VUV spectroscopy of complex fluoride systems Na0.4(Y1−xREx)0.6F2.2 (RE3+ = Nd3+, Tm3+)

Emission and excitation spectra as well as luminescence decay kinetics of complex non-stoichiometric fluoride crystals Na_0.4(Y_1−xNd_x)_0.6F_2.2 (x = 0.005, 0.05, 0.2, 1) and Na_0.4(Y_1−xTm_x)_0.6F_2.2 (x = 0.0005, 0.01, 0.05, 0.1) have been studied in the VUV spectral range at liquid-helium (T ∼ 10 K) temperatures. It has been shown that these crystals show intense broad-band VUV luminescence due to the interconfiguration 5d-4f transitions in Nd³⁺ and Tm³⁺ ions. Remarkable concentration quenching is observed for Nd³⁺ 5d-4f luminescence whereas fast (spin-allowed) 5d-4f luminescence of Tm³⁺ shows no concentration quenching for the studied doping level up to 10%. The spin-allowed 5d-4f luminescence of Tm³⁺ in these crystals was found to be rather weak compared to spin-forbidden 5d-4f luminescence because of efficient nonradiative relaxation from higher-energy 5d states of Tm³⁺ to the lowest-energy 5d level responsible for spin-forbidden 5d-4f luminescence. The studied fluoride systems can be considered as promising active media for the development of VUV solid state lasers with optical pumping.     

Synthesis of green-emitting (Gd,La, Tb)2O(WO4)2 phosphors

Green-emitting (Gd_1−x−yLa_xTb_y)₂O(WO₄)₂ (0 ⩽ x ⩽ 0.05, 0.05 ⩽ y ⩽ 0.15) phosphors were synthesized in a single phase form by the conventional solid-state reaction method, and their photoluminescent properties were characterized. The (Gd_1−x−yLa_xTb_y)₂O(WO₄)₂ phosphors showed strong and broad excitation bands from 230 to 350 nm, corresponding to the energy transition from the 4f⁸ to 4f⁷5d configuration of Tb³⁺ and the charge-transfer (CT) transition of O²⁻−W⁶⁺. The oxytungstate phosphors exhibited typical emission peaks assigned to the transition from ⁵D₄ to ⁷F_J (J = 6, 5, 4, and 3) of Tb³⁺, and the luminescence emission intensity was effectively enhanced by the La³⁺ doping into the host Gd₂O(WO₄)₂ lattice. The highest green emission intensity was obtained for (Gd_0.87La_0.03Tb_0.10)₂O(WO₄)₂, where the relative emission intensity was 63% that of a commercial green-emitting (La_0.52Ce_0.31Tb_0.17)PO₄ phosphor.     

Microstructure and transport properties of Bi1.6Pb0.5Sr2−xLuxCa1.1Cu2.1O8+δ superconductor

The microstructure and electrical properties of the rare-earth Lu doped (Bi, Pb)-2212 superconductor have been investigated. The Lu concentration is varied from x = 0.000 to 0.150 in a general stoichiometry of Bi_1.6Pb_0.5Sr_2?xLu_xCa_1.1Cu_2.1O_8+δ. The X-ray diffractometer and energy dispersive X-ray spectroscopy analyses show that Lu atoms are successfully substituted into the (Bi, Pb)-2212 system and they induce significant changes in the microstructure, hole concentration, critical temperature, self- and in-field critical current density of the system. The flux pinning force (F_P) calculated from the field dependant J_C values shows that the irreversibility lines (IL) of the Lu substituted (Bi, Pb)-2212 shift towards higher fields to different extents depending on the Lu stoichiometry. The samples with x = 0.100 show a maximum F_P of 1395 ± 1 × 10³ N m^?3 as against 30 ± 1 × 10³ N m^?3 for the pure sample. The changes in hole concentration followed by very high enhancement of critical temperature (T_C), self-field J_C, J_C(B) characteristics and F_P due to Lu substitution are of great scientific and technological significance and the results are explained on the basis of microstructural variation with respect to Lu stoichiometry, hole optimization and formation of point defects due to the doping of Lu atoms in Bi_1.6Pb_0.5Sr_2?xLu_xCa_1.1Cu_2.1O_8+δ system.     

