Thermal expansion and structure of orthorhombic CaMnO3

The structure of CaMnO₃ has been studied from room temperature to 800 °C by high-resolution synchrotron X-ray powder diffraction. It is concluded that CaMnO₃ remains orthorhombic in Pbnm over the entire temperature range, with the expansion in the cell volume well fitted to the expression Vol=207.37(2)+0.00563(8)T+1.17(9)×10^-6T². The magnitude of the MnO₆ tilts is estimated from the refined structural parameters and these progressively reduce as the temperate is increased.     

Microstructure and surface morphology of YSZ thin films deposited by e-beam technique

In present study yttrium-stabilized zirconia (YSZ) thin films were deposited on optical quartz (amorphous SiO₂), porous Ni-YSZ and crystalline Alloy 600 (Fe-Ni-Cr) substrates using e-beam deposition technique and controlling technological parameters: substrate temperature and electron gun power which influence thin-film deposition mechanism. X-ray diffraction, scanning electron microscopy (SEM), and atomic force microscopy (AFM) were used to investigate how thin-film structure and surface morphology depend on these parameters. It was found that the crystallite size, roughness and growth mechanism of YSZ thin films are influenced by electron gun power. To clarify the experimental results, YSZ thin-film formation as well evolution of surface roughness at its initial growing stages were analyzed. The evolution of surface roughness could be explained by the processes of surface mobility of adatoms and coalescence of islands. The analysis of these experimental results explain that surface roughness dependence on substrate temperature and electron gun power non-monotonous which could result from diffusivity of adatoms and the amount of atomic clusters in the gas stream of evaporated material.     

Spectroscopic studies of (AsSe)100−xAgx thin films

Thin (AsSe)_100−xAg_x films have been grown onto quartz substrates by vacuum thermal evaporation or pulsed laser deposition from the corresponding bulk materials. The amorphous character of the coatings was confirmed by X-ray diffraction investigations. Their transmission was measured within the wavelength range 400-2500 nm and the obtained spectra were analyzed by the Swanepoel method to derive the optical band gap E_g and the refractive index n. We found that both parameters are strongly influenced by the addition of silver to the glassy matrix: E_g decreases while n increases with Ag content. These variations are discussed in terms of the changes in the atomic and electronic structure of the materials as a result of silver incorporation.     

Application of the NRL tight-binding method to the heavy elements Pb and Po

We have applied the NRL tight-binding (TB) method to study the mechanical and electronic properties of the heavy elements Pb and Po. The predicted properties include ground-state structure, electronic band structure and elastic moduli. Phonon-dispersion curves at T=0 K were also determined. As demonstrated in this paper, the results are in good agreement with the full potential linearized augmented plane wave calculations and the available experimental data. In addition, we performed molecular-dynamics simulations to obtain various temperature-dependent quantities of Pb such as the atomic mean-square displacement, Debye-Waller factor and thermal expansion coefficient. With our TB we have also calculated the vacancy formation energy of Pb. Finally, we report on the effects of spin-orbit coupling, through our TB scheme, on electronic structure and energetic properties.     

Reaction kinetics of α-CuInSe2 formation from an In2Se3/CuSe bilayer precursor film

The reaction pathway and kinetics of α-CuInSe₂ formation from a glass/In₂Se₃/CuSe polycrystalline bilayer precursor film were investigated using time-resolved, in situ high-temperature X-ray diffraction. Bilayer glass/In₂Se₃/CuSe precursor films were deposited on thin glass substrates in a migration enhanced molecular beam epitaxial deposition system. These films were then temperature ramp annealed or isothermally soaked while monitoring the phase evolution. The initial In₂Se₃ and CuSe reactant phases were directly transformed to α-CuInSe₂ without any detectable intermediate phase. Kinetic parameters were estimated using the Avrami and parabolic diffusion controlled reaction models. The parabolic reaction model fitted the experimental data better than the Avrami model over the entire temperature range (230-290 °C) of the set of isothermal experiments, with an estimated activation energy of 162 (±5) kJ/mol.     

A high temperature powder neutron diffraction structural study of the apatite-type oxide ion conductor, La9.67Si6O26.5

High-resolution neutron powder diffraction studies of the oxide ion conductor La_9.67Si₆O_26.5 are reported for temperatures ranging between 25 and 900 °C. The best fit to the data was obtained for space group P6₃ and there was no evidence for any change in symmetry over the temperature range studied. Interstitial oxide ions are identified lying in sites similar to those predicted by previous computer modelling studies, and in agreement with structural studies on related materials. Furthermore, occupancy of these sites is enhanced by Frenkel-type disorder from neighbouring positions. The results thus add further weight to the interpretation that, in these apatite-type systems, the silicate substructure is important for the accommodation of interstitial oxide ions and their migration.     

