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

Abstract 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) 2 ZnCl 4 ·2H 2 O: x Sb 3+ ( x = 0–0.2, x represents the reaction ratio) and (BZA) 2 SbCl 5 are synthesized (BZA = 2,4‐diamino‐6‐phenyl‐1,3,5‐triazine). In (BZA) 2 ZnCl 4 ·2H 2 O: x Sb 3+ crystals, Sb 3+ cations replace partial Zn 2+ cations to form [SbCl 4 ] − tetrahedron. Red light emission caused by the substitution of Sb 3+ for Zn 2+ 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 Sb 3+ in (BZA) 2 SbCl 5 crystal. Sb(1) has a sixfold coordination with Cl to form a [Sb(1)Cl 5 ]∞ 1D zigzag chain. Sb(2) atom adopts a fivefold coordination with Cl and is separated from each other by BZA + cations. (BZA) 2 SbCl 5 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.