Synthesis and properties of Ce1−xGdxO2−x/2 solid solution prepared by flame spray pyrolysis

Flame spray pyrolysis, which produces ultrafine particles, was applied to the synthesis of Ce_1−xGd_xO_2−x/2 solid solutions by substituting Gd from a mole fraction of 0–0.40. The solubility limit of Gd in the Ce_1−xGd_xO_2−x/2 solid solution produced by flame spray pyrolysis was between 0.25 and 0.30, which is consistent with the reported value. The as-prepared Ce_1−xGd_xO_2−x/2 particles had a square morphology and a nanometer range in the equivalent diameter. The small particle size made it possible to reduce the sintering temperature of the Ce_1−xGd_xO_2−x/2 solid solution from 1650 °C to 1400 °C for the ceria-based solid electrolytes produced by the solid state preparation. The maximum ionic conductivity was achieved when the mole fraction of Gd was 0.25. The mole fraction for the highest ionic conductivity was the same as the particles produced by hydrothermal synthesis. However, the ionic conductivity of the Ce_1−xGd_xO_2−x/2 prepared by the flame spray pyrolysis (1.01 × 10⁻² S/cm at 600 °C) was higher than that prepared by the hydrothermal synthesis (7.53 × 10⁻³ S/cm at 600 °C).     

Optical and scintillation properties of Nd-doped complex garnet

Nd 1% doped complex garnet scintillators were prepared by Furukawa and their optical and scintillation properties were investigated on a comparison with previously reported Nd-doped YAG. Chemical compositions of newly developed complex garnets were Lu₂Y₁Al₅O₁₂, Lu₂Y₁Ga₃Al₂O₁₂, Lu₂Gd₁Al₅O₁₂, Lu₂Gd₁Ga₃Al₂O₁₂, Gd₁Y₂Al₅O₁₂, Gd₁Y₂Ga₃Al₂O₁₂, and Gd₃Ga₃Al₂O₁₂. They all showed 50–80% transmittance from ultraviolet to near infrared wavelengths with several absorption bands due to Gd³⁺ or Nd³⁺ 4f–4f transition. In X-ray induced radioluminescence spectra, all samples exhibited intense lines at 310 nm due to Gd³⁺ or 400 nm due to Nd³⁺ depending on their chemical composition. Among them, the highest scintillation light yield was achieved by Lu₂Y₁Al₅O₁₂. Typical scintillation decay times of them resulted 1.5–3 μs. Thermally stimulated glow curve after 1 Gy exposure and X-ray induced afterglow were also investigated.     

The magnetocaloric effect in (Gd0.74Tb0.26)5(SixGe1−x)4 alloys

The magnetic phase transition and magnetocaloric effect of the alloys of Gd_0.74Tb_0.26 and (Gd_0.74Tb_0.26)₅(Si_xGe_1−x)₄ (x = 0.43, 0.50, 0.505) have been investigated by magnetization measurement. Experimental results show that partial substitution of the Gd by Tb in Gd₅(Si_xGe_1−x)₄ system keeps the first order magnetic transition. Although the values of transition temperature decrease, the as-cast (Gd_0.74Tb_0.26)₅(Si_0.43Ge_0.57)₄ and annealed (Gd_0.74Tb_0.26)₅(Si_0.50Ge_0.50)₄ alloys display large magnetic entropy change up to 18.89 J kg^− 1 K^− 1 and 13.79 J kg^− 1 K^− 1 near their transition temperatures in the low magnetic field change of 0–2.0 T, respectively.     

