Correlation of the atomic and electronic structures and the optical properties of the Σ5(2 1 0)/[ 0 01] symmetric tilt grain boundary in yttrium aluminum garnet

A series of atomic models of the Σ5(2 1 0)/[0 0 1] symmetric tilt grain boundary in yttrium aluminum garnet (YAG) are constructed according to the coincident site lattice theory. Calculations performed using empirical potentials show that the O-termination configurations, namely G(1) and G(2), are the most energetically favorable boundary structures. First-principles density functional theory calculations have been further performed to understand the atomic and electronic structures, effective charge, potential distributions and optical properties of G(1) and G(2) grain boundaries. The simulated high-resolution transmission electron microscopy images of G(1) and G(2) are generally in good agreement with the experimental micrographs of the Σ5(2 1 0)/[0 0 1] grain boundaries. Results show that the effective charges of the atoms in the grain boundary region are related to their coordination numbers and bonding lengths. Moreover, the overall total density of states of G(1) and G(2) has been found to have similar features with the bulk YAG, with the exception of some defect states being introduced at the top of the valence band, resulting in the reduction of the band gap. The calculated optical properties show that the refractive indices of both grain boundary models are slightly larger than those of the bulk YAG. This is in agreement with the experimental observation that the refractive index of the polycrystalline YAG is higher than that of its single crystalline counterpart.     

Atomistic structure of the Cu(1 1 1)/α-Al2O3(0 0 0 1) interface in terms of interatomic potentials fitted to ab initio results

We propose an atomistic model to describe the copper/sapphire interface by means of simple interatomic potentials involving only a few fitting parameters. Successful results are achieved when the copper atoms in the monatomic layer closest to the interface have properties different from the bulk. This layer is to accommodate the ionic/covalent bonding in the ceramics to the metallic bonding in copper. For an oxygen terminated interface, we fit the parameters of the potentials to the results of a rigid tensile test (explained in the text) simulated from first principles. The results of atomic relaxation near the interface are shown to be consistent with ab initio and experimental results available in the literature. Calculations reveal highly interesting relaxation dynamics near the interface. In the early stage of relaxation, a periodic network of partial misfit dislocations is formed, which later transforms into an irregular network due to the instability of the layer of copper atoms atop the oxygen atoms. This explains the interface incoherency observed in high-resolution electron microscopy. Calculations based on the FK model reproduce this effect.     

Atomic structure of the Σ5 (310)/[001] symmetric tilt grain boundary in molybdenum

Atomistic simulations offer an important route towards understanding and modeling materials behavior. Incorporating the essential physics into the models of interatomic interactions is increasingly difficult as materials with more complex electronic structures than f.c.c. transition metals are addressed. For b.c.c. metals, interatomic potentials have been developed that incorporate angularly dependent interactions to accommodate the physics of partially filled d-bands. A good test of these new models is to predict the structure of crystal defects and compare them with experimentally observed defect structures. To that end, the Σ5 (310)/[001] symmetric tilt grain boundary in Mo has been fabricated and characterized by HREM. The experimentally observed structure is found to agree with predictions based on atomistic simulations using angular-force interatomic potentials developed from model generalized pseudopotential theory (MGPT), but disagrees with predictions based on radial-force potentials, such as those obtained from the Finnis–Sinclair method or the embedded atom method (EAM).     

Early stage oxidation of Ni–Cr binary alloy (1 1 1), (1 1 0) and (1 0 0) surfaces: A combined density functional and quantum chemical molecular dynamics study

First-principles and tight-binding quantum chemical molecular dynamics were used in this study. The chemisorption energies of O and OH on the Ni–Cr (1 1 0) surface are lower than those of other surfaces. The oxygen 2p orbitals hybridise with Ni 3d, 4s and small amounts of p orbitals for the (1 0 0) surface while Ni p orbitals have no contribution for the (1 1 0) surface, which might reduce the adsorption energy. Additionally, oxygen acquires the maximum depth into the Ni–Cr (1 1 0) surface. Applied strain increases the oxygen diffusivity. This study reveals that the Ni–Cr (1 1 0) surface is easier for oxygen diffusion accordingly oxidation accelerates.     

