Electric field gradient at Ru nuclei in the series of intermetallic compounds Ce1−xLaxRu2 synthesized at high pressure

Parameters of the electric quadrupole interaction for the first excited state (E=89.7 keV) of ⁹⁹Ru nuclei for a number of the cubic Laves phase compounds Ce_1−xLa_xRu₂, synthesized at high pressure, were determined by the perturbed angular γγ-correlation method. Compounds were synthesized at 8 GPa. It was revealed that the decrease of the average valence of a rare earth ion, caused by the substitution of La for Ce, results in the monotonous decrease of the quadrupole frequency ν_Q from 43.3 MHz for CeRu₂ to 33.1 MHz for LaRu₂.     

Luminescent properties of HTP AgGd1−xW2O8:Eux and AgGd1−x(W1−yMoy)2O8:Eux phosphor for white LED

Intense red phosphors, AgGd_1−xEu_x(W_1−yMo_y)₂O₈ (x=0.0-1.0, y=0.0-1.0), have been synthesized through traditional solid-state reaction and characterized by X-ray diffraction (XRD) and photoluminescence (PL). XRD results reveal that AgGd_1−xEu_xW₂O₈ synthesized at 1000 °C has a tetragonal crystal structure, which is named as high temperature phase (HTP) AgGdW₂O₈. All phosphors compositions with Eu³⁺ show red and green emission on excitation either in the charge-transfer or Eu³⁺ levels. Analysis of the emission spectra with different Eu³⁺ concentrations reveal that the optimum dopant concentration for Eu³⁺ is x=0.6 in the HTP AgGd_1−xEu_xW₂O₈ (x=0.0-1.0). Studies on the AgGd_0.4Eu_0.6(W_1−yMo_y)₂O₈ (y=0.0-1.0) and AgGd_1−xEu_x(W_0.7Mo_0.3)₂O₈ (x=0.0-1.0) show that the emission intensity is maximum for compositions with y=0.3 and x=0.5, respectively, and a decrease in emission intensity is observed for higher y or x values. The Mo⁶⁺ and Eu³⁺ co-doped AgGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped AgGd(WO₄)₂ in UV region. The intense emission of the tungstate/molybdate phosphors under 394 and 465 nm excitations, respectively, suggests that these materials are promising candidates as red-emitting phosphors for near-UV/blue GaN-based white LED for white light generation.     

Crystal structure and photoluminescence of (Y1−xCex)2Si3O3N4

Oxonitridosilicate phosphors with compositions of (Y_1−xCe_x)₂Si₃O₃N₄ (x=0−0.2) have been synthesized by solid state reaction method. The structures and photoluminescence properties have been investigated. Ce³⁺ ions have substituted for Y³⁺ ions in the lattice. The emission and excitation spectra of these phosphors show the characteristic photoluminescence spectra of Ce³⁺ ions. Based on the analyses of the diffuse reflection spectra and the PL spectra, a systematic energy diagram of Ce³⁺ ion in the forbidden band of sample with x=0.02 is given. The best doping Ce content in these phosphors is ∼2 mol%. The quenching temperature is ∼405 K for the 2 mol% Ce content sample. The luminescence decay properties were investigated. The primary studies indicate that these phosphors are potential candidates for application in three-phosphor-converted white LEDs.     

Highly active Ce1−xCuxO2 nanocomposite catalysts for the low temperature oxidation of CO

A series of Ce_1−xCu_xO₂ nanocomposite catalysts with various copper contents were synthesized by a simple hydrothermal method at low temperature without any surfactants, using mixed solutions of Cu(II) and Ce(III) nitrates as metal sources. These bimetal oxide nanocomposites were characterized by means of XRD, TEM, HRTEM, EDS, N₂ adsorption, H₂-TPR and XPS. The influence of Cu loading (5-25 mol%) and calcination temperature on the surface area, particle size and catalytic behavior of the nanocomposites have been discussed. The catalytic activity of Ce_1−xCu_xO₂ nanocomposites was investigated using the test of CO oxidation reaction. The optimized performance was achieved for the Ce_0.80Cu_0.20O₂ nanocomposite catalyst, which exhibited superior reaction rate of 11.2 × 10⁻⁴ mmol g⁻¹ s⁻¹ and high turnover frequency of 7.53 × 10⁻² s⁻¹ (1% CO balanced with air at a rate of 40 mL min⁻¹, at 90 °C). No obvious deactivation was observed after six times of catalytic reactions for Ce_0.80Cu_0.20O₂ nanocomposite catalyst.     

