Synthetic-Method-Dependent Antimony Bromides and Their Photoluminescent Properties

Abstract

Recently, excellent optical properties of low-dimensional organic–inorganic metal halides, stemming from their tunable structure and optoelectronic properties, have been demonstrated. The synthetic method is critical because it is highly related to the structure and properties of the halide. Herein, we obtain two different antimony bromides, (Bmpip)2SbBr5 and (Bmpip)3Sb2Br9, which both possess the P21/c space group having different crystal structures, and this confirms the important influence of synthesis on the single-crystal structure. (Bmpip)2SbBr5 contains Bmpip+ and [SbBr5]2– pyramids, and (Bmpip)3Sb2Br9 consists of Bmpip+ and Sb-based dimers [Sb2Br9]3–. Under 400 nm excitation, (Bmpip)2SbBr5 exhibits a 640 nm orange emission with a quantum yield of ∼11.5% owing to Sb 5s2 electron luminescence. A diode was fabricated by (Bmpip)2SbBr5 and commercial phosphors and showed a high color render index of 92. Our work reveals the effect of the preparation method on the crystal structure. A luminescent material was finally identified.

Tunable Bright White Light Emission with Ultra‐High Color Rendering Index Induced by Trigonal Bipyramid Unit

“…This blue emission could be originated from the [Sb 2 Cl 10 ] 4− units, similar with the reported (C 3 H 12 N 2 ) 2 Sb 2 Cl 10 . [ 14 ] The EDS analysis and elemental mapping of Sb 3+ doping samples indicate the homogeneous distribution of In, Sb, and Cl, confirming the successful Sb doping in (C 13 H 14 N) 2 InCl 5 (Figure S6, Supporting Information). The actual doping amount of Sb was also presented in Table S6, Supporting Information, indicating that the doping limit of (C 13 H 14 N) 2 In 1− x Sb x Cl 5 is around 5%.…”

Achieving Near‐unity Photoluminescence Quantum Yields in Organic‐Inorganic Hybrid Antimony (III) Chlorides with the [SbCl5] Geometry

“…The lifetimes of these emission bands were found in close proximity to each other at the scale of ≈4 μs (Figure 5d, Table 2). It has been known that the strong broadband STE emission of Sb 3+ originates from the transition of triplet 3 P n =2,1,0 to ground state 1 S 0 [29, 45, 46] . However, the structural differences between the A 2 SbCl 5 and A 2 Sb 2 Cl 8 series may result in different orientation of the 5s 2 lone pair of Sb 3+ (as shown in Scheme 1).…”

“…For example, (MePPh 3 ) 2 SbCl 5 , [24] [TEA] 2 SbCl 5 (TEA + =tetraethylammonium), [25, 26] (TEBA) 2 SbCl 5 (TEBA + =tetraethylbenzylammonium), [25, 26] (PPN) 2 SbCl 5 (PPN + =bis(triphenylphosphoranylidene)‐ ammonium), [27] and (DTA) 2 SbCl 5 ⋅DTAC (DTAC=dodecyl trimethyl ammonium chloride) all have PLQY>90 % [28] . Unlike the antimony chlorides, other halides such as antimony bromides generally produce lower PLQY [29, 30] . Lower dimensional perovskites, especially 0D metal halides usually have self‐trapped exciton (STE) that promotes efficient broadband emission [31–34] .…”

“…For instance, Liu et al. demonstrated using different solvents can obtain (Bmpip) 3 Sb 2 Br 9 and (Bmpip) 2 SbBr 5 that has PLQY of <1 % and 11.5 %, respectively [29] …”

“…[28] Unlike the antimony chlorides, other halides such as antimony bromides generally produce lower PLQY. [29,30] Lower dimensional perovskites, especially 0D metal halides usually have self-trapped exciton (STE) that promotes efficient broadband emission. [31][32][33][34] Therefore, selecting bulky organic cations to isolate the metal halide and intentionally aim for 0D structures to have better PL performances is of particular interests.…”