Spectroscopic properties of Tm3+/Al3+ co-doped sol–gel silica glass

Tm³⁺/Al³⁺ co-doped silica glass was prepared by sol–gel method combined with high temperature sintering. Glasses with compositions of xTm₂O₃–15xAl₂O₃–(100 − 16x) SiO₂ (in mol%, x = 0.1, 0.3, 0.5, 0.8 and 1.0) were prepared. The high thulium doped silica glass was realized. Their spectroscopic parameters were calculated and analyzed by Judd–Ofelt theory. Large absorption cross section (4.65 × 10⁻²¹ cm² at 1668 nm) and stimulated emission cross section (6.00 × 10⁻²¹ cm² at 1812 nm), as well as low hydroxyl content (0.180 cm⁻¹), long fluorescence lifetime (834 μs at 1800 nm), large σ_em × τ_rad (30.05 × 10⁻²¹ cm² ms) and large relative intensity ratio of the 1.8 μm (³F₄ → ³H₆) to 1.46 (³H₄ → ³F₄) emissions (90.33) are achieved in this Tm³⁺/Al³⁺ co-doped silica glasses. According to emission characteristics, the optimum thulium doping concentration is around 0.8 mol%. The cross relaxation (CR) between ground and excited states of Tm³⁺ ions was used to explain the optimum thulium doping concentration. These results suggest that the sol–gel method is an effective way to prepare Tm³⁺ doped silica glass with high Tm³⁺ doping and prospective spectroscopic properties.     

Controlled processing of (Gd,Ln)2O3:Eu (Ln = Y,Lu) red phosphor particles and compositional effects on photoluminescence

Synthesis of (Gd_0.95−xLn_xEu_0.05)₂O₃ (Ln = Y and Lu, x = 0–0.95) powders via ammonium hydrogen carbonate (AHC) precipitation has been systematically studied. The best synthesis parameters are found to be an AHC/total cation molar ratio of 4.5 and an ageing time of 3 h. The effects of Y³⁺ and Lu³⁺ substitution for Gd³⁺, on the nucleation kinetics of the precursors and structural features and optical properties of the oxides, have been investigated. The results show that (i) different nucleation kinetics exist in the Gd–Y–Eu and Gd–Lu–Eu ternary systems, which lead to various morphologies and particle sizes of the precipitated precursors. The (Gd,Y)₂O₃:Eu precursors display spherical particle morphologies and the particle sizes increase along with more Y³⁺ addition. The (Gd,Lu)₂O₃:Eu precursors, on the other hand, are hollow spheres and the particle sizes increase with increasing Lu³⁺ incorporation, (ii) the resultant oxide powders are ultrafine, narrow in size distribution, well dispersed and rounded in particle shape, (iii) lattice parameters of the two kinds of oxide solid solutions linearly decrease at a higher Y³⁺ or Lu³⁺ content. Their theoretical densities linearly decrease with increasing Y³⁺ incorporation, but increase along with more Lu³⁺ addition and (iv) the two kinds of phosphors exhibit typical red emissions at ∼613 nm and their charge-transfer bands blue shift at a higher Y³⁺ or Lu³⁺ content. Photoluminescence/photoluminescence excitation intensities and external quantum efficiency are found to decrease with increasing value of x, and the fluorescence lifetime mainly depends on the specific surface areas of the powders.     

Visible quantum cutting through downconversion in Eu3+-doped K2GdZr(PO4)3 phosphor

K₂Gd_1?xZr(PO₄)₃:Eu_x³⁺ (0.02 ≤ x ≤ 0.1, x is in mol.%) were prepared by solid-state reaction method and their photoluminescence properties were investigated in ultra-violet (UV) and vacuum ultra-violet (VUV) region. The phenomenon of visible quantum cutting through downconversion was observed for the Gd³⁺–Eu³⁺ couple in this Eu³⁺-doped K₂GdZr(PO₄)₃ system. Visible quantum cutting, the emission of two visible light photons per absorbed VUV photon, occurred upon the 186 nm excitation of Gd³⁺ at the ⁶G_J level via two-step energy transfer from Gd³⁺ to Eu³⁺ by cross-relaxation and sequential transfer of the remaining excitation energy. The results revealed that the efficiency of the energy transfer process from Gd³⁺ to Eu³⁺ in the Eu³⁺-doped K₂GdZr(PO₄)₃ system could reach to 155% and K₂GdZr(PO₄)₃:Eu³⁺ was effective quantum cutting material.     