Hydrogen sorption in the LaNi5-xAlx-H system (0 ≤ x ≤ 1)

A thermodynamic assessment of hydrogen sorption in LaNi_5-xAl_x-H (0 ≤ x ≤ 1) alloys was performed combining experimental and theoretical investigations. The occurrence of sloped plateaux in Pressure Composition Isotherms (PCI) is discussed on the basis of compositional inhomogeneities and of possible re-distribution of metallic elements between the hydrogen rich and the hydrogen poor phases.In order to provide input for the thermodynamic assessment, literature data were reviewed and PCI experiments were performed at increasing temperatures on alloys with different Al contents. The presence of a compositional distribution was investigated using Rietveld refinement of X-Ray diffraction patterns, volumetric and calorimetric measurements, both on as received and annealed samples with LaNi_4.8Al_0.2 nominal composition. Moreover, ab initio energies of formation for LaNi₅, LaAl₅ and the respective hydrides were calculated. A full CALPHAD assessment of the Gibbs energy for LaNi_5-xAl_xH_y (0 ≤ x ≤ 1, 0 ≤ y ≤ 7) phase was obtained, showing a good agreement between experimental and calculated results.The presence of sloped and flat plateaux has been related to the occurrence of ortho- and para-equilibrium conditions.     

Crystal structure,band structure and electrical properties of κ-(BEDT-TTF)2SbF6 grown on a Si(0 0 1) electrode

The new κ-(BEDT-TTF)₂SbF₆ phase was grown by electrodeposition on a Si(0 0 1) electrode. This new phase was characterized by X-ray diffraction (XRD) and electronic conductivity measurements, accompanied by calculations of electronic band structures and Fermi surfaces. Below T = 120 K, a decrease in the electronic conductivity suggests a phase transition, attributed to anion ordering.     

Structural and optical properties of epitaxial ZnO thin films on 4H–SiC (0 0 0 1) substrates prepared by pulsed laser deposition

Epitaxially grown ZnO thin films on 4H–SiC (0 0 0 1) substrates were prepared by using a pulsed laser deposition (PLD) technique at various substrate temperatures from room temperature to 600 °C. The crystallinity, in-plane relationship, surface morphology and optical properties of the ZnO films were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) measurements, respectively. XRD analysis showed that highly c-axis oriented ZnO films were grown epitaxially on 4H–SiC (0 0 0 1) with no lattice rotation at all substrate temperatures, unlike on other hexagonal-structured substrates, due to the very small lattice mismatch between ZnO and 4H–SiC of ～5.49%. Further characterization showed that the substrate temperature has a great influence on the properties of the ZnO films on 4H–SiC substrates. The crystalline quality of the films was improved, and surfaces became denser and smoother as the substrate temperature increased. The temperature-dependent PL measurements revealed the strong near-band-edge (NBE) ultraviolet (UV) emission and the weak deep-level (DL) blue-green band emission at a substrate temperature of 400 °C.     

Mechanism of depolarization with temperature for <0 0 1> (1 − x)Pb(Zn1/3Nb2/3)O3–xPbTiO3 single crystals

The temperature dependence of polarization for Pb(Zn_1/3Nb_2/3)_1?xTi_xO₃ single crystals poled in the [0 0 1]-direction has been investigated. During the application of a temperature increase, the percentage of switched domains and the distortion of the crystalline lattice in (1 ? x)PZN–xPT single crystals were evaluated by X-ray diffraction (XRD) patterns. Using this method, intrinsic and extrinsic contributions to polarization variations were separated in the temperature range from 25 °C to the Curie temperature (T_c). Experimental polarization variations were simulated from microscopic data and details on micro–macro relationships were given. It was found that polarization variation with temperature is caused by the variation of the distortion of the crystalline lattice for temperatures below the Curie temperature and that only 90° domain switching occurs in the vicinity of the Curie temperature. Moreover, the hysteretic behavior of the polarization with temperature is due to motion of domain walls. The understanding of mechanisms of depolarization with temperature and the hysteresis associated with are of interest for the enhancement the pyroelectric properties of the material for detection and energy harvesting applications.     

