Yuwei Duan, Yaxin Wang, Xinhong Zhu, Dong Zhang, Qiang Peng
ABSTRACT Metal halide perovskite solar cells (PSCs) have achieved remarkable advancements in power conversion efficiency (PCE) and operational stability. As of now, the certified PCE of single‐junction PSCs has skyrocketed to over 27.0%, and the operational stability of lab‐scale PSCs has now extended beyond ten of thousand hours. The improvements are attributed to the stabilized perovskite precursor and high‐quality crystallized films. In this review, we provide a comprehensive review of the recent evolution of PSCs, focusing on the perovskite precursor chemistry and its impact on crystallization modulation, including precursor chemistry related to methylammonium, formamidinium, iodide, lead, and precursor solvent‐related reactions. Additionally, the in situ polymerization of bulk additives in the precursor and their role in stabilizing grain boundaries and suppressing lead leakage are also discussed. Finally, the development prospects of metal halide perovskite photovoltaics are outlined.