Structure and electrical conductivity of a novel inorganic solid electrolyte: Na14.5[Al(PO4)2F2]2.5[Ti(PO4)2F2]0.5 (NATP)

A novel inorganic solid electrolyte with a layered framework structure stable up to 1043 K, Na_14.5[Al(PO₄)₂F₂]_2.5[Ti(PO₄)₂F₂]_0.5 (NATP), has been hydrothermally prepared and characterized by single-crystal and powder X-ray diffraction techniques, X-ray fluorescence (XRF) analysis, IR spectroscopic measurement, thermogravimetric and differential thermal analysis (TGA and DTA). NATP crystallizes in the acentric hexagonal space group P3 with a=10.448(2), b=10.448(2), , Z=1, containing a large number of Na⁺ cations in the interlamellar space and the cavities of its framework. There are six different crystallographic Na⁺ cationic sites, in which 8% Na(5) and 12% Na(6) sites are vacant. Electrical conductivity measurements show that Na⁺ cations exhibit a high mobility with two domains for the electrical conductivity versus temperature.     

Crystallographic and magnetic properties of (Nd,Dy)3Fe27.5(Ti,Mo)1.5 compounds

A systematic study of the formation, structure and magnetic properties of (Nd,Dy)₃Fe_27.5(Ti,Mo)_1.5 compounds has been performed. Rietveld analyses of the X-ray patterns of the samples indicate that the concentrations of Ti and Mo affect the formation and structural properties slightly, whereas different rare-earth (Nd and Dy) contents influence them significantly. It is found that high Dy contents make it difficult to form the 3:29-type structures. The Curie temperatures of Nd_2.1Dy_0.9Fe_27.5Ti_1.5−xMo_x decrease monotonically as more Ti was replaced by Mo but their saturation magnetizations remain almost unchanged; in contrast, for Nd_3−yDy_yFe_27.5TiMo_0.5, their saturation magnetizations decrease monotonically with increasing Dy contents while their Curie temperatures are constant.     

Structure and dielectric properties of (Na0.50Bi0.50)1−xBaxTiO3: 0≤x≤0.10

Solid solution of (1−x)Na_0.5Bi_0.5TiO₃-xBaTiO₃ is investigated in the composition range 0.00≤x≤0.10. It is shown that the system exhibits rhombohedral structure up to x=0.055 and then becomes ‘nearly cubic’ for x≥0.06. Temperature dependent dielectric measurements reveals three peaks in the imaginary part of the dielectric constant for compositions exhibiting rhombohedral as well as ‘nearly cubic’ structures. The first of these three peaks exhibits Vogel-Fulcher type relaxation behaviour.     

Crystal structure and ferromagnetism of (n-C3H7)4N[CoFe(dto)3] (dto=C2O2S2)

Recently, we have discovered a new type of first order phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto=C₂O₂S₂), where the charge transfer transition between Fe^II and Fe^III occurs reversibly. In order to elucidate the origin of this peculiar first order phase transition. Detailed information about the crystal structure is indispensable. We have synthesized the single crystal of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃] whose crystal structure is isomorphous to that of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃], and determined its detailed crystal structure. Crystal data: space group P6₃, a=b=10.044(2) Å, c=15.960(6) Å, α=β=90°, γ=120°, Z=2 (C₁₈H₂₈NS₆O₆FeCo). In this complex, we found a ferromagnetic transition at T_c=3.5 K. Moreover, on the basis of the crystal data of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃], we determined the crystal structure of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] by simulation of powder X-ray diffraction results.     

Crystal structure of the quaternary compound CuTa2InTe4 from X-ray powder diffraction

The crystal structure of the new quaternary compound CuTa₂InTe₄ was studied using X-ray powder diffraction data. The powder pattern refined by the Rietveld method indicates that this material crystallizes in the tetragonal system with space group I-4¯2m (No. 121), Z=2, and unit cell parameters a=6.1963(2) Å, c=12.4164(4) Å, c/a=2.00 and V=476.72(3) Å³. The structural and instrumental refinement of 28 parameters led to R_p=10.4%, R_wp=11.1%, R_exp=6.8% and χ²=2.7 for 96 independent reflections.     

