Comparative analysis of crystal field effects and energy level scheme of six-fold coordinated Cr ion in the pyrochlores, Y2B2O7 (B=Ti, Sn)

The electronic energy levels of the six-fold coordinated Cr⁴⁺ ion in the pyrochlores Y₂B₂O₇ (B=Sn⁴⁺, Ti⁴⁺), have been computed using the exchange charge model of crystal field theory. The calculated Cr⁴⁺ energy levels and their trigonal splitting are in good agreement with experimental spectra. Calculations of the crystal field parameters show that the higher crystal field strength in Y₂Sn₂O₇ (in comparison with Y₂Ti₂O₇) arises from increased orbital overlap effects between the Cr⁴⁺ ion and the nearest oxygen ions, which are located at the 48f crystallographic position of the pyrochlore lattice. The increased overlap in Y₂Sn₂O₇ occurs despite the fact that the Cr⁴⁺-O^2- bond distance in Y₂Sn₂O₇ is longer than in Y₂Ti₂O₇. This is attributed to a lack of hybridization (covalent bonding) between the filled 2p orbital of oxygen ion occupying the 48f site of the pyrochlore lattice and the filled Sn⁴⁺ 4d¹⁰ orbital. As a result, a stronger crystal field is experienced by Cr⁴⁺ ions in Y₂Sn₂O₇, even if the Cr⁴⁺-O²⁻ distances are greater in this case, when compared to those in Y₂Ti₂O₇.     

Theoretical calculations of the optical band positions and spin-Hamiltonian parameters for Cr ions in Y2Ti2O7 crystal

The optical band positions and spin-Hamiltonian parameters (g factors g_g_? and zero-field splitting D) for the trigonal Cr³⁺ centers in Y₂Ti₂O₇ crystal are calculated from the complete diagonalization (of energy matrix) method based on the two-spin-orbit-parameter model. In the calculations, the contributions to spectral data from both the spin-orbit parameter of central dⁿ ion and that of ligand ion are considered and the crystal field parameters used are estimated from the superposition model. The calculated results are in reasonable agreement with the experimental values. The defect structures of Cr³⁺ center is suggested.     

Synthesis of Y2Si2O7:Eu nanocrystal and its optical properties

Nanocrystalline Y₂Si₂O₇:Eu phosphor with an average size about 60 nm is easily prepared using silica aerogel as raw material under ultrasonic irradiation and annealing temperature at 300-600 °C and this nanocrystalline decomposes into Y₂O₃:Eu and silica by heat treatment at 700-900 °C. The excitation broad band centered at 283 and 254 nm results from Eu³⁺ substituting for Y³⁺ in Y₂Si₂O₇ and Y₂O₃/SiO₂, respectively. Compared with Y₂O₃:Eu/SiO₂ crystalline, the PL excitation and emission peaks of Y₂Si₂O₇:Eu nanocrystalline red-shift and lead to the enhance of its luminescence intensity due to the different chemical surroundings of Eu³⁺ in above nanocrystallines. The decrease of PL intensity may be ascribed to quenching effect resulting from more defects in Y₂O₃:Eu/SiO₂ crystalline.     

Preparation and luminescent properties of cubic Eu:Y2O3 nanocrystals and comparison to bulk Eu:Y2O3

Y₂O₃:Eu³⁺ nanocrystals were prepared by combustion synthesis. The particle size estimated by X-ray powder diffraction (XRD) was about 10 nm. A blue-shift of the charge-transfer (CT) band in excitation spectra was observed in Y₂O₃:Eu³⁺ nanocrystals compared with bulk Y₂O₃:Eu³⁺. The electronic structure of Y₂O₃ is calculated by density functional method and exchange and correlation have been treated by the generalized gradient approximation (GGA) within the scheme due to Perdew-Burke-Ernzerhof (PBE). The calculated results show that the energy centroid of 5d orbital in nanocrystal has increasing trend compared with that in the bulk material. The bond length and bond covalency are calculated by chemical bond theory. The bond lengths of Y₂O₃:Eu³⁺ nanocrystal are shorter than those of the bulk counterpart and the bond covalency of Y₂O₃:Eu³⁺ nanocrystal also has an increasing trend. By combining centroid shift and crystal-field splitting, the blue-shift of the CT band is interpreted.     

