Role of interfacial crystallites in the crystallization of α-Fe2O3/α-Al2O3(0 0 0 1) thin films

In situ crystallization of α-Fe₂O₃/α-Al₂O₃(0 0 0 1) thin films was studied in real-time synchrotron X-ray scattering experiments. We find the coexistence of α-Fe₂O₃ (hexagonal) and Fe₃O₄ (cubic) interfacial crystallites (∼50-Å-thick), well aligned [0.02° full-width at half-maximum (FWHM)] to the α-Al₂O₃[0 0 0 1] direction, in the sputter-grown amorphous films. As the annealing temperature increases up to 750°C, the cubic stacking of the Fe₃O₄ crystallites gradually changes to the hexagonal α-Fe₂O₃ stacking, together with the growth of the well-aligned (WA) (0.02° FWHM) grains from the α-Fe₂O₃ crystallites. In the meanwhile, heterogeneous nucleation starts to occur on the substrate at ∼600°C, resulting in the formation of misaligned (1.39° FWHM) α-Fe₂O₃ grains. Our study reveals that the interfacial crystallites act as a template for the growth of the WA α-Fe₂O₃ grains.     

Growth of Sm1 – ySryF3 – y (0 < y ≤ 0.31) Crystals and Investigation of Their Properties

Crystallography Reports - Sm1&nbsp;–&nbsp;ySryF3&nbsp;–&nbsp;y (0 &lt; y ≤ 0.31) crystals have been grown from melt by directional solidification in a...     

Optical and electrical properties of as-prepared and annealed (Se80Te20)100 − xAgx (0 ≤ x ≤ 4) ultra-thin films

Optical and electrical properties of the (Se₈₀Te₂₀)_100 ? xAg_x (0 ≤ x ≤ 4) ultra-thin films have been studied. The ultra-thin films were prepared by thermal evaporation of the bulk samples. Thin films were annealed below glass transition temperature (328 K) and in between glass transition temperature and crystallization temperature (343 K). Thin films annealed at 343 K showed crystallization peaks for Se–Te–Ag phases in the XRD spectra. The transmission and reflection of as-prepared and annealed ultra-thin films were obtained in the 300–1100 nm spectral region. The optical band gap has been calculated from the transmission and reflection data. The refractive index has been calculated by the measured reflection data. It has been found that the optical band gap increases, but the refractive index, extinction coefficient, real and imaginary dielectric constant decrease with increase in Ag content. The optical band gap and refractive index show the variation in their values with increase in the annealing temperature. The extinction coefficient increases with increasing annealing temperature. The surface morphology of ultra-thin films has been determined using a scanning electron microscope (SEM). The measured dc conductivity, under a vacuum of 10^? 5 mbar, showed thermally activated conduction with single activation energy in the measured temperature range (288–358 K) and it followed Meyer–Neldel rule. The dc activation energy decreases with increase in Ag content in pristine and annealed films. The results have been analyzed on the bases of thermal annealing effects in the chalcogenide thin films.     

Magnetic behavior,transport properties and nanocrystallization of melt-spun YxCe50 − xCu42Al8 (0 ≤ x ≤ 50) amorphous system

Amorphous Y_xCe_50 ? xCu₄₂Al₈ (0 ≤ x ≤ 50) ribbons prepared by melt-spinning on the Cu wheel were subjected to X-ray diffractometry (XRD), differential scanning calorimetry (DSC) and to the measurements of magnetization and resistivity in the temperature range from 1.7 to 300 K. Effective activation energies, characteristic crystallization temperatures and enthalpies of as-quenched alloys have been determined. Two stages of crystallization have been observed in most samples (except shallow effects in Ce₅₀Cu₄₂Al₈). The activation energies have been calculated from the Kissinger relation to be 247 ± 18 and 570 ± 56 kJ/mol for Y₂₅Ce₂₅Cu₄₂Al₈ and Y₅₀Cu₄₂Al₈, respectively. The absence of the endothermic effect for x = 50, usually associated with a glass transition, below the primary crystallization event, indicates the presence of dispersed polyamorphous packing with a wide range of local glass transitions. The magnetization versus temperature plot for Y₂₅Ce₂₅Cu₄₂Al₈ points to a magnetic ordering at temperatures considerably below 50 K. This observation has been confirmed by the temperature dependence of resistivity, which exhibits a singularity at the same temperature. Moreover, a negative temperature coefficient of resistivity, characteristic of disordered systems, was observed. The electrical resistivity in the Y₂₅Ce₂₅Cu₄₂Al₈ amorphous alloy is governed by the weak localization of electrons.     