Energy transfer and radiative recombination processes in (Gd, Lu)3Ga3Al2O12:Pr3+ scintillators

(Gd_xLu_3−x)Ga₃Al₂O₁₂:0.3 at.%Pr (x = 0.025, 0.05, 0.1, 0.2, 0.4, 0.6) (GLGAG:Pr) polycrystalline powders are prepared by solid-state reaction method. To better understand the luminescence mechanism, the optical diffuse reflectance, photoluminescence emission and excitation, X-ray excited luminescence spectra and decay kinetics of GLGAG:Pr were investigated in detailed, allowing the determination of energy transfer from 5d state of Pr³⁺ to 4f state of Gd³⁺, and the non-radiative relaxation from 5d to 4f state of Pr³⁺. Besides, the former process plays more negative role in the emission quenching of GLGAG:Pr than later one. Pr³⁺ ion is regarded as an ineffective activation ion in Gd-based multicomponent aluminate garnets. In addition, the wavelength-resolved thermoluminescence spectra of GLGAG:Pr were studied after UV and X-ray irradiation. It is revealed that the localized recombination processes from electron traps to lower lying 4f levels of Pr³⁺ occurs without populating the higher 5d levels of Pr³⁺.     

The influence of Dy additions on the magnetocaloric effect in Gd0.97V0.03 alloys

The influence of Dy on the magnetocaloric effect in Gd_0.97 ? xDy_xV_0.03 (x = 0.1, 0.2, 0.3) alloys has been studied. These alloys were prepared by arc melting on a water-cooled copper hearth under an argon atmosphere. The magnetization behavior has been analyzed by X-ray diffraction and a vibrating sample magnetometer. Results indicate that the Curie points of Gd_0.97 ? xDy_xV_0.03 alloys decrease linearly with increasing content of Dy. The values of maximum magnetic entropy change (ΔS_M) and relative cooling power (RCP) for x = 0 ～ 0.2 is larger than that of Gd alone over a wider temperature range. The Gd_0.97 ? xDy_xV_0.03 alloys have promising potential as working substance candidates for magnetic refrigeration due to their tunable Curie temperature and the favorable properties of the magnetocaloric effect.     

Preparation and structure of carbonated calcium hydroxyapatite substituted with heavy rare earth ions

Calcium hydroxyapatite (CaHap) particles substituted five types of heavy rare earth ions (Ln: Y³⁺, Gd³⁺, Dy³⁺, Er³⁺ and Yb³⁺) were synthesized using a precipitation method and characterized using various means. These Ln ions strongly affected the crystal phases and the structures of the products. With increasing Ln/(Ln + Ca) in the starting solution ([X_Ln]), the length and the crystallinity of the particles first increased and then decreased. The rare earth metal-calcium hydroxyapatite (LnCaHap) solid solution particles were obtained at [X_Y] ≤ 0.10 for substituting Y system and at [X_Ln] ≤ 0.01–0.03 for substituting the other Ln systems. LnPO₄ was mixed with LnCaHap at higher [X_Ln] for all Ln systems. A series of yttrium-calcium hydroxyapatite (YCaHap) solid solutions with [X_Y] = 0–0.10 were investigated using XRD, TEM, ICP-AES, IR and TG–DTA in detail.     

Comparative study of Er3+ and Tm3+ co-doped YOF and Y2O3 powders as red spectrally pure upconverters

We prepared Er³⁺ and Tm³⁺ co-doped yttrium oxyfluoride (YOF) powder by combustion synthesis and we observed that under near-infrared (λ = 980 nm) laser excitation the characteristic green (²H_11/2, ⁴S_3/2 → ⁴I_15/2) emission of Er³⁺ was suppressed by energy transfer (ET) mechanisms between Tm³⁺ and Er³⁺. The ET process observed in YOF was much more efficient than that observed in standard Y₂O₃ powder prepared under similar conditions. YOF combines the superior mechanical and thermal properties of oxides with low phonon energy of fluorides. Our results show that this material is a serious candidate for use as a red upconversion phosphor.     

