Multicolor and multimode luminescence regulation and anti-counterfeiting application of lanthanide ions doped Li<sub>0.9</sub>K<sub>0.1</sub>NbO<sub>3</sub> phosphors

Abstract

Multicolor and multimode luminescence materials have important applications in the field of information security encryption. However, the design and synthesis of multicolor multimode luminescent materials is still a challenge, and only several materials have been reported. In this paper, a series of single doped and double doped Li<sub>1–<i>x</i></sub>K<sub><i>x</i></sub>NbO<sub>3</sub>:Pr<sup>3+</sup>/Er<sup>3+</sup>/Tm<sup>3+</sup> phosphors are prepared by high temperature solid state method. The structure, morphology, optical properties and thermoluminescence (TL) spectra are characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM), luminescence spectrometer and self-made heating device. Firstly, the effects of different values of K<sup>+</sup> content on the luminescence and trap distribution of LiNbO<sub>3</sub> materials are studied. The results show that the ionic lattice is distorted when a small quantity of K<sup>+</sup> ions replace Li<sup>+</sup>. With the addition of K<sup>+</sup>, the photoluminescence excitation (PLE) spectra monitored emission of 620 nm shows that the ratios of the absorption peaks from matrix (200–310 nm) to absorption peaks from the intrinsic transition of Pr<sup>3+</sup> ions 4f→5d (310–430 nm) change significantly, showing a double-peak characteristic. When the concentration of K<sup>+</sup> ions is 0.5, the absorption peak from the matrix disappears, which may be due to the phase transition of the matrix lattice caused by excessive K<sup>+</sup> ions or the introduction of a large number of defect energy levels into the matrix lattice. Moreover, K<sup>+</sup> ion doping can regulate the density and distribution of traps. TL curves show that a small quantity of K<sup>+</sup> doping increases the trap density of shallow traps. When a large quantity of K<sup>+</sup> is doped, the phase changes of matrix lattice and the defect density decrease. Secondly, the doping of Li<sub>0.9</sub>K<sub>0.1</sub>NbO<sub>3</sub> matrix by different luminescent centers (Pr<sup>3+</sup>/Er<sup>3+</sup>/Tm<sup>3+</sup>) is studied. The results show that the multicolor luminescence emission in red, blue and green bands and the tunable multimode luminescence (up/down conversion luminescence, afterglow luminescence and photo-stimulated luminescence) are realized by the selective excitation. According to the multicolor and multimode characteristics of the phosphors, a butterfly-shaped anti-counterfeiting pattern is designed. Owing to the different energy level positions of the luminescence centers, dynamic multicolor photoluminescence is realized by selective excitation at different wavelengths. Based on the upconversion luminescence characteristics of Er<sup>3+</sup> and the excellent afterglow characteristics of Pr<sup>3+</sup> in Li<sub>0.9</sub>K<sub>0.1</sub>NbO<sub>3</sub> material, the designed anti-counterfeiting pattern shows the dynamic color change and multicolor, multimode high-order anti-counterfeiting application.