Lattice dynamics of zircon-type NdVO4and scheelite-type PrVO4under high-pressure.

Zircon-type NdVO4and scheelite-type PrVO4have been studied by means of Raman spectroscopy up to approximately 20 GPa. In the first compound, zircon-scheelite and scheelite-fergusonite phase transitions are reported at 6.4(3) and 19.6(4) GPa, respectively. In the case of scheelite-type PrVO4, a reversible phase transition to a PbWO4-III structure is observed at 16.8(5) GPa. In both cases, a scheelite-type structure is recovered in a metastable state at low pressures. The pressure evolution of the Raman modes is also reported. Our experimental findings are supported byab initiocalculations, which allowed us to discuss the role of mechanic and dynamical instabilities in the phase transition mechanisms.

High-pressure phase transformations in NdVO4 under hydrostatic, conditions: a structural powder x-ray diffraction study.

Room temperature angle dispersive powder x-ray diffraction experiments on zircon-type NdVO4 were performed for the first time under quasi-hydrostatic conditions up to 24.5 GPa. The sample undergoes two phase transitions at 6.4 and 19.9 GPa. Our results show that the first transition is a zircon-to-scheelite-type phase transition, which has not been reported before, and contradicts previous non-hydrostatic experiments. In the second transition, NdVO4 transforms into a fergusonite-type structure, which is a monoclinic distortion of scheelite-type. The compressibility and axial anisotropy of the different polymorphs of NdVO4 are reported. A direct comparison of our results with former experimental and theoretical studies on other rare-earth orthovanadates found in literature highlights the importance of the role played by non-hydrostatic stresses in their high-pressure structural behavior.

Experimental and theoretical study on the optical properties of LaVO4 crystals under pressure.

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.

High-pressure structural and vibrational properties of monazite-type BiPO4, LaPO4, CePO4, and PrPO4.

Monazite-type BiPO4, LaPO4, CePO4, and PrPO4 have been studied under high pressure by ab initio simulations and Raman spectroscopy measurements in the pressure range of stability of the monazite structure. A good agreement between experimental and theoretical Raman-active mode frequencies and pressure coefficients has been found which has allowed us to discuss the nature of the Raman-active modes. Besides, calculations have provided us with information on how the crystal structure is modified by pressure. This information has allowed us to determine the equation of state and the isothermal compressibility tensor of the four studied compounds. In addition, the information obtained on the polyhedral compressibility has been used to explain the anisotropic axial compressibility and the bulk compressibility of monazite phosphates. Finally, we have carried out a systematic discussion on the high-pressure behavior of the four studied phosphates in comparison to results of previous studies.

High-pressure structural, elastic, and thermodynamic properties of zircon-type HoPO4 and TmPO4.

Zircon-type holmium phosphate (HoPO4) and thulium phosphate (TmPO4) have been studied by single-crystal x-ray diffraction and ab initio calculations. We report on the influence of pressure on the crystal structure, and on the elastic and thermodynamic properties. The equation of state for both compounds is accurately determined. We have also obtained information on the polyhedral compressibility which is used to explain the anisotropic axial compressibility and the bulk compressibility. Both compounds are ductile and more resistive to volume compression than to shear deformation at all pressures. Furthermore, the elastic anisotropy is enhanced upon compression. Finally, the calculations indicate that the possible causes that make the zircon structure unstable are mechanical instabilities and the softening of a silent B 1u mode.

Assessing Single Upconverting Nanoparticle Luminescence by Optical Tweezers.

We report on stable, long-term immobilization and localization of a single colloidal Er(3+)/Yb(3+) codoped upconverting fluorescent nanoparticle (UCNP) by optical trapping with a single infrared laser beam. Contrary to expectations, the single UCNP emission differs from that generated by an assembly of UCNPs. The experimental data reveal that the differences can be explained in terms of modulations caused by radiation-trapping, a phenomenon not considered before but that this work reveals to be of great relevance.

Effects of pumping wavelength and pump density on the random laser performance of stoichiometric Nd crystal powders.

