Atomistic simulation of the point defects in TaW ordered alloy

Combining molecular dynamics (MD) simulation with modified analytic embedded-atom method (MAEAM), the formation, migration and activation energies of the point defects for six-kind migration mechanisms in B₂-type TaW alloy have been investigated. The results showed that the anti-site defects Ta_W and W_Ta were easier to form than Ta and W vacancies owing to their lower formation energies. Comparing the migration and activation energies needed for six-kind migration mechanisms of a Ta (or W) vacancy, we found that one nearest-neighbour jump (1NNJ) was the most favourable because of its lowest migration and activation energies, but it would lead to a disorder in the alloy. One next-nearest-neighbour jump (1NNNJ) and one third-nearest-neighbour jump (1TNNJ) could maintain the ordered property of the alloy but required higher migration and activation energies. So the 1NNNJ and 1TNNJ should be replaced by straight [100] six nearest-neighbor cyclic jumps (S[100]6NNCJ) (especially) or bent [100] six nearest-neighbour cyclic jumps (B[100]6NNCJ) and [110] six nearest-neighbor cyclic jumps ([110]6NNCJ), respectively.     

Atomistic simulation of the vacancy diffusion in (0 0 1) surface of MoTa alloy

The formation and diffusion of a single Mo or Ta vacancy in the (0 0 1) surface of the B₂-type MoTa alloy have been investigated by using modified analytical embedded-atom method (MAEAM). The results show that the effect of the surface on the vacancy is only down to the sixth layer. It is easier for the vacancy to form in the first layer. Comparing the migration energy of the vacancy migrating in the intra-layer, to the upper layer and to the nether layer via 2NN jump, we find that the vacancy in the first or second layer is preferred to migrate in intra-layer, and that in the third or fourth layer is favorable to migrate to the upper layer. Although 1NN jump will result in an anti-site so that a disorder in the order alloy, it may also occur due to the much lower migration energy especially for the vacancy in the second and third layer to migrate to the first and second layer, respectively.     

Texture of molybdenum thin films on SrTiO3(1 0 0): A RHEED study

The structure of ultrathin Mo films on SrTiO₃(1 0 0) was studied by in situ reflection high-energy electron diffraction (RHEED). A different structure was observed for films less than 20 Å thick than for thicker films. These films were epitaxial and had a metastable structure. Thicker films had the dimensions of equilibrium bcc Mo(1 1 0). Relaxation processes transformed the metastable Mo into bcc Mo, resulting in the following orientation relationships between Mo and SrTiO₃: (1 1 0)[0 0 1]_bcc Mo ∥ (1 0 0)[0 0 1]_SrTiO3 and (1 1 0)[1 1 1]_bcc Mo ∥ (1 0 0)[0 1 1]_SrTiO3. The formation of such specific orientations is related to transformations via the Bain and Needle Path, respectively.     

First-principle study of structural and electronic properties of ternary layered Ta2AlC

The structural and electronic properties of ternary layered Ta₂AlC ceramics have been studied using the first-principle method based on the density-functional theory. We have obtained the equilibrium lattice parameters and the equilibrium atomic positions in the unit cell. The equilibrium lattice parameters are computed to be a=b=3.15 Å and c=13.95 Å. The internal coordinates of Ta are determined to be (1/3, 2/3, 0.092). The band structure and density of states reveal that Ta₂AlC is an electronic conductor. The charge density distribution shows that the Ta and C atoms form a strong Ta-C-Ta covalently bonded chain.     

Calculation of the surface energy of bcc transition metals by using the second nearest-neighbor modified embedded atom method

The surface energies for 24 surfaces of all bcc transition metals Fe, Cr, Mo, W, V, Nb and Ta have been calculated by using the second nearest-neighbor modified embedded atom method. The results show that, for all bcc transition metals, the order among three low-index surface energies E_(1 1 0) < E_(1 0 0) < E_(1 1 1) is in agreement with experimental results and E_(1 1 0) is also the lowest surface energy for various surfaces. So that from surface energy minimization, the (1 1 0) texture should be favorable in the bcc films. This is also consistent with experimental results. The surface energy for the other surfaces increases linearly with increasing angle between the surfaces (h k l) and (1 1 0). Therefore, a deviation of a surface orientation from (1 1 0) can be used to estimate the relative values of the surface energy.     

