Advancing Self‐Assembled Molecules Toward Interface‐Optimized Perovskite Solar Cells: from One to Two

Abstract Perovskite solar cells (PSCs) have rapidly gained prominence as a leading candidate in the realm of solution‐processable third‐generation photovoltaic (PV) technologies. In the high‐efficiency inverted PSCs, self‐assembled monolayers (SAMs) are often used as hole‐selective layers (HSLs) due to the advantages of high transmittance, energy level matching, low non‐radiative recombination loss, and tunable surface properties. However, SAMs have been recognized to suffer from some shortcomings, such as incomplete coverage, weak bonding with substrate or perovskite, instability, and so on. The combination of different SAMs or so‐called co‐SAM is an effective strategy to overcome this challenge. In this Perspective, the latest achievements in molecule design, deposition method, working principle, and application of the co‐SAM are discussed. This comprehensive overview of milestones in this rapidly advancing research field, coupled with an in‐depth analysis of the improved interface properties using the co‐SAM approach, aims to offer valuable insights into the key design principles. Furthermore, the lessons learned will guide the future development of SAM‐based HSLs in perovskite‐based optoelectronic devices.