Structural, elastic and vibrational properties of nanocrystalline lutetium gallium garnet under high pressure.

An ab initio study of the structural, elastic and vibrational properties of the lutetium gallium garnet (Lu3Ga5O12) under pressure has been performed in the framework of the density functional theory, up to 95 GPa. Pressure dependence of the elastic constants and the mechanical stability are analyzed, showing that the garnet structure is mechanically unstable above 87 GPa. Lattice-dynamics calculations in bulk at different pressures have been performed and compared with Raman scattering measurements of the nanocrystalline Tm(3+)-doped Lu3Ga5O12 up to 60 GPa. The theoretical frequencies and pressure coefficients of the Raman active modes for bulk Lu3Ga5O12 are in good agreement with the experimental data measured for the nano-crystals. The contributions of the different atoms to the vibrational modes have been analyzed based on the calculated total and partial phonon density of states. The vibrational modes have been discussed in relation to the internal and external modes of the GaO4 tetrahedron and the GaO6 octahedron. The calculated infrared modes and their pressure dependence are also reported. Our results show that with this nano-garnet size the sample has essentially bulk properties.

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.

Tailoring the Emission Behavior of WO3 Thin Films by Eu3+ Ions for Light-Emitting Applications.

The article reports the successful fabrication of Eu3+-doped WO3 thin films via the radio-frequency magnetron sputtering (RFMS) technique. To our knowledge, this is the first study showing the tunable visible emission (blue to bluish red) from a WO3:Eu3+ thin film system using RFMS. X-ray diffractograms revealed that the crystalline nature of these thin films increased upto 3 wt% of the Eu3+ concentration. The diffraction peaks in the crystalline films are matched well with the monoclinic crystalline phase of WO3, but for all the films', micro-Raman spectra detected bands related to WO3 monoclinic phase. Vibrational and surface studies reveal the amorphous/semi-crystalline behavior of the 10 wt% Eu3+-doped sample. Valence state determination shows the trivalent state of Eu ions in doped films. In the 400-900 nm regions, the fabricated thin films show an average optical transparency of ~51-85%. Moreover, the band gap energy gradually reduces from 2.95 to 2.49 eV, with an enhancement of the Eu3+-doping content. The doped films, except the one at a higher doping concentration (10 wt%), show unique emissions of Eu3+ ions, besides the band edge emission of WO3. With an enhancement of the Eu3+ content, the concentration quenching process of the Eu3+ ions' emission intensities is visible. The variation in CIE chromaticity coordinates suggest that the overall emission color can be altered from blue to bluish red by changing the Eu3+ ion concentration.

White light generation in Dy(3+)-doped oxyfluoride glass and transparent glass-ceramics containing CaF2 nanocrystals.

The radiative emission properties of the Dy3+ ions in an oxyfluoride glass and glass-ceramics have been studied for the generation of white light. The x-ray diffraction pattern of the glass-ceramics shows the formation of CaF2 fluorite-type nanocrystals in the glass matrix after a suitable thermal treatment of the precursor glass, whereas time-resolved optical measurements show the incorporation of the Dy3+ ions in the CaF2 nanocrystals. Intense white light has been observed when the samples are excited with 451 nm laser light. From the visible emission spectra, yellow to blue intensity ratios and the chromaticity color coordinates have been determined. All the color coordinates are found to lie in the white light region of the chromaticity color diagram.

Spontaneous and stimulated emission spectroscopy of a Nd(3+)-doped phosphate glass under wavelength selective pumping.

The influence of the host matrix on the spectroscopic and laser properties of Nd(3+) in a K-Ba-Al phosphate glass has been investigated as a function of rare-earth concentration. Site-selective time resolved laser spectroscopy and stimulated emission experiments under selective wavelength laser pumping show the existence of a very complex crystal field site distribution of Nd(3+) ions in this glass. The peak of the broad stimulated (4)F(3/2)→(4)I(11/2) emission shifts in a non monotonous way up to 3 nm as a function of the excitation wavelength. This behavior can be explained by the relatively moderate inter-site energy transfer among Nd(3+) ions found in this system and measured by using fluorescence line narrowing spectroscopy. The best slope efficiency obtained for the laser emission was 40%.

Nanocrystalline lanthanide-doped Lu3Ga5O12 garnets: interesting materials for light-emitting devices.

