The electronic structure and properties of Ni1−xLixO1−y (0⩽x⩽1/4, 0⩽y⩽1/8)

The electronic structures of NiO, Ni_0.875O, NiO_0.875, Ni_0.875Li_0.125O, Ni_0.875Li_0.125O_0.875 and Ni_0.75Li_0.25O_0.875 with a NaCl-type crystal structure have been calculated using the ab initio linear muffin-tin orbitals method in the LSDA+U approximation. The effect of vacancies in the metal and metalloid sublattices and lithium ions on parameters of the NiO electronic spectrum (the energy gap and the valence band widths, etc.) has been analyzed. It is shown that the defects like the dipole LiV_O and the tripole LiV_OLi impaired stability and could reduce electrical conductivity of the nickel–oxide-based phases.     

Bi7−xAs1+xMo3O21 (0⩽x⩽1) a new pillar structure type: synthesis,crystal structure and conductivity

An original structure of chemical formula Bi₁₃As₃Mo₆O₄₂ has been obtained in the system Bi₂O₃:MoO₃:As₂O₃ by chemical transport reaction in presence of As₂O₃. It crystallizes in the monoclinic system, space group P2₁/n with a=12.7770(11) Å, b=5.5890(4) Å, c=27.971(2) Å and β=101.009(7)°. The structure exhibits infinite [Bi₁₃As₃Mo₆O₄₂]_n complex pillars with a quite different organization compared with original [Bi₁₂O₁₄]_n⁸ⁿ⁺ columns surrounded by (MoO₄) tetrahedra in the Bi_2/3[Bi₁₂O₁₄](MoO₄)₅ prototype structure. Nevertheless, the heavy atoms design almost perfect fluorite subnetwork—a common structural feature of these pillar structures. The conditions of synthesis via solid-state chemistry using basic oxides Bi₂O₃, As₂O₃ and MoO₃ have been established and the phase identified by X-ray powder pattern. The indexing fits single crystal data as well as the values of volumic mass, ρ_exp=7.04(4) g cm⁻³ for ρ_X=7.096 g cm⁻³ for Z=4. This Bi₁₃As₃Mo₆O₄₂ phase shows also an interesting anionic conductivity around σ=7.98×10⁻⁴ S cm⁻¹ at 980 K and is compared with related phases.     

Thermal and X-ray investigations of the quasi-binary system Ag1−xPdxMg (if0 ⩽ x ⩽ 0.5)

It is shown by X-ray diffraction, thermal analysis and microscopy studies that the quasi-binary system Ag_1−xPd_xMg crystallizes with a CsCltype structure and forms single-phase alloys throughout the temperature range investigated. The lattice constants follow Vegard's law. They are described by a = a₀ − bx where a₀ = 331.526 pm and b = 15.756 pm.     

Novel red-emitting phosphors, (Mg(1−x−y)MnxDyy)Al2Si2O8 and (Mg(1−x−y)MnxTmy)Al2Si2O8

Mn⁴⁺ doped and Dy³⁺, Tm³⁺ co-doped MgAl₂Si₂O₈-based phosphors were prepared by conventional solid state reaction at 1,300 °C. They were characterized by thermogravimetry, differential thermal analysis, X-ray powder diffraction, photoluminescence, and scanning electron microscopy. The luminescence mechanism of the phosphors, which showed broad red emission bands in the range of 600–715 nm and had a different maximum intensity when activated by UV illumination, was discussed. Such a red emission can be attributed to the ²E → ⁴A₂ transitions of Mn⁴⁺.     

Glycolate Ti1 − x Fe x (OCH2CH2O)2 − x/2 as a precursor for the preparation of quasi-one-dimensional (1D) solid solutions Ti1 − x Fe x O2 − 2x/2 (0 ≤ x ≤ 0.1)

Quasi-one-dimensional (1D) solid solutions Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} (0 < x ≤ 0.1) with the structure of anatase were prepared by heating the glycolate Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} in an atmosphere of air at a temperature of >450°C. The conditions of formation and the properties of the new glycolate Ti₃Fe₂(OCH₂CH₂O)₉ were described. It was found that the synthesized Ti_{1 ? x} Fe _x O_{2 ? 2x/2} solid solutions exhibit photocatalytic activity in the reaction of hydroquinone oxidation in an aqueous solution on irradiation with UV light. A correlation between the rate of oxidation of hydroquinone and the concentration of iron in the catalyst was established. A procedure for the preparation of titanium dioxide with the structure of anatase doped with iron and carbon (Ti_{1 ? x} Fe _x O_{(2 ? x/2) ? yCy)} and also composites on its basis, which contain an excess amount of carbon, was proposed.     

Radiation damage in Si1−x Ge x heteroepitaxial devices

Results are presented of an extended study on the induced lattice defects and their effects on the degradation of Si_1−x Ge _x devices, subjected to a 20 MeV alpha-ray, 1 MeV electron, 1 MeV fast neutron, and 20 and 86 MeV proton irradiations. The degradation of the electrical device performance increase with increasing fluence, while it decreases with increasing germanium content. In the Si_1−x Ge _x epitaxial layers, electron capture levels associated with an interstitial-substitutional boron complex are induced. The radiation source dependence of performance degradation is attributed to the difference of mass and the probability of nuclear collision for the formation of lattice defects.     

