Crystal structure and physical properties of magnetic shape memory alloys Ni50 − x Cu x Mn29Ga21

The phase composition, crystal structure, and physical properties (magnetization, electrical resistivity, thermoelectric power, relative elongation, and thermal expansion coefficient) of the stoichiometric alloy Ni₅₀Mn₂₅Ga₂₅ and nonstoichiometric alloys Ni_{50 ? x} Cu _x Mn₂₉Ga₂₁ (x = 0, 1, 2) with the thermoelastic martensitic transformation have been investigated. The influence of the chemical composition on the transformations and physical properties of the alloys has been determined.     

Investigation of the influence of nonstoichiometry and doping with carbon and nitrogen on the electronic spectrum of rutile by the coherent potential method

The electronic spectra and magnetic properties of rutile (TiO₂), nonstoichiometric rutile (TiO_{2 ? δ}), and stoichiometric and nonstoichiometric rutiles doped with carbon or nitrogen (TiO_{2 ? y ? δ}C _y and TiO_{2 ? y ? δ}N _y , y(δ) = 0, 0.03, 0.06) have been calculated using the coherent potential method. The used method of investigation has made it possible for the first time to calculate the disordered arrangement of impurity atoms and vacancies in the oxygen sublattice with their arbitrary concentration. The changes in the electronic spectrum and magnetic properties with variations in the concentration of dopants have been investigated. The possible photocatalytic activity of considered compositions has been analyzed.     

Facetting and (n × 1) reconstructions of SrTiO3(1 1 0) surfaces

(n × 1) reconstructions and facetting of the (1 1 0) polar surface of SrTiO₃ are studied by means of a combination of shell model and density functional calculations. The polarity compensation can be achieved through the formation of {1 0 0} nano-facets, which play a crucial role in the reconstruction process. The behaviors of various possible terminations (Sr, Ti, and O) are analyzed, as well as their atomic structure and energetics. Their stability in different chemical environments is discussed, with respect to previous formulations and experimental results. The Sr-terminated surface tends to expose large facets, while the TiO and O terminations are marginally stabilized or even destabilized by (n × 1) reconstructions, respectively. Trend to facetting results from a subtle competition between the thermodynamic stability of the ideal non stoichiometric (n × 1) surfaces, and huge atomic relaxations that contribute to the lowering of the surface energy differently for each termination.     

Effect of stoichiometry on the atomic and electronic structure of BaTiO3 nanoparticles: a first-principles study

We have used density functional theory calculations to investigate the atomic and electronic structure of barium titanate (BaTiO₃) nanoparticles. We studied the local atomic structure of different-sized stoichiometric and nonstoichiometric nanoparticle models in detail. Our results showed that all the stoichiometric BaTiO₃ clusters exhibit dielectric properties and form rhombohedral and monoclinic structures. However, oxygen deficient nonstoichiometric clusters show metallic behaviour and form cubic and tetragonal structures.     

Ab initio simulation of the BaZrO3 (0 0 1) surface structure

Electronic and atomic structures of different terminations of the (0 0 1) non-polar orientation of BaZrO₃ surfaces have been studied using first-principles calculations. We found that surface energies at both possible surface terminations, BaO and ZrO₂, were very close. The (0 0 1)-BaO and (0 0 1)-ZrO₂ terminated surfaces have bandgap values smaller than that of a bulk BaZrO₃ crystal. In addition, the relative surface stability has been analyzed as a function of chemical environment.     

Spin correlations and a mesoscopic structure in Ni-Mn-Ga

The mesoscopic structures of the Heusler alloys Ni_49.1Mn_29.4Ga_21.5 and Ni₂MnGa are studied by small-angle polarized neutron scattering in the temperature range 15 < T < 400 K. The characteristic temperatures of phase transformations (ferromagnetic, martensitic, and premartensitic transformations) and the characteristic sizes of mesoscopic inhomogeneities in them have been determined. Differences in the spin dynamics of these phases and magnetic-nuclear interference upon neutron scattering have been revealed. The evolutions of the mesoscopic structures in the nonstoichiometric and stoichiometric alloys are found to be substantially different.     

First-principles study of electronic properties and stability of Nb5SiB2（001） surface

The density functional calculations are performed to study the electronic structure and stability of Nb 5 SiB 2(001) surface with different terminations.The calculated cleavage energies along the(001) planes in Nb 5 SiB 2 are 5.015 J · m 2 and 6.593 J · m 2 with the break of Nb-Si and Nb-NbB bonds,respectively.There exists a close correlation between the surface relaxation including surface ripple and the cleavage energy:the larger the cleavage energy,the larger the surface relaxation.Moreover,the surface stability of the Nb 5 SiB 2(001) with different terminations has been investigated by the chemical potential phase diagram.From a thermodynamics point of view,the four terminations can be stabilized under different conditions.In chemical potential space,NbB(Nb) and Nb(Si) terminations are just stable in a small area,whereas Si(Nb) and Nb(NbB) terminations are stable in a large area(the letters in brackets represent the subsurface atoms).     