The size and strain effects on the Raman spectra of Ce1−xNdxO2−δ (0≤x≤0.25) nanopowders

Ultrafine Ce_1−xNd_xO_2−δ (x=0-0.25) powders were synthesized by self-propagating room temperature synthesis. Raman spectra were measured at room temperature in the 300-700 cm⁻¹ spectral range. The shift and asymmetric broadening of the Raman F_2g mode at about 454 cm⁻¹ in pure and doped ceria samples could be explained with combined size and inhomogenous strain effects. Increased concentration of O²⁻ vacancies with doping is followed by an appearance of new Raman feature at about 545 cm⁻¹.     

Thermoelectric properties of the Bi2−xYxRu2O7 (x=0-2) pyrochlores

Electrical conductivity and Seebeck coefficient for the Bi_2−xY_xRu₂O₇ pyrochlores with x=0.0,0.5,1.0,1.5,2.0 were measured in the temperature range of 473-1073 K in air. With increasing Bi content, the temperature dependence of the electrical conductivity changed from semiconducting to metallic. The signs of the Seebeck coefficient were positive in the measured temperature range for all the samples, indicating that the major carriers were holes. The temperature dependence of the Seebeck coefficient for the Y₂Ru₂O₇ indicated the thermal activation-type behavior of the holes, while that for the Bi_2−xY_xRu₂O₇ with x=0.0-1.5 indicated the itinerant behavior of the holes. The change in the conduction behavior from semiconductor to metal with increasing Bi content is consistent with the increase in the overlap between the Ru4d t_2g and O2p orbitals, but the mixing of Bi6s, 6p states at E_F may not be ruled out. The thermoelectric power factors for the Bi_2−xY_xRu₂O₇ with x=1.5 and 2.0 were lower than 10⁻⁵ W m⁻¹ K⁻² and those with x=0.0,0.5,1.0 were around 1-3×10⁻⁵ W m⁻¹ K⁻².     

Electrical conductivity of (Er,U)O2+x and (Ce,U)O2+x

The electrical conductivity (σ) of (Er_yU_1−y)O_2+x (y=0.06, 0.20) and (Ce_yU_1−y)O_2+x (y=0.05, 0.15, 0.25) has been measured as a function of oxygen partial pressure in the temperature range of 1100≤T/°C≤1300 by a d.c. 4-probe method. Both of the oxides exhibited Po₂-regions where the electrical conductivity is independent of oxygen partial pressure, which indicates that doped Er and Ce exist as trivalent cations on uranium sites and fix the hole concentration by acting as electron acceptors, i.e. [h]=[Er′_U] and [h]=[Ce′_U], respectively. It is considered that strong oxidization tendency of uranium and reduction tendency of cerium simultaneously render the cerium ions exist exclusively as Ce³⁺ in the uranium dioxide. The electron-hole mobility of (Er_yU_1−y)O_2+x and (Ce_yU_1−y)O_2+x in the Po₂ region where σ is constant has been calculated by the combination of the electrical conductivity and charge carrier concentration; the activation energy (E_H) of each oxide has been obtained from the temperature dependence of the mobility. Small polaron hopping conduction mechanism was confirmed by small magnitude of the mobility (0.018-0.052 cm² V⁻¹ s⁻¹) and the activation energy (0.12-0.22 eV).     

Magnetic properties and magnetic structures of Sr3−xCaxRu2O7

We have measured magnetization curves and powder neutron diffraction of double-layered Ruddlesden-Popper type ruthenate Sr_3−xCa_xRu₂O₇ (x=1.5, 2.0 and 3.0). The field dependence of the magnetization revealed that the transition field of metamagnetic transition along the b-axis shifted to lower fields and that the transition became broad with increasing Sr content. The slope of the magnetization curve also increased with increasing Sr content below the metamagnetic transition. These results indicate that an itinerant component is partly introduced by the Sr substitution. From the magnetic reflection, on cooling below T_N, an additional reflection was observed at (0 0 1) for each x, and the amplitude increased with decreasing temperature. The observed diffraction patterns are very similar to those of Ca₃Ru₂O₇. We conclude that the magnetic structure of the antiferromagnetic ordered phase is basically the same structure with that of Ca₃Ru₂O₇.     

