High charge carrier storage capacity and wide range X-rays to infrared photon sensing in LiLuGeO4:Bi3+,Ln3+ (Ln = Pr, Tb, or Dy) for anti-counterfeiting and information storage applications

Abstract

X-Ray or 254 nm UV-light charged storage phosphors have various promising applications such as in anti-counterfeiting and information storage. However, developing such storage phosphors with high charge carrier storage capacity remains challenging. In this work, photoluminescence spectroscopy, thermoluminescence (TL), and vacuum-referred binding energy (VRBE) diagram were combined to study the trapping and liberation processes of charge carriers in Bi³⁺ and/or Ln³⁺ (Ln = Tb, Pr, or Dy) doped LiLuGeO₄. Unintended defects act as good electron trapping centers, while Bi³⁺, Tb³⁺, and Pr³⁺ act as hole-capturing and recombination centers. Dy³⁺ does not act as an electron trapping center but as a luminescence center by energy transfer from Bi³⁺ → Dy³⁺. The ratios of the integrated TL intensities between 303 K and 650 K for LiLuGeO₄:0.005Bi³⁺, LiLuGeO₄:0.005Bi³⁺,0.005Tb³⁺, or LiLuGeO₄:0.005Bi³⁺,0.005Dy³⁺ after X-ray charging to that of the state-of-the-art BaFBr(I):Eu²⁺ is about 1.24, 0.59, and 0.90, respectively. More than 10 h or 40 h afterglow was measurable in both LiLuGeO₄:0.005Bi³⁺ and LiLuGeO₄:0.005Bi³⁺,0.005Tb³⁺ after X-ray or 254 nm UV-light charging. The stored charge carriers stored can be efficiently excited to produce optically stimulated luminescence with a wide range 365 nm UV-light to 850 nm infrared laser beam. Proof-of-concept colour-tailorable afterglow, X-ray irradiation time or sample mass-dependent dosimetry, and optically-stimulated luminescence with a wide range of 365 nm UV-light to 850 nm infrared laser stimulation will be demonstrated for anti-counterfeiting, information storage, and display applications in the developed Bi³⁺ and/or Ln³⁺-doped LiLuGeO₄. This work not only reports Bi³⁺ and/or Ln³⁺ doped LiLuGeO₄ storage phosphors with excellent charge carrier storage capacity but also deepens our understanding of the afterglow and storage phosphors and luminescence mechanisms, which can guide us to explore new afterglow and storage phosphors for multimode applications.