Stabilizing Precursor Solution and Controlling Crystallization Kinetics Simultaneously for High-Performance Perovskite Solar Cells.

The efficiency of metal halide perovskite solar cells (PSCs) has skyrocketed; however, defects created by aging precursor solutions and during crystallization pose a significant barrier to the reproducibility and efficiency of solar cells. In this work, fluoro-N,N,N″,N″-tetramethylformamidinium hexafluorophosphate (F-(CH3 )4 CN2 PF6 , abbreviated as TFFH) is introduced to stabilize precursor solution and improve crystallization dynamics simultaneously for high-performance formamidinium lead iodide (FAPbI3 )-based perovskite indoor photovoltaics. The TFFH stabilizes the precursor solution by inhibiting oxidation of I- and reducing newly generated I0 to I- , and passivates undercoordinated Pb2+ by interacting with the Pb─I framework. Time-resolved optical diagnostics show prolonged perovskite crystallization dynamics and in situ defect passivation due to the presence of strong FA+ ···TFFH···Pb─I interaction. Simultaneous regulation of precursor solution and crystallization dynamics guarantee larger perovskite grain sizes, better crystal orientation, fewer defects and more efficient charge extraction in PSCs. The optimized PSCs achieve improved reproducibility and better stability and reach an efficiency of 42.43% at illumination of 1002 lux, which is the highest efficiency among all indoor photovoltaics. It is anticipated that the concurrent stabilization of solutions and regulation of crystallization dynamics will emerge as a prevalent approach for enhancing the reproducibility and efficiency of perovskite.

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.