Luminescent properties of KGd1−x(WO4)2:Eux and KGd1−x(WO4)2−y(MoO4)y:Eux phosphors in UV-VUV regions

KGd_1−x(WO₄)_2−y(MoO₄)_y:Eu³⁺_x(0.1?x?0.75, y=0 and 0.2) phosphors are synthesized through traditional solid-state reaction and their luminescent properties in ultraviolet (UV) and vacuum ultraviolet (VUV) regions are investigated. Under 147 nm excitation, these phosphors show characteristic red emission with good color purity. In order to improve their emission intensity, the MoO₄²⁻ (20 wt%) is introduced into the anion of KGd_1−x(WO₄):Eu³⁺_x. The Mo⁶⁺ and Eu³⁺ co-doped KGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped KGd(WO₄)₂ in VUV region. The chromaticity coordination of KGd_0.45(WO₄):Eu³⁺_0.55 is (x=0.669, y=0.331), while that of KGd_0.45(WO₄)_1.8(MoO₄)_0.2:Eu³⁺_0.55 is (x=0.666, y=0.334) in VUV region.     

Preparation and optical properties of Ce activated (Ca1 − x,Srx)Al2Si2O8 phosphors

(Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺, M⁺ (M⁺ = Li⁺, Na⁺, K⁺) phosphors have been prepared by conventional solid-state reaction method. The structural and optical properties of the phosphors were characterized by X-ray diffraction (XRD) technique and spectrophotometer, respectively. A regular variation was found among the XRD patterns of (Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺ phosphors based on the changing of Sr content. With the increase of Sr content, the maximum of emission band presented slight blue shifts (~ 15 nm). The luminescence intensity of CaAl₂Si₂O₈:0.06Ce³⁺ and SrAl₂Si₂O₈:0.06Ce³⁺ were significantly enhanced when K⁺ and Li⁺ were incorporated, respectively.     

Syntheses of optically efficient (La1−x−yCexTby)F3 nanocrystals via a hydrothermal method

Optically efficient cerium and terbium doped lanthanide fluoride (La_1−x−yCe_xTb_y)F₃ nanocrystals with different doping concentrations have been synthesized by a hydrothermal route in the presence of ethylenediamine tetraacetic acid disodium salt (EDTA). The results showed that the formation of nanocrystals with different morphologies depends on terbium ion Tb³⁺ doping concentration, but independent of cerium ion Ce³⁺ doping concentration. With increase in Tb³⁺ doping concentration, the morphologies of nanocrystals evolved from a spherical shape to a plated-like one. In addition, both the photoluminescence quantum yield (PL QY) and the fluorescence lifetime of nanocrystals increased with the increase in Ce³⁺ doping concentration in cerium and terbium co-doped system. The PL QY reached up to 55%, and the lifetime up to 7.3 ms. Transmission electron microscopy (TEM), X-ray diffraction (XRD), selected area electron diffraction (SAED), X-ray fluorescence (XRF), energy dispersive spectroscopy (EDS), ultraviolet-visible (UV-vis) absorption, photoluminescence (PL) and infrared (IR) spectroscopies were employed to characterize the properties of nanocrystals. The growth mechanism of nanocrystals with different morphologies and optical properties of nanocrystals with different doping concentrations were investigated.     

Preparation, structure and oxide ion conductivity in Ce6−xYxMoO15−δ (x=0.1-1.4) solid solutions

The Ce_6−xY_xMoO_15−δ solid solution with fluorite-related structure have been characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), IR, Raman, scanning electric microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) methods. The electric conductivity of samples is investigated by Ac impedance spectroscopy. An essentially pure oxide-ion conductivity of the oxygen-deficiency was observed in pure argon, oxygen and air. The highest oxygen-ion conductivity was found in Ce_5.5Y_0.5MoO_15−δ ranging from 5.9×10⁻⁵ (S cm⁻¹) at 300 °C to 1.3×10⁻² (S cm⁻¹) at 650 °C, respectively. The oxide-ion conductivities remained stable over 80 h-long test at 800 °C. These properties suggested that significant oxide-ionic conductivity exists in these materials at moderately elevated temperatures.     

