Lanthanide‐Doped Hybrid Metal Halide Glasses with Multidimensional Luminescence for X‐Ray Imaging and Photonic Authentication

ABSTRACT Hybrid metal‐halide glasses combine optical homogeneity and processability for scintillators, yet most reported systems rely on a single emissive center and conventional radiation‐to‐light conversion. Here, we report lanthanide (Ln)‐doped BTP 2 MnCl 4 (BTP + = Butyltriphenylphosphonium) hybrid glasses prepared by one‐step melt‐quenching, demonstrating expanded emission channels while preserving optical transparency and the amorphous state. Eu 3+ is selected as a secondary emitter for its spectroscopic complementarity with Mn 2+ . The glasses integrate broadband green Mn 2+ emission with narrow red Eu 3+ lines, whose relative contributions are regulated by Eu 3+ content and excitation wavelength. Distinct thermal responses provide additional temperature modulation, while spectroscopic and time‐resolved measurements support Mn 2+ →Eu 3+ energy transfer. As scintillators, the glasses achieve a light yield of 18 843 photons MeV −1 , a detection limit of 26.7 nGy air s −1 , and an imaging resolution of 28.5 lp mm −1 , with stable radioluminescence under repeated and prolonged irradiation. Beyond conventional imaging, the composition‐, excitation‐, and temperature‐dependent spectral responses enable photonic barcodes for sequential multilevel authentication. Furthermore, the successful preparation of Ln‐ and Sb‐based glasses further demonstrates the generalizability of this glass‐forming strategy. These results extend hybrid metal‐halide glasses beyond conventional scintillation media toward spectrally addressable multifunctional materials, providing a route to integrate x‐ray imaging with multidimensional optical information processing.