MOCVD growth and optical properties of non-polar (1 1–2 0) a-plane GaN on (1 0–1 2) r-plane sapphire substrate

Non-polar a-plane GaN film with crystalline quality and anisotropy improvement is grown by use of high temperature AlN/AlGaN buffer, which is directly deposited on r-plane sapphire by pulse flows. Compared to the a-plane GaN grown on AlN buffer, X-ray rocking curve analysis reveals a remarkable reduction in the full width at half maximum, both on-axis and off-axis. Atomic force microscopy image exhibits a fully coalesced pit-free surface morphology with low root-mean-square roughness (∼1.5 nm). Photoluminescence is carried out on the a-plane GaN grown on r-plane sapphire. It is found that, at low temperature, the dominant emission at ∼3.42 eV is composed of two separate peaks with different characteristics, which provide explanations for the controversial attributions of this peak in previous studies.     

Synthesis and structure–property relations in xCuO–(1 − x)Bi2O3 (0.5 ⩽ x ⩽ 0.9) (C1–C5: x = 0.5, 0.6, 0.7, 0.8, 0.9) glasses

Synthesis of the xCuO–(1 ? x)Bi₂O₃ (0.5 ? x ? 0.9) (C1–C5: x = 0.5, 0.6, 0.7, 0.8, 0.9) glasses was done via nitrate–citrate gel route. Glassy phase is ascertained by XRD studies. Magnetic susceptibility results in the range 4.2–400 K show weak paramagnetic nature with exchange integrals ～0.024–0.13 eV in the glasses. The electron paramagnetic resonance (EPR) in the range 4.2–363 K shows g ≈ 2.0 and the trend of the g-matrix elements g_|| > g_⊥ > g_e for the glasses C1–C5 at 4.2 K are due to the Cu²⁺ (3d⁹) paramagnetic site in the glasses which is in a tetragonally elongated octahedron [O_1/2–CuO_4/2–O_1/2] having D_4h symmetry. IR spectroscopic results show the presence of octahedron [BiO_6/2]^3? and [CuO_6/2]^4? units and pyramidal [BiO_2/2O]^? unit in the glasses.     

Nanostructured Crystals of Fluorite Phases Sr1 – xRxF2 + x (R Are Rare-Earth Elements) and Their Ordering. 15. Concentration Dependence of the Defect Structure of As Grown Nonstoichiometric Phases Sr1 – xRxF2 + x (R = Sm,Gd)

Crystallography Reports - The defect structure of as grown single crystals Sr1&nbsp;–&nbsp;xSmxF2&nbsp;+&nbsp;x (x = 0.14, 0.26) and...     

Structural analysis of xCsCl(1 − x)Ga2S3 glasses

Sulphide glasses doped with rare-earth ions have been demonstrated to be suitable for photonic applications such as optical amplifiers, up-converters and fiber lasers. The substitution of metal halides into the glass network has been shown to result glasses with desirable properties in terms of quantum efficiency and fiber manufacture [J.R. Hector, J. Wang, D. Brady, M. Kluth, D.W. Hewak, W.S. Brocklesby, D.N. Payne, Journal of Non-Crystalline Solids 239 (1998) 176]. To assist in the understanding of this improvement a structural analysis of glasses with a composition xCsCl(1 ? x)Ga₂S₃ has been undertaken in order to examine the nature of the gallium environment. Information collected by high energy X-ray diffraction and neutron diffraction have been analyzed to permit the identification of the structural units as Ga centered tetrahedra. The interconnection between the tetrahedra was found to be predominantly corner sharing.     

Comparative Analysis of the Methods for Obtaining Superconducting Fe1 + ySexTe1 – x Single Crystals

Crystallography Reports - The Fe1&nbsp;+&nbsp;ySexTe1&nbsp;–&nbsp;x single crystals grown by the KCl flux and Bridgman methods have been compared using the same investigation...     

Growth of Pb on Si(3 3 5)–Au surface

The growth, crystallographic structure and electronic properties of ultrathin Pb films grown on a vicinal silicon surface are investigated with reflection high energy electron diffraction (RHEED) and specific resistivity measurement techniques. A Si(3 3 5) surface with a perfect distribution of monoatomic steps separated with (1 1 1) terraces induced by a submonolayer amount of Au is used as a substrate. In the early stage, Pb growth is anisotropic. Apparently, the presence of steps forces the growth of short crystalline Pb chains along the steps. The layer is amorphous in the perpendicular direction. With the increasing thickness, a phase transition takes place between 3 and 4 monolayers (ML) that makes crystalline order also across the terraces. A further increase in thickness causes the layer surface to repeat the substrate morphology. It consists of regularly distributed monoatomic steps and narrow (1 1 1) terraces.     

