Structural properties,phase stability,elastic properties and electronic structures of Cu–Ti intermetallics

The structural properties, phase stabilities, anisotropic elastic properties and electronic structures of Cu–Ti intermetallics have been systematically investigated using first principles based on the density functional theory. The calculated equilibrium structural parameters agree well with available experimental data. The ground-state convex hull of formation enthalpies as a function of Cu content is slightly symmetrical at CuTi with a minimal formation enthalpy (–13.861 kJ/mol of atoms), which indicates that CuTi is the most stable phase. The mechanical properties, including elastic constants, polycrystalline moduli and anisotropic indexes, were evaluated. G/B is more pertinent to hardness than to the shear modulus G due to the high power indexes of 1.137 for G/B. The mechanical anisotropy was also characterized by describing the three-dimensional (3D) surface constructions. The order of elastic anisotropy is Cu₄Ti₃ > Cu₃Ti₂ > α-Cu₄Ti > Cu₂Ti > CuTi > β-Cu₄Ti > CuTi₂. Finally, the electronic structures were discussed and Cu₂Ti is a semiconductor.     

On the La2CuO4-Nd2CuO4 system: Influence of oxygen pressure on the phase diagram,oxygen stoichiometry and transport properties of the T/O and T′ type solid solutions

Abstract

Two types of solid solutions exist in the La₂CuO₄-Nd₂CuO₄ system, with respectively the T/O and T′ type structure of La₂CuO₄ and Nd₂CuO₄. When synthesized in air at high temperature and normal pressure, both solid solutions exhibit semi-conducting properties. A treatment under oxygen pressure causes a slight change in the unit cell parameters of the T/O type solid solution, a significant shift of its upper limit towards higher neodynium contents and a small increase of the average oxidation state of copper. All these modifications result from the insertion of some oxygen species in the T/O type-structure and induce a superconducting behaviour.     

Structural and optical properties of CuSe2 nanocrystals formed in thin solid Cu–Se film

This paper describes the structural and optical properties of Cu–Se thin films. The surface morphology of thin films was investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Formation of Cu–Se thin films is concluded to proceed unevenly, in the form of islands which later grew into agglomerates. The structural characterization of Cu–Se thin film was investigated using X-ray diffraction pattern (XRD). The presence of two-phase system is observed. One is the solid solution of Cu in Se and the other is low-pressure modification of CuSe₂. The Raman spectroscopy was used to identify and quantify the individual phases present in the Cu–Se films. Red shift and asymmetry of Raman mode characteristic for CuSe₂ enable us to estimate nanocrystal dimension. In the analysis of the far-infrared reflection spectra, numerical model for calculating the reflectivity coefficient of layered system, which includes film with nanocrystalite inclusions (modeled by Maxwell-Garnett approximation) and substrate, has been applied.     

The dispersion relations of plasmons in a simplified system of CuO2 layers and Cu−O chains

A simplified model for YBa₂Cu₃O₇ system composed of CuO₂ layers and Cu–O chains has been calculated with the long range effect of the all-neighbors Coulombice-e interactions taken into consideration. Dispersion relations have been worked out and discussed. The most striking consequence from the all-neighbors interaction is that the plasmons have, in the long wavelength limit, in addition to the usual vanishingly small two-dimensional acoustic plasmon energies which result from only nearest neighbor interactions, a non-zero _P ^* consistent with the bulk plasma frequency of a three dimensional system. The data of an optical reflectance from an EELS experiment has been refitted based on calculated results for plasmon dispersion relations in the YBa₂Cu₃O₇ system.     

