In Situ Self‐Elimination of Defects via Controlled Perovskite Crystallization Dynamics for High‐Performance Solar Cells

Understanding and controlling crystallization is crucial for high-quality perovskite films and efficient solar cells. Herein, the issue of defects in formamidinium lead iodide (FAPbI₃ ) formation is addressed, focusing on the role of intermediates. A comprehensive picture of structural and carrier evolution during crystallization is demonstrated using in situ grazing-incidence wide-angle X-ray scattering, ultraviolet-visible spectroscopy and photoluminescence spectroscopy. Three crystallization stages are identified: precursors to the δ-FAPbI₃ intermediate, then to α-FAPbI₃ , where defects spontaneously emerge. A hydrogen-sulfate-based ionic liquid additive is found to enable the phase-conversion pathway of precursors → solvated intermediates → α-FAPbI₃ , during which the spontaneous generation of δ-FAPbI₃ can be effectively circumvented. This additive extends the initial growth kinetics and facilitates solvent-FA⁺ ion exchange, which results in the self-elimination of defects during crystallization. Therefore, the improved crystallization dynamics lead to larger grain sizes and fewer defects within thin films. Ultimately, the improved perovskite crystallization dynamics enable high-performance solar cells, achieving impressive efficiencies of 25.14% at 300 K and 26.12% at 240 K. This breakthrough might open up a new era of application for the emerging perovskite photovoltaic technology to low-temperature environments such as near-space and polar regions.