Inelastic light scattering and photoluminescence in the mixed valence systems Eu3O4, Eu3S4 and Sm3S4

The thermally activated valence fluctuations of Eu₃S₄ and Sm₃S₄ have been studied using light scattering and photoluminescence techniques and are compared with measurements on the non-fluctuating compound Eu₃O₄, Eu₃S₄ exhibits an anomalous vibrational mode which is associated with the frequency factor of hopping, ν₂=1.3×10¹³ sec^?1. In Sm₃S₄ electronic Raman scattering is observed within the ⁷F₉ multiplet of the Sm²⁺ ion. An anomalous frequency shift of the5d-4f photoluminescence emission band in Eu₃S₄ is related to the temperature dependent fluctuation rate which passes through the reference time scale of the photoluminescence. Intra-4f photoluminescence has also been observed in Eu₃S₄ and Sm₃S₄.     

Synthesis of ferromagnetic semiconductor 0.67FeTiO3-0.33Fe2O3 powder by chemical co-precipitation

0.67FeTiO₃-0.33Fe₂O₃ (IH33) solid solution powder was successfully synthesized by a chemical co-precipitation method using a mixture of ferrous and ferric salts as start material. Single phase of IH33 was obtained when the preparation was performed in argon atmosphere in order to protect Fe²⁺ ions from oxidization. Investigation of X-ray photoelectron spectroscopy confirmed the presence of Fe²⁺ ions in the IH33 powder. Magnetic measurement showed that the IH33 powder exhibited room-temperature ferromagnetism with a coercivity of 160 Oe.     

Heat capacity of EuMnO3 and Eu0.7A0.3MnO3 (A=Ca,Sr) compounds

We carried out the heat capacity calculation of the magnetoresistance compounds EuMnO₃ and Eu_0.7A_0.3MnO₃ (where A=Ca and Sr) as a function of temperature from 5 to 100 K, using the Rigid Ion Model (RIM). The results on heat capacity for EuMnO₃ and Eu_0.7A_0.3MnO₃ (A=Ca and Sr) obtained by us are in good agreement with the measured values. Although strong electron–phonon interactions are present in these compounds but the lattice part of the specific heat also deserves proper attention. The parent compound EuMnO₃ exhibits two magnetic transitions at 35 and 47 K due to weak ferromagnetic (FM) component and antiferromagnetic (AF) ordering. In addition, we have reported cohesive energy (φ), molecular force constant (f), compressibility (β), Restrahalen frequency (υ₀), Debye temperature (θ_D) and Gruneisen parameter (γ) in the temperature range 5 K?T?100 K.     

Synthesis and properties of magnetic and luminescent Fe3O4/SiO2/Dye/SiO2 nanoparticles

A simple and reproducible method was developed to synthesize a novel class of Fe₃O₄/SiO₂/dye/SiO₂ composite nanoparticles. As promising candidates for use in bioassays, the obtained nanoparticles have an average diameter of 30 nm, and the thickness of the outer shell of silica could be tuned by changing the concentration of the silicon precursor tetraethyl orthosilicate during the synthesis. These multifunctional nanoparticles were found to be highly luminescent, photostable and superparamagnetic. The luminescence intensity of the nanoparticles was increased as the dye concentration was increased in the preparation process. The color of the luminescence was successfully tuned by incorporating different dyes into the nanoparticles. The measurements of the emission spectra indicated that relative to the dye molecules dissolved in ethanol, the emission of the dye-doped nanoparticles exhibited either a red shift or a blue shift, to which a tentative explanation was given.     

Combustion synthesis and luminescent properties of a new material Li2(Ba0.99,Eu0.01)SiO4:B for ultraviolet light emitting diodes

Using urea as fuel and boric as flux, a novel bluish green emitting phosphor Li₂(Ba_0.99,Eu_0.01)SiO₄:B³⁺ has been successfully synthesized using a combustion method. The material has potential application as the fluorescent material for ultraviolet light-emitting diodes (UV-LEDs). The dependence of the properties of Li₂(Ba_0.99,Eu_0.01)SiO₄:B³⁺ phosphors upon urea concentration, boric acid doping and initiating combustion temperature were investigated. The crystallization and particle sizes of Li₂(Ba_0.99,Eu_0.01)SiO₄:B³⁺ have been investigated by using powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Luminescence measurements showed that the phosphors can be efficiently excited by ultraviolet (UV) to visible region, emitting a bluish green light with peak wavelength of 490 nm. The results showed that the boric acid was effective in improving the luminescence intensity of Li₂(Ba_0.99,Eu_0.01)SiO₄ and the optimum molar ratio of boric acid to barium nitrate was about 0.06. The optimized phosphors Li₂(Ba_0.99,Eu_0.01)SiO₄:B_0.06³⁺ showed 160% improved emission intensity compared with that of the Li₂(Ba_0.99,Eu_0.01)SiO₄ phosphors under UV (λ_ex=350 nm) excitation.     

