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.

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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.

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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.

Re-dispersible Tb(3+) doped LaPO(4) nanorods have been prepared using ethylene glycol (EG) as a capping agent as well as reaction medium at a relatively low temperature of 150 °C. The X-ray diffraction study reveals that all the doped samples are well crystalline with a monoclinic structure of the LaPO(4) phase. The luminescence intensity of (5)D(4)→(7)F(5) transition at 543 nm (green) is more prominent than that of (5)D(4)→(7)F(6) transition at 487 nm (blue) for all the samples. This is related to the polarizing effect from [PO(4)](3-) to the Tb(3+) site. Concentration dependent luminescence study shows that the luminescence intensity of Tb(3+) increases up to 10 at.% and decreases above this. This is due to the concentration quenching effect arising from cross relaxation among Tb(3+)-Tb(3+) ions. The results show that nanoparticles prepared in EG medium gives an enhanced luminescence compared to that prepared in water. This is attributed to the multiphonon relaxation effect from O-H groups surrounding over nanoparticles as well as the extent of increase of agglomeration among particles for samples prepared in water. Significant enhancement in the emission of Tb(3+) is also observed when Ce(3+) is used as the sensitizer in LaPO(4):Tb(3+)nanorods. The optimum concentration of Ce(3+) for maximum luminescence is found to be 7 at.% in Ce(3+) sensitized LaPO(4):Tb(3+) (5 at.%). Based on the energy transfer process from Ce(3+) to Tb(3+), the luminescence of Tb(3+) can be switched OFF and ON by performing oxidation and reduction of Ce(3+)↔Ce(4+) using KMnO(4) and ascorbic acid, respectively. The samples are re-dispersible in water, methanol and can be incorporated into polyvinyl alcohol (PVA) films. They show a dark green emission under ultraviolet radiation.

Herein we report the enhanced green emission from Tb 3+ -doped GdPO 4 nanorods sensitized with Ce 3+ . The increase in the rate of nonradiative transition processes in sensitizer due to efficient energy transfer to activator is realized from steady-state and dynamic luminescence studies. Luminescence quenching due to cross relaxation is least significant up to 20 at. % Ce 3+ and 7 at. % Tb 3+ concentration. The quantum yield of the sample with maximum luminescence, i.e., GdPO 4 :Tb 3+ (5 at. %)/Ce 3+ (7 at. %), is found to be 28%. Also, samples are readily redispersible in water and could be easily incorporated in polymer-based films that show strong green light emission under UV excitation. The luminescence switching (ON and OFF) behavior is examined using alternately an oxidizing agent (KMnO 4 ) and then a reducing agent (ascorbic acid) through a redox reaction (Ce 3+ /Ce 4+ ). Both GdPO 4 :Tb 3+ and GdPO 4 :Tb 3+ / Ce 3+ are observed to be paramagnetic.

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