ABSTRACT Self‐assembled monolayers (SAMs) have precipitated a paradigm shift in the design of hole transport layers (HTLs) for p–i–n perovskite solar cells, emerging as the cornerstone of modern, high‐efficiency devices. This review comprehensively charts the evolution of SAM‐based HTLs from fundamental molecular‐level insights to their pivotal role in commercial‐scale applications and record‐breaking perovskite/silicon tandem cells. We delve into the intricate structure–property–performance relationships that govern SAMs’ function, examining how meticulous engineering of anchoring groups, π‐bridges, and functional headgroups dictates critical features such as energy level alignment, interfacial defect passivation, and perovskite crystallization control. The discussion extends beyond champion efficiencies to critically assess the scalability of deposition techniques, the limitations of operational stability under real‐world conditions, and the pathways for integration into tandem architectures. Furthermore, we highlight the transformative potential of machine learning in accelerating the discovery and optimization of next‐generation SAM materials. Finally, we provide a forward‐looking perspective on molecular design strategies required to overcome existing challenges and fully unlock SAM potential for stable, high‐performance photovoltaics.
Ullah et al. (Sat,) studied this question.