Extended X-ray absorption fine-structure (EXAFS) of a complex oxide structure: a full multiple scattering analysis of the Au L3-edge EXAFS of Au2O3

Crystalline Au₂O₃ was obtained by hydrothermal synthesis at 3000 atm and its extended X-ray absorption fine-structure (EXAFS) at the Au L₃-edge was measured at room temperature. A detailed full multiple scattering (MS) analysis using FEFF8 theory shows that only a small number of scattering paths contribute significantly to the EXAFS of Au₂O₃. Because of the complex unit cell (low local symmetry) of the Au₂O₃ structure, contributions of MS paths are almost negligible. The results indicate that FEFF8 theory provides a good reference for the analysis of Au-O phases.     

Ab initio Hartree-Fock calculations of LaMnO3 (110) surfaces

We present the results of ab initio Hartree-Fock calculations of the LaMnO₃ (110) surface. Using seven-plane slabs, periodic in 2D and containing three formula units, we compare the properties of a stoichiometric surface with oxygen vacancies, and non-stoichiometric, defect-free surfaces, analyze the dispersion of the effective charges near the surface, and calculate the surface energy before and after relaxation, for both ferromagnetric and antiferromagnetic spin orderings in a slab.     

Size-dependent microstructure and europium site preference influence fluorescent properties of Eu-doped Ca10(PO4)6(OH)2 nanocrystal

In this study, Eu³⁺-doped nanocrystalline Ca₁₀(PO₄)₆(OH)₂ (Ca_10−xEu_x(PO₄)₆(OH)₂) with different particle sizes have been prepared by the thermal decomposition of precursors. Size-dependent microstructure could be observed in nanocrystalline Ca_10−xEu_x(PO₄)₆(OH)₂. The lattices of Ca_10−xEu_x(PO₄)₆(OH)₂ nanocrystals were more distorted in comparison with the bulk, and the smaller the particle size, the more distorted the lattices. Room temperature photoluminescence showed europium site preference was also size-dependent, with the majority of Eu³⁺ ions occupying Ca(II) sites in the bulk, but more and more Eu³⁺ ions occupying Ca(I) sites in Ca_10−xEu_x(PO₄)₆(OH)₂ with decreasing particle size. Fluorescent properties of Ca_10−xEu_x(PO₄)₆(OH)₂ were considered to be influenced by both microstructure and site preference of Eu³⁺ ions. An abnormal strong intensity of ⁵D₀-⁷F₀ transition was observed in bulk and larger Ca_10−xEu_x(PO₄)₆(OH)₂ nanocrystals, but the relative intensities of ⁵D₀-⁷F₀ transition to ⁵D₀-⁷F_1,2,3,4 transition of Eu³⁺ became weaker as the particle sizes decreased. As the particle sizes became smaller, the ratios of the red emission transition (⁵D₀-⁷F₂) to the orange emission transition (⁵D₀-⁷F₁) (R/O values) first increased by comparing the bulk sample with 96 nm sample, and then decreased by comparing 96 nm sample to 57 nm sample. The quenching concentrations of Ca_10−xEu_x(PO₄)₆(OH)₂ samples increased with decreasing particle size. Possible mechanisms responsible for these phenomena were proposed. Since nanosized Ca_10−xEu_x(PO₄)₆(OH)₂ showed higher fluorescent intensities, higher R/O values and higher quenching concentrations, this material is considered to be a promising phosphor.     