Phase relation studies in Pb1−xM′xF2+x systems (0.0⩽x⩽1.0; M′=Nd3+, Eu3+ and Er3+)

In this communication we report the synthesis and characterization of a series of compounds with the general composition Pb_1−xM′_xF_2+x, (0.0⩽x⩽1.0; M′=Nd³⁺, Eu³⁺ and Er³⁺) to elucidate the detailed phase relations between PbF₂ and M′F₃. These three rare-earth fluorides were selected so as to delineate the effect of ionic size on the phase relations. In all the three systems, fluorite-type solid solutions are formed at the PbF₂ rich end. The solid solubility limits of NdF₃, EuF₃ and ErF₃ in the PbF₂ lattice, as observed from this study, are 30, 25 and 15 mol%, respectively. In PbF₂–NdF₃ system, beyond the fluorite-type solid solutions, NdF₃ phase is observed. However, in both PbF₂–EuF₃ and PbF₂–ErF₃ systems, certain fluorite related ordered phases, namely, a rhombohedral phase with about 40 mol% of EuF₃ or ErF₃ in PbF₂, and a tetragonal phase with 45–50 mol% of ErF₃ in PbF₂, are observed. In all the three systems, no solubility of the PbF₂ in the hexagonal or orthorhombic rare-earth fluoride lattice is observed. This is the first report on phase relation in these three systems under short annealed and slow cooled condition.     

The structure changes in Sn1− x Ti x alloys at transition from liquid to solid state

The structures of Sn_{1– x} Ti _x (x = 0.00; 0.02, 0.05, 0.15, 0.25; 0.35; 0.45) alloys were studied by X-ray diffraction at different temperatures. The structure factors, pair correlation functions, and parameters obtained were analysed. It is shown that the structures of the liquid alloys are inhomogeneous in the pre-crystallisation temperature region. The solidified phases are in agreement with the equilibrium phase diagram. The X-ray diffraction data were used for the specification of the liquidus line position.     

Hydrogenation characteristics of Ti2NiOx compounds (0 ⩽ x < 0.5)

The hydrogenation characteristics of Ti₂NiO_x compounds (0 ⩽ x < 0.5) were investigated using combined TG-DTA techniques. The presence of oxygen in Ti₂Ni affects the hydrogen uptake capacity, the stability of the hydrides and the phase transition behavior of the corresponding hydrogen-containing compounds. Oxygen atoms occupy some of the available hydrogen interstitial sites and also influence the electron concentration, and possibly they reduce the enthalpy of formation of the hydrides. The cooling rate affects the maximum hydrogen uptake at room temperature, with rapid cooling giving the highest hydrogen content. These rate effects are tentatively explained on the basis of a model involving two types of hydrogen-occupied interstitial sites.     

Electronic structure and related properties for quasi-binary (GaP)1−x (ZnSe) x crystals

The results of pseudopotential calculations of the band structure and related electronic and optical properties of quasi-binary (GaP)_1?x (ZnSe) _x crystals in the zinc blende structure are presented. Trends in bonding and ionicity are discussed in terms of electronic charge densities. Moreover, the composition dependence of the refractive index and dielectric constants are reported. The computed values are in reasonable agreement with experimental data. The results suggest that for a proper choice of the composition x, (GaP)_1?x (ZnSe) _x could provide more diverse opportunities to achieve the desired electronic and optical properties of the crystals which would improve the performances of devices fabricated on them.     

LiNi1-xAlxO2(x=0～1.0)固溶体结构的XRD研究

利用溶胶凝胶法制备了新型锂离子二次电池正极材料LiNi_1-xAl_xO₂(x=0,0.1～1.0)固溶体,X射线衍射结果表明,在0≤x≤1范围内,材料均为具有α-NaFeO₂型结构的LiNi_1-xAl_xO₂固溶体单相.随着Al固溶量的增加,晶胞参数发生变化,a轴缩短,c/a比增大,晶胞体积V₀减小,材料的层状属性更加明显.     

Sr(Ag1−xLix)2Se2 and [Sr3Se2][(Ag1−xLix)2Se2] Tunable Direct Band Gap Semiconductors

Synthesizing solids in molten fluxes enables the rapid diffusion of soluble species at temperatures lower than in solid-state reactions, leading to crystal formation of kinetically stable compounds. In this study, we demonstrate the effectiveness of mixed hydroxide and halide fluxes in synthesizing complex Sr/Ag/Se in mixed LiOH/LiCl. We have accessed a series of two-dimensional Sr(Ag_1−xLi_x)₂Se₂ layered phases. With increased LiOH/LiCl ratio or reaction temperature, Li partially substituted Ag to form solid solutions of Sr(Ag_1−xLi_x)₂Se₂ with x up to 0.45. In addition, a new type of intergrowth compound [Sr₃Se₂][(Ag_1−xLi_x)₂Se₂] was synthesized upon further reaction of Sr(Ag_1−xLi_x)₂Se₂ with SrSe. Both Sr(Ag_1−xLi_x)₂Se₂ and [Sr₃Se₂][(Ag_1−xLi_x)₂Se₂] exhibit a direct band gap, which increases with increasing Li substitution (x). Therefore, the band gap of Sr(Ag_1−xLi_x)₂Se₂ can be precisely tuned via fine-tuning x that is controlled by only the flux ratio and temperature.     