The composition dependence and new assignment of the Raman spectrum in lithium tantalate

The Raman scattering spectra of lithium tantalate crystals with different compositions were investigated. The comparison of the Raman data obtained for the congruent and the near-stoichiometric crystals reveals some differences in the shape and the number of Raman peaks, which lead to a new assignment of the long-wavelength optical phonons. And quantitative relationships between the linewidth of Raman peaks (142 cm⁻¹ for E-phonon and 861 cm⁻¹ for A₁-phonon) and the crystal composition were firstly presented. Two local Raman lines, 278 and 750 cm⁻¹, were found for the congruent crystals and attributed to the intrinsic defects, Li vacancy and anti-site Ta ion, respectively.     

Magnetic properties of YFe12−xMox compounds and magnetocaloric effect of YFe9.5Mo2.5

The characterization and magnetic properties of YFe_12−xMo_x (x=2.0, 2.5 and 3.0) with the ThMn₁₂-type structure, and the magnetocaloric effect of YFe_9.5Mo_2.5 were investigated. A directional growth was observed in YFe₁₀Mo₂ alloy. A broad peak in the zero-field-cooling (ZFC) magnetization curve of the YFe_12−xMo_x compounds is ascribed to the existence of ferromagnetic clusters with different site moments and scattered orientations of the moments. The broad range of the peak is reduced with increasing Mo content. A weak peak is observed near 190 K in the ZFC curve of YFe₉Mo₃, which is associated with the 8i sites being mostly occupied by Mo atoms. YFe_9.5Mo_2.5 has a magnetic entropy change of −1.09 J/kg K for a field change of 5 T at 277 K.     

Structural properties and diffusion processes of the Cu3Au (0 0 1) surface

The surface relaxation and surface energy of both the mixed AuCu and pure Cu terminated Cu₃Au (0 0 1) surfaces are simulated and calculated by using the modified analytical embedded-atom method. We find that the mixed AuCu termination is energetically preferred over the pure Cu termination thereby the mono-vacancy diffusion is also investigated in the topmost few layers of the mixed AuCu terminated Cu₃Au (0 0 1) surface. In the mixed AuCu terminated surface the relaxed Au atoms are raised above Cu atoms for 0.13 Å in the topmost layer. All the surface atoms displace outwards, this effect occurs in the first three layers and changes the first two inter-layer spacing. For mono-vacancy migration in the first layer, the migration energies of Au and Cu mono-vacancy via two-type in-plane displace: the nearest neighbor jump (NNJ) and the second nearest neighbor jump (2NNJ), are calculated and the results show that the NNJ requires a much lower energy than 2NNJ. For the evolution of the energy requirements for successive nearest neighbor jumps (SNNJ) along three different paths: circularity, zigzag and beeline, we find that the circularity path is preferred over the other two paths due to its minimum energy barriers and final energies. In the second layer, the NN jumps in intra- and inter-layer of the Cu mono-vacancy are investigated. The calculated energy barriers and final energies show that the vacancy prefer jump up to a proximate Cu site. This replacement between the Cu vacancy in the second layer and Cu atom in the first layer is remunerative for the Au atoms enrichment in the topmost layer.     

Scanning tunneling microscopy investigation of clean (2 1 1) surface of Ta and Mo

Scanning tunneling microscopy was used to obtain images from clean (2 1 1) surfaces of Ta and Mo under the same ultrahigh vacuum conditions. In the case of tantalum the surface is very rough, and single extending atomic chains reach distances up to 100 Å. Those furrows are a surface reconstruction based on creation of (1 1 0) “micro-facets” along the [1 1 1] direction or (1 1 1)fcc micro-facets with a more dense structure than (1 1 0)bcc plane. In contrast, the (2 1 1) surface of Mo is smooth, and single atomic rows are visible on high resolution STM images. Step bunching occurs on the Mo surface, reducing the number of terrace edges.     

