Abstract Perovskite solar cells (PSCs) have attracted considerable attention in photovoltaics due to their unique optoelectronic properties and low production costs. Recent advancements have identified self‐assembled monolayers (SAMs) as novel interfacial modification materials that demonstrate exceptional performance as hole transport layers in p‐i‐n structured PSCs. Thanks to the rapid development of SAMs, the power conversion efficiency of PSCs has exceeded 27%. However, the progress of SAM materials has encountered bottlenecks, facing challenges such as molecular aggregation, poor wettability, and long‐term stability. Therefore, comprehensive review and analysis of SAM is crucial for developing SAM materials. This paper reviews the research progress of SAMs in recent years, systematically analyzes the structural design and functional roles of SAMs in PSCs, and provides an outlook on the design of novel SAMs and their commercialization. It is believed that this review will help the development of functional and new SAMs for practical application of PSCs.
Jia et al. (2025) studied this question.