Multiexcitonic Emission of Organic–Inorganic (C₄H₁₂N)₂ZrCl₆:Sb³⁺ Perovskites across the Full Visible Region for Anticounterfeiting Applications

Abstract

Hybrid lead-free halide perovskites have attracted substantial attention because of their superior optical properties. However, it is difficult for most metal perovskite materials with a single dopant to achieve multimode excitation and tunable or full-spectrum emission, leading to rare applications in white-light-emitting diodes and smart anticounterfeiting. Herein, a series of Sb 3+doped organic−inorganic halide hybrid (TMA) 2 ZrCl 6 (TMA = C 4 H 12 N) microcrystals with intriguing excitation-dependent luminescence is reported. The prepared (TMA) 2 ZrCl 6 :Sb 3+ perovskites exhibited three emission groups under variable excitation, corresponding to intrinsic host self-trapped excitons, dopant-induced extrinsic free excitons, and self-trapped excitons. The multiexcitonic emission modes in (TMA) 2 ZrCl 6 :Sb 3+ enabled dynamic color transfer by controlling the excitation wavelength. Tunable emission, high-efficiency luminescence (photoluminescence quantum yield up to 94.31%), and excellent environmental stability provide unique advantages in anticounterfeiting and solidstate lighting. The results offer fundamental insights into the color kinetics of antimony-doped hybrid metal halides, facilitating opportunities for multifunctional applications.

Near-unity photoluminescence quantum yield in zero-dimensional lead-free indium-based hybrid perovskites by antimony doping

“…S7, ESI†). Compared to our recently reported (TMA) 2 ZrCl 6 :Sb 3+ , 36 it has more excellent fluorescence efficiency although it shows single-band emission. The corresponding Commission Internationale de l'Elcairage (CIE) of the sample was (0.503, 0.468), showing a bright yellow light with a color purity of 91.5%, as shown in Fig.…”

RGB tri-luminescence in organic–inorganic zirconium halide perovskites

“…15,16 In particular, Bi 3+ , Sb 3+ , and Te 4+ can be doped into A 2 BX 6 perovskite structures, providing additional luminescence energy levels. 3,17–22 Among such materials, Cs 2 ZrCl 6 :1.5%Sb has been used in a stable single-component WLED with a record half-lifetime of 2003 h. 19 Co-doped Cs 2 HfCl 6 :Bi 3+ /Te 4+ microcrystals show warm-white emission and were applied to a WLED with a CRI of 75.4 and CIE colour coordinate of (0.370, 0.393). 23…”

Excited State Regulated Emission in Hybrid Indium Halides via Crystal Structure Switch

“…To address these issues, various metal cations have been used to replace Pb 2+ to reduce the toxicity of materials. In 3+ , Bi 3+ , and Te 4+ with ns 2 electron configurations, which are like Pb 2+ , have been extensively studied. − Therefore, low-dimensional indium-based halides are environmentally friendly and exhibit advantages such as tunable emission. They are regarded as one of the most promising candidates.…”