Laser slope and threshold properties have been investigated in Nd stoichiometric crystal powders as a function of pump wavelength and pump beam size. Above a given pumped area, the laser slope and the threshold pump energy per unit area are invariant and the known theoretical expressions are well fulfilled. Likewise, the size of the stimulated emission zone as a function of the pump beam area has been measured, also showing a different behavior above or below a given pumped area value which coincides with the one mentioned above. In conclusion, two different operating regimes with different performances are clearly observed as a function of the pump beam area.

Temperature evolution of the luminescence decay of Sr0.33Ba0.67Nb2O6 : Pr3+.

This article presents a spectroscopic investigation of Sr(0.33)Ba(0.67)(NbO2)3, doped with 1 mol% of Pr(3+). Photoluminescence and luminescence kinetics were measured at different temperatures at ambient (ferroelectric phase) and 76 kbar pressures (paraelectric phase). The photoluminescence spectrum is dominated by (1)D2 → (3)H4 transition of Pr(3+) in both phases. At ambient pressure when the system is excited with UV radiation, the intensity of dominant (1)D2 → (3)H4 emission evidently increases in the 200-293 K temperature range. This effect is attributed to enhancement of the excitation of the (1)D2 state through the praseodymium trapped exciton state, which at higher temperatures does not populate the higher lying (3)P0 state. Additionally, under UV radiation the material exhibits afterglow luminescence activated by temperature that can also have an impact on the increase of the (1)D2 emission. We propose that the afterglow luminescence is related to the existence of electron traps. At a pressure of 76 kbar the depth of the electron traps decreases in comparison to the ones observed at ambient pressure. However, the phase transition does not change the number of electron traps.

White light upconversion in Yb-sensitized (Tm, Ho)-doped KLu(WO4)2 nanocrystals: the effect of Eu incorporation.

Monoclinic Yb-sensitized (Tm, Ho)-doped KLu(WO4)2 nanocrystals of ~100 nm size have been synthesized by the modified Pechini sol-gel method. Their diode laser near-infrared (~980 nm) excited upconversion emission properties have been characterized at power densities in the range 30-355 W cm(-2). Bright white light composed of blue ~475 nm, green ~540 nm, and red ~650 nm emissions, corresponding to Tm(3+ 1)G4 → (3)H6, Ho(3+ 5)S2, (5)F4 → (5)I8, and Ho(3+ 5)F5 → (5)I8 electronic transitions, respectively, was generated by adjusting the Yb, Tm, and Ho contents in KLu(WO4)2 nanocrystalline samples. Chromaticity coordinates of the emitted white light can be tuned by modifying the excitation power density. The effect of Tm and Ho on the luminescence dynamics has been described by analyzing the upconverted emission intensity dependence on the excitation power, as well as from Stokes and decay time measurements. The effect on upconversion properties of further codoping with Eu in these (Tm, Ho, Yb)-doped KLu(WO4)2 nanocrystals has also been studied.

Analysis of vacuum ultraviolet electronic spectra of Ce3+ and Pr3+ ions in Ca9Lu(PO4)7: crystal-field calculations and simulation of optical spectra.

The 4f-5d excitation and emission spectra of Ce(3+) and Pr(3+) ions in Ca9Lu(PO4)7 as recently reported (2012 J. Phys.: Condens. Matter 24 385502) were further analyzed and simulated by employing the effective Hamiltonian model for the 4f(N) and 4f(N-1)5d electronic configurations of impurity lanthanide ions and the exchange charge model of crystal-field theory. The multi-site effect on the 4f-5d transition spectra was explicitly discussed from the points of view of the local structure and site occupation ratios of lanthanide ions in Ca9Lu(PO4)7. An excellent agreement between the predicted and measured spectra confirms the validity of the performed calculations. Based on these energy level and intensity calculation results, the radiative lifetimes of the 5d-4f emissions of Ce(3+) and Pr(3+) ions have been modeled to show nearly independent temperature trends. Comparison with the measured lifetimes suggests the nonradiative relaxation process in this host is probably related to the intrinsic defect states. In addition to the studies of the 4f-5d transitions, a general theoretical scheme to calculate the lowest 4f-6s transition energy of the Ce(3+) ion was proposed for the first time on the basis of the ligand polarization model. The predicted 6s energy position of the Ce(3+) ion in Ca9Lu(PO4)7 is solid evidence corroborating our previous spectroscopic assignment.

High pressure luminescence spectra of CaMoO4:Ln3+ (Ln = Pr, Tb).