Crystallization kinetics of a-Se75Te25 − xGax (x = 0, 5, 10 and 15 at wt %) glassy system

Bulk glasses of a-Se₇₅Te_25 ? xGa_x (x = 0, 5, 10 and 15 at wt %) have been prepared by melt quenching technique. These samples were structurally characterized by using X-ray diffraction. Kinetic of crystallization in these glasses was studied under non-isothermal conditions using differential thermal analysis (DTA). DTA is performed at different heating rates of 5, 10, 15, 20 and 30 °C/min. The values of glass transition (T_g) and crystallization peak temperature (T_p) are found to be composition and heating-rate dependent. The obtained results have been analyzed in terms of activation energy of glass transition (E_g) using Kissinger's and Mahadevan et al. relations. Values of E_g obtained by the two relations are in agreement with each other. The results indicate that the crystallization process is a three-dimensional growth.     

Calorimetric study and Kissinger analysis of melt-spun DyMn6−xGe6−xFexAlx (1 ⩽ x ⩽ 2.5) alloys

Thermal properties of rapidly quenched alloys from the DyMn_6?xGe_6?xFe_xAl_x (1 ? x ? 2.5) series produced by melt-spinning have been investigated by differential scanning calorimetry (DSC). The DSC curves show two exothermic effects connected with crystallization processes. Crystallization temperatures and enthalpies ΔH have been estimated. The systematic changes in these parameters allow concluding that the crystallization exothermic events are independent. Effective activation energies E have been determined using the Kissinger analysis and relatively high values up to 480 ± 20 kJ/mol for DyMn₄Ge₄Fe₂Al₂ have been found indicating high thermal stability of the amorphous state in this alloy series.     

Nanostructured Crystals of Fluorite Phases Sr1 – xRxF2 + x (R Are Rare-Earth Elements) and Their Ordering. 13: Crystal Structure of SrF2 and Concentration Dependence of the Defect Structure of Nonstoichiometric Phase Sr1 – xLaxF2 + x As Grown (x = 0.11, 0.20, 0.32, 0.37, 0.47)

Crystallography Reports - The defect structure of as-grown SrF2 and nonstoichiometric phases Sr1&nbsp;–&nbsp;xLaxF2&nbsp;+&nbsp;x (x = 0.11, 0.20, 0.32, 0.37, 0.47) single...     

Square-wave voltammetry and impedance spectroscopy in tin doped melts with the compositions xNa2O · 15Al2O3 · (85 − x)SiO2 (x = 8.5, 11 and 16)

Glasses with the base compositions xNa₂O · 15Al₂O₃ · (85 ? x)SiO₂ (x = 8.5, 11 and 16) doped with 0.5 mol% SnO₂ were investigated by both square-wave voltammetry and impedance spectroscopy in the temperature range from 1300 to 1600 °C. Each recorded square-wave voltammogram exhibits a well pronounced peak attributed to the Sn²⁺/Sn⁴⁺-redox pair. Impedance spectra were measured in a frequency range from 0.1 to 10⁵ s^?1 as a function of the superimposed dc-potential and were simulated using an equivalent circuit taking into account the resistivity of the melt, the electrochemical double layer, a resistor attributed to a kinetically hindered electron transfer and a Warburg parameter which accounts for the diffusion process of Sn⁴⁺ and Sn²⁺ to and from the electrode. Additionally, two impedance elements, a resistor and a capacitance both attributed to adsorption processes were necessary to fit the impedance spectra.     

Electronic properties calculation of Ge1 − x − ySixSny ternary alloy and nanostructure