High temperature ferromagnetism of the vacuum-annealed (In1−xFex)2O3 powders

(In_1−xFe_x)₂O₃ (x = 0.02, 0.05, 0.2) powders were prepared by a solid state reaction method and a vacuum annealing process. A systematic study was done on the structural and magnetic properties of (In_1−xFe_x)₂O₃ powders as a function of Fe concentration and annealing temperature. The X-ray diffraction and high-resolution transmission electron microscopy results confirmed that there were not any Fe or Fe oxide secondary phases in vacuum-annealed (In_1−xFe_x)₂O₃ samples and the Fe element was incorporated into the indium oxide lattice by substituting the position of indium atoms. The X-ray photoelectron spectroscopy revealed that both Fe²⁺ and Fe³⁺ ions existed in the samples. Magnetic measurements indicated that all samples were ferromagnetic with the magnetic moment of 0.49-1.73 μ_B/Fe and the Curie temperature around 783 K. The appearance of ferromagnetism was attributed to the ferromagnetic coupling of Fe²⁺ and Fe³⁺ ions via an electron trapped in a bridging oxygen vacancy.     

Structure, transport and magnetic properties in La2xSr2−2xCo2xRu2−2xO6

The perovskite solid solutions of the type La_2xSr_2−2xCo_2xRu_2−2xO₆ with 0.25≤x≤0.75 have been investigated for their structural, magnetic and transport properties. All the compounds crystallize in double perovskite structure. The magnetization measurements indicate a complex magnetic ground state with strong competition between ferromagnetic and antiferromagnetic interactions. Resistivity of the compounds is in confirmation with hopping conduction behaviour though differences are noted especially for x=0.4 and 0.6. Most importantly, low field (50 Oe) magnetization measurements display negative magnetization during the zero field cooled cycle. X-ray photoelectron spectroscopy measurements indicate the presence of Co²⁺/Co³⁺ and Ru⁴⁺/Ru⁵⁺ redox couples in all compositions except x=0.5. Presence of magnetic ions like Ru⁴⁺ and Co³⁺ gives rise to additional ferromagnetic (Ru-rich) and antiferromagnetic sublattices and also explains the observed negative magnetization.     

Combustion synthesis and luminescence properties of NaY1−xEux(WO4)2 phosphors

The red phosphors NaY_1−xEu_x(WO₄)₂ with different concentrations of Eu³⁺ were synthesized via the combustion synthesis method. As a comparison, NaEu(WO₄)₂ was prepared by the solid-state reaction method. The phase composition and optical properties of as-synthesized samples were studied by X-ray powder diffraction and photoluminescence spectra. The results show that the red light emission intensity of the combustion synthesized samples under 394 nm excitation increases with increase in Eu³⁺ concentrations and calcination temperatures. Without Y ions doping, the emission spectra intensity of the NaEu(WO₄)₂ phosphor prepared by the combustion method fired at 900 °C is higher than that prepared by the solid-state reaction at 1100 °C. NaEu(WO₄)₂ phosphor synthesized by the combustion method at 1100 °C exhibits the strongest red emission under 394 nm excitation and appropriate CIE chromaticity coordinates (x=0.64, y=0.33) close to the NTSC standard value. Thus, its excellent luminescence properties make it a promising phosphor for near UV InGaN chip-based red-emitting LED application.     

Superconductivity in CoSr2(Y1−xCax)Cu2O7+δ

The roles of aliovalent Ca^II-for-Y^III substitution and high-pressure-oxygen annealing in the process of ‘superconducterizing’ the Co-based layered copper oxide, CoSr₂(Y_1−xCa_x)Cu₂O_7+δ (Co-1212), were investigated. The as-air-synthesized samples up to x=0.4 were found essentially oxygen stoichiometric (−0.03≤δ≤0.00). These samples, however, were not superconducting, suggesting that the holes created by the divalent-for-trivalent cation substitution are trapped on Co in the charge reservoir. Ultra-high-pressure heat treatment carried out at 5 GPa and 500 °C for 30 min in the presence of Ag₂O₂ as an excess oxygen source induced bulk superconductivity in these samples. The highest T_c was obtained for the high-oxygen-pressure treated x=0.3 sample at ∼40 K.     