Optical properties of (ZnO)0.5(P2O5)0.5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Binary (ZnO)_0.5(P₂O₅)_0.5 glasses doped with Eu₂O₃ and nanoparticles of Gd₂O₃:Eu were prepared by conventional melt-quench method and their luminescence properties were compared. Undoped (ZnO)_0.5(P₂O₅)_0.5 glass is characterized by a luminescent defect centre (similar to L-centre present in Na₂O-SiO₂ glasses) with emission around 324 nm and having an excited state lifetime of 18 ns. Such defect centres can transfer the energy to Eu³⁺ ions leading to improved Eu³⁺ luminescence from such glasses. Based on the decay curves corresponding to the ⁵D₀ level of Eu³⁺ ions in both Gd₂O₃:Eu nanoparticles incorporated as well as Eu₂O₃ incorporated glasses, a significant clustering of Eu³⁺ ions taking place with the latter sample is confirmed. From the lifetime studies of the excited state of L-centre emission from (ZnO)_0.5(P₂O₅)_0.5 glass doped with Gd₂O₃:Eu nanoparticles, it is established that there exists weak energy transfer from L-centres to Eu³⁺ ions. Poor energy transfer from the defect centres to Eu³⁺ ions in Gd₂O₃:Eu nanoparticles doped (ZnO)_0.5(P₂O₅)_0.5 glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between luminescent centre and Eu³⁺ ions.     

In situ pressure-induced solid-state amorphization in Sm2(MoO4)3, Eu2(MoO4)3 and Gd2(MoO4)3 crystals: chemical decomposition scenario

The effect of pressure on the phase transformations in Sm₂(MoO₄)₃, Gd₂(MoO₄)₃ and Eu₂(MoO₄)₃ crystals has been studied in situ using synchrotron radiation. All three isostructural compounds undergo a structural phase transition at 2.2-2.8 GPa to a new phase, which is interpreted as a possible precursor of amorphization. Amorphization in these crystals occurs irreversibly over a wide pressure range, and its mechanism, interpreted as a chemical decomposition, is found to be weakly affected by the degree of hydrostaticity.     

Study on preparation and fluorescence characteristic of coordinated Eu2O3/polymer hybrid films

The cyclohexane solution of TTA (trifluorothenoyl-acetone), phen (8-hydroxylquinoline) and PS (polystyrene), the ethyl acetate solution of TTA, phen and PMMA (polymethyl methacrylate) were used as flowing liquid, the coordinated Eu₂O₃/polymer hybrid colloids were successively produced by focused pulsed laser ablation of Eu₂O₃ target in interface of solid and flowing liquid. As solvent in the hybrid colloids has volatilized, the coordinated Eu₂O₃/polymer hybrid films were obtained. The hybrid colloids and films were characterized by TEM, UV-vis spectrum, fluorescence spectrum, TG-FTIR and X-ray photoelectron spectrum. The results show the coordinated Eu₂O₃ nanoparticles with average size of less than 20 nm are surrounded by the three-dimensional network and are properly incorporated into the PMMA and PS matrix, the hybrid films can emit intense red light under ultraviolet radiation, and their emission fluorescence spectra display same characteristic emission peaks of Eu³⁺ ions. The Eu₂O₃ hybrid films have better thermo stability than the related pure polymers because of strong interaction between surface europium ions of the nanoparticles and polymer. Because the coordinated Eu₂O₃ nanoparticles were wrapped by polymer, they have higher chemical stability than the related europium complex.     

