Accurate prediction of refractive index of inorganic oxides by chemical formula

A method is proposed for estimation of mean refractive index of a complex inorganic oxide whose chemical composition is known. This method is based on using mean refractive indices of simple oxides. Applicability of the method has been tested for a representative set of ∼120 known oxide crystals. It has been shown that mean refractive index can be predicted with possible error of 0-15% depending on the chemical nature of the compound. The majority of oxides show acceptable difference <5% between theoretical and experimental refractive index values and the mean error level for a set of 124 oxide crystals is as low as ∼5%. Refractive indices of a set of simple oxides are estimated by the Lorenz-Lorentz relation. Full table of refractive indices of simple oxides for all elements of Periodic Table is proposed.     

Half-metallic ferromagnetism in I2-VI compounds with non-magnetic dopants

First-principles calculations based on the tight-binding linear muffin-tin orbital (TB-LMTO) method were performed to investigate the occurrence of spin polarization in the alkali metal oxides (M₂O) [M: Li, Na, K, Rb] in antifluorite (anti- CaF₂-type) structure with non-magnetic (N, P, As, Sb and Bi) dopants. The calculations reveal that non-magnetic substitutional doping at anion site can induce stable half-metallic ferromagnetic ground state in I₂-VI compounds. Total energy calculations show that the antifluorite ferromagnetic state is energetically more stable than the antifluorite non-magnetic state at equilibrium volume. Ground state properties such as equilibrium lattice constant and bulk modulus were calculated. The calculated magnetic moment is found to be 1.00 μ_B per dopant atom. The magnetic moment is mainly contributed by p orbitals of dopant atom.     

Synthesis,photophysical properties,and photocatalytic applications of Bi doped NaTaO3 and Bi doped Na2Ta2O6 nanoparticles

Phase formation and photophysical properties of bismuth doped sodium tantalum oxide (perovskite, defect pyrochlore) nanoparticles prepared by a hydrothermal method were studied in detail. It was revealed that the synthesis conditions like NaOH concentration and bismuth precursor (NaBiO₃·2H₂O) markedly affect the crystal structure of sodium tantalum oxide. At low NaOH concentration and high bismuth precursor (NaBiO₃·2H₂O) content, Bi doped Na₂Ta₂O₆ (defect pyrochlore) phase was predominantly formed, while at higher NaOH concentration, Bi doped NaTaO₃ (perovskite) phase was formed. It was observed that the defect pyrochlore (Bi doped Na₂Ta₂O₆) phase was formed and stabilized by the presence of dopant precursor (NaBiO₃·2H₂O). The chemical analysis of the samples confirmed the doping of Bi³⁺ cations in both phases. Doping of bismuth enabled visible light absorption up to 500 nm in perovskite and defect pyrochlore type sodium tantalum oxide. Bi doped NaTaO₃ samples showed better performance for the photocatalytic degradation of rhodamine B than that of Bi doped Na₂Ta₂O₆, under visible light irritation (λ>420 nm). The present results shed light on phase formation of sodium tantalate and these results are useful in understanding properties of NaTaO₃ based compounds, synthesized by the hydrothermal method.     

Ferromagnetic behavior of high-purity ZnO nanoparticles

ZnO nanoparticles with the wurtzite structure were prepared by chemical methods at low temperature in aqueous solution. The size of the nanoparticles is in the range from about 10 to 30 nm. Ferromagnetic properties were observed from 2 K to room temperature and above. Magnetization versus temperature, M(T), and isothermal M(H) measurements were obtained. The coercive field clearly shows ferromagnetism above room temperature. An exchange bias was observed, and we related this behavior to the core-shell structure present in the samples. The chemical synthesis, structure, and defects in the bulk related to oxygen vacancies are the main factors for the observed magnetic behavior.     

Thermochromism in (Ba,Sr)-Mn oxides

Manganese based ceramic samples with composition given by the formula MeMnO₃ (Me=Ba, Sr) were prepared by solid state reaction. The preparation conditions were varied over a wide range of temperatures and the optimum sintering temperature was obtained. These materials present a change of color at low temperature (at approximately 140 K). To find the probable reason for the change of color, the materials have been characterized by various advanced techniques like X-ray diffraction (XRD), photoluminiscence, scanning and transmission electron microscopy (SEM and TEM). Studies were made at room and at low temperature. These thermochromic materials have hexagonal perovskite-like structure.     