Hopping conductivity of distorted K2NiF4-type (Ca1+xNd1−x)CrO4

Orthorhombic distorted K₂NiF₄-type (Ca_1+xNd_1?x)CrO₄ (0.00 ≤ x ≤ 0.15) was synthesized using a standard ceramic technique. The cell parameters (a and c) decreased, whereas the cell parameter (b) increased with the increase in x. The variation in the global instability index (GII) indicated that the crystal stability of (Ca_1+xNd_1?x)CrO₄ was not influenced by the Cr⁴⁺ ion content. At all temperatures, the electrical conductivity (σ) of (Ca_1+xNd_1?x)CrO₄ increased with the increase in x. (Ca_1+xNd_1?x)CrO₄ was a p-type semiconductor and exhibited hopping conductivity in a small-polaron model in the temperature range of 290 K ≤ T ≤ 713 K. The Cr⁴⁺ ion acts as an acceptor, and the electron transfer through the Cr³⁺–O–Cr⁴⁺ path becomes active as a result of the Cr⁴⁺ ion content and the Cr–O(1) distance.     

Hydrogen content in proton-conducting perovskites CaZr1 − x Sc x O3 − x /2 (x = 0.0–0.2)

The hydrogen content in CaZr_{1 ? x} Sc _x O_{3 ? x/2} (x = 0.00–0.20) and BaZr_0.9Y_0.1O_3-α (for comparison) was studied by powder nuclear microanalysis. The samples were saturated with heavy water (D₂O) vapors at 350 and 400°C in air. The chemical expansion of the CaZr_0.95Sc_0.05O_3-α and BaZr_0.95Y_0.05O_3-α samples at 700°C was measured at different water vapor pressures. A model was suggested to explain the lowered hydrogen content in oxides based on CaZrO₃.     

Double perovskite Sr2FeMoO6−xNx (x=0.3, 1.0) oxynitrides with anionic ordering

Two new oxynitride double perovskites of composition Sr₂FeMoO_6?xN_x (x=0.3, 1.0) have been synthesized by annealing precursor powders obtained by citrate techniques in flowing ammonia at 750 °C and 650 °C, respectively. The polycrystalline samples have been characterized by chemical analysis, x-ray and neutron diffraction (NPD), Mössbauer spectroscopy and magnetic measurements. They exhibit a tetragonal structure with a=5.5959(1) Å, c=7.9024(2) Å, V=247.46(2) Å³ for Sr₂FeMoO_5.7N_0.3; and a=5.6202(2) Å, c=7.9102(4) Å, V=249.85(2) Å³ for Sr₂FeMoO₅N; space group I4/m, Z=2. The nitridation process seems to extraordinarily improve the long-range Fe/Mo ordering, achieving 95% at moderate temperatures of 750 °C. The analysis of high resolution NPD data, based on the contrast existing between the scattering lengths of O and N, shows that both atoms are located at (O,N)2 anion substructure corresponding to the basal ab plane of the perovskite structure, whereas the O1 site is fully occupied by oxygen atoms. The evolution of the 〈Fe–O〉 and 〈Mo–O〉 distances suggests a shift towards a configuration close to Fe⁴⁺(3d⁴, S=2):Mo⁵⁺(4d¹, S=1/2). The magnetic susceptibility shows a ferrimagnetic transition with a reduced saturation magnetization compared to Sr₂FeMoO₆, due to the different nature of the magnetic double exchange interactions through Fe–N–Mo–N–Fe paths in contrast to the stronger Fe–O–Mo–O–Fe interactions. Also, the effect observed by low-temperature NPD seems to reduce the ordered Fe moments and enhance the Mo moments, in agreement with the evolution of the oxidation states, thus decreasing the saturation magnetization.     

Nonstoichiometry and structural intergrowth in the CaFexMn1−xO3−y (0 ≤ x ≤ 1) system

An electron diffraction and microscopy study of the CaFe_xMn_1−xO_3−y system treated at 1100°C in air has been performed. An increase of y is accompanied by an increase of the cubic perovskite substructure parameter, the nonstoichiometry being accommodated in several ways. The system contains two solid solutions of the perovskite-type (P) and of the brownmillerite-type (B) and also an intermediate phase (x = 0.6) which makes disordered intergrowth with the B-type solid solution. These results are discussed in terms of multitwinning, randomly dispersed oxygen deficiency, and ordered and disordered intergrowth formation.