Ionic conductivity of high-purity Gd-doped ceria solid solutions

The Ce_1−xGd_xO_2−δ (0.02 ≤ x ≤ 0.3) solid solutions with ∼30 ppm SiO₂ were prepared through the conventional mixed-oxide method from high-purity CeO₂ and Gd₂O₃ powders. The ionic conductivity (especially the grain boundary (GB) conduction) in this system was studied as a function of dopant content, over the temperature range of 250–750 °C in air, using an impedance spectroscopy. The GB impedance played an important role in the total conduction in the samples with low Gd content (usually x ≤ 0.1), but decreased sharply with increasing Gd content. Both the total and GB conductivities maximized at the composition x = 0.15, and this composition also had the lowest activation energies for the total and GB conduction. The maximum total conductivity at 700 °C, σ_t = 4.07 (Ω m)⁻¹ with the activation energy, E_t = 0.77 eV, was found for the composition x = 0.15.     

Phase relations and high temperature-XRD studies of Gd2−xNdxTi2O7 solid solutions

A series of compositions with the general formula Gd_2−xNd_xTi₂O₇ (0.0 ≤ x ≤ 2.0) was prepared by ceramic sintering and characterized by powder XRD. Nd³⁺ has been used as a surrogate for Am³⁺, an actinide found in spent nuclear fuel. One end member, Gd₂Ti₂O₇, had the pyrochlore structure and formed solid solutions with Nd₂Ti₂O₇ up to the nominal composition Gd_1.2Nd_0.8Ti₂O₇. An increase in lattice parameter was observed as a function of x in the series Gd_2−xNd_xTi₂O₇ in the composition range 0.0 ≤ x ≤ 0.8. Compositions Gd_2−xNd_xTi₂O₇ in the range 0.8 ≤ x ≤ 1.4 were biphasic. From x ≥ 1.6, the solid solutions are monoclinic, isotypic with Nd₂Ti₂O_7. These results were explained based on the radius (r_A/r_B) ratio of the cations. High temperature-XRD studies on cubic pyrochlores showing thermal expansion are reported.     

Optical characterization of YAl3(BO3)4:Dy3+–Tm3+ phosphors under near UV excitation

Dy³⁺ and Tm³⁺ co-doped YAl₃(BO₃)₄ (YAB) phosphors were prepared by solid-state reaction method at 1200 °C/3 h. The average crystallite size was determined as 52.09 nm from the X-ray diffraction measurements. Upon 352 and 359 nm near ultra violet excitation, the YAB:Dy³⁺–Tm³⁺ phosphors exhibit Dy³⁺:⁴F_9/2 → ⁶H_J (J = 15/2, 13/2, 11/2) and Tm³⁺:¹D₂ → ³F₄ transitions with different luminescence intensity. The photoluminescence emission and decay measurements revealed the energy transfer from Dy³⁺ to Tm³⁺ ions under 359 nm excitation only. The energy transfer between Dy³⁺ and Tm³⁺ takes place in Dy³⁺–Tm³⁺ clusters through exchange interaction mechanism. The Commission International de I’Eclairage chromaticity coordinates of YAB:Tm³⁺ phosphor (λ_ex = 359 nm) were found very close to the European Broadcasting Union and National Television Standard Committee illuminants. The emission color of the studied phosphors could be tuned from blue-to-white as a function of excitation wavelength. The YAB:Dy³⁺–Tm³⁺ phosphors can be used as potential candidates in display technology.     

Effects of excitation wavelength and Y3+ content on luminescent properties of YMO4:Dy3+ (M = V,P) phosphors induced by ultraviolet excitation