Photoluminescence and thermoluminescence characterization of Eu- and Dy -activated Ca3(PO4)2 phosphor

Rare-earth-doped polycrystalline Ca₃(PO₄)₂:Eu, Ca₃(PO₄)₂:Dy and Ca₃(PO₄)₂:Eu,Dy phosphors prepared by a modified solid-state synthesis has been studied for its X-ray diffraction, thermoluminescence (TL) and photoluminescence (PL) characteristics. The PL emission spectra of the phosphor suggest the presence of Eu³⁺ ion in Ca₃(PO₄)₂:Eu and Dy³⁺ ion in Ca₃(PO₄)₂:Dy lattice sites. The TL glow curve of the Ca₃(PO₄)₂:Eu compounds has a simple structure with a prominent peak at 228 °C, while Ca₃(PO₄)₂:Dy peaking at 146 and 230 °C. TL sensitivity of phosphors are compared with CaSO₄: Dy and found 1.52 and 1.20 times less in Ca₃(PO₄)₂:Eu and Ca₃(PO₄)₂:Dy phosphors, respectively. The Ca₃(PO₄)₂:Eu,Dy phosphors shows switching behavior under two different excitation wavelengths and enhancement in PL intensity of Dy³⁺ ions were reported. The paper discusses the photoluminescence and thermoluminescence behavior of Eu³⁺ and Dy³⁺ ion in Ca₃(PO₄)₂ hosts, it may be applicable to solid-state lighting as well as thermoluminescence dosimetry applications.     

Synthesis and thermal stability of Zn3N2 powder

This paper reports that Zn₃N₂ powder of high quality has been synthesized by a nitridation reaction of Zn powder with NH₃ gas (flow rate 500 ml/min) at the nitridation temperature of 600 °C for 120 min. X-ray diffraction indicates that Zn₃N₂ is cubic in structure with the lattice constant being a=9.788 Å. X-ray photoelectron spectroscopy shows the differences of chemical bonding states between Zn₃N₂ and ZnO, and confirms the formation of N-Zn bonds. Thermal gravimetric analysis and differential thermal analysis are employed to investigate the thermal decomposition behavior of Zn₃N₂ powder. It is found that Zn₃N₂ is unstable when exposed to open air above 500 °C.     

Synthesis and structure of the monolayer hydrate K0.3CoO2·0.4H2O

The monolayer hydrate (MLH) K_0.3CoO₂·0.4H₂O was synthesized from K_0.6CoO₂ by extracting K⁺ cations using K₂S₂O₈ as an oxidant and the subsequent intercalation of water between the layers of edge-sharing CoO₆ octahedra. A hexagonal structure (space group P6₃/mmc) with lattice parameters a=2.8262(1) Å, c=13.8269(6) Å similar to the MLH Na_0.36CoO₂·0.7H₂O was established using high-resolution synchrotron X-ray powder diffraction data. The K/H₂O layer in the K-MLH is disordered, which is in contrast to the Na-MLH. At low temperatures metallic and paramagnetic behavior was found.     

Atomic Diffusion in Cu/Si （111） and Cu/SiO2/Si （111） Systems by Neutral Cluster Beam Deposition

The Cu films are deposited on two kinds of p-type Si （111） substrates by ionized duster beam （ICB） technique. The interface reaction and atomic diffusion of Cu/Si （111） and Cu/SiO2/Si （111） systems are studied at different annealing temperatures by x-ray diffraction （XRD） and Rutherford backscattering spectrometry （RBS）. Some significant results are obtained： For the Cu/Si （111） samples prepared by neutral dusters, the interdiffusion of Cu and Si atoms occurs when annealed at 230℃. The diffusion coefficients of the samples annealed at 230℃ and 500℃ are 8.5 ×10^-15 cm^2.s^-1 and 3.0 ×10^-14 cm^2.s^-1, respectively. The formation of the copper-silicide phase is observed by XRD, and its intensity becomes stronger with the increase of annealing temperature. For the Cu/SiO2//Si （111） samples prepared by neutral dusters, the interdiffusion of Cu and Si atoms occurs and copper silicides are formed when annealed at 450℃. The diffusion coefficients of Cu in Si are calculated to be 6.0 ×10^-16 cm^2.s^-1 at 450℃, due to the fact that the existence of the SiO2 layer suppresses the interdiffusion of Cu and Si.     

