Metal-Ion-Doped Manganese Halide Hybrids with Tunable Emission for Advanced Anti-Counterfeiting

Stimuli-responsive luminescent materials have received great attention for their potential application in anti-counterfeiting and information encryption. Manganese halide hybrids have been considered an efficient stimuli-responsive luminescent material due to their low price and adjustable photoluminescence (PL). However, the photoluminescence quantum yield (PLQY) of PEA₂MnBr₄ is relatively low. Herein, Zn²⁺- and Pb²⁺-doped PEA₂MnBr₄ samples are synthesized, and show an intense green emission and orange emission, respectively. After doping with Zn²⁺, the PLQY of PEA₂MnBr₄ is elevated from 9% to 40%. We have found that green emitting Zn²⁺-doped PEA₂MnBr₄ could transform to a pink color after being exposed to air for several seconds and the reversible transformation from pink to green was achieved by using heating treatment. Benefiting from this property, an anti-counterfeiting label is fabricated, which exhibits excellent "pink-green-pink" cycle capability. Pb²⁺-doped PEA₂Mn_0.88Zn_0.12Br₄ is acquired by cation exchange reaction, which shows intense orange emission with a high QY of 85%. The PL of Pb²⁺-doped PEA₂Mn_0.88Zn_0.12Br₄ decreases with increasing temperature. Hence, the encrypted multilayer composite film is fabricated relying on the different thermal responses of Zn²⁺- and Pb²⁺-doped PEA₂MnBr₄, whereby the encrypted information can be read out by thermal treatment.