Photoluminescence spectra and luminescence kinetics of pure CaMoO(4) and CaMoO(4) doped with Ln(3+) (Ln = Pr or Tb) are presented. The spectra were obtained at high hydrostatic pressure up to 240 kbar applied in a diamond anvil cell. At ambient pressure undoped and doped samples exhibit a broad band emission extending between 380 and 700 nm with a maximum at 520 nm attributed to the MoO(4)(2-) luminescence. CaMoO(4) doped with Pr(3+) or Tb(3+) additionally yields narrow emission lines related to f-f transitions. The undoped CaMoO(4) crystal was characterized by a strong MoO(4)(2-) emission up to 240 kbar. In the cases of CaMoO(4):Pr(3+) and CaMoO(4):Tb(3+), high hydrostatic pressure caused quenching of Pr(3+) and Tb(3+) emission, and this effect was accompanied by a strong shortening of the luminescence lifetime. In doped samples, CaMoO(4):Pr(3+) and CaMoO(4):Tb(3+), quenching of the emission band attributed to MoO(4)(2-) was also observed, and at pressure above 130 kbar this luminescence was totally quenched. The effects mentioned above were related to the influence of the praseodymium (terbium) trapped exciton PTE (ITE-impurity trapped exciton) on the efficiency of the Pr(3+) (Tb(3+)) and MoO(4)(2-) emissions.

Interconfigurational 5d → 4f luminescence of Ce3+ and Pr3+ in Ca9Lu(PO4)7.

Ca(9)Lu(PO(4))(7):Ce (3+) and Ca (9)Lu (PO (4))(7):Pr (3+) polycrystalline materials were synthesized by solid state reaction at high temperature. The materials were characterized by powder x-ray diffraction (XRPD). The luminescence spectroscopy and the excited state dynamics of these compounds were investigated upon excitation with UV/VUV synchrotron radiation. Both materials showed efficient and fast 5d-4f emission upon direct VUV excitation into the 5d levels but only Ca(9)Lu(PO(4))(7):Ce (3+) revealed luminescence upon excitation across the bandgap. The decay kinetics of the 5d-4f emission upon VUV intra-center excitation is characterized by a decay time of 29 ns for Ce (3+) and 17 ns for Pr (3+) with no significant build-up after the excitation pulse. For the both compounds, no significant temperature dependence of the 5d-4f emission lifetime was observed within the range 8-300 K.

First measurement of chiral dynamics in π- γ → π- π- π+.

The COMPASS Collaboration at CERN has investigated the π- γ → π- π- π+ reaction at center-of-momentum energy below five pion masses, sqrt[s]<5m(π), embedded in the Primakoff reaction of 190 GeV pions impinging on a lead target. Exchange of quasireal photons is selected by isolating the sharp Coulomb peak observed at smallest momentum transfers, t'<0.001 GeV2/c2. Using partial-wave analysis techniques, the scattering intensity of Coulomb production described in terms of chiral dynamics and its dependence on the 3π-invariant mass m(3π)=sqrt[s] were extracted. The absolute cross section was determined in seven bins of sqrt[s] with an overall precision of 20%. At leading order, the result is found to be in good agreement with the prediction of chiral perturbation theory over the whole energy range investigated.

High pressure luminescence spectra of CaMoO4:Pr3+.

Steady state and time resolved luminescence measurements of CaMoO(4) doped with Pr(3+) as a function of hydrostatic pressure in the 1-175 kbar range are presented. It has been observed that with increasing pressure the spectral features shift towards lower energies, the decay times of both (3)P(0) and (1)D(2) emitting levels become shorter and the intensity of the (3)P(0) emission decreases to complete quenching at about 110 kbar, whereas that of the (1)D(2) emission increases in the 0-100 kbar range and then rapidly decreases when the pressure exceeds 127 kbar. A variation of the structure of the spectral manifolds indicates that a pressure induced phase transition of the host lattice occurs in the 80-100 kbar range. The quenching of the luminescence and the shortening of the decay times have been accounted for by means of a model that takes into account the role played by a praseodymium trapped exciton in the excited state dynamics of the investigated material.

Hyperfine structure of Ho3+ levels and electron-phonon coupling in YPO4 single crystals.

