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Trivalent dysprosium-doped Lu3Ga5O12 nano-garnets have been prepared by sol-gel method and characterized by X-ray powder diffraction, high-resolution transmission electron microscopy, dynamic light scattering, and laser excited spectroscopy. Under a cw 457 nm laser excitation, the white luminescence properties of Lu3Ga5O12 nano-garnets have been studied as a function of the optically active Dy3+ ion concentration and at low temperature. Decay curves for the 4F9/2 level of Dy3+ ion exhibit non-exponential nature for all the Dy3+ concentrations, which have been wellfitted to a generalized energy transfer model for a quadrupole-quadrupole interaction between Dy3+ ions without diffusion. From these data, a simple rate-equations model can be applied to predict that intense white luminescence could be obtained from 1.8 mol% Dy3+ ions-doped nano-garnets, which is in good agreement with experimental results. Chromaticity color coordinates and correlated color temperatures have been determined as a function of temperature and are found to be within the white light region for all Dy3+ concentrations. These results indicate that 2.0 mol% Dy3+ ions doped nano-garnet could be useful for white light emitting device applications. [ABSTRACT FROM AUTHOR]

A pressure-induced shift of the emission spectrum corresponding to the near infrared 4F3/2 → 4I9/2 transition of Nd3+ ions in a calcium gadolinium germanium garnet was obtained in the interval from ambient conditions up to 23 GPa in order to test its suitability as an optical pressure sensor. Although several Nd3+ non-equivalent centers are present in this garnet, which complicates the assignation of the optical transitions, the R1,R2 → Z5 transitions are unequivocally characterised and fit the requirements of an ideal optical pressure sensor. Results obtained for these emission peaks indicate large pressure coefficients of -8.8 and -10.8 cm-1 GPa-1; meanwhile, the rest of the R1,R2 → Z1-4 emissions remain almost unchanged under pressure. This behaviour is ascribed to the influence of the crystal-field at high pressure on the Z5 Stark level of the ground state and can be easily reproduced exclusively by varying the cubic term of fourth rank of the crystal-field Hamiltonian, which accounts for the Nd3+ ions and is related to medium Nd3+-oxygen distances. These coefficients are larger than those found for the R-lines of Cr3+ in ruby, -7.56 cm-1 GPa-1, suggesting that this system may be a good candidate for a luminescence pressure sensor. [ABSTRACT FROM AUTHOR]

Dysprosium-doped oxyfluoride glasses and nanocrystalline glass ceramics have been synthesized and studied by x-ray diffraction, absorption, and visible and near-infrared emission spectra. The samples emit intense white light when populating the 4F9/2 level with a 451 nm laser light and, from the visible emission spectra, yellow to blue intensity ratios and chromaticity color coordinates have been calculated and their relative variation have been discussed based on the concentration of Dy3+ ions and the heat treatment conditions used to prepare the glass ceramics. Infrared emission has also been observed in glasses and glass ceramics after laser excitation at 800 nm, showing bands at 1.33 and 1.67 μm, useful for optical amplification in fiber amplifiers. [ABSTRACT FROM AUTHOR]

Ultraviolet and visible upconversion emissions under infrared excitation have been obtained and compared in Nd3+-doped oxyfluoride glasses and glass ceramics prepared by different methods. The mechanisms involved in such processes have been analyzed. A spectroscopy study comparing absorption and upconversion excitation spectra has been carried out in order to discern in each case the mechanism involved in the origin of the upconversion emissions, i.e., two- or three-photon involved excited state absorption or energy transfer processes. The shape of the absorption and emission spectra and the relative upconversion efficiencies have been compared and explained taking into account the final distribution of the luminescent ions in the glassy and nanocrystalline phases. [ABSTRACT FROM AUTHOR]

The doping distribution of Tm3+ ions in a transparent oxyfluoride glass ceramic has been investigated. Optical absorption, luminescence, and excitation measurements have been performed in order to determine the environment in which Tm3+ ions and the infrared emissions they give rise to are located. An interesting result has been found: the main contribution to the 1465 nm emission (S band) is due to Tm3+ ions in the crystalline phase for low doping level. However, when the Tm3+ concentration is high the S-band emission comes from the small portion of Tm3+ that remains in the vitreous phase. It has been concluded that cross relaxation (CR) processes are responsible for the quenching of the S-band emission in the crystalline phase for high doping concentration. Lifetime measurements of the 3H4 level have also been taken and the probability of CR processes deduced. [ABSTRACT FROM AUTHOR]

