Using Ligand Engineering to Produce Efficient and Stable Pb–Sn Perovskite Solar Cells with Antioxidative 2D Capping Layers

Pb–Sn binary halide perovskites are a promising photovoltaic material due to their low toxicity and optical absorption spectrum well matched to the solar spectrum. However, the ready oxidation of Sn²⁺ to Sn⁴⁺ makes the material system currently too unstable to commercialize. Herein, ligand engineering based on antioxidative tyramine (hydrochloride, TACl) is presented for the first time to increase the stability of this material system. Using this strategy, we generate a two-dimensional (2D) capping layer on top of a standard three-dimensional Pb–Sn film. After capping, the surface defects can be passivated and the TACl-based 2D perovskite effectively protected Sn²⁺ from oxidation, which stabilized the Sn–Pb perovskite composition, avoiding the Pb-based perovskite formation. It is further found that the TACl treatment suppressed the halide segregation and improved the perovskite film photostability. Cell efficiency increases from 16.25 to 18.28% and device lifetime (T₈₀) increases from less than 100 to over 1000 h. Our finding suggests that tuning ligand form/function represents a potentially highly productive direction to explore when trying to produce stable tin-based perovskite devices.