Artificially nanostructured Cu:Al2O3 films produced by pulsed laser deposition

The processes leading to the formation of Cu:Al₂O₃ composite films on Si (001) with a well defined nanostructure by alternate pulsed laser deposition (a-PLD) in vacuum are investigated. Alternately amorphous Al₂O₃ layers and Cu nanocrystals nucleated on the Al₂O₃ surface are formed, according to the PLD sequence. The Al₂O₃ deposited on the Cu nanocrystals fills in the space between them until they are completely buried, and subsequently, a continuous dense layer with a very flat surface (within 1 nm) is developed. The nucleation process of the nanocrystals and their resulting oblate ellipsoidal shape are discussed in terms of the role of the energetic species involved in the PLD process and the metal–oxide interface energy. Received: 4 July 2000 / Accepted: 5 July 2000 / Published online: 13 September 2000     

Interface interaction and wetting of Sc<Subscript>2</Subscript>O<Subscript>3</Subscript> exposed to Cu–Al and Cu–Ti melts

Scandia is a thermodynamically stable oxide and could be used as a structural material for a crucible in order to avoid a melt contamination. In the present study wetting experiments of Cu–Al and Cu–Ti melts on Scandia substrate were preformed at 1423 K by a sessile drop method. It was established that Al and Ti additions lead to the improved wetting and that the final contact angle decreases with increasing the additives concentration. For Al containing melts, the contact angle changes gradually with time, and a relatively thick interaction layer, which consists of Al₂O₃, Sc₂O₃, and metallic channels, was formed at the Sc₂O₃/Cu–Al interface. For Ti containing melts, the final contact angle is achieved already during heating, and an extremely thin layer based on a Ti–Sc–O compound was detected by AES at the Sc₂O₃/Cu–Ti interface. The results of a thermodynamic analysis, which takes into account the formation free energy of the oxides, involved in the systems, and the thermodynamic properties of the liquid solutions are in a good agreement with the experimental observations.     

The behavior of 3d electrons and defects in TiAl-based alloys containing V and Cu studied by positron annihilation

Information of defects and 3d electrons in transition metals (Ti, V, Cu) and TiAl-based alloys (Ti₅₀Al₅₀, Ti₅₀Al₄₈V₂, Ti₅₀Al₄₈Cu₂) can be extracted from the positron lifetime and coincidence Doppler broadening spectra. The results show that the 3d electron signals for the transition metals Ti, V and Cu increase with the number of 3d electrons. The 3d electron signal and the electron density for binary TiAl alloy are relatively low due to the (Ti)3d-(Al)3p interactions. The addition of V and Cu atoms to TiAl alloy leads to the increase in the electron densities in bulk and the defects on grain boundaries simultaneously, as well as the enhancement of the 3d electron signal. The 3d electron signal in the spectrum of Ti₅₀Al₄₈Cu₂ alloy is higher than that of Ti₅₀Al₄₈V₂ alloy.     

Theoretical investigations of 3d-metal adsorption on the α-AL<Subscript>2</Subscript>O<Subscript>3</Subscript> (0001) surface

Theoretical investigations of adsorption of 3d-metals from Ti to Cu on the α-Al₂O₃ (0001) surface are presented. The influence of adsorbates on the atomic and electronic structure of the aluminum oxide surface is considered. Values of the adsorption energy are calculated, and the equilibrium adatom positions on the surface are determined. A comparative analysis of the properties and mechanisms of 3d-metal interaction with atoms of the substrate is performed.     

Density-functional study of Mo4S6 on Au(111)

The adsorption site and energetics of Mo₄S₆ on the unreconstructed (111) gold surface was determined by density-functional band-structure calculations. Mo₄S₆ adsorbs preferably via three S atoms at Au–Au bridging sites and three Mo atoms at adjacent threefold hollow sites of the Au(111) surface. The perfectly tetrahedral free cluster becomes trigonally distorted upon adsorption, which indicates the presence of attractive Au–S and Au–Mo interactions. The work of separation amounts to 4.2 eV including gradient corrections. Small peak shifts in the density of electronic states indicate electron transfer from Au to S states and from Mo to Au states, such that a Bader analysis yields a neutral cluster. Electron density difference maps, which visualize the electron redistribution between cluster and substrate in the interface region, show that the electron redistribution is confined to the cluster-surface contact region. PACS 61.46.+w; 73.22.-f; 72.20.-v     

Domain structure and optical property of epitaxial indium oxide film deposited on MgO(100) substrate