The band structure of Ge_{1 ? x ? y}Si_xSn_y ternary alloys, which are easier to grow than binary Ge_1-xSn_x alloys, and clearly offer a wider tunability of their direct band-gap and other properties, was calculated and investigated by using the empirical pseudo-potential plane wave method with modified Falicov pseudo-potential formfunction. The virtual crystal approximation (VCA) and 2 × 2 × 2 super-cell (mixed atoms) method were adopted to model the alloy. In order to calculate all of these properties, the empirical pseudo-potential code was developed. The lattice constant of the alloy varies between 0.543 to 0.649 nm. The regions in the parameter space that corresponds to a direct or indirect band gap semiconductor are identified. The Ge_{1 ? x ? y}Si_xSn_y ternary alloy shows the direct band gap for appropriate composition of Si, Ge and Sn. The direct energy gap is in the range 0–1.4 eV (from the VCA calculation), and 0–0.8 eV (from the super-cell calculation), depending on the alloy composition. Therefore, this alloy is a promising material for optoelectronic applications in both visible and infrared range, such as interband lasers or, solar cells. Furthermore, strain-free heterostructures based on such alloys are designed and, using the effective-mass Hamiltonian model, the electronic structure of GeSiSn quantum wells with arbitrary composition is investigated, in order to understand their properties and the potential of their use in devices.     

Amorphous Ni59Nb40PtxM1−x (M = Ru, Sn) electrocatalysts for oxygen reduction reaction

The oxygen reduction reaction, ORR, on amorphous Ni₅₉Nb₄₀Pt₁, Ni₅₉Nb₄₀Pt_0.6Ru_0.4 and Ni₅₉Nb₄₀Pt_0.6Sn_0.4 electrocatalysts was analyzed by electrochemical techniques such as cyclic voltammetry, CV; rotating disk, RDE, and ring-disk electrodes, RRDE, in a 0.5 M H₂SO₄ solution. The reduced amount of platinum and the incorporation of transition metals in the amorphous catalysts were found to have significant effect on the kinetic parameters of the cathodic reaction. The kinetics study (RRDE) performed on the amorphous catalysts showed a high activity towards the ORR, preferentially proceeding via multi-electron (4e^?) charge transfer pathway toward water formation, with less than 2.8% H₂O₂ in the region of PEMFC applications. The performance on Ni₅₉Nb₄₀Pt₁ was different, which may be related to changes in the electrode surface enrichment of one or two of the amorphous alloy constituents. The performance towards the cathodic reaction allows to envisage that incorporation of small amounts of Pt in the catalyst, may lead to the fabrication of good amorphous electrocatalytic materials with possible applications as cathode electrodes in polymer electrolyte fuel cells.     

Nano-heterogeneous structure of (1-x)KNbO3–xSiO2 glasses in the low glass-forming oxide content range 0.05 ≤ x ≤ 0.3

Glasses with a high content of niobium oxide are of significant interest for electro-optics and nonlinear optics. In the present paper we report the results of the investigation of the submicroscopic structure and nonlinear optical properties of (1-x)KNbO₃–xSiO₂ (KNS) glasses (x = 0.05–0.30) by XRD, SANS, electron microscopy and second harmonic generation (SHG) technique. Vitreous samples were fabricated by rapid melt cooling, via pressing the melt by steel plates, quenching between rotating metal rolls or splat cooling in air or nitrogen flow. Glasses with x < 0.15 are shown to possess a micro-inhomogeneous structure with regions enriched by SiO₂. On the contrary, as-quenched glasses with x > 0.15 are found by SANS to be homogeneous, but form nanostructures enriched by SiO₂ after heat-treatment. At temperatures below ~(T_g + 50 °C), SiO₂-enriched regions grow slightly, whereas their chemical composition shifts considerably closer to SiO₂. The data on the nano-inhomogeneous structure enables clarifying the complicated T_g(x) dependence of KNS glasses. SHG-active KNbO₃ phase precipitates at later stages of crystallization when the glass starts to lose its transparency, and crystallization of perovskite-like KNbO₃ is accompanied by the enhancement of SHG efficiency by several orders of magnitude.     

AlN buffer layer growth for GaN epitaxy on (1 1 1) Si: Al or N first?

AlN is generally used as buffer layer for the epitaxial growth of GaN on Si(1 1 1) substrate. In this work, we specifically address the relationship between the way the AlN growth is initiated on the Si(1 1 1) surface and the overall properties of the final GaN epitaxial layer. The growth is performed by molecular beam epitaxy with ammonia (NH₃) as nitrogen source. Two procedures have been compared: exposing the Si surface first to NH₃ or Al. The AlN nucleation is followed in real-time by reflection high-energy electron diffraction and critical stages are also investigated in real space using scanning tunnelling microscopy and transmission electron microscopy. Atomic force microscopy, X-ray diffraction and photoluminescence are also used to assess the properties of the final GaN epitaxial layer. It is shown that best results in terms of GaN overall properties are obtained when the growth is initiated by exposing the Si(1 1 1) surface to NH₃ first. This is mainly due to the fact that almost an order of magnitude decrease of the dislocation density is obtained.