Nanocrystalline Lu(3)Ga(5)O(12), with average particle sizes of 40 nm, doped with a wide variety of luminescent trivalent lanthanide ions have been prepared using a sol-gel technique. The structural and morphological properties of the powders have been investigated by x-ray powder diffraction, high resolution transmission electron microscopy and Raman spectroscopy. Structural data have been refined and are presented for Pr(3+), Eu(3+), Gd(3+), Ho(3+), Er(3+) and Tm(3+) dopants, while room temperature excited luminescence spectra and emission decay curves of Eu(3+)-, Tm(3+)- and Ho(3+)-doped Lu(3)Ga(5)O(12) nanocrystals have been measured and are discussed. The Eu(3+) emission spectrum shows typical bands due to 5D(0)-->7F(J) (J = 0, 1, 2, 3, 4) transitions and the broadening of these emission bands with the non-exponential behaviour of the decay curves indicates the presence of structural disorder around the lanthanide ions. Lanthanide-doped nanocrystalline Lu(3)Ga(5)O(12) materials show better luminescence intensities compared to Y(2)O(3), Gd(3)Ga(5)O(12) and Y(3)Al(5)O(12) nanocrystalline hosts. Moreover, the upconversion emission intensity in the blue-green region for the Tm(3+)- and Ho(3+)-doped samples shows a significant increase upon 647.5 nm excitation with respect to other common oxide hosts doped with the same lanthanide ions.

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.

Luminescence properties of Sm(3+)-doped P(2)O(5)-PbO-Nb(2)O(5) glass under high pressure.

Samarium doped lead phosphate glass modified with niobium having a composition (in mol%) of 55P(2)O(5)+39.5PbO+5Nb(2)O(5)+0.5Sm(2)O(3) has been prepared by the conventional melt quenching technique. The emission spectra and the decay curves for the (4)G(5/2) level of Sm(3+) ions have been measured as a function of pressure up to 23.6 GPa at room temperature. A discontinuity in the observed shifts and crystal-field splittings as a function of pressure around 9-10 GPa suggests that a phase transition is taking place in the glass matrix. The [Formula: see text], (6)H(7/2) and (6)H(9/2) transitions are shifted towards the lower energy side with magnitudes of -7.1, -7.6 and -5.5 cm(-1) GPa(-1) up to 8.9 GPa (phase 1) and -5.6, -4.9 and -4.4 cm(-1) GPa(-1) beyond 10.3 GPa (phase 2), respectively. A much stronger increase in the splitting of the [Formula: see text] and [Formula: see text] Stark levels with pressure is observed in phase 1 than in phase 2. The lifetime of the (4)G(5/2) level decreases from 2.29 ms (0 GPa) to 0.64 ms (23.6 GPa) with pressure. The decay curves of the (4)G(5/2) level exhibit non-exponential behavior for all the pressures and were fitted by the generalized Yokota-Tanimoto model to probe the nature of the energy transfer process. The best fits with S = 6 indicate that the energy transfer between donor and acceptor is of dipole-dipole type. The crystal-field splitting experienced by the Sm(3+) ions in the title glass are found to be larger than those found in borate, K-Ba-Al phosphate and tellurite glasses.

Photoluminescence and energy transfer studies of Dy(3+)-doped fluorophosphate glasses.

Dy(3+)-doped fluorophosphate glasses with composition (in mol%) (56-x/2)P(2)O(5)+17K(2)O+(15-x/2)BaO+8Al(2)O(3) + 4AlF(3)+ xDy(2)O(3), x=0.01, 0.05, 0.1, 1.0 and 2.0, have been prepared by melt quenching technique. The luminescence spectra and lifetimes of (4)F(9/2) level of Dy(3+) ions in these glasses have been measured using the 457.9 nm line of argon ion laser as an excitation source. The free-ion calculation and Judd-Ofelt analysis have been performed. The room temperature emission spectra corresponding to (4)F(9/2)-->(6)H(J) (J=7/2, 9/2, 11/2, 13/2 and 15/2) transitions of Dy(3+) ions were measured. The fluorescence decay from (4)F(9/2) level have been measured by monitoring the intense (4)F(9/2)-->(6)H(13/2) transition. The lifetime of the decay is obtained by taking the first e-folding times of the decay curves and is found to decrease with increase in Dy(3+) ions concentration due to concentration quenching. The decay curves are found to be perfectly single exponential for samples with low Dy(3+) ion concentration. The non-exponential decay curves observed for higher concentrations are well fitted to the Inokuti-Hirayama model for S=6, which indicates that the energy transfer between the donor and acceptor is of dipole-dipole nature. The energy transfer parameter and donor to acceptor interaction increases with Dy(3+) ions concentration due to increase of energy transfer from Dy(3+) (donor) to unexcited Dy(3+) (acceptor) ions.

ESR and photoluminescence properties of Cu doped ZnS nanoparticles.

