Study on the Structure-Luminescence Relationship and Anti-Counterfeiting Application of (Ca,Sr)-Al-O Composite Fluorescent Materials.

Abstract

A novel long-lasting luminescent composite material based on the (Ca,Sr)-Al-O system was synthesized using a solution combustion method. (Ca,Sr)₃Al₂O₆ is the primary phase, with SrAl₂O₄ as a controllable secondary phase. Compared to conventional single-phase SrAl₂O₄ phosphors, the introduction of a calcium-rich hexaaluminate matrix creates additional defects and a specific trap distribution at the composite interface, significantly improving carrier storage and release efficiency. Eu²⁺ + Nd³⁺ synergistic doping enables precise control of the trap depth and number. Under 365 nm excitation, Eu²⁺ emission is located at ~515 nm, with Nd³⁺ acting as an effective trap center. Under optimal firing conditions at 700 °C (Eu²⁺ = 0.02, Nd³⁺ = 0.003), the afterglow lifetime exceeds 30 s. Furthermore, The (Ca,Sr)₃Al₂O₆ host stabilizes the lattice and optimizes defect states, while synergizing with the SrAl₂O₄ secondary phase to improve the afterglow performance. This composite phosphor exhibits excellent dual-mode anti-counterfeiting properties: long-lasting green emission under 365 nm excitation and transient blue-violet emission under 254 nm excitation. Based on this, a screen-printing ink was prepared using the phosphor and ethanol + PVB, enabling high-resolution QR code printing. Pattern recognition and code verification can be performed both in the UV on and off states, demonstrating its great potential in high-security anti-counterfeiting applications. Compared to traditional single-phase SrAl₂O₄ systems, this study for the first time constructed a composite trap engineering of the (Ca,Sr)₃Al₂O₆ primary phase and the SrAl₂O₄ secondary phase, achieving the integration of dual-mode anti-counterfeiting functionality with a high-resolution QR code fluorescent ink.