Glass-like thermal conductivities in (La1-x1Yx1)2(Zr1-x2Yx2)2O7-x2 (x = x1 + x2, 0 ⩽ x ⩽ 1.0) solid solutions

The evolution of structure and thermal conductivity (k) has been studied for a range of Y–La₂Zr₂O₇ solid solutions. Within the pyrochlore range (x < 0.40) Y³⁺ solely substitutes for La³⁺ below a critical composition factor (x = 0.15), above which it substitutes for both La³⁺ and the Zr⁴⁺. A glass-like k, approaching the amorphous limit, is observed within a certain composition range (0.20 ? x < 0.40). The glass-like k behaviour is attributed to a phonon localization effect that arises from small and weakly bound Y³⁺ cations (rattlers) oscillating locally and independently in oversized anionic cages [(La/Y)O₈]. The ultralow and glassy k makes Y³⁺-doped La₂Zr₂O₇ pyrochlores promising candidate materials for high temperature thermal barrier coating topcoats.     

Dislocation interaction of layers in the Ge/Ge-seed/GexSi1−x/Si(0 0 1) (x ∼ 0.3–0.5) system: Trapping of misfit dislocations on the Ge-seed/GeSi interface

High-resolution electron microscopy has been applied to study the dislocation redistribution between Ge and GeSi layers at the atomic scale. Ge_0.3Si_0.7 (30 nm in thickness) and Ge_0.5Si_0.5 (10 nm) buffer layers buried between the Si(0 0 1) substrate and the plastically relaxed Ge layer 0.5 μm thick remain in a metastable (stressed) state during the growth of Ge/Ge-seed/Ge_xSi_1?x/Si(0 0 1) (x ～ 0.3–0.5) heterostructures, though the buffer layer thickness is several times greater than the critical value for insertion of misfit dislocations (MDs). An ordered grid of edge MDs is observed only on the Ge/GeSi interface; the mean distance between the MDs is ～10 nm (which is close to the equilibrium value for the non-stressed Ge/Si system). After 30 min of annealing at 700 °С, the Ge_0.3Si_0.7 buffer layer still remains in a metastable state, and the edge MDs are located only on the Ge/GeSi interface with the same dislocation spacing of ～10 nm. At the same time, approximately one-half of MDs in the structure with the Ge_0.5Si_0.5 buffer layer passes through the Ge/GeSi interface to the GeSi/Si(0 0 1) interface, and the buffer layer plastically relaxes by almost 100%. An assumption is put forward that there exists a barrier for the MD transition from the Ge layer to the GeSi layer, which results in MD trapping on this interface. The magnitude of this barrier depends on the difference in the compositions of the main Ge (x = 1) film and the Ge_xSi_1?x buffer layer, and increases with increasing this difference.     

Epitaxial Ni–Mn–Ga/MgO(1 0 0) thin films ranging in thickness from 10 to 100 nm

Thin films of Ni–Mn–Ga alloy ranging in thickness from 10 to 100 nm have been epitaxially grown on MgO(1 0 0) substrate. Temperature-dependent X-ray diffraction measurements combined with room-temperature atomic force microscopy and transmission electron microscopy highlight the structural features of the martensitic structure from the atomic level to the microscopic scale, in particular the relationship between crystallographic orientations and twin formation. Depending on the film thickness, different crystallographic and microstructural behaviours have been observed: for thinner Ni–Mn–Ga films (10 and 20 nm), the L2₁ austenitic cubic phase is present throughout the temperature range being constrained to the substrate. When the thickness of the film exceeds the critical value of 40 nm, the austenite-to-martensite phase transition is allowed. The martensitic phase is present with the unique axis of the pseudo-orthorhombic 7M modulated martensitic structure perpendicular to the film plane. A second critical thickness has been identified at 100 nm where the unique axis has been found both perpendicular and parallel to the film plane. Magnetic force microscopy reveals the out-of-plane magnetic domain structure for thick films. For the film thickness below 40 nm, no magnetic contrast is observed, indicating an in-plane orientation of the magnetization.     

