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Trap engineering in ZnGa2O4:Tb3+ through Bi3+ doping for multi-modal luminescence and advanced anti-counterfeiting strategy

Yiping Wu,Meng Wu,Jingjie Yu,Yuru Wang,Jinlong Wang,Yingwei Xu,Yanjie Zhang

Optical information encryption based on luminescence materials have received much attention recently. However, the single luminescence mode of the luminescence materials greatly limits its anti-counterfeiting application with high safety level. Here, a series of luminescence materials of Tb 3+ and Bi 3+ co-doped ZnGa 2 O 4 phosphors with great correspondence in photoluminescence (PL), persistent luminescence (PersL), and thermoluminescence (TL) modes was synthesized by the conventional solid-phase method for the application in multi-modal anti-counterfeiting fields. Under the excitation of 254 nm, ZnGa 1.99 O 4 :0.01 Tb 3+ , yBi 3+ (y = 0.001,0.002) sample exhibited a broad blue emission band (the transition from [GaO 6 ]) at 440 nm and the characteristic emission peaks of Tb 3+ at 495 nm, 550 nm, 591 nm and 625 nm, corresponding to the transitions of 5 D 4 - 7 F n (n = 6, 5, 4, 3), respectively. Interestingly, the co-doping of Bi 3+ ions improve the crystallinity and particle size of the phosphor, subsequently enhanced the PL intensity of Tb 3+ to 6 times that of Tb 3+ singly doped ZnGa 2 O 4 phosphor. Further, the flexible films with multi-modal luminescence properties have been fabricated through the unique TL and PersL characteristics of ZnGa 2 O 4 : Tb 3+ , Bi 3+ phosphors, including “Optical information storage film”, “snowflake and characters” and “QR code”. Moreover, a set of optical information encryption is obtained by combining ZnGa 2 O 4 :Tb 3+ , Bi 3+ phosphor and red emitting phosphor. The results indicate that ZnGa 2 O 4 :Tb 3+ , Bi 3+ phosphor with multi-modal stimulus response can be expected to be potentially used in the applications of optical information storage and anti-counterfeiting fields.