%0 Journal Article %T Crystallization Control for Ambient Printed FA-Based Lead Triiodide Perovskite Solar Cells. %A Yin L %A Huang W %A Fang J %A Ding Z %A Jin C %A Du Y %A Lang L %A Yang T %A Wang S %A Cai W %A Liu C %A Zhao G %A Yang Y %A Liu SF %A Bu T %A Zhao K %J Adv Mater %V 35 %N 51 %D 2023 Dec 12 %M 37572021 %F 32.086 %R 10.1002/adma.202303384 %X Upscalable printing of high-performance and stable perovskite solar cells (PSCs) is highly desired for commercialization. However, the efficiencies of printed PSCs lag behind those of their lab-scale spin-coated counterparts owing to the lack of systematic understanding and control over perovskite crystallization dynamics. Here, the controlled crystallization dynamics achieved using an additive 1-butylpyridine tetrafluoroborate (BPyBF4 ) for high-quality ambient printed α-formamidinium lead triiodide (FAPbI3 ) perovskite films are reported. Using in situ grazing-incidence wide-angle X-ray scattering and optical diagnostics, the spontaneous formation of α-FAPbI3 from precursors during printing without the involvement of  δ-FAPbI3 is demonstrated. The addition of BPyBF4 delays the crystallization onset of α-FAPbI3 , enhances the conversion from sol-gel to perovskite, and reduces stacking defects during printing. Therefore, the altered crystallization results in fewer voids, larger grains, and less trap-induced recombination loss within printed films. The printed PSCs yield high power conversion efficiencies of 23.50% and 21.60% for a 0.09 cm-2 area device and a 5 cm × 5 cm-area module, respectively. Improved device stability is further demonstrated, i.e., approximately 94% of the initial efficiency is retained for over 2400 h under ambient conditions without encapsulation. This study provides an effective crystallization control method for the ambient printing manufacture of large-area high-performance PSCs.