Nanoparticles of Zn1-xCuxS with Cu concentrations of x=0.0, 0.1, 0.2, 0.3 and 0.4 were prepared by a co-precipitation reaction method from homogeneous solutions of zinc and copper salts. Both the ZnS and ZnS:Cu nanoparticles excited at about 370 nm exhibits a broad green emission band peaking around 491 nm, which confirms the characteristic feature of Zn2+ as well as Cu2+ ions as luminescent centers in the lattice. The TEM micrographs showed spherical morphology for ZnS nanocrystals and the average size of the particles was estimated to be around 8.5 nm. At liquid nitrogen temperature, ESR signal characteristic of Cu2+ ions was observed in samples of all concentrations. ESR spectra analysis also indicated that Cu2+ ions enter the host lattice by replacing Zn2+ ions with distorted tetrahedral site symmetry.

Fluorescence properties of Nd3+-doped tellurite glasses.

The compositional and concentration dependence of luminescence of the (4)F(3/2)-->(4)I(J) (J=13/2, 11/2 and 9/2) transitions in four Nd(3+)-doped tellurite based glasses has been studied. The free-ion energy levels obtained for 60TeO(2)+39ZnO(2)+1.0Nd(2)O(3) (TZN10) glass have been analysed using the free-ion Hamiltonian model and compared with similar results obtained for Nd(3+):glass systems. The absorption spectrum of TZN10 glass has been analysed using the Judd-Ofelt theory. Relatively longer decay rates have been obtained for Nd(3+)-doped phosphotellurite glasses. The emission characteristics of the (4)F(3/2)-->(4)I(11/2) transition, of the Nd(3+):TZN10 glass, are found to be comparable to those obtained for Nd(3+):phosphate laser glasses. The non-exponential shape of the emission decay curves for the (4)F(3/2)-->(4)I(11/2) transition is attributed to the presence of energy transfer processes between the Nd(3+) ions.

Luminescence and optical absorption properties of Nd(3+) ions in K-Mg-Al phosphate and fluorophosphate glasses.

Absorption and emission properties and fluorescence lifetimes for the [Formula: see text] transition of Nd(3+) ions embedded in P(2)O(5)-K(2)O-MgO-Al(2)O(3) (PKMA)-based glasses modified with AlF(3) and BaF(2) are reported at room temperature. The observed energy levels of Nd(3+) ions in these glasses have been analysed through a semi-empirical free-ion Hamiltonian model. The spin-orbit interaction and net electrostatic interaction experienced by the Nd(3+) ions follow the trend as PKMA>PKMA+AlF(3)> PKMA+BaF(2) glasses. Judd-Ofelt analysis has been carried out on the absorption spectra of 1.0 mol% Nd(3+)-doped glasses to predict the radiative properties for the fluorescent levels of the Nd(3+) ion. Branching ratios and stimulated emission cross-sections show that the [Formula: see text] transition of the glasses under investigation has the potential for laser applications. The Inokuti-Hirayama model has been applied to investigate the non-radiative relaxation of the Nd(3+) ion emitting state, (4)F(3/2). Based on the decay curve analysis, concentration quenching of the (4)F(3/2) emission has been attributed to a cross-relaxation process between the Nd(3+) ions.

Photoluminescence from the (5)D(0) level of Eu(3+) ions in a phosphate glass under pressure.

The pressure dependence of the luminescence from [Formula: see text] transitions of Eu(3+) ions in 58.5P(2)O(5)-9Al(2)O(3)-14.5BaO-17K(2)O-1Eu(2)O(3) glass has been investigated up to 38.3 GPa at room temperature. The relative luminescence intensity ratio of [Formula: see text] to [Formula: see text] transitions of the Eu(3+) ions is found to decrease with increasing pressure, indicating a lowering of the asymmetry around the Eu(3+) ions with pressure. The [Formula: see text] transitions exhibit pressure-induced red shifts of different magnitude, which suggests a decrease in Slater parameters (F(k)) and in the spin-orbit coupling parameters (ζ) for the Eu(3+) ions. Stark components of the (7)F(1) level have been used to evaluate the crystal-field (CF) parameters B(20) and B(22), which are in turn used to estimate the CF strength experienced by the Eu(3+) ions in the glass. The observed increase in the CF strength parameter is found to have an almost cubic dependence on pressure. Luminescence decay curves for the [Formula: see text] transition are found to be single exponential over the entire pressure range studied. The lifetime did not change under pressure up to 5 GPa, although a significant change in the CF strength is noticed in this pressure range. The reduction of lifetime observed at pressures above 5 GPa could be partially due to an increase of pressure-induced defect centres. Such a process can then explain the hysteresis observed in the variation of lifetime and crystal-field strength on the release of pressure.

Fluorescence properties of Eu3+ ions doped borate and fluoroborate glasses containing lithium, zinc and lead.