Local electronic structure of Cu2O,CuO and YBa2Cu3O7−δ

Cu 3d and O 2p electronic states of Cu₂O, CuO, and the highT _c compound YBa₂Cu₃O_7– have been probed by means of high resolution x-ray emission spectroscopy (XES). The CuL and OK XES bands are compared in detail with recently reported x-ray photoelectron and ultraviolet photoelectron spectroscopy (XPS and UPS) measurements and densities of states obtained by local density functional (LDF) theory. The XES data show that the hybridization between Cu 3d and O 2p states is completely modified in CuO and YBa₂Cu₃O_7–, whered-d correlation energy is large, as compared to LDF predictions. Such is not the case for Cu₂O where agreement between theory and experiment is good.The Cu 3d states are found to be highly localized in YBa₂Cu₃O_7– (though less so than in CuO). The O 2p states lie at lower binding energies than in the simpler oxides and are mainly situated above the Cu 3d states. The respective positions of the centre of gravity of the OK emission bands on an x-ray energy scale indicate that the oxygen sites are less well screened by the O 2p states in the highT _c compound. This provides indirect evidence for the presence ofd-like states at the oxygen sites.     

First principles calculations of the structural,electronic and optical properties of the mixed fluorides SrxCd1−xF2

In the present work, we have investigated the structural, electronic and optical properties of SrF₂ and CdF₂ and their ternary mixed Sr_xCd_1?xF₂ alloys at some selected concentrations x (x?=?0.25, 0.50, 0.75 and 1). The parent compounds SrF₂ and CdF₂ crystallize in Fm-3?m space group, whereas the alloys adopt the cubic structure with Pm-3?m space group for the composition x?=?0.25 and 0.75 and the tetragonal structure with space group P4/mmm for x?=?0.50. The calculations were performed using the full-potential linearized augmented plane wave (FP-LAPW) method. The exchange-correlation potential was handled with Wu and Cohen GGA approximation (WC-GGA). Moreover, the Engel–Vosko's (EV-GGA) formalism and the modified Becke Johnson (mBJ) approximation were also applied to improve the electronic band structure calculations. The computed structural parameters for SrF₂ and CdF₂ such as the equilibrium lattice constants and the bulk moduli are in good agreement with the available experimental and theoretical data. It is found that the lattice parameters increase with increasing composition (x) while the bulk modulus decreases for Sr_xCd_1?xF₂ alloys. The calculated band structures reveal an indirect band gap (W-Γ), (X-Γ) and (M-Γ) for CdF₂, SrF_{2 and} Sr_xCd_1?xF₂ for x?=?0.25, 0.75 and x?=?0.5, respectively. The optical constants, including the dielectric function, refractive index, reflectivity, absorption, extinction coefficient and the energy loss function were calculated using both WC-GGA and mBJ schemes for a radiation up to 40?eV. This is the first quantitative theoretical prediction of the optical properties for these alloys that requires experimental confirmation.     

Study of the effect of the substitution of O by F,S, and Cl on the superconductivity of Y1Ba2Cu3O7−δ

We have studied the superconducting transitions of Y₁Ba₂Cu₃D _x O_7–x– samples where O has been replaced by D=F, S, or Cl andx=0.2-2. No single phase compounds were obtained forx>0.2. No dramatic increase inT _c was registered. Generally the results can be interpreted as a dilution of the highT _c 1 2 3 phase by other phases as the dopant concentration increases, ultimately suppressingT _c completely. Possibly there is an increase ofT _c for an intermediate dopant range,x, in the Cl series.     

CsCl effect on the optical properties of the 80GeS2–20Ga2S3 base glass

Optical properties of chalcogenide glasses belonging to the series (80GeS₂–20Ga₂S₃)_100−x (CsCl) _x with x=0;5;10;15;20 were investigated. The linear refractive indices (n ₀) were determined by prism measurements at four wavelengths: 633 nm, 825 nm, 1311 nm, and 1511 nm. Z-scan experiments were performed at 800 nm to measure the non-linear indices (n ₂) and the absorption coefficients (β). CsCl additions in the base glass (80GeS₂–20Ga₂S₃) are characterized by a white shift of the transmission in the visible range and a strong decrease of both n ₀ and n ₂. As the same time, β is also decreasing and this results in a figure of merit FOM=2βλ/n ₂ that remains relatively low at 800 nm, meaning that this series of highly non-linear glasses should be very suitable for optical switching applications at telecommunication wavelengths.     