An origin of light induced centers in the visible range in ferroelectric oxides: possible role of the states of charge transfer vibronic excitons

A light induced absorption peculiarity connected with an absorption peak in the visible range for SBN/Ce was detected. The analysis of these data together with investigation results for a visible range center (VIS-center) absorption study in SBN/Ce and Cr, in nominally pure strontium barium niobate (SBN) as well as in Ba_0.77Ca_0.23TiO₃ crystals give support to charge transfer vibronic excitons (CTVEs) as origin of the phenomenon. While the fast (with relaxation time ∼1 ns at T∼300 K) response can be connected with transitions between excited branches of the adiabatic potential of the CTVE phase, the slow (with relaxation time ∼50 s at T∼230 K for SBN/Cr) response is connected with transitions between ground and first excited CTVE phase branches. The additional contribution to the latter effect due to the absorption of recharged oxygen ions which are in the framework of charge transfer induced by the CTVE cannot be disregarded. The explanation of the main results of the experiments shows that the VIS-center phenomena can be induced by the CTVE-states.     

Extracting d-orbital occupancy from magnetic Compton scattering in bilayer manganites

We consider the shape of the magnetic Compton profile (MCP), J_mag(p_z), in La_1.2Sr_1.8Mn₂O₇ for momentum transfer p_z along the [110] direction and the associated reciprocal form factor B(r) defined by taking the one-dimensional Fourier transform of J_mag(p_z). B(r) is shown to contain a prominent dip at r≈1 Å, where the minimum value B_min of B(r) can be related to the occupancies of the e_g orbitals of dx²−y² and d3z²−r² symmetry in the system. We illustrate our procedure in detail by analyzing the measured MCP at 5 K and the MCP computed within the framework of the local spin density approximation (LSDA) and comment on the differences between the measured and computed e_g occupancies as a reflection of the limitations of the LSDA in treating electron correlation effects.     

A threshold of Vo/Vo to room temperature ferromagnetism of hydrogenated Mn doped ZnO nanoparticles

Hydrogenated Mn doped Zn_1−xMn_xO (x = 0.03, 0.04, 0.08) nanoparticles were prepared by co-precipitation method. With the increase of Mn ions concentration, the magnetization of the hydrogenated Zn_1−xMn_xO increased. Photoluminescence spectra of samples annealed in Ar and H₂ respectively were performed and the visible bands were fitted with Gaussian analysis. It is concluded that the sharp magnetization enhancement could be attributed to the long-rang interaction between bound-magnetic-polarons led by the singly charged oxygen vacancy (Vo⁺).     

Energy expression of the chemical bond between atoms in metal oxides

The chemical bond between atoms in metal oxides is expressed in an energy scale. Total energy is partitioned into the atomic energy densities of constituent elements in the metal oxide, using energy density analysis. The atomization energies, ΔE_M for metal atom and ΔE_O for O atom, are then evaluated by subtracting the atomic energy densities from the energy of the isolated neutral atom, M and O, respectively. In this study, a ΔE_O vs. ΔE_M diagram called atomization energy diagram is first proposed and used for the understanding of the nature of chemical bond in various metal oxides. Both ΔE_M and ΔE_O values reflect the average structure as well as the local structure. For example their values vary depending on the vertex, edge or face sharing of MO₆ octahedron, and also change with the overall density of binary metal oxides. For perovskite-type oxides it is shown that the ΔE_O value tends to increase by the phase transition from cubic to tetragonal phase, regardless of the tilting-type or the 〈1 0 0〉 displacement-type transition. The bond formation in spinel-type oxides is also understood with the aid of the atomization energies. The present approach based on the atomization energy concept will provide us a new clue to the design of metal oxides.     

Study of phase transition in ZrO2 doped with Pb3O4

Electrical conductivity of ZrO₂ doped with Pb₃O₄ has been measured at different temperatures for different molar ratios (x=0, 0.01, 0.02, 0.03, 0.04, 0.05 and 0.06). The conductivity increases due to migration of vacancies, created by doping. The conductivity increases with increase in temperature till 180 °C and thereby decreases due to collapse of the fluorite framework. A second rise in conductivity at higher temperatures beyond 500-618 °C is due to phase transition of ZrO₂. DTA and X-ray powder diffraction were carried out for confirming doping effect and transition in ZrO₂.The addition of Pb₃O₄ to ZrO₂ shifted the phase transition of ZrO₂ due to the interaction between Pb₃O₄ and ZrO₂.     