Indium oxide (In₂O₃) film has been deposited on MgO(100) substrate at 600 °C by metalorganic chemical vapor deposition (MOCVD). The crystal structure and epitaxial relationship of the sample were examined by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The results showed a clear epitaxial relationship of In₂O₃(111)||MgO(100) with In₂O₃[011?]||MgO<072> or In₂O₃[01$\overline{1}$]||MgO<011>. A multiple domain structure was found inside the In₂O₃ film and a theoretical model clarifying the geometrical relationships between each domain and the substrate has been proposed. Scanning electron microscopy (SEM) micrograph showed that the main surface features were triangle-shaped grains on the film. The absolute average transmittance of the obtained film in the visible range was over 93%.     

Synthesis of copper alloys with extended solid solubility and nano Al2O3 dispersion by mechanical alloying and equal channel angular pressing

Cu–4.5 wt % Cr and Cu–4.5 wt % Cr–3 wt % Ag alloys, with and without nanocrystalline Al₂O₃ dispersions (particle size <10 nm), were synthesized by mechanical alloying/milling and consolidated by equal-channel angular pressing (ECAP) at ambient temperature. Microstructural characterization and phase analysis by X-ray diffraction, as well as scanning and transmission electron microscopy, provided evidence for the formation of a Cu-rich extended solid solution with nanometric (<30 nm) crystallite size after 25 h of milling, with uniformly dispersed alumina nanoparticles embedded in it. Consolidation of Cu–4.5 wt % Cr–3 wt % Ag alloy with 10 wt % nanocrystalline Al₂O₃ by eight ECAP passes was shown to result in a composite with an exceptionally large hardness of 390 VHN and enhanced wear resistance. The electrical conductivity of the pellets of the latter alloy without Al₂O₃ is about 30% IACS (international annealing copper standard), whereas pellets with 5 or 10 wt % Al₂O₃ dispersion exhibit a conductivity of about 20–25% IACS. Thus, the present room temperature synthesis and consolidation route appear to offer a promising avenue for developing high-strength, wear/erosion-resistant Cu-based electrical contacts with nano-ceramic dispersion.     

Balmer Hβ vs. Dβ line intensity in the collisions of H+, H2 +, H3 +, D+, D2 +, and D3 + ions with “realistic” metal surface at energies below 1 keV

The intensities of hydrogen H_β and deuterium D_β spectral lines of the Balmer series were measured as a function of collision energy when H⁺, H₂ ⁺, H₃ ⁺, D⁺, D₂ ⁺, and D₃ ⁺ ions impinged on Al, Ti, Cu, Mo, W, and Pb targets. The collision energies were kept in the 100–1000 eV range. The target surface was contaminated with hydrocarbons from the vacuum pumping system and possibly also by oxygen molecules due to limited vacuum conditions. At projectile velocities above 200 km/s the luminescence of backscattered deuterium atoms is about 30–50% weaker than that of hydrogen atoms.     

Nanoscale Analysis of Multilayer Interfaces of W/Al2O3/Ti/Cu

W, Al₂O₃ and Ti films were deposited onto a Cu substrate by means of the rf magnetron sputtering method. After deposition, the foils were annealed at various temperatures in vacuum and the interfaces of the films were observed by a field-emission transmission electron microscopy (FE-TEM), after preparing a cross-sectional thin foil using a focused ion beam (FIB) machine. After annealing the foil at 473 and 623 K, no reaction phases were identified at each interface of W/Al₂O₃, Al₂O₃/Ti and Ti/Cu-substrate. However, from the results of compositional analysis at the interface of Al₂O₃/Ti bilayer, after heat-treatment at 623 K, the formation of an oxide layer was suggested even though it was not clearly observed. On the other hand, after heat-treatment at 823 K, the formation of CuTi₂, Cu₃Ti₂ and Cu₄Ti phases were identified at the interface of Ti/Cu bilayers from the compositional analysis of reaction layers after heat-treatment at different temperatures, and the diffusion coefficients and activation energies in the phases were evaluated. In this paper, the influence of heat-treatment on the interfacial behavior of multilayer are discussed on the basis of nanoscale analysis by EDS and HRTEM images.     

