Organic−Inorganic Hybrid Tin Halide Single Crystals with Sulfhydryl and Hydroxyl Groups: Formation, Optical Properties, and Stability

Lead (Pb)-free halide hybrid materials have received a great deal of attention because of their potential in optoelectronic applications. However, heteroatom-based amine lead-free tin halide hybrid single crystals have not been well investigated yet. Detailed synthetic processes, growth, crystal structures, and stability of (ACH₂CH₂NH₃)₂SnBr₆ (A = OH or SH) and (BCH₂CH₂NH₃)₂SnI₄ (B = I or SH) single crystals were investigated. Interestingly, (IH₃NCH₂CH₂SSCH₂CH₂NH₃)₂HPO₃ exhibited orange-red photoluminescence (PL) at about 620 nm with an average PL lifetime of about 912 ns. (HSCH₂CH₂NH₃)₂SnI₄ single crystals exhibited a PL peak at 620 nm with an average PL lifetime of about 0.607 ns. More importantly, (HSCH₂CH₂NH₃)₂SnI₄ single crystals exhibited reversible red−black color transformations when exposed to a H₃PO₂ solution and an ambient atmosphere, which was attributed to oxidation from Sn²⁺ to Sn⁴⁺, rather than from I⁻ to I₃⁻ (I₂). The intriguing characteristics should provide guidance for further optoelectronic applications of these Pb-free halide hybrid materials.