Preparation of dense TiN1 − X (X = 0–0.4) by pulsed electric current sintering: Densification and mechanical behavior

Bulks of TiN_1 − X in the range of X = 0–0.4 with high density were prepared by a new method which comprises the reaction between TiN with TiH₂ through pulsed electric current sintering. X-ray diffractograms revealed that single fcc phase with nitrogen vacancies was achieved after sintering; further observation by scanning electron microscopy showed homogeneous structure in all samples and larger grain size by increasing the amount of TiH₂. The maximum Vickers hardness measured on the samples was approximately 31 GPa at X = 0.3. An increase in hardness was observed in non-stoichiometric samples even its larger grain size. The grain size-indent diagonal ratio was calculated from 1.2 at X = 0 to 5.6 at X = 0.4. The addition of TiH₂ showed an improvement in both densification and hardness without significant degradation of fracture toughness. Based on these results, the mechanical properties of TiN_1 − X bulks can be controlled as a function of TiH₂/TiN ratios in order to be used for different applications.     

Thermal stability of Al1−xInxN (0 0 0 1) throughout the compositional range as investigated during in situ thermal annealing in a scanning transmission electron microscope

The thermal stability of Al_1?xIn_xN (0 ? x ? 1) layers was investigated by scanning transmission electron microscopy (STEM) imaging, electron diffraction, and monochromated valence electron energy loss spectroscopy during in situ annealing from 750 to 950 °C. The results show two distinct decomposition paths for the layers richest in In (Al_0.28In_0.72N and Al_0.41In_0.59N) that independently lead to transformation of the layers into an In-deficient, nanocrystalline and a porous structure. The In-richest layer (Al_0.28In_0.72N) decomposes at 750 °C, where the decomposition process is initiated by In forming at grain boundaries and is characterized by an activation energy of 0.62 eV. The loss of In from the Al_0.41In_0.59N layer was initiated at 800 °C through continuous desorption. No In clusters were observed during this decomposition process, which is characterized by an activation energy of 1.95 eV. Finally, layers richest in Al (Al_0.82In_0.18N and Al_0.71In_0.29N) were found to resist thermal annealing, although the initial stages of decomposition were observed for the Al_0.71In_0.29N layer.     

Thermoelectric performance of polycrystalline Sn1-xCuxSe (x = 0–0.03) prepared by high pressure method

P-type Sn_1-xCu_xSe (x = 0–0.03) polycrystal was prepared through melting synthesis and high pressure (6.0 GPa) sintering (HPS) method. The composition and microstructure of the samples was analyzed, and the thermoelectric transport properties were investigated in the temperature range of 303 K–823 K. The results indicate that the electrical conductivity increases as Cu content increases. An observable improvement is found for the Seebeck coefficient when x is 0.01. In addition, the total thermal conductivities (κ_tot) of all samples decrease with rising temperature, and reach its minimum values at 773 K. As a result, the maximum power factor (PF) and ZT_max value are 378 μW m⁻¹ K⁻² and 0.79 for Sn_0.97Cu_0.03Se at 823 K, respectively.     

Structural,magnetic and magnetoelastic properties of Laves-phase Tb0.3Dy0.6Nd0.1(Fe1-xCox)1.93 compounds (0 ≤ x ≤ 0.40)

Structure, magnetization and magnetostriction of Tb_0.3Dy_0.6Nd_0.1(Fe_1-xCo_x)_1.93 (0 ≤ x ≤ 0.40) compounds have been investigated. X-ray diffraction (XRD) analysis shows the presence of single Laves phase with a cubic MgCu₂-type structure. The easy magnetization direction (EMD) is observed to be <111> direction when x ≤ 0.10, and deviates away with further increasing Co contents. The Co contributes an opposite role in the resultant magnetocrystalline-anisotropy compared to Tb. A small amount of Co substitution for Fe can enhance the Curie temperature for x ≤ 0.25. The magnetocrystalline-anisotropy compensation can be achieved in this system. A minimum in anisotropy is obtained for the Tb_0.3Dy_0.6Nd_0.1(Fe_0.8Co_0.2)_1.93 compound, which has good magneto-elastic properties, e.g., the large saturation magnetostriction λ_S (∼930 ppm) and the high low-field magnetostriction λ_a (∼670 ppm/3 kOe), and may make it technological interest in the field of magnetostrictive materials.     

Influence of hydrogen on the deformation morphology of vanadium (1 0 0) micropillars in the α-phase of the vanadium–hydrogen system

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