Organophosphorus chemistry for emerging perovskite photovoltaics: fundamentals to functional strategies

Despite remarkable progress, defect-assisted non-radiative recombination, interfacial energy losses, ion migration, and environmental vulnerability remain major obstacles to the commercialization of perovskite solar cells (PSCs). In this context, organophosphorus compounds have attracted increasing attention as multifunctional materials capable of addressing these challenges. Owing to their tunable electronic structures, strong coordination ability, moderate Lewis basicity, and excellent chemical stability, these molecules can effectively regulate crystallization, passivate defects, optimize interfacial energetics, and enhance charge transport. This review comprehensively summarizes the emerging applications of organophosphorus chemistry in PSCs, critically discussing their roles as phosphonium cations, mixed-dimensional engineering agents, crystallization and defect-passivation additives, and interfacial modifiers. Particular emphasis is placed on the underlying molecular mechanisms by which phosphorus-containing materials suppress defects, align energy levels, mitigate ion migration, and reinforce structural durability. Furthermore, recent advances in dual-interface passivation and self-assembled monolayer engineering for charge-selective contacts, encompassing both metal-oxide-free electron-transport layers and efficient hole-selective interfaces, are critically discussed. Finally, we address key challenges related to molecular design, interfacial reactivity, and structure–property–performance relationships, providing future perspectives on design strategies for highly efficient, stable, and scalable PSC technologies.