Study on bacteria adherence properties of Mo surface-modified layer in Ti6Al4V alloy prepared by plasma surface alloying technique

Mo surface-modified layer in Ti₆Al₄V alloy was prepared using plasma surface alloying technique. Microstructure of the modified layer was analyzed using X-ray photoelectron spectroscopy (XPS), rough-meter and GDA750 glow discharge optical emission spectrometer. Phase composition of the Mo surface-modified layer was characterized by D/max 2500 X-ray diffraction. Results show that the Mo surface-modified layers consist of pure Mo surface layer with 〈1 1 0〉 and 〈2 1 1〉 orientations and diffusion layer. Mo 3d, O 1s, C 1s and Ti 2p, O 1s, C 1s XPS spectra are recorded at topsurface in the Mo-modified layer and titanium substrate respectively. Because of the different roughness and microstructure, the Mo surface-modified layer can to some extent inhibit bacteria adherence.     

Investigation of Ni/Ta contacts on 4H silicon carbide upon thermal annealing

Nickel and Tantalum thin films with 3:5 thickness ratios were deposited in succession onto 4H-SiC substrate at room temperature. The samples were then heated in situ in vacuum at 650, 800 or 950 °C for 30 min. Glancing angle X-ray diffraction (XRD), Auger electron spectroscopy (AES) and current-voltage (I-V) technique were used for characterising the interfacial reactions and electrical properties. Amorphous Ni-Ta can be formed by solid-state reaction at 650 °C. The minor dissolved Ni in the Ta metal promotes the reaction between Ta and SiC. With increasing annealing temperature up to 950 °C, the dominant carbide changes from Ta₂C to TaC and a layer structure is developed. Electrical measurements show that ohmic contact is formed after annealing at or above 800 °C.     

Superconducting molybdenum nitride epitaxial thin films deposited on MgO and α-Al2O3 substrates by molecular beam epitaxy

Molybdenum nitride Mo₂N_x films were grown on MgO(0 0 1) and on α-Al₂O₃(0 0 1) substrates by molecular beam epitaxy under nitrogen radical irradiation. X-ray photoelectron spectroscopy revealed that the composition of the film varied in the range of Mo₂N_1.4-Mo₂N_2.8 depending on the growth temperature. The deposition at 973 K gave well-crystallized films on both substrates. The high-resolution reciprocal space mapping by X-ray diffraction showed that the nitrogen-rich γ-Mo₂N crystalline phase (the composition: Mo₂N_1.4) was epitaxially grown on MgO at 923 K with a slight tetragonal distortion (a = 0.421 and c = 0.418 nm) to fit the MgO lattice (a = 0.421 nm). On α-Al₂O₃(0 0 1), nitrogen-rich γ-Mo₂N (Mo₂N_1.8) was grown at 973 K with (1 1 1) planes parallel to the substrate surface. X-ray diffraction analysis with a multi-axes diffractometer revealed that the γ-Mo₂N on α-Al₂O₃(0 0 1) had a slight rhombohedral distortion (a = 0.4173(2) and α = 90.46(3)°). Superconductivity was observed below 2.8-3 K for the films grown at 973 K on MgO and on α-Al₂O₃(0 0 1).     

A photoelectron spectroscopic study of the carburization of MoO3

MoO₃ and Mo samples containing copper were treated with different hydrocarbon/hydrogen gas mixtures. The formation of Mo₂C was followed by X-ray photoelectron spectroscopy (XPS). Spectra taken in the Mo 3d, C 1s, O 1s, Cu 2p and Cu KLL regions demonstrated that the treatment with the hydrocarbon/hydrogen gas mixtures led to the formation of Mo₂C. From the comparison of the effects of various hydrocarbons on the XP spectra of Mo 3d we can state that the reduction of MoO₃ starts at the lowest temperature for C₂H₆/H₂ (600 K) followed by CH₄/H₂ (700 K) and C₄H₁₀/H₂ (723 K). Binding energies of Mo 3d_5/2 characteristic for Mo₂C are measured in the range of 227.7-228.0 eV. These values were attained at 900 K for CH₄/H₂, at 800 K for C₂H₆/H₂ and at 873 K for C₄H₁₀/H₂. Addition of copper to MoO₃ catalyzed its reduction and promoted the carburization process.     