Single crystal diffraction with X-rays and neutrons: High quality at high pressure?

Abstract

Single crystal X-ray and neutron diffraction is essential for determining occupancies, positional as well as static and dynamic displacement parameters in crystalline matter by measuring Bragg, satellite or diffuse reflections. In our contribution a new low-temperature high pressure cell for neutron single crystal diffraction will be presented. It is designed to operate from a few K to ambient temperature in “orange” cryostats at pressures up to at least 3 GPa. We will present first neutron diffraction results obtained at E4/HMI Berlin and discuss the quality of the data and the significance of the results. A software package has been written (as a part of the PROMETHEUS system), which deals with the data reduction for both X-ray and neutron high pressure cell single crystal data. Likewise a data collection program has been developed for single crystal data collection on four-circle diffractometers using Merrill-Bassett cells. A series of single crystal experiments on H₂O and D₂O ice VI and KDP (KH₂PO₄) show that results of very high quality can be obtained routinely including even higher order terms in the atomic displacement parameters.     

Local icosahedral order and thermodynamics of simulated amorphous Fe

Local icosahedral order and thermodynamics of amorphous Fe have been analyzed in detail for models containing 3000 atoms, which were obtained by the molecular dynamics (MD) method. Models were obtained by cooling from the melt. Local order in models has been analyzed by using the technique proposed by Honeycutt and Andersen; we found an existence of icosahedral order in the system. Moreover, structural properties of models were also studied via radial distribution function (RDF), static structure factor, mean atomic distances, coordination number and bond-angle distributions. Glass transition temperature, heat capacity and potential energy of the system were found in addition to the evolution of structure and mean-squared displacement (MSD) of atoms upon cooling from the melt toward the glassy state. We found the glass transition temperature of simulated liquid Fe via temperature dependence of potential energy and it is close to that observed previously in the literature, i.e. T_g≈1070 K. Calculations showed that structural properties of amorphous Fe models with the Pak-Doyama interatomic potential agreed well with the experimental data.     

Quantum Stark broadening of 3s–3p spectral lines in Li-like ions; Z-scaling and comparison with semi-classical perturbation theory

Quantum mechanical results for the electron impact Stark widths of the 3s–3p transitions in ten Li-like ions from C IV to P XIII are carried out. The atomic structure is obtained through a scaled Thomas-Fermi-Dirac-Amaldi potential (SST numerical code) with relativistic corrections. The distorted wave method is used for the calculation of the S-Matrix, and Feshbach resonances are included by means of the Gailitis method. A comparison with other theoretical and available experimental results is done. Except for Ne VIII, we find that the agreement between our quantum results and the experiments gets better when Z increases, which is not the case for the available close-coupling quantum ones. The behavior of the Stark width with the charge Z and the electron temperature T_e is also studied and in contrast to previous studies, an improved agreement with experimental Z-scaling is obtained. We show that the relative difference between widths of the two fine structure lines of the same multiplet increases with Z from 0.5% for C IV to about 12% for P XIII, proving the increasing importance of fine structure effects. The importance of the Feshbach resonances is discussed and a comparison with available semi-classical perturbation results is given.     

Theoretical and experimental analysis on spectral,hyperpolarizability and dielectric properties of semi-organic nonlinear optical crystal: Potassium boromalate hydrate (PBH)

Semi-organic potassium boromalate hydrate KBC₈H₈O₁₀·H₂O (PBH) salt was synthesized by reflux method and grown as single crystals by slow evaporation technique. The single crystal X-ray diffraction, Fourier transform infra red (FT-IR) and Fourier transform Raman spectral analyses were carried out to confirm the grown crystals. The factor group analysis was performed and the possible vibrational modes were predicted for PBH. The first order hyperpolarizability value calculated by quantum chemical calculations is well supported by the results obtained from Kurtz–Perry powder technique. The transparency in the entire blue, green and IR region makes it a valid candidate for the NLO applications. From the dielectric studies it is inferred that conductance predominates at low frequency region due to the exchange of electrical charges at crystal surface which results in the local displacement of electrons in the direction of the applied field.     

