GdVO 4 nanoparticles doped with Dy3+ have been prepared using urea hydrolysis method in ethylene glycol medium. Linear decrease in the unit cell volume indicates the quantitative substitution of Gd3+ lattice sites by Dy3+ in GdVO4. The luminescence intensity of electric dipole transition at 573 nm is more than that of magnetic dipole transition at 483 nm. This has been attributed to the asymmetric environment of Dy3+ ion in GdVO4. Luminescence intensity decreases with increasing Dy3+ concentrations due to concentration quenching. This is supported by lifetime decay studies. There is no particle size effect on the peak positions of Dy3+ emission. There is an increase in the decay lifetime for F49/2 level with increase in heat treatment from 500 to 900 °C. This is attributed to the reduction in nonradiative process arose from surface inhomogeneities. The decay lifetime data follow the biexponential to monoexponential nature with increase of Dy3+ concentrations. There is an increase in the quantum yield with the increase in heat treatment temperature.
Nanoparticles of GdVO4 doped with Eu3+ and core/shell of GdVO4:Eu3+/GdVO4 are prepared by urea hydrolysis method using ethylene glycol as capping agent as well as reaction medium at 130 °C. Unit cell volume increases when GdVO4 is doped with Eu3+ indicating the substitution of Gd3+ lattice sites by Eu3+. From luminescence study, it is confirmed that there is no particle size effect on emission positions of Eu3+. Optimum luminescence intensity is found to be in 5–10 at. % Eu3+. Above these concentrations, luminescence intensity decreases due to concentration quenching effect. There is an enhancement in luminescence intensity of core/shell nanoparticles. This has been attributed to the reduction in surface inhomogenities of Eu3+ surroundings by bonding to GdVO4 shell. The lifetime for D50 level increases with annealing and core/shell formation.
Crystalline nanoneedles of Eu3+-doped GdPO4 and Eu3+-doped GdPO4 covered with GdPO4 shell (core shell) have been prepared at relatively low temperature of 150 °C in ethylene glycol medium. From luminescence study, asymmetric ratio of Eu3+ emission at 612 nm (electric dipole transition) to 592 nm (magnetic dipole transition) is found to be less than one. Maximum luminescence was observed from the nanoparticles with Eu3+ concentration of 5 at. %. For a fixed concentration of Eu3+ doping, there is an improvement in emission intensity for core-shell nanoparticles compared to that for core. This has been attributed to effective removal of surface inhomogeneities around Eu3+ ions present on the surface of core as well as the passivation of inevitable surface states, defects or capping ligand (ethylene glycol) of core nanoparticles by bonding to the shell. Lifetime for D50 level of Eu3+ was found to increase three times for core-shell nanoparticles compared to that for core confirming the more Eu3+ ions with symmetry environment in core shell. For 5 at. % Eu3+-doped GdPO4, quantum yield of 19% is obtained. These nanoparticles are redispersible in water, ethanol, or chloroform and thus will be useful in biological labeling. The dispersed particles are incorporated in polymer-based films that will be useful in display devices.
Nanoparticles of Tb3+ -doped GdPO 4 (Tb 3+ = 0, 2, 5, 7, 10, and 20 atom-%) have been prepared at a relatively low temperature of 160°C in ethylene glycol medium. The particles crystallize in a monoclinic structure with an average crystallite size of 30-50 nm. From the luminescence study of Tb 3+ -doped GdPO 4 , the magnetic dipole transition ( 5 D 4 Ǟ 7 F 5 ) at 545 nm (green) was found to be more prominent than the electric dipole transition ( 5 D 4 Ǟ 7 F 6 ) at 484 nm (blue). Maximum luminescence intensity and lifetime was observed for 7 atom-% Tb
3+. Above 7 atom-% Tb 3+ , a decrease in luminescence was observed. This has been attributed to a con-
Crystalline LaVO4:Eu(3+) nanophosphors (NPs) codoped with metal ions (M(n+) = Li(+), Sr(2+), and Bi(3+)) are prepared in ethylene glycol (EG) medium at temperature ∼140 °C in 3 h. A mixture of monoclinic and tetragonal phases is observed. The ratio of tetragonal to monoclinic phases increases with increase of Li(+) and Sr(2+) concentration, but this is opposite in case of Bi(3+) concentration. Lattice expansion occurs in the case of Li(+) and Sr(2+) codoping. Li(+) ions occupy the interstitial sites instead of La(3+) sites. Lattice contraction occurs in case of Bi(3+) codoping indicating substitution of La(3+) sites. Luminescence intensity is improved by codoping of M(n+) irrespective of crystal structure. Charges of Li(+) and Sr(2+) are different from that of La(3+) (host lattice), whereas the charge of Bi(3+) is same as that of La(3+). One interesting observation is in magnetic dipole transition that the intensity of the peak at 594 nm is more than that at 587 nm in the case of charge imbalance, whereas the reverse occurs in the case of charge balance. LaVO4:Eu(3+) nanophosphors prepared in water medium have more luminescence intensity when compared to those prepared in ethylene glycol, and this is related to variation of ratio of tetragonal to monoclinic phases. The luminescence intensity is also enhanced as annealing temperature increases from 600 to 800 °C due to the improved crystallinity. Lifetime data are analyzed on the basis of exponential and nonexponential decay equations. Samples are dispersible in polar medium due to capping of particles by EG. Polymer films are prepared by dispersion of NPs in poly(vinyl alcohol), and extra borax is added in order to make cross-link between polymer molecules. Samples of NPs in the forms of powder, dispersion in liquid medium, and film show the red emission.
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