First principles study of the electron structures of CaCu3Mn4O12 and CaCu3Ti4O12

The electronic structures of CaCu₃Mn₄O₁₂ and CaCu₃Ti₄O₁₂ are investigated from HF SCF LCAO calculation. In CaCu₃Mn₄O_12, the band and the density of states show a spin asymmetric ferrimagnetic character with a small energy gap. The Mn spin is anti-aligned with the Cu spin, and the total spin moment is 9 μ_B. Our calculation correctly reproduces the observed antiferromagnetic insulating character of CaCu₃Ti₄O₁₂. The gap in the band structure, which is 2.15 eV, reasonably agrees with the experimental value 1.5 eV. The electron density populations at different planes show clearly that the electron density has symmetric character. A tilted Mn(Ti) orbital implies a typical tilted three-dimensional network of MnO₆ (TiO₆) octahedra due to doping of the Jahn–Teller ion Cu. There is no covalency between Ca, Cu and Mn(Ti) atoms. In contrast, there are stronger bonds and somewhat likely covalency between Cu and O atoms, and also between Mn(Ti) and O atoms.     

Features of the crystal structure of disperse carbides in alpha titanium

Investigations of disperse nonmetallic inclusions in unalloyed alpha titanium VT1-0 have been performed by using transmission electron (including scanning and high-resolution) microscopy. Characteristic electron energy losses spectroscopy has shown that these inclusions are titanium carbide particles. It has been revealed that the disperse carbides are formed in the titanium hcp matrix as a phase based on the fcc sublattice of titanium atoms. The inclusion–matrix orientation relationship corresponds to the well-known Kurdyumov–Sachs and Nishiyama–Wassermann relationships [ 2[`11] 0 ]<sub>\upalpha</sub> ||[ 011 ]<sub>\updelta</sub> \text and ( 000[`1] )_\upalpha ||( 1[`1] 1 )_\updelta {\left[ {2\overline {11} 0} \right]_{{\upalpha }}}\parallel {\left[ {011} \right]_{{\updelta }}}{\text{ and }}{\left( {000\overline 1 } \right)_{{\upalpha }}}\parallel {\left( {1\overline 1 1} \right)_{{\updelta }}} .     

Effect of preparation method on the properties of deposited copper-palladium deep-oxidation catalysts

Activity of alumocopper-palladium catalysts (0.5 at.% Pd, 0.1–3.0 at.% Cu) which differ in preparation method in CO, C₂H₄ and CH₄ oxidation is studied. It is shown that preliminary modification of a carrier by copper leads to an enhancement of catalyst activity as compared with an alumopalladium one. With the methods of EDRS, TPR-TRS, and TPR of adsorbed CO and O₂, the Pd/Cu/Al₂O₃, Cu/Pd/Al₂O₃ and (Pd−Cu)/Al₂O₃, systems are studied. It is established that premodification of the carrier leads to a weakening of its interaction with the second metal while the combined deposition from one impregnating solution in subsequent thermal treatment is accompanied by a strong metal aggregation. Institute of Physicoorganic Chemistry, National Academy of Sciences of Belarus, 13, Surganov St., Minsk, 220072. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 1, pp. 114–120, January–February, 1998.     

Synthesis of Cr-based mixed oxides by reactive ion beam mixing of Cr/X interfaces (X=Al or Si)

The 3 keV O₂⁺\mathrm{O}_{2}^{+} reactive ion beam mixing of Cr/X interfaces (X=Al or Si) has been used to synthesize Cr-based mixed oxide thin films. The kinetics of growth, composition, and electronic structure of those films has been studied using X-ray photoelectron spectroscopy, Auger electron spectroscopy, ultraviolet photoelectron spectroscopy, and factor analysis. Initially, for low ion doses, Cr₂O₃ species are formed. Later, with increasing the ion dose, Cr₂O₃ species are first transformed into Cr³⁺–O–X species, and subsequently, those Cr³⁺–O–X species are transformed into Cr⁶⁺–O–X species. This sequential transformation, Cr₂O₃→Cr³⁺–O–X→Cr⁶⁺–O–X, is accompanied by a slight increase of the oxygen concentration and a decrease of the Cr/X ratio in the films formed leading to the synthesis of custom designed Cr-based mixed oxides. The changes observed in the valence band and Auger parameters further support the formation of Cr–X mixed oxide species. Angle resolved X-ray photoelectron spectroscopy shows that for low ion doses, when only Cr₂O₃ and Cr³⁺–O–X species coexist, Cr³⁺–O–X species are located nearer the surface than Cr₂O₃ species, whereas for higher ion doses, when only Cr³⁺–O–X and Cr⁶⁺–O–X species coexist, the Cr⁶⁺–O–X species are those located nearer the surface.     