Theoretical investigation of electronic,magnetic, transport and optical properties of the pure and doped cuprate superconductor HgBa2CuO4+δ

We report detailed DFT calculations and Monte Carlo simulations on the pure and doped cuprate superconductor HgBa₂CuO_4+δ. For the pure compound (δ = 0), we have obtained an insulating behavior with strong antiferromagnetic copper spin correlations in the CuO₂ plane. The high value of the calculated Néel temperature T_N = 333 K reflects the large in-plane exchange interaction J = -145 meV. The obtained optical properties and critical exponents demonstrate the anisotropic quasi-2D character of this type of materials. As for the doped compound the electronic structure and the transport properties have been investigated for various values of doping. Based on these data, we suggest a prediction of the value of optimum doping for HgBa₂CuO_4+δ(δ_optimal = 0.125).     

Core–shell nanostructures and nanocomposites of Ag@TiO2: effect of capping agent and shell thickness on the optical properties

Two different shell-forming reagents viz. titanium isopropoxide and titanium hydroxyacylate, have been employed to obtain core–shell nanostructures of Ag@TiO₂. However, nanocomposites were formed when the shell-forming agent, titanium isopropoxide, was added before breaking the micelles. Titanium hydroxyacylate has been used for the first time as a shell-forming agent which resulted in uniform core–shell structures of Ag@TiO₂ with core diameter ranging from 10 to 40 nm and a shell thickness of 10–50 nm. The low rate of hydrolysis of titanium hydroxyacylate than titanium isopropoxide (used in other methods) appears to be responsible for the uniform shell thickness. The presence of capping agent (2-mercaptoethanol) disrupts the formation of a uniform shell structure of Ag@TiO₂. HRTEM, IR, and XPS studies of Ag@TiO₂ synthesized using capping agent show the formation of Ag₂S coated with an amorphous layer of TiO₂. A red shift of 25 and 10 nm was observed in the surface plasmon band of silver for Ag@TiO₂ core–shell structures (compared with that of silver nanoparticles) synthesized using titanium hydroxyacylate and titanium isopropoxide, respectively. The presence of capping agent (2-mercaptoethanol) masks the surface plasmon peak. Photoluminescence studies show an increase in the emission intensity for the core–shell structures when compared to that of TiO₂ nanoparticles.     

Structural,morphologic and optical characterization of In(2−x)Al x S3

Aluminum-doped indium sulfide thin films are deposited on glass by spray pyrolysis technique. The structure and the surface morphology of these films were characterized by X-ray diffraction and atomic force microscopy. The effects of aluminum ratio z and substrate temperature T _s, on the film structure and grain size are discussed. The influence of aluminum ratio on surface morphology is revealed by scanning electron microscope. Besides, energy dispersive spectrometry technique is used to compare atomic aluminum concentration in the film with aluminum ratio z in spray solution. Optical properties are studied by a spectrophotometer in the wavelength range 350–850 nm, at room temperature. Optical transmission and grain size are found to be maximal for z = 1.8 %. Moreover, band-gap energy is found to increase with aluminum ratio.     

Structural characterization and magnetic properties of NiMg3x/2Cr0.9Fe1.1 − x O4

Magnesium-substituted nickel–chrome ferrites have been studied using X-ray diffraction and Mössbauer spectroscopy. A single cubic spinel phase was obtained in the range 0.0?≤?x?≤?0.4. The lattice parameter was found to decrease with the increase of Mg concentration. The Mössbauer spectra measured at 295 and 78 K of all samples showed magnetic patterns interpreted in term of the tetrahedral and octahedral sites occupancies. The magnetic hyperfine field of both sites decrease with the increase of the Mg concentration. The magnetic properties as a function of the Mg concentration have been explained on the basis of the cation distribution among the two crystallographic sites driven from the Mössbauer measurements.     

