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Silica films with Ln3+-doped LaF3 nanoparticles were prepared by sol gel method and their luminescent properties were studied as a function of the temperature. Significant improvements in the luminescent properties, in terms of the lifetime for the 4I13/2 level of Er3+ (∼10.9 ms), 4F3/2 level of Nd3+ (∼171 μs), and 5F3 level of Ho3+ (∼6 μs), were obtained when corresponding nanoparticles are incorporated in silica films rather than the bare ions. In addition to the LaF3 as the low phonon energy matrix, the absence of lanthanide ion clustering, and the increased distance between the OH groups of the silica matrix and the lanthanide ions, are responsible for the observed improvements in the luminescent properties for nanoparticle incorporated silica films. Lifetime values could be further improved by incorporating core−shell nanoparticles (the doped LaF3 core surrounded by an undoped shell of LaF3) in the silica matrix, as a result of further reduction of the nonradiative pathways.

In the present manuscript it is demonstrated that BiPO(4) is a better alternative to lanthanide phosphate host for making lanthanide ion-based luminescent materials. Hexagonal and monoclinic forms of BiPO(4) phase were prepared based on the reaction of Bi(3+) and PO(4)(3-) ions in ethylene glycol medium at 100 and 185 °C, respectively. From the differential thermal analysis (DTA) studies it is confirmed that the difference in the nucleation mechanism rather than the phase transition is responsible for the monoclinic phase formation at low temperatures (125 °C). Monoclinic BiPO(4) is quite stable and forms random solid solutions with lanthanide phosphates having both monoclinic (monazite) and tetragonal (xenotime) structures, as confirmed by XRD, FTIR and (31)P solid state nuclear magnetic resonance studies. On excitation corresponding to the (1)S(0)→(3)P(1) transition of Bi(3+) in BiPO(4):Ln samples, energy transfer from host to lanthanide ions takes place. The studies are quite relevant as there is a growing interest all over the world in replacing lanthanide based host used for different applications with easily available, easily purifiable and cheap main group elements (like Sb, Bi etc.) based hosts.

Eu(3+) co-doped Y(2)O(3):Tb nanoparticles were prepared by the combustion method and characterized for their structural and luminescence properties as a function of annealing temperatures and relative concentration of Eu(3+) and Tb(3+) ions. For Y(2)O(3):Eu,Tb nanoparticles annealed at 600 and 1200 °C, variation in the relative intensity of excitation transitions between the (7)F(6) ground state and low spin and high spin 4f(7)5d(1) excited states of Tb(3+) is explained due to the combined effect of distortion around Y(3+)/Tb(3+) in YO(6)/TbO(6) polyhedra and the size of the nanoparticles. Increase in relative intensity of the 285 nm peak (spin-allowed transition denoted as peak B) with respect to the 310 nm peak (spin-forbidden transition denoted as peak A) with decrease of Tb(3+) concentration in the Y(2)O(3):Eu,Tb nanoparticles heated at 1200 °C is explained based on two competing effects, namely energy transfer from Tb(3+) to Eu(3+) ions and quenching among the Tb(3+) ions. Back energy transfer from Tb(3+) to Eu(3+) in these nanoparticles is found to be very poor.

Multinuclear solid-state NMR spectroscopy and powder X-ray diffraction (XRD) experiments are applied to comprehensively characterize a series of pure and lanthanide-doped LaF3 nanoparticles (NPs) that are capped with di-n-octadectyldithiophosphate ligands (Ln3+ = diamagnetic Y3+ and Sc3+ and paramagnetic Yb3+ ions), as well as correlated bulk microcrystalline materials (LaF3, YF3, and ScF3). Solid-state 139La and 19F NMR spectroscopy of bulk LaF3 and the LaF3 NPs reveal that the inorganic core of the NP retains the LaF3 structure at the molecular level; however, inhomogeneous broadening of the NMR powder patterns arises from distributions of 139La and 19F NMR interactions, confirming a gradual change in the La and F site environments from the NP core to the surface. 139La and 19F NMR experiments also indicate that low levels (5 and 10 mol %) of Ln3+ doping do not significantly change the LaF3 structure in the NP core. Similar doping levels of paramagnetic Yb3+ ions severely broaden 19F resonances, but only marginally effect 139La powder patterns, suggesting that the dopant ions are uniformly distributed throughout the NP core and occupy vacant La sites. Measurements of 139La T1 and T2 relaxation constants are seen to vary between the bulk material and NPs and between samples with diamagnetic and paramagnetic dopants. 45Sc NMR experiments confirm that the dopants are integrated into the La sites of the LaF3 core. Solid-state 1H and 31P magic-angle spinning (MAS) NMR spectra aid in probing the nature of the capping ligands and their interactions at the NP surface. 31P cross-polarization (CP)/MAS NMR experiments identify not only the dithiophosphate head groups but also thiophosphate and phosphate species which may form during NP synthesis. Finally, 19F-31P CP/MAS and 1H MAS experiments confirm that ligands are coordinated to the NP surface.