Optical properties of Eu[sup 3+] ions in oxyfluoride glass ceramics and in the precursor glasses (30 SiO[sub 2], 15 Al[sub 2]O[sub 3], 29 CdF[sub 2], 22 PbF[sub 2], 1.5 YF[sub 3], and 2.5 EuF[sub 3], in mol %) have been analyzed and compared. The Eu[sup 3+] ions in the glass ceramics are incorporated into a crystalline environment with higher symmetry and lower energy coupled phonons. Emission measurements indicate that this crystalline phase is EuF[sub 3], instead of Pb[sub x]Cd[sub 1-x]F[sub 2] as generally considered. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We report optical absorption and luminescence measurements in pure and trivalent neodymium (Nd3+) doped LaVO4 crystals up to 25 GPa. Nd3+ luminescence has been employed as a tool to follow the structural changes in the crystal. We also present band-structure and crystal-field calculations that provide the theoretical framework to accurately explain the observed experimental results. In particular, both optical absorption and luminescence measurements evidence that a phase transition takes place close to 12 GPa. They also provide information on the pressure dependence of the band-gap as well as the emission lines under compression. We found drastic changes in the optical properties of LaVO4 when the phase transition to a BaWO4-II structure occurs, which can be related to changes in the coordination number of vanadium ions and in the local sites of Nd3+. Reported results are analyzed in comparison with those of previous X-ray diffraction and Raman experiments, as well as with the features of related compounds. For the first time, a consistent picture is reported explaining the behavior of the optical and electronic properties of LaVO4 at high-pressures. [ABSTRACT FROM AUTHOR]

Synthetic chalcomenite-type cupric selenite CuSeO3∙2H2O has been studied at room temperature under compression up to pressures of 8 GPa by means of single-crystal X-ray diffraction, Raman spectroscopy, and density-functional theory. According to X-ray diffraction, the orthorhombic phase undergoes an isostructural phase transition at 4.0(5) GPa with the thermodynamic character being first-order. This conclusion is supported by Raman spectroscopy studies that have detected the phase transition at 4.5(2) GPa and by the first-principles computing simulations. The structure solution at different pressures has provided information on the change with pressure of unit–cell parameters as well as on the bond and polyhedral compressibility. A Birch–Murnaghan equation of state has been fitted to the unit–cell volume data. We found that chalcomenite is highly compressible with a bulk modulus of 42–49 GPa. The possible mechanism driving changes in the crystal structure is discussed, being the behavior of CuSeO3∙2H2O mainly dominated by the large compressibility of the coordination polyhedron of Cu. On top of that, an assignation of Raman modes is proposed based upon density-functional theory and the pressure dependence of Raman modes discussed. Finally, the pressure dependence of phonon frequencies experimentally determined is also reported. [ABSTRACT FROM AUTHOR]

We report optical absorption and luminescence measurements in pure and trivalent neodymium (Nd3+) doped LaVO4 crystals up to 25 GPa. Nd3+ luminescence has been employed as a tool to follow the structural changes in the crystal. We also present band-structure and crystal-field calculations that provide the theoretical framework to accurately explain the observed experimental results. In particular, both optical absorption and luminescence measurements evidence that a phase transition takes place close to 12 GPa. They also provide information on the pressure dependence of the band-gap as well as the emission lines under compression. We found drastic changes in the optical properties of LaVO4 when the phase transition to a BaWO4-II structure occurs, which can be related to changes in the coordination number of vanadium ions and in the local sites of Nd3+. Reported results are analyzed in comparison with those of previous X-ray diffraction and Raman experiments, as well as with the features of related compounds. For the first time, a consistent picture is reported explaining the behavior of the optical and electronic properties of LaVO4 at high-pressures.

The thermal sensing capability of the Tm 3+ -doped yttrium orthoaluminate nanoperovskite in the infrared range, synthetized by a sol-gel method, was studied. The temperature dependence of the infrared upconverted emission bands located at around 705 nm ( 3 F 2,3 → 3 H 6 ) and 800 nm ( 3 H 4 → 3 H 6 ) of YAP: Tm 3+ nanoperovskite under excitation at 1210 nm was analyzed from RT up to 425 K. Calibration of the optical sensor has been made using the fluorescence intensity ratio technique, showing a high sensitivity in the near-infrared compared to other trivalent rare-earth based optical sensors working in the same range. In addition, a second calibration procedure of the YAP: Tm 3+ optical sensor was performed by using the FIR technique on the emission band associated to the 3 H 4 → 3 H 6 transition in the physiological temperature range (293-333 K), showing a very high relative sensitivity compared with other rare-earth based optical temperature sensors working in the physiological range. Moreover, the main advantage compared with other optical sensors is that the excitation source and the upconverted emissions do not overlap, since they lie in different biological windows, thus allowing its potential use as an optical temperature probe in the near-infrared range for biological applications.