High-temperature ferromagnetism in Si1 ? x Mn x (x ≈ 0.5) nonstoichiometric alloys

It has been found that the Curie temperature (T _C ?? 300 K) in nonstoichiometric Si_{1 ? x} Mn _x alloys slightly enriched in Mn (x ?? 0.52?C0.55) in comparison to the stoichiometric manganese monosilicide MnSi becomes about an order of magnitude higher than that in MnSi (T _C ?? 30 K). Deviations from stoichiometry lead to a drastic decrease in the density of charge carries (holes), whereas their mobility at about 100 K becomes an order of magnitude higher than the value characteristic of MnSi. The high-temperature ferromagnetism is ascribed to the formation of defects with the localized magnetic moments and by their indirect exchange interaction mediated by the paramagnetic fluctuations of the hole spin density. The existence of defects with the localized magnetic moments in Si_{1 ? x} Mn _x alloys with x ?? 0.52?C0.55 is supported by the results of numerical calculations performed within the framework of the local-density-functional approximation. The increase in the hole mobility in the nonstoichiometric material is attributed to the decay of the Kondo (or spin-polaron) resonances presumably existing in MnSi.     

Surface rumpling of cubic CaTiO3 from density functional theory

In this paper, the structure of cubic CaTiO3 （001） surfaces with CaO and TiO2 terminations has been studied from density functional calculations. It has been found that the Ca atom has the largest relaxation for both kinds of terminations, and the rumpling of the CaO-terminated surface is much larger than that of TiO2-terminated surface. Also we have found that the metal atom relaxes much more prominently than the O atom does in each layer. The CaO-terminated surface is slightly more energetically favourahle than the TiO2-terminated surface from the analysis of the calculated surface energy.     

Accounting for nonstoichiometry of niobium carbide NbC y upon milling to a nanocrystalline state

The dependence of the size of particles in the prepared nanocrystalline powders on the composition of nonstoichiometric compounds within their homogeneity intervals has been considered in terms of the high-energy ball milling model. It has been shown that the effect of nonstoichiometry on the milling manifests itself in the concentration dependences of the main characteristics (parameters of the crystal structure, energy of interatomic bonds, elastic properties) of the milled nonstoichiometric compound. The results of model calculations performed for nonstoichiometric cubic niobium carbides NbC _y have been compared with the experimental data on milling of the NbC_0.93 carbide.     

Superconducting critical current of sputtered Nb-Ge films

The temperature dependence of the superconducting critical current density J_c(T) in zero applied field from 4.2 K to T_c has been measured for 15 films of Nb-Ge with varying composition, deposition conditions, and radiation damage. The results show (i) the enhanced superconductivity observed in stoichiometric Nb₃Ge as well as nonstoichiometric films is “bulk like” rather than filamentary, (ii) a simple correlation of the form which is reasonably independent of how the T_c has been achieved, and (iii) some additional evidence that the enhanced T_c of the films is not due to their chemical composition alone.     

X-ray spectra and specific features of the structure of lithium-sodium cobaltite Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Na<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>CoO<Subscript>2</Subscript>

The electronic structure and specific features of the structure of nonstoichiometric cobaltite Li _x Na _y CoO₂ (x = 0.42, y = 0.36) have been studied comprehensively. The calculated multiplet for the lowspin state of the Co³⁺ ion agrees with the experimental spectra. It has been established using X-ray absorption spectra measured in the total photoelectric effect yield and total fluorescence yield modes that the Li _x Na _y CoO₂ cobaltite is stoichiometric with respect to the alkali metal near its surface and is defective inside. It has been demonstrated that the charge compensation in the case of an alkali metal deficit in LixNayCoO₂ is due to holes in O 2p states.     

Optical properties of Li1−xNb1−xEu2xO3 solid solutions

Abstract

The effects of europium substitution on crystalline solubility, structural changes and optical properties of LiNbO₃ is reported. Li_1?xNb_1?xEu_2xO₃ solid solutions exist over a very limited range of europium concentrations (x ≤ 0.01). The solid solutions were characterized by X-ray powder diffraction and density measurements. Within the range of compositions of the solid solutions, the optical properties (emission and excitation spectra) of the Eu³⁺ ions have been characterized. The obtained optical data indicate that two equally abundant europium luminescent species exist in the stoichiometric speciments; these correspond to the Eu³⁺ ions occupying the Li⁺ and Nb⁵⁺ sites, in agreement with the replacement mechanism which is inferred from density measurements. Other Eu³⁺ luminescent species which appear to be closely related with lithium deficiency were found to exist in nonstoichiometric samples, in addition to those which are present in the stoichiometric materials.     

