Role of Gd3+ ion on downshifting and upconversion emission properties of Pr3+, Yb3+ co-doped YNbO4 phosphor and sensitization effect of Bi3+ ion

Abstract

Dual-mode luminescence (downshifting-DS and upconversion-UC) properties of Pr3+/Yb3+ co-doped Y1−xGdxNbO4 (x = 0.0, 0.5, and 1.0) phosphors synthesized by solid state reaction technique have been explored with and without Gd3+ ion. The structural characterizations (XRD, SEM, and FTIR) confirm the pure phase of YNbO4 phosphor. Further, with the Gd3+ ion co-doping, the YNbO4 phosphors having a random shape and the large particle size are found to be transformed into nearly spherical shape particles with the reduced particle size. The optical band gaps (Eg) of Y1−xGdxNbO4 (x = 0.00, 0.25, 0.50, and 1.00) calculated from UV-Vis-NIR measurements are ∼3.69, 4.00, 4.38, and 4.44 eV, respectively. Moreover, YNbO4 phosphor is a promising blue emitting material, whereas Y1−x−y−zPryYbzGdxNbO4 phosphor gives intense green, blue, and red emissions via dual-mode optical processes. The broad blue emission arises due to (NbO4)3− group of the host with λex = 264 nm, whereas Pr3+ doped YNbO4 phosphor gives dominant red and blue emissions along with comparatively weak green emission on excitation with λex = 300 nm and 491 nm. The concentration dependent variation in emission intensity at 491 nm (3P0→3H4 transition) and 612 nm (1D2→3H4 transition); at 612 nm (1D2→3H4 transition) and 658 nm (3P0→3F2 transition) of Pr3+ ion in YNbO4 phosphor with λex = 300 nm and 491 nm excitations, respectively, has been thoroughly explored and explained by the cross-relaxation process through different channels. The sensitization effect of Bi3+ ion co-doping on DS properties of the phosphor has also been studied. The observed DS results have been optimized by varying the concentration of Pr3+ and Bi3+ ions, and the results are explained by the well-known simple band structure model. The study of Gd3+ co-doping reveals noticeable differences in DS characteristics of Y1−xPrxNbO4 phosphors: the overall decrement and increment (except for 612 nm emission) in intensity of DS emission on excitation with λex = 264 nm and 491 nm, respectively. These observations have been thoroughly explained, and the 1D2→3H4 transition (612 nm) of Pr3+ ion is found to be strongly dependent on surrounding environment of the host matrix. The UC properties of Y0.95−xPrxYb0.05NbO4 phosphors have been explored using Near Infra-Red (NIR) excitation. The material gives intense green and relatively weak blue and red UC emissions with λex = 980 nm. Interestingly, the UC emission intensity is further enhanced in the case of Y0.949−xPr0.001Yb0.05GdxNbO4 phosphors. In addition, the less explored laser induced heating effect with the pump power as well as the irradiation time on the UC emission has been explored in Y0.949−xPr0.001Yb0.05GdxNbO4 (x = 0, 0.5, and 0.949) phosphor samples, and subsequently, this feature has been found to be superior for Gd0.949Pr0.001Yb0.05NbO4 phosphor. The comparative study between the two hosts, viz., YNbO4 and GdNbO4 shows that GdNbO4 is better than YNbO4 for UC emission behavior; however, a reverse is observed as for as DS behavior is concerned only for the particular excitation wavelength (λex = 264 nm).