Inhibition of Sn Oxidation in FASnI Perovskite Precursor Solution and Enhanced Stability of Perovskite Solar Cells by Reductive Additive.

Tin-based halide perovskite solar cells (Sn-PSCs) have attracted a progressive amount of attention as a potential alternative to lead-based PSCs (Pb-PSCs). Sn-perovskite films are fabricated by a solution process spin-coating technique. However, the efficiency of these devices varies significantly with the different batches of precursor solution due to the poor chemical stability of SnI-DMSO and the oxidation of Sn to Sn. This study investigated the origin of Sn oxidation before film formation, and it was identified that the ionization of SnI in dimethyl sulfoxide (DMSO) causes the oxidation of free Sn and I ions. To address these issues, this study introduces the reductive additive 4-fluorophenylhydrazine hydrochloride (4F-PHCl) in the FASnI perovskite precursor solution. The hydrazine functional (-NH-NH) group converted detrimental Sn and I defects back to Sn and I in precursor solution while retaining the properties of the perovskite solution. Furthermore, the addition of 4F-PHCl in the precursor solution effectively slows the crystallization process, enhancing the crystallinity of FASnI perovskite films and guaranteeing the Sn/I stoichiometric ratio, ultimately leading to a power conversion efficiency (PCE) of 10.86%. The hydrophobic fluorinated benzene ring in 4F-PHCl ensures moisture stability in perovskite films, allowing unencapsulated PSCs to retain over 92% of their initial PCE in an N-filled glovebox for 130 days. Moreover, the 4F-PHCl-modified encapsulated PSCs showed superior operational stability for 420 h and maintained 95% of their initial PCE for 300 h under maximum power point tracking at 1 sun continuous illumination. This study's findings provide a promising pathway to create a controlled Sn-based perovskite precursor solution for highly reproducible and stable Pb-free Sn-PSCs.