Y_0.99VO₄:0.01Dy³⁺, Y_0.99PO₄:0.01Dy³⁺ and Y_xVO₄:0.01Dy³⁺ phosphors were synthesized by chemical co-precipitation method. All the samples were characterized by X-ray powder diffraction (XRD) and photoluminescence spectroscopy. XRD results show that the samples only have single tetragonal structure and the crystallinity of Y_0.99VO₄:0.01Dy³⁺ phosphor is higher than that of Y_0.99PO₄:0.01Dy³⁺ phosphor when the heat treatment process is same. Photoluminescence excitation spectra results show that the Y_0.99VO₄:0.01Dy³⁺ and Y_0.99PO₄:0.01Dy³⁺ phosphors can be efficiently excited by ultraviolet light from 250 nm to 380 nm, the former have a wide Dy³⁺–O^2? charge transfer band ranging from 260 nm to 350 nm including a peak at 310 nm, the latter have four peaks at 294 nm, 326 nm, 352 nm and 365 nm. Emission spectra of all the samples exhibit a strong blue emission (483 nm) and another strong yellow emission (574 nm). Moreover, the yellow-to-blue emission intensity ratio and color temperature of emission of Dy³⁺ are strongly related to excitation wavelength in Y_0.99PO₄:0.01Dy³⁺ phosphor, but it is almost not in Y_0.99VO₄:0.01Dy³⁺ phosphor. For Y_xVO₄:0.01Dy³⁺ (x = 0.94, 0.97, 0.99, 1.01, 1.03) phosphors, with increasing value of x, the body color of phosphor changes from yellow to white and the strongest peak in excitation spectra shifts a little to shorter wavelength. It is detrimental to luminous intensity when Y³⁺ content deviate stoichiometric ratio, but the influence of Y³⁺ on the color temperature of emission of YVO₄:Dy³⁺ phosphor is slight.     

The preparation and magnetic properties of GdxBiY2−xFe5O12 nanoparticles

Gd_xBiY_2−xFe₅O₁₂ (x = 0, 0.1, 0.2, 0.4, 0.6, 0.8) nanocrystals were synthesized by sol–gel method. Samples were characterized by using of X-ray diffraction (XRD), thermal gravity analysis (TGA), differential thermal analysis (DTA), transmission electron microscopy (TEM), and vibrating sample magnetometer (VSM).The average size of the particles was calculated by Scherrer's formula from XRD data, which are from 43 to 50 nm. The effect of Gd³⁺ substitution for Y³⁺ on magnetic properties of BiY₂Fe₅O₁₂ has been investigated.     

Yellow-emitting (Ca2Lu1−xCex)(ScMg)Si3O12 phosphor and its application for white LEDs

Luminescence properties of the yellow-emitting (Ca₂Lu_1?xCe_x)(ScMg)Si₃O₁₂ (CLSM:xCe³⁺ x = 0.01–0.15) phosphor are investigated for various Ce³⁺ concentrations. Different Ce³⁺ emission sites and energy transfers between them are observed, resulting in a red shift of the emission spectra from 530 to 575 nm with increasing x from 0.01 to 0.15. Combining with blue (460 nm) InGaN LEDs, CLSM:Ce³⁺ shows excellent performances for phosphor-converted white LEDs with higher color rendering index R_a of 87.4–87.9 and lower color temperature T_C of 5034–5814 K, especially for warm pcWLEDs with a high color rendering (R_a > 80) and a low color temperature (T_C < 4000 K). Thermal quenching behaviors depending on Ce³⁺ concentrations and temperatures are discussed.     

EPR and vibrational studies of YVO4:Tm3+, Yb3+ single crystal

A well oriented YVO₄ single crystal, with 5% Yb³⁺ and 2% Tm³⁺ nominal doping, was investigated using the Raman and EPR techniques.The EPR measurements suggest that Yb³⁺ ions occupy eight-coordinated Y³⁺ sites forming bisdisphenoids of the D_2d symmetry. An inhomogeneous distribution of rare-earth ions leads to a significant distortion of the local point symmetry (C₁). It seems that strong dipole–dipole interactions between Yb³⁺ ions are responsible for the distortion. As a result, two types of ytterbium magnetic centers appear. They correspond to paired magnetic centers and distorted isolated paramagnetic centers that are strongly sensitive to the magnetic field directions and some imperfections of the crystal. Pair centers can be recorded through the rotation around the c-crystal axis, whereas isolated centers can be measured when the crystal is rotated around the a-crystal axis. With the increasing temperature, the ytterbium signal disappeared at about 23 K and a group of narrow lines became visible. These lines, observed in the range of 240–550 mT, correspond to the Gd³⁺ (S = 7/2) ions, doped to the structure unintentionally from the basic materials.