematically examines recent advancements in SAMs for optimizing inverted PSCs. We begin by discussing the typical configuration of SAMs and highlight key optimization strategies: molecular design, co‐SAM engineering, and post‐treatment techniques. The modulated anchoring behavior along with molecular packing of SAMs is emphasized, as well as corresponding impacts on performance. Additionally, SAM modifications have been shown to significantly enhance buried defect passivation and regulate the crystallization kinetics of perovskite films, leading to substantial improvements in PSC performance. Finally, we provide insights into the future directions for SAM development, aiming to fully realize their potential in perovskite photovoltaics.