Influence of elastic properties on superplasticity in doped yttria-stabilized zirconia

We report the first principles calculations of elastic and electronic properties of yttria-stabilized tetragonal zirconium dioxide (YZP) doped with GeO₂, TiO₂ and SiO₂. Electronic structure and isotropic elastic properties of YZP do not change upon addition of dopants. Addition of dopants affects the shear C₆₆ elastic constant that decreases with the increasing dopant concentration. A simple model that connects elastic softening to enhancement of superplasticity in doped fine-grained zirconia ceramics is proposed.     

Effect of temperature on excited state life-times of rare earth doped zinc oxide phosphors

Doped zinc oxide phosphors were synthesized and excited by high-peak power pulsed UV laser at room temperature as well as at liquid nitrogen temperature. There is considerable decrease in the values of life-time at low temperature (77 K), whereas mixed trend is observed in life-time values with change in concentration of didymium, which indicates the perturbation effect in host material. The increased fluorescence quantum yield, emission efficiency and down-conversion phenomena of these selective radiative transitions, in doped phosphors, make them a very promising material for laser medium, vacuum fluorescent displays, fluorescent lamps, information storage and optoelectronic industry.     

Electron paramagnetic resonance, optical and electrical properties of vanadyl doped alkali germanoborate glasses

Glasses with composition xGeO₂.(0.30−x)M₂O.0.70B₂O₃ (M=Li, K) containing 2.0 mol% of V₂O₅ have been prepared in the range 0.00≤x≤0.15 by normal melt quenching method. Electron paramagnetic resonance (EPR), optical transmission and absorption spectra and dc conductivity of these glasses have been studied. Spin Hamiltonian parameters (SHPs) of VO²⁺ ions, dipolar hyperfine coupling parameter, P, Fermi contact interaction parameter, K and molecular orbital coefficients (α² and γ²) have been calculated. In GeO₂·Li₂O·B₂O₃ glasses there is no change in the tetragonality of the V⁴⁺O₆ complex and the size of 3d_xy orbit also remains unchanged with increase in GeO₂ content. In GeO₂·K₂O·B₂O₃ glasses, there is an increase in the tetragonality of the V⁴⁺O₆ complex and the 3d_xy orbit expands with increase in GeO₂ content. Values of the theoretical optical basicity, Λ_th, have also been reported. Optical band gap decreases with increase in GeO₂ content. The dc conductivity of these glasses decreases and the activation energy increases with increase in GeO₂:M₂O ratio.     

Structural studies of rhodium doped Sr2RuO4

The influence of Rh doping on the structure of Sr₂RuO₄ has been investigated using neutron powder diffraction methods. The metallic Ru rich compounds adopt a regular K₂NiF₄-type structure, space group I4/mmm, with Ru-O-Ru bond angles of 180°. The structures of the nonmetallic Rh rich compounds crystallise in space group I4/acd and are characterised by tilting of the MO₆ octahedra reducing the Ru-O-Ru angle to about 160°. Irrespective of Rh content the MO₆ polyhedra are not regular octahedra but are elongated along the c direction. The temperature dependence of the structure of Sr₂Ru_0.9Rh_0.1O₄ was investigated and revealed this elongation to be weakly temperature dependent.     

General relationships for isovalent cation substitution into oxides with the rocksalt structure

Isovalent cation substitution into rocksalt oxides, MO, has been investigated using atomistic simulation. A strain related parameter, ε, is established that relates the size of a substitutional cation to the host lattice ion for which it has been substituted. This has allowed us to identify relationships between solution energy, defect volume and a strain parameter, which are general for any rocksalt oxide host lattice and as such are predictive for any combination of a divalent cation and rocksalt host lattice.     

The formation of oxide nanoparticles on the surface of natural clinoptilolite

Nanoparticles of NiO, ZnO and Cu₂O crystallize when the Ni-, Zn- and Cu-exchanged natural clinoptilolite, respectively, are dehydrated by heating in air at 550 °C. The dehydration of Mn-exchanged clinoptilolite does not lead to the crystallization of manganese oxide but affects the crystallinity of the host clinoptilolite lattice, which becomes amorphous. The NiO, ZnO and Cu₂O nanoparticles are found to be randomly dispersed in the clinoptilolite matrix. The particle size varies from 2 to 5 nm and exceeds the aperture of the clinoptilolite channel (approximately 0.4 nm), suggesting that the crystallization of the oxide phases takes place on the surfaces of clinoptilolite microcrystals.