On the symmetry and structure of the double perovskites Ba2LnRuO6 (Ln=La, Pr and Nd)

The structures of the double perovskites Ba₂LnRuO₆ (Ln=La, Pr and Nd) at room temperature were re-investigated by profile analysis of X-ray diffraction data. It has been shown that neither the triclinic nor the monoclinic P2₁/n space group correctly describes their structures. Ba₂LaRuO₆ is actually rhombohedral, space group , cell parameters a=6.03196(10) Å and α=60.298(2)°. On the other hand, both Ba₂PrRuO₆ and Ba₂NdRuO₆ are found to be cubic, space group , with the cell parameters a=8.48416(6) and 8.47061(5) Å, respectively.     

High-pressure Raman spectroscopic studies on orthophosphates Ba3(PO4)2 and Sr3(PO4)2

By using diamond anvil cell (DAC), high-pressure Raman spectroscopic studies of orthophosphates Ba₃(PO₄)₂ and Sr₃(PO₄)₂ were carried out up to 30.7 and 30.1 GPa, respectively. No pressure-induced phase transition was found in the studies. A methanol:ethanol:water (16:3:1) mixture was used as pressure medium in DAC, which is expected to exhibit nearly hydrostatic behavior up to about 14.4 GPa at room temperature. The behaviors of the phosphate modes in Ba₃(PO₄)₂ and Sr₃(PO₄)₂ below 14.4 GPa were quantitatively analyzed. The Raman shift of all modes increased linearly and continuously with pressure in Ba₃(PO₄)₂ and Sr₃(PO₄)₂. The pressure coefficients of the phosphate modes in Ba₃(PO₄)₂ range from 2.8179 to 3.4186 cm⁻¹ GPa⁻¹ for ν₃, 2.9609 cm⁻¹ GPa⁻¹ for ν₁, from 0.9855 to 1.8085 cm⁻¹ GPa⁻¹ for ν₄, and 1.4330 cm⁻¹ GPa⁻¹ for ν₂, and the pressure coefficients of the phosphate modes in Sr₃(PO₄)₂ range from 3.4247 to 4.3765 cm⁻¹ GPa⁻¹ for ν₃, 3.7808 cm⁻¹ GPa⁻¹ for ν₁, from 1.1005 to 1.9244 cm⁻¹ GPa⁻¹ for ν₄, and 1.5647 cm⁻¹ GPa⁻¹ for ν₂.     

New fabrication of a strained Si/Si1−yGey dual channel on a relaxed Si1−xGex virtual substrate using a Ge-rich layer formed by oxidation

This paper presents a new method of forming a Si/SiGe dual channel on a Si_0.8Ge_0.2 virtual substrate. Generally, in a CMOS process using a Si/SiGe dual channel, due to several processes involving ion-implantation, annealing and dry-etching after the deposition of the Si/SiGe dual channel, the surface can be damaged, leading to reduced electrical properties. However, if the dual channel is formed during a specific stage of the CMOS process, the defects of the dual channel can be reduced and the thermal stability will be excellent. Therefore, in this paper, a method for minimizing the defects of the dual channel is presented. This method uses the segregation of the Ge in the oxidation process of a SiGe. A Si/SiGe dual channel formed using this method achieved results that were identical to a dual channel deposited using the chemical vapor deposition (CVD) method.     

Structure and electrical properties of SrO-borovanadate (V2O5)0.5(SrO)0.5−y(B2O3)y glassses