The influence of glass composition on the fluorescence properties of Eu3+ ions doped borate and fluoroborate glasses modified with Li+, Zn2+ and Pb2+ cations have been investigated. The magnitude of splittings of 7F1 levels are analyzed using crystal-field (CF) analysis. The relative intensities of 5D0 --> 7F2 to 5D0 --> 7F1 transitions, crystal-field strength parameters and decay times of the 5D0 level have been determined and are found to be lower for Pb based glasses than those of Zn/Li based glasses. The lifetimes of 5D0 level are found to increase when borate glasses are modified with pure fluorides than with oxides and oxyfluorides. The fluorescence decay of 5D0 level fits perfect single exponential in the Eu3+:glass systems studied which indicates the absence of energy transfer between Eu3+ ions in these glasses.

Spectroscopic investigation and optical characterization of Eu3+ ions in K-Nb-Si glasses.

This paper reports on the effect of concentration of Eu(3+) ions in K2O-Nb2O5-SiO2-Eu2O3 (KNbSiEu) glasses prepared by the melt quenching technique. By using the Judd-Ofelt (JO) theory, the intensity parameters Ωλ (λ=2, 4, 6) have been determined from the absorption and emission spectra of Eu(3+) ions under different constraints. The radiative properties of some of the excited states of Eu(3+) ions have been calculated. The decay curves of (5)D0 level exhibited single exponential for all the Eu(3+) ions concentrations. From these results, it is suggested that the strong red emission at 616 nm corresponding to the (5)D0→(7)F2 transition could be used for the development of optical display devices.

Dy(3+)-doped zinc fluorophosphate glasses for white luminescence applications.

Dysprosium (Dy(3+)) ions doped zinc fluorophosphate (PKAZLFDy: P2O5-K2O-Al2O3-ZnF2-LiF-Dy2O3) glasses have been prepared and investigated their spectroscopic properties using absorption, emission and decay measurements. Judd-Ofelt analysis has been carried out to obtain the intensity parameters and in turn predicted radiative properties for the (4)F9/2 level of 1.0 mol% of Dy2O3 doped glass. Visible luminescence spectra have been obtained due to (4)F9/2→(6)HJ (J=11/2, 13/2, 15/2) transitions of Dy(3+) ions under 385 nm excitation. The yellow-to-blue luminescence intensity ratios and chromaticity coordinates of Dy(3+) ions in these glasses have been analyzed as a function of Dy(3+) ion concentration. The decay profiles for the (4)F9/2 level exhibit perfectly single exponential at lower concentrations (up to 1.0 mol%) and turn into non-exponential for higher concentrations (>1.0 mol%) due to energy transfer between donor (excited state Dy(3+) ion) and acceptor (ground state Dy(3+) ion). The results reveal that these glasses emit bright white light which is suitable for the development of W-LEDs.

Optical properties of Eu³+ ions in phosphate glasses.

Eu(3+)-doped phosphate (P(2)O(5)+K(2)O+SrO+Al(2)O(3)+Eu(2)O(3)) glasses with varying Eu(2)O(3) concentration have been prepared by standard melt quenching technique and are characterized through various spectroscopic techniques at room temperature. Luminescence spectra of these glasses exhibit the characteristic emission of Eu(3+) ion with an intense and most prominent red emission attributed to (5)D(0)→(7)F(2) transition. Crystal-field analysis has been carried out to estimate the local symmetry in the vicinity of Eu(3+) ions. Judd-Ofelt parameters have been evaluated from the luminescence intensity ratios of (5)D(0)→(7)F(J) (J=2, 4 and 6) to (5)D(0)→(7)F(1) transitions as well as absorption spectrum under different constraints. Decay rates for the (5)D(0) level of Eu(3+) ions have been recorded by monitoring the emission at around 609 nm corresponding to (5)D(0)→(7)F(2) transition. The experimental lifetime for the (5)D(0) level in title glasses is independent of Eu(3+) ion concentration.

Spectroscopic characterization of alkali modified zinc-tellurite glasses doped with neodymium.

Neodymium doped zinc-tellurite glasses of composition TeO(2)-ZnO-Na(2)O-Li(2)O have been prepared and characterized for their thermal, structural and optical properties. Differential thermal analysis revealed reasonably good forming tendency of the glass composition. FTIR spectra were used to analyze the functional groups present in the glass. Judd-Ofelt intensity parameters were derived from the absorption spectrum and used to calculate the radiative lifetime, branching ratio and stimulated emission cross-section for (4)F(3/2)-->(4)I(9/2, 11/2, 13/2) transitions. The quantum efficiency of the (4)F(3/2) level is comparable to the typical values obtained for the Nd(2)O(3)-doped glasses. The decay properties for higher concentration of Nd(2)O(3) were analyzed using Inokuti-Hirayama model to investigate the non-radiative relaxation of the (4)F(3/2) emitting level. The experimental values of branching ratio and saturation intensity of (4)F(3/2)-->(4)I(11/2) transition and calculated spectroscopic quality factor indicate the favourable lasing action in these glasses.