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 solid-state lighting. The results offer fundamental insights into the color kinetics of antimony-doped hybrid metal halides, facilitating opportunities for multifunctional applications.