Crystallographic Investigations into Properties of Acentric Hybrid Perovskite Single Crystals NH(CH₃)₃SnX₃ (X = Cl, Br)

Abstract

The hybrid perovskites with special optoelectronic properties have attracted more attention to the scientific and industrial applications. However, because of the toxicity and instability of lead complexes, there is interest in finding a nontoxic substitute for the lead in the halides perovskites and solving the ambiguous crystal structures and phase transition of NH(CH 3 ) 3 SnX 3 (X = Cl, Br). Here, we report the bulk crystal growths and different crystal morphologies of orthorhombic hybrid perovskites NH(CH 3 ) 3 SnX 3 (X = Cl, Br) in an ambient atmosphere by bottom-seeded solution growth (BSSG) method. More importantly, detailed structural determination and refinements, phase transition, band gap, band structure calculations, nonlinear optical (NLO) properties, XPS, thermal properties, and stability of NH(CH 3 ) 3 SnX 3 (X = Cl, Br) single crystals are demonstrated. NH(CH 3 ) 3 SnCl 3 single crystal undergoes reversible structural transformation from orthorhombic space group Cmc2 1 (no. 36) to monoclinic space group Cc (no. 9) and NH(CH 3 ) 3 SnBr 3 belongs to the orthorhombic space group Pna2 1 (no. 33) by DSC, single-crystal X-ray diffraction and temperature-dependent SHG measurements, which clarify the former results. These results should pave the way for further studies of these materials in optoelectronics.

Progress in organic-inorganic hybrid halide perovskite single crystal: growth techniques and applications

“…NH(CH3)3SnX3 (X = Cl, Br) bulk single crystals were also harvested with the same TSSG method (Fig. 1h, i) [48].…”

Organic‐Inorganic Hybrid Perovskite Single Crystals: Crystallization, Molecular Structures, and Bandgap Engineering

“…Recently, based on previous work, Tao et al. adopted the TSSG method to grow MA/FASnI 3 and NH(CH 3 ) 3 SnX 3 (X=Cl, Br) single crystals (Figure f) ,…”

Organic–inorganic metal halide hybrids beyond perovskites

“…LEDs (Figure 2(c)), optically pumped lasers (Figure 2(d)), etc [32][33][34]. To address the toxicity issue of Pb, 3D tin halide perovskites have been developed [35][36][37][38][39]. However, bivalent Sn 2+ could be easily oxidized to Sn 4+ , resulting in the instability of the material itself and morphological change into other species [40].…”