Solution combustion-synthesized BaAl₂O₄: Eu²⁺, Nd³⁺, and Pr³⁺ blue–green long-afterglow phosphors are prepared and systematically investigated. First, XRD confirms the BaAl₂O₄ host and screens for trace residual features. SEM reveals the agglomerated granular morphology typical of combustion products. XPS verifies the valence states (Eu²⁺, Nd³⁺, Pr³⁺) and the chemical environment of the host lattice. UV-Vis diffuse reflectance spectra, transformed via the Kubelka–Munk function and analyzed using Tauc plots (indirect-allowed), indicate a wide band gap of the BaAl₂O₄ host with small, systematic shifts upon Nd³⁺/Pr³⁺ co-doping. PL measurements show Eu²⁺ 4f–5d emission and co-dopant-assisted excitation/defect pathways without altering the Eu²⁺ emission band shape. Afterglow lifetime and decay analyses correlate trap depth/distribution with the extended persistence. Finally, we demonstrate anti-counterfeiting by (i) snowflake printing and (ii) a binary 3 × 3 grid printed with two afterglow inks of different lifetimes to realize multi-level authentication. The sequential evidence links structure, chemistry, optical absorption, carrier trapping, and practical readout, providing a coherent basis for performance enhancement and application.

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.