Intense ultraviolet and blue upconversion emissions in Yb-Tm codoped stoichiometric Y7O6F9 powder

Stoichiometric Y₇O₆F₉ powder codoped with Yb³⁺-Tm³⁺ was synthesized via co-precipitation and subsequent calcining route. The results of X-ray diffraction and transmission electron microscopy reveal that when the calcining temperature is beyond 800 °C, orthorhombic YF₃ nanoparticles can be completely oxidized into orthorhombic Y₇O₆F₉ powder. Under the excitation of a 980 nm laser, Y₇O₆F₉ powder exhibits multicolor UC emission in regions spanning the UV to the NIR. In addition, the upconversion emission intensities of YF₃, Y₇O₆F₉ and Y₂O₃ powders were compared under the same dopant condition (Yb/Tm=5/0.5 mol%). The low phonon energy revealed by Raman spectra helped to understand the high efficient upconversion emission of Y₇O₆F₉ and the main phonon vibration of Y₇O₆F₉ lies at 472 cm⁻¹, which is far lower that of Y₂O₃ (at 708 cm⁻¹). Our results indicate that orthorhombic rare earth ions doped Y₇O₆F₉ is an efficient matrix for UV and blue UC emission, and has potential applications in color displays, anti-counterfeiting and multicolor fluorescent labels.     

Effect of Eu,Tb codoping on the luminescent properties of Y2O3 nanorods

Red-emitting Y₂O₃:Eu³⁺ and green-emitting Y₂O₃:Tb³⁺ and Y₂O₃:Eu³⁺, Tb³⁺ nanorods were synthesized by hydrothermal method. Their structure and micromorphology have been analyzed by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). The photoluminescence (PL) property of Y₂O₃:Eu³⁺,Tb³⁺ phosphor was investigated. In the same host (Y₂O₃), upon excitation with ultraviolet (UV) irradiation, it is shown that there are strong emissions at around 610 and 545 nm corresponding to the forced electric dipole ⁵D₀-⁷F₂ transition of Eu³⁺ and ⁵D₄-⁷F₅ transition of Tb³⁺, respectively. Different qualities of Eu³⁺and Tb³⁺ ions are induced into the Y₂O₃ lattice. From the excitation spectrum, we speculate that there exists energy transfer from Tb³⁺ to Eu³⁺ ions .The emission color of powders reveals regular change in the separation of light emission. These powders can meet with the request of optical display material for different colors or can be potentially used as labels for biological molecules.     

Density functional analysis of the magnetic structures of Sr2MGe2O7 (M=Mn,Co)

To examine the difference between the magnetic structures of Sr₂MGe₂O₇ (M=Mn, Co), we evaluated their spin exchange interactions by performing energy-mapping analysis based on density functional theory calculations. The calculated intra- and inter-layer spin exchanges correctly predict the G-type and C-type antiferromagnetic structures of Sr₂MnGe₂O₇ and Sr₂CoGe₂O₇, respectively, and the Curie–Weiss temperatures estimated from these spin exchanges are also in good agreement with the experiment. The ∥c and ⊥c orientations of the spins in the ordered magnetic structures of Sr₂MnGe₂O₇ and Sr₂CoGe₂O₇, respectively, were also examined by considering spin–orbit coupling.     

An interpretation of the optical properties of Cr-activated pyrochlores, Y2Ti2O7 and Y2Sn2O7

A qualitative model is proposed to explain the differences between the optical properties of the six-coordinated Cr⁴⁺ ion in the pyrochlores, Y₂Sn₂O₇ and Y₂Ti₂O₇. It is shown that polarization of the electron density of the oxygen ions occupying the 48f sites of the pyrochlore lattice is responsible for the observed differences in the optical properties.     

Structural and optical properties of Er, Yb co-doped Y2O3 thin films

Thin Er³⁺, Yb³⁺ co-doped Y₂O₃ films were grown on (1 0 0) YAG substrates by pulsed laser deposition. Ceramic targets having different active ion concentration were used for ablation. The influence of the rare-earth content and oxygen pressure applied during the deposition on the structural, morphological and optical properties of the films were investigated. The films deposited at the lower pressure, 1 Pa, and at 1/10 Er to Yb doping ratio are highly textured along the (1 1 1) direction of the Y₂O₃ cubic phase. In addition to the crystalline structure, these films possess smoother surface compared to those prepared at the higher pressure, 10 Pa. All other films are polycrystalline, consisting of cubic and monoclinic phases of Y₂O₃. The rougher surface of the films produced at the higher-pressure leads to higher scattering losses and different behavior of the reflectivity spectra. Optical anisotropy in the films of less than 0.004 was measured regardless of the monoclinic structure obtained. Waveguide losses of about 1 dB/cm at 633 nm were obtained for the films produced at the lower oxygen pressure.     

Upconversion emission enhancement of TiO2 coated lanthanide-doped Y2O3 nanoparticles

To investigate the upconversion emission,this paper synthesizes Tm3+ and Yb3+ codoped Y2O3 nanoparticles,and then coats them with TiO2 shells for different coating times.The spectral results of TiO2 coated nanoparticles indicate that upconversion emission intensities have respectively been enhanced 3.2,5.4,and 2.2 times for coating times of 30,60 and 90 min at an excitation power density of 3.21×102 W.cm 2,in comparison with the emission intensity of non-coated nanoparticles.Therefore it can be concluded that the intense upconversion emission of Y2O3:Tm3+,Yb3+ nanoparticles can be achieved by coating the particle surfaces with a shell of specific thickness.     