Eu2O3在η-Al2O3和SiO2上固体-固体表面相互作用的研究

用穆斯堡尔谱和X射线衍射技术研究了Eu₂O₃在η-Al₂O₃和硅胶上的固体表面吸附。 关键词：     

Optical and fluorescence spectroscopy of Eu2O3-doped P2O5-K2O-KF-MO-Al2O3 (M = Mg, Sr and Ba) glasses

Fluorophosphate glasses of composition, P₂O₅ + K₂O + KF + MO + Al₂O₃ + xEu₂O₃ (M = Mg, Sr and Ba; x = 0.01, 0.05, 0.1, 1.0, 2.0, 4.0 and 6.0 mol%) were prepared and characterized their optical properties. Crystal-field (CF) analysis revealed a relatively weak CF strength around Eu³⁺ ions in the Ba based fluorophosphate glasses. The Judd-Ofelt parameters have been estimated from the oscillator strengths of ⁷F₀ → ⁵D₂, ⁷F₀ → ⁵D₄ and ⁷F₀ → ⁵L₆ absorption transitions of Eu³⁺ ions and were used to evaluate the radiative properties of the ⁵D₀ → ⁷F_J (J = 0-4) transitions. Considerable variation has been observed in the relative intensity ratio of ⁵D₀ → ⁷F₂ to ⁵D₀ → ⁷F₁ transitions of Eu³⁺ ions due to change in the alkaline earth metal ions. The decay of the ⁵D₀ level shows single exponential and less sensitive to Eu³⁺ ions concentration as well as MgO/SrO/BaO modifiers.     

Effect of rare earth (Pr2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3 and Er2O3 ) on the acoustic properties of glass belonging to bismuth-borate system

Bismuth-borate glasses doped with some rare earth ions were studied with respect to the density, molar volume and the elastic moduli, Poisson’s ratio, Debye temperature, microhardness, softening temperature, acoustic impedance, diffusion constant and latent heat of melting. Ultrasonic velocities were measured by the pulse echo overlap technique at a frequency of 10 MHz and at room temperature. From these velocities and density values, various elastic moduli were calculated. The correlation of elastic stiffness, the cross link density, and the fractal bond connectivity of these glasses are discussed. The derived experimental values of shear modulus, bulk modulus, Young’s modulus, and Poisson’s ratio for our glasses are compared with the theoretically calculated values in terms of the bond compression model and Makishima-Mackenize theory.     

Synthesis and characterization of spherical core-shell particles SiO2@AgEu(MoO4)2

Submicron spherical SiO₂ particles have been coated with AgEu(MoO₄)₂ phosphor layers by a sol-gel process, followed by surface reaction at high temperature, to get core/shell structured SiO₂@AgEu(MoO₄)₂ particles. X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the resulted core-shell phosphors. The luminescent properties of the core-shell structured phosphors have also been measured at room temperature, and their photoluminescence (PL) spectra are similar to the pure AgEu(MoO₄)₂ phosphor prepared by the same sol-gel method exhibiting red emission.     

Synthesis of Y2O3:(Li,Eu) films using phosphor powders coated with SiO2 nano particles

Y_1.9−xLi_0.1Eu_xO₃ (x=0.02, 0.05, 0.08, and 0.12) films were fabricated by spin-coating method. A colloidal silica suspension with Y_1.9−xLi_0.1Eu_xO₃ phosphor powder was exploited to obtain the highly stable and effective luminescent films onto the glass substrate. After heating as-prepared Y_1.9−xLi_0.1Eu_xO₃ films at 700 °C for 1 h, the phosphor films exhibit a high luminescent brightness as well as a strong adhesiveness on the glass substrate. The emission spectra of spin-coated and pulse-laser deposited Y_1.82Li_0.1Eu_0.08O₃ films were compared. The cathodoluminescence of the phosphor films was carried out at the anode voltage 1 kV.     

Synthesis and characterization of Ce doped silica (SiO2) nanoparticles

A series of silica doped with different mol percentages of Ce³⁺ concentration was synthesized using a sol-gel method to determine the dependence of photoluminescence wavelengths and intensity on the concentrations of the dopants. Sol-gel glasses are porous networks that have been densified through chemical processing and heat treatment. Rare-earths (REs) are insoluble in silica; due to this insolubility RE ions in silicate glasses enter as network modifiers and compete for non-bridging oxygen in order to complete their coordination. The morphological, structural, thermal and optical properties of the phosphors were characterized by X-ray diffraction, scanning electron microscopy, UV-vis absorption, photoluminescence, thermogravimetric analyses and differential scanning calorimeter. Silica (SiO₂) gel containing Ce³⁺ ions was sputter coated with Au (gold) in order to monitor surface morphology of the samples. The highest emission intensity was found for the sample with a composition of 0.5 mol% Ce³⁺. Cerium doped silica glasses had broad blue emission corresponding to the ²D_3/2-²F_J transition at 448 nm but exhibited apparent concentration quenching above concentrations of 0.5 mol% Ce³⁺.     