YB48 the metal rich boundary of YB66; crystal growth and thermoelectric properties

It was discovered that the well-known higher boride YB₆₆, one of the first reported phonon glass electron crystals (PGEC), could be obtained in a much more metal-rich composition than previously thought possible. Using the floating zone growth method, YB₄₈ single crystals with YB₆₆ crystal structure could be obtained, and their thermoelectric properties measured. This expansion of the homogeneity range of the well-known YB₆₆ compound is surprising and a new Y atomic site was discovered. YB₄₈ exhibits much higher power factors than YB₆₆ which increase rapidly with increasing temperature. The obtained dimensionless figure of merit of this compound at 990 K is approximately 30 times higher than that of previously reported YB₆₆ samples, and higher than any other pristine higher boride. This discovery reveals YB₄₈ as a promising high temperature thermoelectric material.     

A high-pressure Raman and X-ray diffraction study of the perovskite SrCeO3

A high-pressure structural study of SrCeO₃ has been performed at room temperature by Raman spectroscopy and X-ray diffraction up to 32 and 45 GPa, respectively. A first-order reversible phase transition is observed at about 12 GPa in both techniques. A second weak structural change, taking place between 18 and 25 GPa, can be suspected from Raman data. The increase in the number of Raman bands and diffraction lines is an indication that the symmetry is lowered and the compound does not evolve towards the ideal cubic perovskite structure. A Rietveld analysis of X-ray data was performed for the low-pressure phase and the atomic positions and the cell lattice parameters variations are reported in this paper. The volume compressibility derived from Raman modes (5.6×10⁻¹² Pa⁻¹), involving mainly bond-stretching for each type of polyhedron, is found to be close to the one obtained from volume cell variations measured by X-ray diffraction (7.9×10⁻¹² Pa⁻¹).     

Disorder-dependent photoluminescence in Ba0.8Ca0.2TiO3 at room temperature

The photoluminescence (PL) emission in structurally disordered Ba_0.8Ca_0.2TiO₃ (BCT20) powders was observed at room temperature with laser excitation at lines 355 and 460 nm. The structural evolution perovskite-like titanate BCT20 powders prepared by a soft chemical processing at different annealing temperatures were accompanied by X-ray diffraction (XRD) and X-ray absorption near-edge structure (XANES). Intermediate oxycarbonate phase was identified and your influence with PL emission was discarding. BCT20 annealed at 500 °C displays intense PL emission. The results indicate relationship between broad PL band and order-disorder degree.     

Inorganic-inorganic nanocomposite: Surface and conductive properties

Our previous experiences with incorporation of polyoxometalates (POMs) in different substrates have been very successful, because new nanocomposites with better conductive, catalytical and biochemical characteristics have been obtained. The results of intercalation of different mass% of ammonium decavanadate (ADV) in Al-pillared interlayered clays (Al-PILCs) are presented.The Al-PILCs were prepared using natural raw material, bentonite, containing a high percentage of montmorillonite (MM). Synthesis of ADV has been described in a previous paper. The structure of ADV hexahydrate was determined at low temperature, 100 K. A kappa refinement was performed to estimate the atomic charges.A sol-gel procedure was applied to obtain Al-PILCs composite intercalated with ADV hexahydrate (from 2 to 5 mass% of ADV). Structure and morphological properties of the new material, a nanocomposite of Al-PILCs-ADV, were investigated by X-ray powder diffraction (XRPD) and atomic force microscopy (AFM). To understand better how ADV is incorporated in the MM substrate, specific surface areas, pore structures and pore distributions were determined.Electrical and dielectric properties of the new materials were investigated by thermally stimulated depolarization currents (TSDCs) and broadband dielectric relaxation spectroscopy (DRS). The electrical conductivity of the nanocomposite was found to increase, in relation to MM, by intercalating with a small amount of ADV.     

Band structure and photocatalytic properties of perovskite-type compound Ca2NiWO6 for water splitting

An oxide semiconductor Ca₂NiWO₆, with double-perovskite crystal structure, was synthesized by solid-state reaction method. The compound Ca₂NiWO₆ was characterized by X-ray diffraction, UV-visible diffuse reflectance, and photoluminescence. The photocatalytic properties of the compound for water splitting were investigated under UV and visible light irradiation. The results showed H₂ evolution was not observed over the compound under visible light irradiation (λ>420 nm) with a 300 W xenon arc lamp when using methanol (CH₃OH) as electron donor, although the compound was responsive to visible light region. Based on the experimental results, a possible band structure was proposed through theoretical calculation of the electronic structure by using the full potential-linearized augmented plane wave (F-LAPW). The band structure and photocatalytic properties were attributed to the special crystal and electronic structures. Due to the oxygen vacancies in the compound, which worked as electron-hole recombination centers, the photocatalytic activity of the compound was low.     