SrO-borovanadate glasses with nominal composition (V₂O₅)_0.5(SrO)_0.5−y(B₂O₃)_y, 0.0≤y≤0.4 were prepared by a normal quench technique and investigated by direct current (DC) electrical conductivity, inductively coupled plasma (ICP) spectroscopy, infrared (IR) spectroscopy and X-ray powder diffraction (XRD) studies in an attempt to understand the nature of mechanism governing the DC electrical conductivity and the effect of addition of B₂O₃ on the structure and electrical properties of these glasses. XRD patterns confirm the amorphous nature of the present glasses and actual compositions of the glasses were determined by ICP spectroscopy. The temperature dependence of DC electrical conductivity of these glasses has been studied in terms of different hopping models. The IR results agree with previous investigations on similar glasses and it has been concluded that similar to SrO-vanadate glasses, metavandate chain-like structures of SrV₂O₆ and individual VO₄ units also occur in SrO-borovanadate glasses. The SrV₂O₆ and VO_n polyhedra predominate in the low B₂O₃-containing SrO-borovanadate glasses as B substitutes into the V sites of the various VO_n polyhedra and only when the concentration of B₂O₃ exceeds the SrO content do BO_n structures appear. This qualitative picture of three distinct structural groupings for Sr-vanadate and Sr-borovanadate glasses is consistent with the proposed glass structure on previous IR and extended X-ray absorption fine structure (EXAFS) studies on these types of glasses. The conductivity results were analyzed with reference to theoretical models existing in the literature and the analysis shows that the conductivity data are consistent with Mott's nearest neighbor hopping model. Analysis of the conductivity data shows that they are consistent with Mott's nearest neighbor hopping model. However, both Mott VRH and Greaves models are suitable to explain the data. Schnakenberg's generalized polaron hopping model is also consistent with temperature dependence of activation energy. However, various model parameters such as density of states, hopping energy, etc. obtained from the best fits were not found to be in accordance with the prediction of the Mott model.     

Enhancement of Curie temperature and room-temperature magnetoresistance in double perovskite (Sr1.6Ba0.4)FeMoO6

The effects of A-site average cation size 〈r_A〉 and anti-site defects on Curie temperature (T_C) and room-temperature magnetoresistance (MR) in (Sr_2−xBa_x)FeMoO₆ (x=0, 0.4 and 1.6) have been investigated. By Ba doping, not only the room-temperature MR but also the T_C have been enhanced. The larger MR in the Ba-doped samples compared with the prototype Sr₂FeMoO₆ is associated with the lower saturation field. The optimization of T_C and MR in (Sr_1.6Ba_0.4)FeMoO₆ other than in the reported (Sr_0.4Ba_1.6)FeMoO₆ can be understood according to the two competing effects: anti-site defects and chemical pressure.     

(4×2) and (2×4) reconstructions of GaAs and InP(001) surfaces

Received: 21 March 1997/Accepted: 12 August 1997     

ZnO-Fe3O4 composite prepared by sol-gel method with H2 deoxidation

Fe doped ZnO powder samples (Fe/Zn=0.05 and 0.1) were prepared by sol-gel method with H₂ deoxidation at 450 ^°C for several hours or just heated in air at the same temperature. It was showed by vibrating sample magnetometer (VSM) that samples heat treated in H₂ could show strong ferromagnetism at room temperature while samples treated in air only show very weak magnetism. XRD using Co kα X-ray revealed that the samples heated in H₂ were not pure phase but like a granular system and the magnetism mainly results from Fe₃O₄ in samples while samples heated in air showed pure ZnO phase. Our work indicated that H₂ deoxidation treatment may be an effective technique to fabricate such magnetic semiconductor-like materials with Curie temperature higher than room temperature.     

Effect of interfacial diffusion on microstructure and properties of FePt/B4C multifunctional multilayer composite films

FePt/B₄C multilayer composite films were prepared by magnetron sputtering and subsequent annealing in vacuum. By changing Fe layer thickness of [Fe/Pt]₆/B₄C films, optimal magnetic property (8.8 kOe and remanence squareness is about 1.0) is got in [Fe(5.25 nm)/Pt(3.75 nm)]₆/B₄C sample whose composition is Fe rich and near stoichiometric ratio. The characterizations of microstructure demonstrate that the diffusion of B and C atoms into FePt layer depends strongly on B₄C interlayer thickness. When B₄C interlayer thickness of [Fe(2.625 nm)/Pt(3.75 nm)/Fe(2.625 nm)/B₄C]₆ films is bigger than 3 nm, stable value of grain size (6-6.5 nm), coercivity (6-7 kOe) and hardness (16-20 GPa) is observed. Finally, the multifunctional single FePt/B₄C composite film may find its way to substitute traditional three-layer structure commonly used in present data storage technology.