合金元素对钢中NbC异质形核影响的第一性原理研究

为了探索不同合金元素对Nb C异质形核的影响,本文利用第一性原理研究了合金元素X(X=Cr,Mn,Mo,W,Zr,V,Ti,Cu和Ni)对ferrite(100)/Nb C(100)界面性质的影响,并且分析了上述合金元素掺杂前后界面的黏附功、界面能和电子结构.研究结果表明,Cr,V和Ti掺杂的界面具有负的偏聚能,说明它们容易偏聚到ferrite/Nb C界面,但Mn,W,Mo,Zr,Cu和Ni却难以偏聚到此界面.当Mn,Zr,Cu和Ni取代界面处的Fe原子后,界面的黏附强度降低,即这些合金减弱铁素体在Nb C上的形核能力.然而Cr,W,Mo,V和Ti引入界面后,其黏附功比掺杂前的界面要大,且界面能均降低,即提高了界面的稳定性.因此,W,Mo,V和Ti,尤其是Cr,能够有效地促进铁素体形核和细化晶粒.电子结构分析表明,Zr和Cu引入界面后,界面处的Zr,Cu原子和C原子的相互作用变弱;然而Cr和W引入界面后,Cr,W和C原子之间形成了很强的非极性共价键,提高了ferrite/Nb C界面的结合强度.     

XPS and SIMS characterisation of TiOxNy solar absorber films

Solar thermal collectors have been prepared with thin TiO_xN_y films deposited using ion beam assisted deposition, on Si and Cu substrates. The films are amorphous and x and y were controlled by altering the O₂/N₂ ratio in the gas source. After annealing at temperatures of 200 – 400 °C, films have been depth profiled using Secondary Ion Mass Spectrometry. Profiles reveal the degradation of the film, particularly for films on Cu substrates, by migration of the substrate atoms through the films, to the sample surface. In general, films with x<1 and y>1 show improved temperature stability, ultimately at the expense of a reduced transmission window. Contrary to previous suggestions in the literature, the degradation mechanism initially involves the formation of a nitrogen rich phase, rather than an oxide at the film surface. On copper substrates, the nature of the films and of this phase, formed by diffusion of the substrate atoms, have been investigated by X-ray photoelectron spectroscopy (XPS). These investigations reveal complex behaviour in the early stages of film failure, with the suggestion that the initial films, at least near the surface, are two phase, and the reaction layer mixes the TiO_xN_y with some Ti replacement by ions from the Cu substrate.     

Thermal oxidation behaviors and structures of Fe-9Cr-1Mo alloy

Isothermal oxidation behaviors of Fe-9Cr-1Mo alloy were investigated at 600, 700, 750 and 850 ^°C for 72 h in air atmosphere. The oxidation rates were measured using a thermogravimetric analyzer (TGA). The structure and composition of the oxide scale were characterized by X-ray diffraction (XRD), energy dispersive spectrometry (EDS) and conversion electron Mössbauer spectrometry (CEMS). In this study it was found that the oxide layers form duplex structures consisting of Fe and Cr oxides. CEMS spectra are composed of one doublet due to dispersed Fe ³⁺ in Cr₂O₃ oxidation layers produced at high temperatures and two magnetic components due to Fe-Cr-Mo alloy substrate and hematite (Fe, Cr)₂O₃ with lower hyperfine field than pure hematite (52 T). Fe rich oxides are formed at the surface by oxidation at relatively low temperatures of 600 ^°C and 700 ^°C, while Cr rich (Fe, Cr)-oxides are formed in the top surface layers by oxidation at higher than 750 ^°C.     

Elastic properties of Nb-based alloys by using the density functional theory

A first-principles density functional approach is used to study the electronic and the elastic properties of Nb₁₅X(X = Ti, Zr, Hf, V, Ta, Cr, Mo, and W) alloys. The elastic constants c₁₁ and c₁₂, the shear modulus C', and the elastic modulus E_〈100〉 are found to exhibit similar tendencies, each as a function of valence electron number per atom (EPA), while c₄₄ seems unclear. Both c₁₁ and c₁₂ of Nb₁₅X alloys increase monotonically with the increase of EPA. The C' and E_〈100〉 also show similar tendencies. The elastic constants (except c₄₄) increase slightly when alloying with neighbours of a higher d-transition series. Our results are supported by the bonding density distribution. When solute atoms change from Ti(Zr, Hf) to V(Ta) then to Cr(Mo, W), the bonding electron density between the central solute atom and its first neighbouring Nb atoms is increased and becomes more anisotropic, which indicates the strong interaction and thus enhances the elastic properties of Nb-Cr(Mo, W) alloys. Under uniaxial 〈100〉 tensile loading, alloyed elements with less (more) valence electrons decrease (increase) the ideal tensile strength.     

