High pressure luminescence of Nd3+ in YAlO3 perovskite nanocrystals: A crystal-field analysis.

Pressure-induced energy blue- and red-shifts of the 4F3/2 → 4I9/2,11/2 near-infrared emission lines of Nd3+ ions in YAlO3 perovskite nano-particles have been measured from ambient conditions up to 29 GPa. Different positive and negative linear pressure coefficients have been calibrated for the emission lines and related to pressure-induced changes in the interactions between those Nd3+ ions and their twelve oxygen ligands at the yttrium site. Potentiality of the simple overlap model, combined with ab initio structural calculations, in the description of the effects of these interactions on the energy levels and luminescence properties of the optically active Nd3+ ion is emphasized. Simulations show how the energies of the 4f3 ground configuration and the barycenters of the multiplets increase with pressure, whereas the Coulomb interaction between f-electrons decreases and the crystal-field strength increases. All these effects combined explain the wavelength blue-shifts of some near-infrared emission lines of Nd3+ ions. Large pressure rates of various emission lines suggest that a YAlO3 perovskite nano-crystal can be a potential candidate for near-infrared optical pressure sensors.

Structural and luminescence properties of Ho(3+)/Yb(3+)-doped Lu3Ga5O12 nano-garnets for phosphor applications.

Lu3Ga5O12 nano-garnet powders doped with Ho(3+)/Yb(3+) ions have been prepared using a citrate sol-gel technique. The structural and morphological properties have been investigated by X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. The materials are found to exist in single phase of cubic garnet structure with an average particle size of around 45 nm. The Ho(3+)/Yb(3+)-doped Lu3Ga5O12 nano-garnet powders give rise to an intense green and weak red emission of Ho3+ ions under 457.5 nm direct excitation. Moreover, when the Yb3+ ions are excited at 950 nm a very bright green luminescence of the Ho3+ ions is observed by the naked eyes even for such low laser power as 10 mW and the intensity of the red emission have been increased compared to that found under direct excitation of the Ho3+ ions. The power dependency and dynamics of the infrared-to-visible upconverted luminescence confirm the existence of different two-photon energy transfer processes. All these results have been compared with those obtained for other garnets doped with similar lanthanide ions which suggest that the Lu3Ga5O12 nano-garnets are potential materials for light emitting devices.

Role of the local structure and the energy trap centers in the quenching of luminescence of the Tb3+ ions in fluoroborate glasses: a high pressure study.

The concentration and pressure dependent luminescence properties of the Tb(3+) ions in a lithium fluoroborate glasses have been studied by analyzing the deexcitation processes of the (5)D(4) level at ambient conditions as well as a function of pressure up to 35 GPa at room temperature. The luminescence spectra of Tb(3+) ions have been measured as a function of pressure and observed a continuous redshift as well as a progressive increase in the magnitude of the crystal-field splittings for the (5)D(4)-->(7)F(3,4,5) transitions. Monitoring the (5)D(4)-->(7)F(5) transition, the luminescence decay curves have been measured and analyzed in order to understand the dynamics of the deexcitation of the Tb(3+) ions in these glasses. At ambient conditions a nonexponential behavior has been found for doping concentrations as low as 0.1 mol % of Tb(4)O(7), although no cross-relaxation channels exist to explain this behavior. The modelization of the energy transfer processes surprisingly shows that the nonexponential character of the decay curves of the (5)D(4) level with concentration or with pressure has to be ascribed to energy transfer to traps without migration of energy between Tb(3+) ions. For all the experimental situations the nonexponential character of the decay curves is well described by the generalized Yokota-Tanimoto model with a dipole-dipole interaction between the Tb(3+) ions and the nearby luminescence quenching traps. The luminescence properties observed with releasing pressure are slightly different to those obtained while increasing pressure suggesting a local structural hysteresis in the lithium fluoroborate glass matrix giving rise to the generation of a new distribution of environments for the Tb(3+) ions.

Investigation on the Luminescence Properties of InMO4 (M = V5+, Nb5+, Ta5+) Crystals Doped with Tb3+ or Yb3+ Rare Earth Ions.

We explore the potential of Tb- and Yb-doped InVO4, InTaO4, and InNbO4 for applications as phosphors for light-emitting sources. Doping below 0.2% barely change the crystal structure and Raman spectrum but provide optical excitation and emission properties in the visible and near-infrared (NIR) spectral regions. From optical measurements, the energy of the first/second direct band gaps was determined to be 3.7/4.1 eV in InVO4, 4.7/5.3 in InNbO4, and 5.6/6.1 eV in InTaO4. In the last two cases, these band gaps are larger than the fundamental band gap (being indirect gap materials), while for InVO4, a direct band gap semiconductor, the fundamental band gap is at 3.7 eV. As a consequence, this material shows a strong self-activated photoluminescence centered at 2.2 eV. The other two materials have a weak self-activated signal at 2.2 and 2.9 eV. We provide an explanation for the origin of these signals taking into account the analysis of the polyhedral coordination around the pentavalent cations (V, Nb, and Ta). Finally, the characteristic green (5D4 → 7F J ) and NIR (2F5/2 → 2F7/2) emissions of Tb3+ and Yb3+ have been analyzed and explained.

Structural study of the Eu3+ environments in fluorozirconate glasses: role of the temperature-induced and the pressure-induced phase transition processes in the development of a rare earth's local structure model.

The correlation between the optical properties of the Eu(3+) ions and their local structures in fluorozirconate glasses and glass-ceramics have been analyzed by means of steady-state and time-resolved site-selective laser spectroscopies. Changes in the crystal-field interaction, ranging from weak to medium strength values, are observed monitoring the luminescence and the lifetime of the Eu(3+) ions in different local environments in the glass. As key roles in this study, the Eu(3+) luminescence in the thermally-induced crystallization of the glass and the pressure-induced amorphization of the crystalline phase of the glass-ceramic experimentally states the existence of a parent local structure for the Eu(3+) ions in the glass, identified as the EuZrF(7) crystalline phase. Starting from the ab initio single overlap model, crystal-field calculations have been performed in the glass and the glass-ceramic. From the site-selective measurements, the crystal-field parameters sets are obtained, giving a suitable simulation of the (7)F(J) (J=0-6) Stark energy level diagram for the Eu(3+) ions in the different environments present in the fluorozirconate glass. A simple geometrical model based on a continuous distortion of the parent structure is proposed for the distribution of local environments of the Eu(3+) ions in the fluorozirconate glass.