“…The new third-generation solar cells, such as perovskite solar cells (PSCs), dye-sensitized solar cells, and quantum dot solar cells, have received increasing interests recently as a result of the facile fabrication process, low-cost raw material, and superior theoretical PCEs. − In particular, PSCs with lead (Pb)-based halide perovskites as light absorbers exhibit several unique and excellent optical/electronic properties, including adjustable band gaps, high optical absorption coefficients, high mobility, and long diffusion length of charge carriers, leading to a rapid boosting rate of PCEs of PSCs from 3.8 to 25.7% in the last 14 years. − Therefore, the newly developed PSCs are considered as the most potential replacements to traditional silicon-based solar cells for large-scale and sustainable photovoltaic power generation. , Although the PCEs of Pb-based PSCs have reached 25.7% recently, the large-scale applications of Pb-based organic–inorganic hybrid PSCs still face many crucial challenges. − First, the band gaps of Pb-based organic–inorganic perovskites currently used in high-performance PSCs are generally 1.5–1.6 eV, which are much larger than the theoretical optimal band gap of 1.3–1.4 eV for solar cells calculated according to the Shockley–Queisser (S–Q) theory . Second, the toxicity of Pb is extremely harmful to the environment and humans. − To overcome these problems, numerous researchers are trying to develop new Pb-free or Pb-less halide perovskites using non-toxic metals, including tin (Sn), bismuth (Bi), and germanium (Ge), to achieve sustainable and clean perovskite photovoltaics. − Among various alternatives to Pb 2+ cations, Sn 2+ cations have similar electronic structures to Pb 2+ and comparable ion radii (the ionic radii of Sn 2+ and Pb 2+ are 110 and 119 pm, respectively). − Therefore, partial or complete replacement of Pb 2+ in perovskites by Sn 2+ will not lead to significant lattice distortions in the perovskite structure .…”