Photoluminescence in the mixed valence compound Eu3S4

We have investigated the 5d-4f interband and the intra-4f photoluminescence of Eu₃S₄. An anomalous shift of the interband luminescence can be explained by temperature dependent valence fluctuations. The ferromagnetic ordering of Eu₃S₄ is also verified.     

Synthesis and properties of a new copper(II)-hafnium phosphate Cu0.5Hf2(PO4)3

Phosphates of general formula M_0.5Hf₂(PO₄)₃ with M=Cd²⁺, Ca²⁺, Sr²⁺ and Cu²⁺ were prepared by coprecipitation and characterized by several physical techniques. The compounds containing Cd²⁺, Ca²⁺, Sr²⁺ belong to the Nasicon-type structure, whereas Cu_0.5Hf₂(PO₄)₃ exhibited substantially different DRX patterns. Combined temperature programmed reduction (TPR) and temperature-programmed oxidation (TPO) showed that the copper in Cu_0.5Hf₂(PO₄)₃ was distributed between two energetically different sites in proportions respectively equal to 40 and 60%. Electron Paramagnetic Resonance (EPR) investigations confirmed the TPR/TPO results and revealed that the two sites hosting the Cu²⁺ ions are of orthorhombic symmetry. Moreover, the Cu²⁺ ions might be reduced by hydrogen to Cu⁺. These results were also supported by the UV–visible studies that showed the disappearance, under reducing conditions, of the band corresponding to crystal field transitions of Cu²⁺ ions and the emergence of a new peak attributed to the transitions between (3d)¹⁰ and (3d)⁹(4s)¹ Cu⁺ levels. At the same time, IR spectroscopy confirmed that protons entered the open lattice framework of the material and gave rise to a new protonated phase containing monovalent copper Cu_0.5^IH_0.5Hf₂(PO₄)₃. This redox process was proven to be reversible without any subsequent change in the network of the phosphate.     

Luminescence studies on ZnO-P2O5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Zinc phosphate glasses doped with Gd₂O₃:Eu nanoparticles and Eu₂O₃ were prepared by conventional melt-quench method and characterized for their luminescence properties. Binary ZnO-P₂O₅ glass is characterized by an intrinsic defect centre emission around 324 nm. Strong energy transfer from these defect centres to Eu³⁺ ions has been observed when Eu₂O₃ is incorporated in ZnO-P₂O₅ glasses. Lack of energy transfer from these defect centres to Eu³⁺ in Gd₂O₃:Eu nanoparticles doped ZnO-P₂O₅ glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between the luminescent centre and Eu³⁺ ions. Both doped and undoped glasses have the same glass transition temperature, suggesting that the phosphate network is not significantly affected by the Gd₂O₃:Eu nanoparticles or Eu₂O₃ incorporation.     

Factors affecting coercivity in (Y,Sm,Tm)3(FeGa)5O12 and (Y,Sm,Lu,Ca)3(FeGe)5O12 LPE films

Factors which influence coercivity, H_c, in (Y,Sm,Lu,Ca)₃(FeGe)₅O₁₂ films and in (Y,Sm,Tm)₃(FeGa)₅O₁₂ films grown by LPE have been identified. An anomalous layer at the film-substrate interface exhibits coercivity values different from that of the middle, bulk, portion of the film. The contribution of the transient layer at the substrate interface could be reduced by increasing the rotation rate while immersing the substrate into the melt. Films containing Ga show lower coercivities than films containing CaGe possibly because films with Ga are more uniform in composition. Films with Ga show increased coercivities with increasing growth rates and with increasing Sm content throughout the film.     

Glassy-ferromagnetic behavior in Eu0.5Sr0.5CoO3

Polycrystalline perovskite cobalt oxide Eu_0.5Sr_0.5CoO₃ was prepared by the conventional solid-state reaction method. X-ray powder patterns indicated the prepared samples are pure, cubic perovskite structure (Pm3?m), and with no evidence of any secondary phases. The dc magnetization and ac susceptibility measurements were carried out to investigate the magnetic properties of the sample, and which indicated that cluster-glasses properties are suppressed with the increasing of the coercive field. We denied the possibility of spin-glasses and the existence of the Hopkinson effect in Eu_0.5Sr_0.5CoO₃ through the temperature-dependent ac susceptibility measurements, and explained the magnetic behavior of Eu_0.5Sr_0.5CoO₃ with the competition between magnetic anisotropy and the external magnetic field.