Though fluorescence‐tag‐based anti‐counterfeiting technology has distinguished itself with cost‐effective features and huge information loading capacity, the clonable decryption process of spatial‐resolved anti‐counterfeiting cannot meet the requirements for high‐security‐level anti‐counterfeiting. Herein, we demonstrate a spatial‐time‐dual‐resolved anti‐counterfeiting system based on new organic–inorganic hybrid halides BAPPZn2(ClyBr1−y)8 (BAPP=1,4‐bis(3‐ammoniopropyl)piperazinium, y=0–1) with ultra‐long room‐temperature phosphorescence (RTP). Remarkably, the afterglow lifetime can be facilely tuned by regulating the halide‐induced heavy‐atom effect and can be identified by the naked eyes or with the help of a simple machine vision system. Therefore, the short‐lived unicolor fluorescence and lasting‐time‐tunable RTP provide the prerequisites for unicolor‐time‐resolved anti‐counterfeiting, which lowers the decryption‐device requirements and further provides the design strategy of advanced portable anti‐counterfeiting technology.

Zero-dimensional metal halide perovskites have captured intense research interest owing to their unique optoelectronic properties. Particularly, metal halides with the ns 2 electronic configuration are of great interest owing to the high-temperature sensitivity of their photoluminescence, which could be applied to remote optical thermometry (ROT). Herein, all-inorganic and lead-free halide perovskite Te 4+doped Cs 2 InCl 5 •H 2 O single crystals (SCs) were prepared through the hydrothermal method and showed a strong temperature dependence of photoluminescence lifetime. Upon Te 4+ doping, the nonemissive Cs 2 InCl 5 •H 2 O SC exhibits a bright orange emission at 660 nm with a wide full width at half maximum of 180 nm. The strong phonon-exciton coupling promotes the formation of self-trapped excitons in the soft lattice of the zero-dimensional Te 4+ -doped Cs 2 InCl 5 •H 2 O SC. The Te 4+ ions with the 5s 2 electronic configuration endow the Te 4+ -doped Cs 2 InCl 5 •H 2 O SC with a strong temperaturedependent photoluminescence lifetime. This SC reaches a maximum specific sensitivity of 0.062 K −1 at 320 K, thereby showing the potential advantages of indium-based metal halide perovskites in ROT applications.

Though fluorescence‐tag‐based anti‐counterfeiting technology has distinguished itself with cost‐effective features and huge information loading capacity, the clonable decryption process of spatial‐resolved anti‐counterfeiting cannot meet the requirements for high‐security‐level anti‐counterfeiting. Herein, we demonstrate a spatial‐time‐dual‐resolved anti‐counterfeiting system based on new organic–inorganic hybrid halides BAPPZn2(ClyBr1−y)8 (BAPP=1,4‐bis(3‐ammoniopropyl)piperazinium, y=0–1) with ultra‐long room‐temperature phosphorescence (RTP). Remarkably, the afterglow lifetime can be facilely tuned by regulating the halide‐induced heavy‐atom effect and can be identified by the naked eyes or with the help of a simple machine vision system. Therefore, the short‐lived unicolor fluorescence and lasting‐time‐tunable RTP provide the prerequisites for unicolor‐time‐resolved anti‐counterfeiting, which lowers the decryption‐device requirements and further provides the design strategy of advanced portable anti‐counterfeiting technology.