Hf1−xSixOy dielectric films deposited by UV-photo-induced chemical vapour deposition (UV-CVD)

Hf_1−xSi_xO_y is an attractive candidate material for high-k dielectrics. We report in this work the deposition of ultra-thin Hf_1−xSi_xO_y films (0.1 ≤ x ≥ 0.6) on silicon substrate at 450 °C by UV-photo-induced chemical vapour deposition (UV-CVD) using 222 nm excimer lamps. Silicon(IV) and hafnium(IV) organic compounds were used as the precursors. Films from around 5 to 40 nm in thickness with refractive indices from 1.782 to 1.870 were grown. The deposition rate was found to be of 6 nm/min at a temperature of 450 °C. The physical, interfacial and electrical properties of hafnium silicate (Hf_1−xSi_xO_y) thin films were investigated by using X-ray photoelectron spectroscopy, ellipsometry, FT-IR, C-V and I-V measurements. XRD showed that they were basically amorphous, while Fourier transform infrared spectroscopy (FT-IR), clearly revealed Hf-O-Si absorption in the photo-CVD deposited Hf_1−xSi_xO_y films. Surface and interfacial properties were analysed by TEM and XPS. It is found that carbon content in the films deposited by UV-CVD is very low and it also decreases with increasing Si/(Si + Hf) ratio, as low as about 1 at.% at the Si/(Si + Hf) ratio of 60 at.%.     

Raman characterization of Pb2Na1−xLaxNb5−xFexO15 and Pb0.5(5−x)LaxNb5−xFexO15 (0≤x≤1) solid solutions

The ferroelectric compounds Pb₂Na_1−xLa_xNb_5−xFe_xO₁₅ and Pb_0.5(5−x)La_xNb_5−xFe_xO₁₅ (0≤x≤1) with the tungsten bronze type structure have been investigated using Raman spectroscopy. The evolution of the spectra as a function of composition at room temperature is reported. In the frequency range 200-1000 cm⁻¹ three main A₁ phonons around 240 (υ₁), 630 (υ₂) and 816 (υ₃) cm⁻¹ were observed. The broadening of the Raman lines for high values of x originates from a significant structural disorder. This is in good agreement with the relaxor character of these compositions. The lowest-frequency part of the spectra, below 180 cm⁻¹, reveals a structural change in the studied solid solutions. The behaviour of the Raman shift of the υ₁ mode confirms that in Pb₂Na_1−xLa_xNb_5−xFe_xO₁₅, a clear anomaly occurs in the vicinity of x=0.4.     

Room temperature magnetic entropy change and magnetoresistance in La0.70(Ca0.30−xSrx)MnO3:Ag 10% (x=0.0−0.10)

The magnetic and magnetocaloric properties of polycrystalline La_0.70(Ca_0.30−xSr_x)MnO₃:Ag 10% manganite have been investigated. All compositions are crystallized in single phase orthorhombic Pbnm space group. Both, the insulator–metal transition temperature (T^IM) and Curie temperature (T_c) are observed at 298 K for x=0.10 composition. Though both T^IM and T_c are nearly unchanged with Ag addition, the MR is increased. The MR at 300 K is found to be as large as 31% with magnetic field change of 1 T, whereas it reaches up to 49% at magnetic field of 3 T for the La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample. The maximum entropy change (ΔS_Mmax) at near its T_c (300.5 K) is 7.6 J kg⁻¹ K⁻¹ upon the magnetic field change of 5 T. The La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample having good MR (31%^1 T, 49%^3 T) and reasonable change in magnetic entropy (7.6 J kg⁻¹.K⁻¹, 5 T) at 300 K can be a potential magnetic refrigerant material at ambient temperatures.     

Increase of Tc in the 1:2:3 superconductors YBCO and (CaxLa1−x)(LauBa1−u)2Cu3Oy after slow cooling or low temperature annealing

The well known phenomenon of the increase of T_c of YBCO after slow cooling or low temperature annealing without change of the oxygen content, was found also for the YBCO like tetragonal superconductors of (Ca_xLa_1−x)(La_uBa_1−u)₂Cu₃O_y (this compound has been previously denoted as CLBLCO, CLBCO or CaLaBaCuO). It has been observed at 150 and 100 °C for oxygen underdoped, optimally- and overdoped ceramics. The products retain their tetragonal unit cells. The possible reasons of this phenomenon are discussed.