Substrate temperature influenced structural, electrical and optical properties of dc magnetron sputtered MoO3 films

Molybdenum oxide (MoO₃) films were deposited on glass and (1 1 1) silicon substrates by sputtering of metallic molybdenum target in an oxygen partial pressure of 2 × 10⁻⁴ mbar and different substrate temperatures in the range 303-623 K using dc magnetron sputtering technique. X-ray photoelectron spectrum of the films formed at 303 K showed asymmetric Mo 3d_5/2 and Mo 3d_3/2 peaks due to the presence of mixed oxidation states of Mo⁵⁺ and Mo⁶⁺ while those deposited at substrate temperatures ≥473 K were in Mo⁶⁺ oxidation state of MoO₃. The films formed at substrate temperatures ≥473 K were polycrystalline in nature with orthorhombic α-phase MoO₃. Fourier transform infrared spectra of the films showed an absorption band at 1000 cm⁻¹ correspond to the stretching vibration of MoO, the characteristic of the α-MoO₃ phase. The electrical resistivity increased from 3.3 × 10³ to 8.3 × 10⁴ Ω cm with the increase of substrate temperature from 303 to 473 K respectively due to improvement in the crystallinity of the films. Optical band gap of the films increased from 3.03 to 3.22 eV with the increase of substrate temperature from 303 to 523 K.     

CoPt alloy grown on the WSe2(0 0 0 1) van der Waals surface

The structural and magnetic properties of 3-nm-thick CoPt alloys grown on WSe₂(0 0 0 1) at various temperature are investigated. Deposition at room temperature leads to the formation of a chemically disordered fcc CoPt alloy with [1 1 1] orientation. Growth at elevated temperatures induces L1₀ chemical order starting at 470 K accompanied with an increase in grain size and a change in grain morphology. As a consequence of the [1 1 1] growth direction, the CoPt grains can adopt one of the three possible variants of the L1₀ phase with tetragonal c-axis tilted from the normal to the film plane direction at 54°. The average long-range order parameter is found to be 0.35(±0.05) and does not change with the increase in the deposition temperature from 570 to 730 K. This behavior might be related to Se segregation towards the growing facets and surface disorder effects promoted by a high surface-to-volume ratio. Magnetic studies reveal a superparamagnetic behavior for the films grown at 570 and 730 K in agreement with the film morphology and degree of chemical order. The measurements at 10 K reveal the orientation of the easy axis of the magnetization lying basically in the film plane.     

Deformation of single crystal sample using D-DIA apparatus coupled with synchrotron X-rays: In situ stress and strain measurements at high pressure and temperature

We present a technique for high pressure and high temperature deformation experiment on single crystals, using the Deformation-DIA apparatus at the X17B2 beamline of the NSLS. While deformation experiments on polycrystalline samples using D-DIA in conjunction with synchrotrons have been previously reported, this technical paper focuses on single crystal application of the technique. Our single crystals are specifically oriented such that only [1 0 0] slip or [0 0 1] slip in (0 1 0) plane is allowed. Constant applied stress (sigma <300 MPa) and specimen strain rates were monitored using in situ time-resolved X-ray diffraction and radiography imaging, respectively. Rheological properties of each activated slip system in the crystals can be revealed using this technique. In this paper, we describe the principle of sample preparation (e.g. [1 1 0]_c and [0 1 1]_c orientations) to activate specific slip systems (i.e. [1 0 0](0 1 0) and [0 0 1](0 1 0), respectively), stress measurement and procedures of the deformation experiments.     