Structural,electronic, stability and reduction properties of perovskite surfaces: The case of rhombohedral BaCeO3

The (100), (110) and (111) surfaces of rhombohedral phase BaCeO₃ perovskite with two kinds of surface terminations are investigated using a periodic DFT + U method. We show that the lowest energy for surface formation via crystal cutting (cleavage energy) corresponds to (100) terminations. Out of all studied terminations, only BaO(100) and BaCeO(110) are stable with respect to precipitation of oxide phases and metals in respective ranges of oxygen chemical potentials, whereas CeO2(100) termination is not stable with respect to CeO₂ precipitation for all temperatures and oxygen partial pressures. Analyzing the electronic properties of the surfaces, we have established that reduction of the cerium oxidation state occurs in response to the local stoichiometry (lack of surface oxygen's, etc.) rather than as a result of breaking of cerium–oxygen bonds and formation of under-coordinated cerium ions. This equally applies to cerium reduction in the case of surface vacancy formation. We have calculated the vacancy formation energies as these can be viewed as a measure of surface activity in the catalytic reaction with various adsorbates. We find that CeO2 termination of the (100) surface and modified O2 termination of the (110) surface (O termination) have the lowest vacancy formation energies.     

First principle study of SrTiO3 (0 0 1) surface and adsorption of NO on SrTiO3 (0 0 1)

The results of first-principles calculations about the two possible terminations of (0 0 1) surface of SrTiO₃ perovskite and adsorption of NO on SrTiO₃ (0 0 1) surface were presented. Both surface parameters (atomic structures and electronic configurations) and adsorption parameters (bond, energy and charge) of NO on SrTiO₃ (0 0 1) surface, which have never been investigated before as far as we know were investigated using density functional theory calculations with the local-density approximation (DFT-LDA). It was found that the two possible terminations of SrTiO₃ (0 0 1) surface have large surface relaxation, which leads to surface polarization and exhibits different reactivity toward the dissociative adsorption of NO. The electronic states of TiO₂-terminated surface have larger difference than that of bulk, so it is more favorable for adsorption of NO than SrO-terminated surface.     

Silicon MOS structures with nonstoichiometric metal-oxide semiconductors

MOS structures are formed by oxidative annealing of tin, tungsten, palladium, nickel, and zinc thin films on silicon, and their high-frequency C-V characteristics are measured. The energy spectra of the density of surface states taken of SnO_{2 ? x} , WO_{3 ? x} and PdO_x nonstoichiometric oxides are found to have common features.     

Cesium adsorption on the β2-GaAs(001) surface

The results of first-principles calculations of the cesium adsorption energy on the β2-GaAs(001) surface performed within approaches of the density functional theory are presented for two possible terminations of the surface. It is shown that, among the considered high-symmetry positions, the energy-preferred position for cesium is position T ₃ when the surface layer contains arsenic and position T ₄ for gallium terminated surface. Cesium introduces insignificant perturbations in the positions of surface-layer atoms, and surface dimers do not break even in the case of adsorption at the dimer bridge and top positions. It is shown that cesium bonding to the GaAs (001) substrate can be explained by sp hybridization of arsenic and gallium orbitals as well as by formation of cesium states mixed with delocalized states of a clean surface. At low coverage, more preferable adsorbate sites are those with nearest neighbor arsenic atoms for both surface terminations.     

Investigation of structural vacancies in titanium monoxide by electron-positron annihilation

Local atomic environment of vacancies in nonstoichiometric titanium monoxide ranging in composition from TiO_0.74 to TiO_1.26 was studied by electron-positron annihilation. Analysis of the Doppler broadening spectra of the annihilation gamma line for titanium and liquid oxygen showed that positrons in titanium monoxide are trapped by titanium vacancies. Experiments revealed that the lifetime of positrons in ordered and disordered titanium monoxide TiO _y increases with increasing oxygen content y and varies from 184 to 210 ps. Data on the valence electron density permitted the prediction that the lifetime of free positrons in stoichiometric titanium monoxide is about 140 ps and the lifetime of positrons localized in an oxygen vacancy is about 170 ps. The method used to analyze the gamma-line Doppler broadening spectra makes it possible to determine the type and number of atoms around a vacancy and to investigate order-disorder phase transformations in nonstoichiometric compounds.     

Preferable solar cell absorber – Near stoichiometric or stoichiometric CBD CIAS thin films?

Near stoichiometric and stoichiometric [CuIn_(1 − x)Al_(x)Se₂] (CIAS) thin films are prepared by chemical bath deposition (CBD) technique. X-ray diffraction (XRD) analysis have been employed to estimate the structural properties of CBD CIAS thin films and also to identify the near stoichiometric in particular defect free Cu-poor CBD CIAS thin films as preferable solar cell absorber material.     

Short-range order and nonstoichiometry in titanium monoxide TiO<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> from DFT calculations

Structural models of short-range order in the arrangement of structural vacancies have been proposed for stoichiometric and nonstoichiometric compositions of titanium monoxide TiO _y . A combined effect of the short-range order and nonstoichiometry on the ground-state energy and the electronic structure of the compound has been investigated using the first-principles methods. The energetically favorable models of short-range order reproduce the local distribution of atoms and vacancies, which is characteristic of the Ti₅O_5(mon) and Ti₅O_5(cub) superstructures. In these models, the correlations between the vacancies of the metal sublattice and the vacancies of the nonmetal sublattice make a more significant contribution to the decrease in the energy of the compound as compared with the correlations between the vacancies in only one of the sublattices.