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)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.

Tailoring the π–π stacking interaction among organic cations in hybrid metal halide crystals towards tunable light emission

“…0D OIMHs with optically active ions such as Mn 2+ and Sb 3+ as a metal center always feature typical optical emission due to the intrinsic electronic transition of these metal ions. 12–15 For instance, the (MTP) 2 MnBr 4 (MTP: methyltriphenylphosphonium) 12 and (BZA) 2 SbCl 5 (BZA = 2,4-diamino-6-phenyl-1,3,5-triazine) 13 crystals which possess a 0D structure display strong blue and orange emissions under the excitation of ultra violet (UV) light. However, in OD OIMHs with Zn 2+ or Cd 2+ as metal centers, the optical emission mostly originates from the electronic transition of the organic component or the self-trapped excitons (STEs).…”

Excitation-Dependent Emission in Sb3+-Doped All-Inorganic Rare-Earth Double Perovskites for Anticounterfeiting Applications

“…Recently, lead-free perovskites, such as double perovskites and low-dimensional perovskites, have attracted great interest in realizing excitation-dependent emission due to several intrinsic advantages including high photoluminescence quantum yields (PLQYs), low-toxicity, and low-cost solution processing. − These systems possess unique soft lattices and strong quantum confinement, which endow them with broadband self-trapped exciton (STE) emission. − The existence of multiple emission centers, including STEs, ligands, and doping ions, renders them a perfect platform to achieve excitation-dependent emission. − For example, Kuang et al reported a zero-dimensional (0D) indium–antimony alloyed halide perovskite, BAPPIn 1.996 Sb 0.004 Cl 10 , which emits bright yellow light and white light with PLQYs of ca. 100 and 44% at 320 and 365 nm excitation, respectively .…”

Cationic Engineering Strategy to Achieve Controllable Room‐Temperature‐Phosphorescence in Hybrid Zinc Halides

“…In this context, low-dimensional organic-inorganic metal halide (OIMH) family can be considered a new highly promising candidate for RTP material with synergistic merits of both inorganic and organic components. [14][15][16][17] Specifically, the inherent RTP properties of organic substrates significantly contribute to the diversification of luminescent properties of hybrid halides. Meanwhile, the soft crystal lattice results in large deformation of metal halide units under the photoexcitation due to a strong electron-phonon coupling effect, which is in favor of the formation of triplet excited states as well as associated phosphorescence.…”