High resolution spectroscopy (the finest being 0.01 cm(-1)) was applied in the 75-25,000 cm(-1) and 9-300 K ranges to a 1 mol% holmium doped Y PO(4) single crystal with two purposes: (1) to study the hyperfine splitting of Ho(3+) energy levels of interest for possible quantum manipulation media and (2) to analyze the electron-phonon interaction. The hyperfine structure was clearly revealed for a high number of lines in a wide wavenumber range (up to ~21,500 cm(-1)) and for a large number of multiplets. Several hyperfine patterns were monitored, differing in the number of components (a maximum of 16 could be easily distinguished in a single beautiful pattern), in their separation, and in their relative statistical weight. These features were all understood in terms of a crystal-field model, whose results are in good agreement with experiments and account for the involved level symmetry, the type of transitions (electric and magnetic dipole allowed), and the contribution of a second-order (pseudoquadrupolar) hyperfine coupling between close levels. The electron-phonon interaction, investigated through the thermally induced line shift, was critically discussed in the framework of single phonon coupling and of two phonon Raman scattering models.

Random lasing in Nd:LuVO4 crystal powder.

Room temperature random lasing action is demonstrated for the first time in a low concentrated neodymium doped vanadate crystal powder. Laser threshold and emission efficiency are comparable to the ones obtained in stoichiometric borate crystal powders. The present investigation provides a complete picture of the random lasing characteristics of Nd-doped vanadate powder both in the spectral and temporal domain, together with a simplified model which accounts for the most relevant features of the random laser.

Temperature and pressure dependence of the optical properties of Cr3+-doped Gd3Ga5O12 nanoparticles.

Since the crystal-field strength at the Cr(3+) site is very close to the excited-state crossover (ESCO), this work investigates the optical properties of Cr(3+)-doped Gd(3)Ga(5)O(12) (GGG) nanoparticles as a function of temperature and pressure in order to establish the effect of the ESCO on the optical behaviour of nanocrystalline GGG. Luminescence, time-resolved emission and lifetime measurements have been performed on GGG:0.5% Cr(3+) nanoparticles in the 25-300 K temperature range, as well as under hydrostatic pressure up to 20 GPa. We show how low temperature and high pressure progressively transforms Cr(3+)(4)T(2) --> (4)A(2) broadband emission into a ruby-like (2)E --> (4)A(2) luminescence. This behaviour together with the lifetime dependence on pressure and temperature are explained on the basis of the spin-orbit interaction between the (4)T(2) and (2)E states of Cr(3+).

Observation of a J(PC)=1-+ exotic resonance in diffractive dissociation of 190   GeV/c π- into π- π- π+.

The COMPASS experiment at the CERN SPS has studied the diffractive dissociation of negative pions into the π- π- π+ final state using a 190 GeV/c pion beam hitting a lead target. A partial wave analysis has been performed on a sample of 420,000 events taken at values of the squared 4-momentum transfer t' between 0.1 and 1 GeV2/c2. The well-known resonances a1(1260), a2(1320), and π2(1670) are clearly observed. In addition, the data show a significant natural-parity exchange production of a resonance with spin-exotic quantum numbers J(PC)=1-+ at 1.66 GeV/c2 decaying to ρπ. The resonant nature of this wave is evident from the mass-dependent phase differences to the J(PC)=2-+ and 1++ waves. From a mass-dependent fit a resonance mass of (1660±10(-64)(+0)) MeV/c2 and a width of (269±21(-64)(+42)) MeV/c2 are deduced, with an intensity of (1.7±0.2)% of the total intensity.

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.

Optical transition probabilities in Er3+- and Tm3+-doped LiLa9(SiO4)6O2 crystals.

In this work, Er(3+) and Tm(3+)-doped LiLa(9)(SiO(4))(6)O(2) crystals have been grown from an Li(2)MoO(4) flux in the 1360-940 °C temperature range. Optical absorption spectra have been measured to obtain the experimental oscillator strengths of the transitions from the ground state to the excited levels. Judd-Ofelt calculations have been performed to estimate the Ω(2), Ω(4) and Ω(6) intensity parameters. The dynamics of selected Er(3+) and Tm(3+) manifolds have been investigated under selective pulsed excitation in order to determine the energy gap law by comparing the observed decay rates with the Judd-Ofelt predictions.