Silica-coated Y2O3:Eu nanoparticles and their luminescence properties

Crystalline Y₂O₃:Eu is of paramount significance in rare earth materials and research on luminescence spectra. In this work, the nanocrystalline Y₂O₃:Eu was coated with silica by a facile solid state reaction method at room temperature. The transmission electron microscope (TEM) photographs showed that the prepared Y₂O₃:Eu particle is polycrystalline with the size of 20 nm, the size of silica-coated particle is about 25 nm. The XPS spectra indicated that the silica layer is likely to interact with Y₂O₃:Eu by a Si-O-Y chemical bond. The luminescence spectra showed that the intensity of ground samples is lower than that of unground ones, the intensity of silica-coated phosphors is higher than that of the ground samples, while almost the same as that of the unground ones. Therefore, the silica coating decreases the surface defects of nanoparticles of the nanocrystalline Y₂O₃:Eu, thus increasing their luminescent intensity.     

Characterization of Y2O3 gate dielectric on n-GaAs substrates

Physical and electrical properties of sputtered deposited Y₂O₃ films on NH₄OH treated n-GaAs substrate are investigated. The as-deposited films and interfacial layer formation have been analyzed by using X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). It is found that directly deposited Y₂O₃ on n-GaAs exhibits excellent electrical properties with low frequency dispersion (<5%), hysteresis voltage (0.24 V), and interface trap density (3 × 10¹² eV⁻¹ cm⁻²). The results show that the deposition of Y₂O₃ on n-GaAs can be an effective way to improve the interface quality by the suppression on native oxides formation, especially arsenic oxide which causes Fermi level pinning at high-k/GaAs interface. The Al/Y₂O₃/n-GaAs stack with an equivalent oxide thickness (EOT) of 2.1 nm shows a leakage current density of 3.6 × 10⁻⁶ A cm⁻² at a V_FB of 1 V. While the low-field leakage current conduction mechanism has been found to be dominated by the Schottky emission, Poole-Frenkel emission takes over at high electric fields. The energy band alignment of Y₂O₃ films on n-GaAs substrate is extracted from detailed XPS measurements. The valence and conduction band offsets at Y₂O₃/n-GaAs interfaces are found to be 2.14 and 2.21 eV, respectively.     

Synthesis and luminescent properties of Y6W2O15:Eu phosphors

In this paper, a novel phosphor, Y₆W₂O₁₅:Eu³⁺ was synthesized by thermal decomposition and phase transition of its decatungstate gel precursor. With stepwise increase of temperature to 750 °C, a crystalline phase of Y₆W₂O₁₅:Eu³⁺forms that gives intense red emission when excited at 466 nm, the emission is attributed to the Eu³⁺ ions transitions from ⁵D₀ excited states to ⁷F_J (J=0-4) ground states. The long excitation wavelength proves the Eu³⁺ transition follows the photoexcitation of the oxygen-metal (O→W lmct) charge transfer bands in yttrium tungstate. Some structural information regarding Y₆W₂O₁₅ provided by luminescence is in accord with that characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The long-wavelength excitation properties of this material may find application in the production of red phosphors for white light-emitting diodes (LEDs).     

Unified calculations of the optical and electron paramagnetic resonance spectral data for Ce ion in Y3Ga5O12 crystal

Seven crystal field energy levels (obtained from the optical spectra) and three g factors g_x, g_y and g_z (obtained from electron paramagnetic resonance (EPR) spectra) for Ce³⁺ ion in Y₃Ga₅O₁₂ crystal are calculated together by diagonalizing a complete energy matrix. The Hamiltonian of this energy matrix includes all the interactions for 4f¹ ion Ce³⁺ in rhombic crystal field and under an external magnetic field, and so the optical and EPR data can be studied in a unified way. The calculated crystal field energy levels are in better agreement with the experimental values than the calculated values in the previous paper, and the g factors (which have not been calculated previously) are explained reasonably. The results are discussed.     