Phase relations and optical properties of semiconducting ternary sulfides in the system Cu–Sn–S

The ternary system Cu–Sn–S was re-investigated and the phase diagram Cu₂S–SnS₂ studied in detail by differential thermal analysis and X-ray diffractometry. Three phases of composition Cu₄SnS₄, Cu₂SnS₃ and Cu₂Sn_3+xS_7+2x(0≤×≤1) were found exhibiting melting points at 833, 856 and 803 °C, respectively. Ellipsometric and diffuse reflectance measurements revealed that the latter two sulfides possess a fundamental band gap of 0.93 eV followed by a higher transitions. For the first time it could be demonstrated that Cu₂Sn₃S₇ has semiconducting properties and an absorption coefficients of the order 10⁵ cm⁻¹.     

Cu1.5[Cr(CN)6]⋅6.5H2O nanoparticles: synthesis, characterization, and magnetic properties

We have synthesized nanoparticles of Cu_1.5[Cr(CN)₆]⋅6.5H₂O of varying size by using poly(vinylpyrrolidone) (PVP) as a protecting polymer. The particle size variation has been achieved by varying the amount of the PVP surfactant with the reactants. The prepared nanoparticles have been investigated by using X-ray diffraction, transmission electron microscopy, and direct-current magnetization techniques. The nanoparticles crystallize in a face centred cubic structure (space group: Fm3m). The approximate particle sizes for the three samples are 18, 9, and 5 nm, respectively. Non-PVP nanoparticles (18 nm) show a magnetic ordering temperature of 65 K. A decrease in the magnetic ordering temperature was observed with decreasing particle size. These nanoparticles are magnetically very soft, showing negligibly small values of the coercivity and remanent magnetization. The maximum magnetization and spontaneous magnetization values at 5 K are found to decrease with decreasing particle size. The observed magnetization behaviour of the nanoparticles has been attributed to the increasing surface spin disorder with decreasing particle size.     

Magnetic behavior in the incommensurate phase ∼LaCrS3:: effect of the partial substitution of Cr by Ti on the magnetic properties

Dilution of the magnetic interactions between Cr³⁺ ions by Ti³⁺ ions was observed in the CrS₂ layer of the misfit-layer compound ∼LaCrS₃. Pure ∼LaCrS₃ has complex magnetic properties which are reminiscent of spin glass behavior. This magnetic behavior comes from both the modulated character of the structure and the magnetic frustration of the planar-antiferromagnetic-triangular network of Cr³⁺ ions. Thus, there is a large hysteresis between the zero field cooled and the field cooled magnetic susceptibility curves below the transition temperature (≈75 K). Formation of a solid solution ∼LaCr_1−xTi_xS₃ by the addition of Ti³⁺ ions results in the decrease of transition temperature up to a doping level of x≈0.5, where the transition is no longer observed. The magnetic behavior of the phase with x≈0.5 is similar to that of several random exchange antiferromagnetic compounds.     

The effect of Ag adsorption on the structural,electronic, and optical properties of the ZnO(101̅0) surface: A first-principles study

The effect of the Ag adsorption on the structural, electronic and optical properties of the clean ZnO$(10\bar{1}0)$ surface was investigated using the first principles method. The obtained results show that adsorbed Ag atoms transfer charge to the surface which results in a charge accumulation in near-surface region accompanied with a decrease of the work function. On the other hand, our results show that the adsorption of Ag atoms leads also to the new optical absorption peaks in the visible region which could improve ZnO photocatalytical properties.     

Structural and electrical properties of LiCo3/5Cu2/5VO4 ceramics

The LiCo_3/5Cu_2/5VO₄ compound is prepared by a solution-based chemical method and characterized by the techniques of X-ray diffraction, scanning electron microscopy and complex impedance spectroscopy. The X-ray diffraction study shows an orthorhombic unit cell structure of the material with lattice parameters a=13.8263 (30) Å, b=8.7051 (30) Å and c=3.1127 (30) Å. The nature of scanning electron micrographs of a sintered pellet of the material reveals that grains of unequal sizes (～0.2–3 μm) present an average grain size with a polydisperse distribution on the surface of the sample. Complex plane diagrams indicate grain interior and grain boundary contributions to the electrical response in the material. The electrical conductivity study reveals that electrical conduction in the material is a thermally activated process. The frequency dependence of the a.c. conductivity obeys Jonscher’s universal law.