Reaction‐Diffusion and Crystallization Kinetics Modulation of Two‐Step Deposited Tin‐Based Perovskite Film via Reducing Atmosphere

The two-step deposition method effectively mitigates the efficiency decline observed in tin-based perovskite solar cells (TPVSCs) with increasing cell area, stemming from film in-homogeneity. However, the high solubility of SnI₂ in the conventionally used solvent isopropyl alcohol, coupled with the absence of effective modulation of reaction-diffusion process, results in inadequate film coverage and conversion. In this study, we introduce formic acid as the second-step solvent and introduce dithiothreitol (DTT) to regulate reaction-diffusion/crystallization kinetics meticulously. Moreover, this research underscores a fundamental principle that the suitable binding energy ranging from -1.38 to -10.10 kcal mol^-1 between ligands and Sn²⁺ significantly enhances the effectiveness of two-step crystallization control. Notably, a uniform perovskite film is achieved on large-scale substrate, and TPVSCs processed with DTT exhibit the highest efficiencies of 12.68 % for 0.04 cm² device and 11.30 % for 1 cm² device among tin-based perovskite devices in two-step sequential deposition method, even in the absence of dimethyl sulfoxide. This study lays the groundwork for the potential scale-up development of lead-free perovskite solar cells.