Self-reduction-induced BaMgP2O7:Eu2+/3+: a multi-stimuli-responsive phosphor for X-ray detection, anti-counterfeiting and optical thermometry

Abstract

Mixed-valence Eu^2+/3+-activated phosphors have attracted wide attention due to their excellent luminescence tunability. Steady control of the Eu²⁺/Eu³⁺ ratio is the key to achieving reproducible Eu^2+/3+ co-doped materials. In this work, BaMgP₂O₇:xEu^2+/3+ (BMPO:Eu, x = 0.001–0.20) was successfully prepared by the traditional solid-state method in air. Eu³⁺ undergoes selective self-reduction at Ba²⁺ sites surrounded by a [P₂O₇] framework, leading to quantitive Eu²⁺/Eu³⁺. The phosphors exhibit a blue-violet emission band at ∼410 nm due to 5d–4f transitions of Eu²⁺ and a group of red emission peaks from ⁵D₀–⁷F_J of Eu³⁺. Controllable multicolor emissions are realized by regulating the Eu content and excitations. A linear response of overall luminescence intensity to irradiation dose makes the phosphor appropriate for X-ray detection. The combination of UV-blue excitation-dependent color evolution and X-ray luminescence qualifies the phosphors with great potential for multi-level anti-counterfeiting. In addition, Eu³⁺ presents abnormal anti-thermal quenching, so that the fluorescence intensity ratio (FIR) of Eu²⁺/Eu³⁺ changes in the temperature range of 300–520 K, suggesting a promising application in optical thermometry. Therefore, selectively partial self-reduction in a multi-cationic host is an effective strategy to design mixed-valence co-doped materials, providing a multiplicity of applications.