Abnormally enhanced Eu emission in Y2O2SO4:Eu inherited from their precursory dodecylsulfate-templated concentric-layered nanostructure

A new nanostructure-mediated approach was demonstrated to synthesize Eu³⁺-doped yttrium oxysulfates Y₂O₂SO₄:Eu³⁺ giving rise to abnormally enhanced Eu³⁺ emission. Yttrium and europium salts, sodium dodecylsulfate (SDS), and urea at various Eu³⁺ concentrations were reacted in aqueous solution at 80, 85, and 87 °C to yield Eu³⁺-doped dodecylsulfate-templated yttrium oxide mesophases with straight-layered (S-type), concentric-layered (C-type) and layer-to-hexagonal transient-layered (T-type) structures, respectively. On calcination at 1000 °C, all of these mesophases were converted into Y₂O₂SO₄:Eu³⁺ to exhibit luminescence bands including the ⁵D₀-⁷F₂ transition with a tendency in intensity to saturate or reach a maximum at 10-12 mol% Eu doping. The Eu³⁺ emissions for Y₂O₂SO₄:Eu³⁺ mediated by the T- and C-type mesophases were enhanced in intensity by a factor of about two and three times, respectively, stronger than those for not only compositionally the same sulfate Y₂O₂SO₄:Eu³⁺ obtained from yttrium-based sulfates but also Y₂O₃:Eu³⁺ obtained in the SDS-free system. In contrast, the emission intensities for the S-type-mesophase-mediated Y₂O₂SO₄:Eu³⁺ were close to those for the latter sulfates. The abnormally enhanced emission is likely based on specific deformation of sulfate groups induced through the conversion of concentric dodecylsulfate-layers to straight sulfate-layers in the oxysulfate framework upon calcination.     

Effects of Tb doping on the photoluminescence of Y2O3:Tb nanophosphors

The effects of Tb doping on the photoluminescence (PL) of Y₂O₃:Tb nanophosphors have been investigated. Nanophosphors were prepared by the glycine-nitrate solution combustion technique using yttria and terbia powders as precursors. PL excitation spectra at room temperature consist of two overlapping bands centered at 277 and 304 nm, whereas emission spectra comprise several groups of lines corresponding to the ⁵D₄→⁷F_J (J=1-6) 4f electronic transitions of the Tb⁺³ ions. A direct comparison of nanophosphor and bulk concentration-quenching curves was obtained by annealing the nanophosphor powder and converting it to bulk material without altering the Tb concentration. The peak in the nanophosphor concentration-quenching curve occurs at a concentration ∼3 times higher than that of the bulk.     

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.     

Influence of postdeposition annealing on structural properties and electrical characteristics of thin Tm2O3 and Tm2Ti2O7 dielectrics

We describe the structural properties and electrical characteristics of thin thulium oxide (Tm₂O₃) and thulium titanium oxide (Tm₂Ti₂O₇) as gate dielectrics deposited on silicon substrates through reactive sputtering. The structural and morphological features of these films were explored by X-ray diffraction, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and atomic force microscopy, measurements. It is found that the Tm₂Ti₂O₇ film annealed at 800 °C exhibited a thinner capacitance equivalent thickness of 19.8 Å, a lower interface trap density of 8.37 × 10¹¹ eV⁻¹ cm⁻², and a smaller hysteresis voltage of ∼4 mV than the other conditions. We attribute this behavior to the Ti incorporated into the Tm₂O₃ film improving the interfacial layer and the surface roughness. This film also shows negligible degrees of charge trapping at high electric field stress.     

Synthesis of Gd2Ti2O7:Eu, V phosphors by sol-gel process and its luminescent properties

A red-emitting phosphor material, Gd₂Ti₂O₇:Eu³⁺, V⁴⁺, by added vanadium ions is synthesized using the sol-gel method. Phosphor characterization by high-resolution transmission electron microscopy shows that the phosphor possesses a good crystalline structure, while scanning electron microscopy reveals a uniform phosphor particle size in the range of 230-270 nm. X-ray photon electron spectrum analysis demonstrates that the V⁴⁺ ion promotes an electron dipole transition of Gd₂Ti₂O₇:Eu³⁺ phosphors, causing a new red-emitting phenomenon, and CIE value shifts to x=0.63, y=0.34 (a purer red region) from x=0.57, y=0.33 (CIE of Gd₂Ti₂O₇:Eu³⁺). The optimal composition of the novel red-emitting phosphor is about 26% of V⁴⁺ ions while the material is calcinated at 800  °C. The results of electroluminescent property of the material by field emission experiment by CNT-contained cathode agreed well with that of photoluminescent analysis.     

Quantum-chemical ab initio study of the crystal-field and charge transfer energies of nanocrystalline Y2O3: Eu

The 4f energy levels and crystal-field parameters for several clusters representing the local coordination surroundings of Eu³⁺ in the bulk and nanocrystalline cubic Y₂O₃: Eu³⁺ crystals are obtained by using a method based on the combination of the DV-X_α calculation and the effective Hamiltonian method initialized by M.F. Reid et al. (J. Phys.: Condens. Matter, 2011, 23: 045501). The results are in reasonable agreement with the measured energy levels and the crystal-field parameters obtained from the least-square fitting. The charge transfer energies are also obtained for all the clusters from the DV-X_α calculation. The results indicate that, compared with the bulk Y₂O₃: Eu³⁺ crystal, the charge transfer band in the excitation spectra is red-shifted in the nanocrystal.