Heat capacity anomaly in UO2 in the vicinity of 1300 K: an improved description based on high resolution X-ray and neutron powder diffraction studies

X-ray and neutron powder diffraction studies of UO₂ were performed under controlled oxygen partial pressure between room temperature and 1673 K. More than 40 neutron diffraction patterns were recorded. The thermal expansion coefficient of UO₂ and the temperature dependence of Debye-Waller factors for oxygen and uranium atoms were determined. The dependence of Debye-Waller factors as a function of temperature is linear and the thermal expansion coefficient follows the classical Debye regime within the temperature range 300-1000 K. Above 1200 K, a departure from this quasi-harmonic behavior is clearly observed. Both an abnormal increase of the thermal expansion and of the oxygen sublattice disorder are evidenced. The departure of the lattice parameter from a linear thermal variation is found to be thermally activated with an effective activation energy close to 1 eV, very similar to the activation energy already found for the electrical conductivity. This new result suggests that polarons may affect the mean lattice parameter. A new thermodynamic model is then proposed to explain the heat capacity thermal variation by only three contributions: harmonic phonons, thermal expansion and polarons.     

Atomically controlled surfaces with step and terrace of β-Ga2O3 single crystal substrates for thin film growth

The surface of β-Ga₂O₃ (1 0 0) single crystal grown with floating zone method was treated by chemical-mechanical-polishing (CMP) for 30-120 min followed by annealing in oxygen atmosphere at temperature 600-1100 °C for 3-6 h. The evolution of the step arrangement was investigated with reflection high energy electron diffraction and atomic force microscopy. Atomically smooth surfaces with atomic step and terrace structure of β-Ga₂O₃ substrates were successfully obtained after just CMP treatment as well as CMP treatment and post annealing at 1100 °C for 3 h. The uniform step height was 0.57 nm, and smooth terrace width was 100 nm, where the misorientation angle was about 0.36°. The obtained atomically smooth surface provides a potential application for the high-quality epitaxial film growth.     

Crystal chemistry of layered carbide, Ti3(Si0.43Ge0.57)C2

 The crystal structure of a layered ternary carbide, Ti₃(Si_0.43Ge_0.57)C₂, was studied with single-crystal X-ray diffraction. The compound has a hexagonal symmetry with space group P6₃/mmc and unit-cell parameters a=3.0823(1) Å, c=17.7702(6) Å, and V=146.21(1) Å³. The Si and Ge atoms in the structure occupy the same crystallographic site surrounded by six Ti atoms at an average distance of 2.7219 Å, and the C atoms are octahedrally coordinated by two types of symmetrically distinct Ti atoms, with an average C-Ti distance of 2.1429 Å. The atomic displacement parameters for C and Ti are relatively isotropic, whereas those for A (=0.43Si+0.57Ge) are appreciably anisotropic, with U₁₁ (=U₂₂) being about three times greater than U₃₃. Compared to Ti₃SiC₂, the substitution of Ge for Si results in an increase in both A-Ti and C-Ti bond distances. An electron density analysis based on the refined structure shows that each A atom is bonded to 6Ti atoms as well as to its 6 nearest neighbor A site atoms, whether the site is occupied by Si or Ge, suggesting that these bond paths may be significantly involved with electron transport properties.     

Simulation of displacement cascades in Ni–Al ordered alloys

Abstract

Molecular dynamics was used to investigate defect production induced by displacement cascades in ordered intermetallic alloys NiAl and Ni₃Al. The composite potentials obtained from the embedded atom potentials (EAM) and the universal function of Biersack and Ziegler were used. The number of point defects and their final structure produced by displacement cascades were investigated and compared with the standard NRT prediction. Crystalline structure, atomic mixing and chemical disordering were also studied during the evolution of the cascades, by measuring their characteristic parameters in the cells of the subdivided crystal.     

X-ray diffraction study of KOCN at room temperature

The room temperature structure of KOCN has been successfully refined in space group I4/mcm. The OCN anion is disordered through 180° head-tail flipping and the positional coordinates and displacement parameters could not be separated for the N and O end atoms. The displacement parameters are compared for isomorphous KOCN, KN₃ and KSCN.