Electronic structures and ferroelectric properties of ABi2Ta2O9 (A=Ca, Sr, and Ba)

The electronic structures of ABi₂Ta₂O₉ (A=Ca, Sr, and Ba) were calculated by using first-principles under optimized structure. As the size of A-site cation decreases from that of Ba²⁺ to Ca²⁺, the band-gap between O 2p and Ta 5d increases from 2.0 to 2.9 eV, which responses to the stronger orbital hybridizations between Ta 5d and O 2p orbits favoring improvement of the ferroelectric property, decrease in leakage current, and increase in both spontaneous polarization and Curie temperature by the structural distortion. In contrast to CaBi₂Ta₂O₉ and SrBi₂Ta₂O₉, the hybridization between Ba 5p orbits and O 2p orbits in BaBi₂Ta₂O₉ has better structural stability.     

Preparation of a novel Ni/Co-based alloy gradient coating on surface of the crystallizer copper alloy by laser

A high wear-resistant gradient coating made of Ni/Co-based alloys on the surface of a Cu alloy substrate was synthesized using a YAG laser induced in situ reaction method. The coating consists of three layers: the first is a Ni-based alloy layer, the second and third are Co-based alloy layers. The microhardness increases gradually from 98 HV in the Cu alloy substrate to the highest level of 876 HV in the third layer. The main phase of the Co-based alloy layer is CoCr₂(Ni,O)₄, coexisting with the Fe₁₃Mo₂B₅, Cr(Co(Mo, and FeCr_0.29Ni_0.16C_0.06 phases. Wear tests indicate that the gradient coating has good bond strength and wear properties with a wear coefficient of 0.31 (0.50 for the Cu alloy substrate). Also, the wear loss of the coating is only 0.01 g after it has been abraded for 60 min, which is only one fifth of that of the Cu alloy of the crystallizer. Wear tests of the gradient coating reveal good adhesive friction and wear properties when sliding against steel under dry conditions. This novel technique may have good application to make an advanced coating on the surface of the Cu alloy crystallizer in a continuous casting process.     

X-ray photoelectron spectroscopy study of pyrolytically coated graphite platforms submitted to simulated electrothermal atomic absorption spectrometry conditions

The present work is part of an ongoing project aiming to a better understanding of the mechanisms of atomization on graphite furnace platforms used for electrothermal atomic absorption spectrometry (ETAAS). It reports the study of unused pyrolytic graphite coated platforms of commercial origin, as well as platforms thermally or thermo-chemically treated under simulated ETAAS analysis conditions. X-ray photoelectron spectroscopy (XPS) was employed to study the elements present at the surfaces of the platforms. New, unused platforms showed the presence of molybdenum, of unknown origin, in concentrations up to 1 at.%. Species in two different oxidations states (Mo⁶⁺ and Mo²⁺) were detected by analyzing the Mo 3d spectral region with high resolution XPS. The analysis of the C 1s region demonstrated the presence of several signals, one of these at 283.3 eV related to the presence of Mo carbide. The O 1s region showed also various peaks, including a signal that can be attributed to the presence of MoO₃. Some carbon and oxygen signals were consistent with the presence of CO and C-O- (probably C-OH) groups on the platforms surfaces. Upon thermal treatment up to 2900 °C, the intensity of the Mo signal decreased, but peaks due to Mo oxides (Mo⁶⁺ and Mo⁵⁺) and carbide (Mo²⁺) were still apparent. Thermo-chemical treatment with 3 vol.% HCl solutions and heating up to 2900 °C resulted in further diminution of the Mo signal, with complete disappearance of Mo carbide species. Depth profiling of unused platforms by Ar⁺ ion etching at increasing time periods demonstrated that, upon removal of several layers of carbonaceous material, the Mo signal disappears suggesting that this contamination is present only at the surface of the pyrolytic graphite platform.     

Area-selective epitaxy of GaAs by migration-enhanced epitaxy with As2 and As4 arsenic sources

We demonstrate area-selective epitaxy by migration-enhanced epitaxy with As₂ and As₄ as arsenic sources. The distinct whisker structure growing in [1 1 1]B direction is obtained when employing As₂ as an arsenic source, while (1 1 1)B facet is formed with As₄. The difference in the facet formation can be explained by the formation of As-trimer, which significantly reduces the growth rate of the (1 1 1)B surface. With As₂, area-selective epitaxy can be achieved at lower arsenic pressure condition, where less As-trimers are formed. Therefore, growth in the [1 1 1]B direction is enhanced.