A nonporous laminar coordination polymer of formula [Cu 2 I 2 (2-aminopyrazine)] n is prepared by direct reaction between CuI and 2-aminopyrazine, two industrially available building blocks. The fine tuning of the reaction conditions allows obtaining [Cu 2 I 2 (2-aminopyrazine)] n in micrometric and nanometric sizes with same structure and composition. Interestingly, both materials show similar reversible thermo- and pressure-luminescent response as well as reversible electrical response to volatile organic solvents such as acetic acid. X-ray diffraction studies under different conditions, temperatures and pressures, in combination with theoretical calculations allow rationalizing the physical properties of this compound and its changes under physical stimuli. Thus, the emission dramatically increases when lowering the temperature, while an enhancement of the pressure produces a decrease in the emission intensity. These observations emerge as a direct consequence of the high structural flexibility of the Cu 2 I 2 chains which undergo a contraction in CuCu distances as far as temperature decreases or pressure increases. However, the strong structural changes observed under high pressure lead to an unexpected effect that produces a less effective CuCu orbital overlapping that justifies the decrease in the intensity emission. This work shows the high potential of materials based on Cu 2 I 2 chains for new applications., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A structural transformation from the zircon-type structure to an amorphous phase has been found in YVO4:Eu(3+) nanoboxes at high pressures above 12.7 GPa by means of x-ray diffraction measurements. However, the pair distribution function of the high-pressure phase shows that the local structure of the amorphous phase is similar to the scheelite-type YVO4. These results are confirmed both by Raman spectroscopy and Eu(3+) photoluminescence which detect the phase transition to a scheelite-type structure at 10.1 and 9.1 GPa, respectively. The irreversibility of the phase transition is observed with the three techniques after a maximum pressure in the upstroke of around 20 GPa. The existence of two (5)D0-->(7)F0 photoluminescence peaks confirms the existence of two local environments for Eu(3+), at least for the low-pressure phase. One environment is the expected for substituting Y(3+) and the other is likely a disordered environment possibly found at the surface of the nanoboxes.

The compression process in the α-phase of europium trimolybdate was revised employing several experimental techniques. X-ray diffraction (using synchrotron and laboratory radiation sources), Raman scattering and photoluminescence experiments were performed up to a maximum pressure of 21 GPa. In addition, the crystal structure and Raman mode frequencies have been studied by means of first-principles density functional based methods. Results suggest that the compression process of α-Eu2(MoO4)3 can be described by three stages. Below 8 GPa, the α-phase suffers an isotropic contraction of the crystal structure. Between 8 and 12 GPa, the compound undergoes an anisotropic compression due to distortion and rotation of the MoO4 tetrahedra. At pressures above 12 GPa, the amorphization process starts without any previous occurrence of a crystalline-crystalline phase transition in the whole range of pressure. This behavior clearly differs from the process of compression and amorphization in trimolybdates with [Formula: see text]-phase and tritungstates with α-phase.

We describe the results of x-ray absorption experiments carried out to deduce structural and chemical information in Eu(3+) doped, transparent, oxyfluoride glass and nanostructured glass-ceramic samples. The spectra were measured at the Pb and Eu-L(III) edges. The Eu environment in the glass samples is observed to be similar to that of EuF(3). Complementary x-ray diffraction experiments show that thermal annealing creates β-PbF(2) type nanocrystals. X-ray absorption indicates that Eu ions act as seeds in the nanocrystal formation. There is evidence of interstitial fluorine atoms around Eu ions as well as Eu dimers. X-ray absorption at the Pb-L(III) edge shows that after the thermal treatment most lead atoms form a PbO amorphous phase and that only 10% of the lead atoms remain available to form β-PbF(2) type nanocrystals. Both x-ray diffraction and absorption point to a high Eu content in the nanocrystals. Our study suggests new approaches to the oxyfluoride glass-ceramic synthesis in order to further improve their properties.

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.

Hypersensitivity to pressure and temperature is observed in the near-infrared emission lines of the Nd(3+) ion in a Cr(3+),Nd(3+):Gd(3)Sc(2)Ga(3)O(12) crystal, associated to the R(1,2)((4)F(3/2))→Z(5)((4)I(9/2)) and R(1,2)((4)F(3/2))→Z(1)((4)I(9/2)) transitions. The former emissions show large linear pressure coefficients of -11.3 cm(-1)/GPa and -8.8 cm(-1)/GPa, while the latter show high thermal sensitivity in the low temperature range. Thus this garnet crystal can be considered a potential optical pressure and/or temperature sensor in high pressure and temperature experiments up to 12 GPa and below room temperature, used in diamond anvil cells and excited with different UV and visible commercial laser due to the multiple Cr(3+) and Nd(3+) absorption bands., (© 2012 Optical Society of America)