Angular dependence of surface acoustic wave characteristics in AlN thin films on a-plane sapphire substrates

AlN thin films have been grown on a-plane sapphire (Al₂O₃(112̄0)) substrates. X-ray diffraction measurements indicate the films are fully c-plane (0001) oriented with a full width at half maximum of the AlN(0002) rocking curves of 0.92. The epitaxial growth relationships have been determined by the reflection high energy electron diffraction analysis as AlN[11̄00]//Al₂O₃[0001] and AlN[112̄0]//Al₂O₃[11̄00]. Angular dependence of important surface acoustic wave (SAW) characteristics, such as the phase velocity and electromechanical coupling coefficient, has been investigated on the AlN(0001)/Al₂O₃(112̄0) structure. While the SAW is excited at all propagation angles with an angular dispersion of the phase velocity in the range of 5503–6045 m/s, a higher velocity shear-horizontal (SH) mode is observed only at 0°, 105° and 180° off the reference Al₂O₃[11̄00] over a 180° angular period. The phase velocity of the SH mode shows dispersion (6089–6132 m/s) as a function of the SAW wavelength. Temperature coefficients of frequency are also demonstrated for both modes. PACS 81.15.Hi; 77.84.-s; 77.65.Dq     

Network structure and thermal property of a novel high temperature seal glass

In this study, novel glasses based on SrO–La₂O₃–Al₂O₃–B₂O₃–SiO₂ system are investigated for solid oxide fuel and electrolyzer cells. The network structure evolution of the glasses with increasing B₂O₃:SiO₂ ratio was studied using Raman spectroscopy. The thermal properties of the glasses, including glass transition temperature T _g and glass softening temperature T _d , were studied using dilatometry. The thermal stability of the glasses was investigated using X-ray diffraction. The study shows that as the B₂O₃:SiO₂ ratio increases, the SrO–La₂O₃–Al₂O₃–B₂O₃–SiO₂ glass micro-heterogeneity and the amount of non-bridging oxygen atoms increase. Correspondingly, the T _g of the SrO–La₂O₃–Al₂O₃–B₂O₃–SiO₂ glasses changes from 635 to 775°C, and the T _d changes from 670 to 815°C. Glass thermal stability decreases with B₂O₃:SiO₂ ratio increase. The glass without B₂O₃ is thermally stable after being kept at 850°C for 200 hrs.     

Structural and magnetic properties of MoS2 monolayer zigzag nanoribbon doped by Ti,V, Cr,and Mn

In order to find new functions of monolayer MoS₂ in nanoelectronics or spin electronic devices, using spin-polarized density functional theory (DFT) calculations with on-site coulomb interaction (U), we investigated substitutional doping of Mo atoms of monolayer zigzag MoS₂ nanoribbon (ZZ-MoS₂ NR) by transition metals (TM) (where TM = Ti, V, Cr, Mn) at the Mo-edge, S-edge, and the middle of the NRs. The results of this study indicate the NR widened irrespective of the doped TM position and type, and the Mo-edge was found as the easiest substitutional position. For ZZ-MoS₂ NR doped by Mn, Cr or V atoms, the preferred magnetic coupling state is the edge atoms of S at the S-edge, exhibiting the same spin polarization with TM (named the FM1 state), attributing the NR with metallic magnetism. For Ti-doped monolayer ZZ-MoS₂ NR, in addition to the FM1 state, other preferred magnetic coupling state was observed in which the edge atoms of S at the S-edge exhibit the opposite spin polarization with that of Ti (named the FM2 state). Thus, the NR doped by Ti atom possesses metallic (FM1 state) or half-metallic (FM2 state) magnetism. The total magnetic moments of the ZZ-MoS₂ NR doped by TM follows a linear relationship as a function of the TM dopants (Mn, Cr, V, and Ti). Under $>4\text{\%}$ applied strain, the NR doped by Ti atom only presents the characteristics of half-metallic magnetism as the initial one in the FM2 state, and its total magnetic moment always remained 0 μB, i.e., it was not affected by the width of the NR. This study provides a rational route of tuning the magnetic properties of ZZ-MoS₂ NRs for their promising applications in nanoelectronics and spin electronic devices.