Antimony Doped Hybrid Zinc Halide Crystals with Tunable Light Emission and Long‐Term Stability

• Published in: Advanced optical materials 2024-04, Vol.12 (12), p.n/a
• Main Authors: Zhang, Yaqing, Jiang, Yan, Zhang, Qi, Liu, Qingyi, Guo, Weiping, Zhang, Wei, Li, Lingyun, Feng, Ya‐Nan, Yu, Yan
• Format: Article
• Language: English
• Subjects: Antimony; Cations; Coordination; Crystals; hybrid halide crystals; Light emission; Metal halides; Photoluminescence; Sb3; Stability; Substitution reactions; Tetrahedra; tunable light emission; Waveguides
• ISSN: 2195-1071; 2195-1071
• DOI: 10.1002/adom.202302641

As a class of emerging photoluminescent materials, hybrid halide crystals have drawn research attention for their potential application in the fields of light‐emitting, security, and waveguide. Nevertheless, hybrid halide crystals containing antimony with long‐term stability and tunable light emission are still increasingly in demand. In this work, serial new hybrid halide crystals (BZA)2ZnCl4·2H2O:xSb3+ (x = 0–0.2, x represents the reaction ratio) and (BZA)2SbCl5 are synthesized (BZA = 2,4‐diamino‐6‐phenyl‐1,3,5‐triazine). In (BZA)2ZnCl4·2H2O:xSb3+ crystals, Sb3+ cations replace partial Zn2+ cations to form [SbCl4]− tetrahedron. Red light emission caused by the substitution of Sb3+ for Zn2+ enhances as the doping rate increases, resulting in the tunable emission from light blue to pink and finally to dark red. There are two kinds of Sb3+ in (BZA)2SbCl5 crystal. Sb(1) has a sixfold coordination with Cl to form a [Sb(1)Cl5]∞ 1D zigzag chain. Sb(2) atom adopts a fivefold coordination with Cl and is separated from each other by BZA+ cations. (BZA)2SbCl5 crystal shows bright orange‐yellow light emission with a photoluminescence quantum yield of 45%. Moreover, the organic–inorganic hybrid metal halide crystals containing antimony have excellent long‐term stability, with phase and luminescence keeping nearly unchanged after more than six months in ambient air. Hybrid antimony halide crystals (BZA)2ZnCl4·2H2O:xSb3+ (x = 0–0.20) and (BZA)2SbCl5 (BZA = 2,4‐diamino‐6‐phenyl‐1,3,5‐triazine) with tunable emission are synthesized. The (BZA)2ZnCl4·2H2O:xSb3+ crystals emit light with color changing from light blue to pink and finally to dark red as the doping rate increases, while the (BZA)2SbCl5 crystal exhibits bright orange–yellow light emission. The crystals have excellent long‐term stability of phase and luminescence.