Controlled Structural Transformation in Sb‐Doped Indium Halides A₃InCl₆ and A₂InCl₅∙H₂O Yields Reversible Green‐to‐Yellow Emission Switch

Abstract

Lead halide perovskites have demonstrated promising emission tunability achieved by composition engineering, which makes them viable in several potential applications. Determining how to effectively control the crystalline structural transformation and composition in lead‐free halide perovskites is of great importance. Herein, a controllable synthetic method is reported to obtain the 0D metal halide perovskite derivatives (Cs1−xRbx)2InCl5∙H2O and (Cs1−xRbx)3InCl6, through synergistic regulation of the Cs/Rb feed ratios and the reaction solvent. When hydrochloric acid (HCl) is used as the reaction solvent, (Cs1−xRbx)2InCl5∙H2O is obtained at a high Cs/Rb feed ratio greater than 2:1, while (Cs1−xRbx)3InCl6 is obtained at a low Cs/Rb feed ratio of less than 2:5. However, when anhydrous methanol (MeOH) is used as the reaction solvent, only the (Cs1−xRbx)3InCl6 structure is obtained at all Cs/Rb feed ratios. In addition, a reversible crystalline structural transformation is demonstrated between (Cs0.67Rb0.33)2InCl5∙H2O and (Cs0.67Rb0.33)3InCl6 by immersing the as‐prepared products into MeOH and HCl sequentially, which generates a novel green/yellow reversible emission switch. The Sb3+ ion self‐trapped exciton emission and stability of the synthesized (Cs1−xRbx)2InCl5∙H2O and (Cs1−xRbx)3InCl6 are systematically investigated. The results are helpful for promoting the diverse photonics and optoelectronics applications of these environmentally stable perovskite derivatives.

Antimony doped tin(iv) hybrid metal halides with high-efficiency tunable emission, WLED and information encryption

“…52 Huang et al observed green emission with PLQY up to 90% in Sb 3+ -doped (Cs 0.29 Rb 0.71 ) 3 InCl 6 , which was attributed to relatively weak electron–phonon coupling and Jahn–Teller distortion. 36 Wei et al achieved high-efficiency green emission by doping Sb 3+ in Cd-based halides. The emission peaks of these halides are all between 500–530 nm.…”

“…The green emission of [Bzmim] 3 SbCl 6 (Bzmim = 1-benzyl-3-methylimidazolium) reported by Huang et al 28 comes from SbCl 6 clusters in the lattice, and Peng et al reported a series of Sb halides, whose red emission comes from SbCl 5 clusters in the compound. 6,29 After doping Sb 3+ in other metal halides, it can achieve blue, 30 green, [31][32][33][34][35][36] yellow, 33,[35][36][37][38][39][40] orange, 31,33 red, 25,39,41,42 near-infrared, 43 and white emission. 38,40 Li et al reported that Sb 3+ doped (BTPP) 2 MnCl 4 (BTPP = benzyltriphenylphosphonium) halides with excitation-dependent dual emission achieve tunable emission colors from green to orange, and (BTPP) 2 MnCl 4 :2.0%Sb crystals exhibit green and orange emission under 254 and 365 nm UV lamps, respectively.…”

Cu substitution boosts self-trapped exciton emission in zinc-based metal halides for sky-blue light-emitting diodes

“…The red shift is due to the decreasing of temperature causing the valence band to move to a higher energy level. 44,45 The influence of temperature variation on the PL intensity and shift of emission can be distinctly observed in the pseudocolor mapping of Cu:(PEA) 2 ZnCl 4 and Cu:(PEA) 2 ZnBr 4 (Fig. 3c and f).…”

“…43 In addition, in metal halides, the shift of the emission peak caused by temperature change is normally associated with lattice distortion and valence band shift. 43,44 The peaks of Cu:(PEA) 2 ZnX 4 are all red-shifted with decreasing temperature. The red shift is due to the decreasing of temperature causing the valence band to move to a higher energy level.…”

Efficient Yellow Emission and Near-Unified Photoluminescence Quantum Yield of Sb3+ in a One-Dimensional Confinement Cadmium Chloride Lattice

“…Figure 1d shows the high-resolution XPS spectra of the 3d orbitals of Sb elements in 8.8% Sb:(TDMP)CdCl 4 and (TDMP)CdCl 4 . The peaks at 530 and 539 eV in the figure come from the 3d 5/2 and 3d 3/2 orbitals of Sb 3+ , 36 respectively. This result further indicates that the Sb in these compounds is trivalent Sb 3+ , not other valences.…”