The field of perovskite optoelectronics and electronics has rapidly advanced, driven by excellent material properties and a diverse range of fabrication methods available. Among them, triple-cation perovskites such as CsFAMAPbI3 offer enhanced stability and superior performance, making them ideal candidates for advanced applications. However, the multicomponent nature of these perovskites introduces complexity, particularly in how their structural, optical, and electrical properties are influenced by thermal annealing─a critical step for achieving high-quality thin films. Here, we propose a comprehensive mechanistic picture of the thin film formation process of CsFAMAPbI3 during the thermal annealing step through systematic and comparative analyses, identifying two key thermally induced phase transitions: the crystallization of the perovskite phase facilitated by solvent evaporation and the formation of the PbI2 phase due to thermal decomposition. Our results reveal that the crystallization process during annealing proceeds from the surface to the bulk of the films, with a significant impact on the film's morphology and optical characteristics. Controlled annealing enhances field-effect transistor device performance by promoting defect passivation and complete perovskite crystallization, while prolonged annealing leads to excessive PbI2 formation, accelerating ion migration and ultimately degrading device performance. These insights offer valuable guidance for optimizing the design and performance of perovskite-based electronic and optoelectronic devices.
Keywords: defect passivation; field effect transistor; perovskite; phase conversion; thermal annealing.