摘要: The disordered crystal growth and undesired degradation of perovskite films limit the further improvement of perovskite solar cells (PSCs) performance and their commercialization. Herein, an in situ modulation strategy is proposed for preparing high-quality and stable perovskite film through adjustment of phase transformation kinetics. Benefiting from the in situ reaction between chloroformamidinium hydrochloride (ClFACl) and FA cations, the impurity intermediate phase in the perovskite film is inhibited and the α-FAPbI₃ phase is induced to grow along a preferred (001) orientation. Furthermore, the introduction of ClFACl and in situ formation of guanidinium salts (FA-Gua) strengthen the intermolecular interactions in the interior of crystals, which restrains the α-phase degradation of the as-prepared perovskite films under humid and thermal treatments. With crystal orientation optimization and defects reduction, the PSCs with in situ formed FA-Gua yield a champion efficiency of 25.85% and demonstrate excellent phase stability under long-term thermal and humid ageing conditions. This in situ chemical modulation strategy expands the avenue toward optimization of crystallization orientation and α-phase stabilization, promoting the development of PSCs with enhanced performance and stability.