Metallization of Ge(0 0 1)-p(2 × 1) surface as result of thermal fluctuations

We present a theoretical study of the metallization of Ge(0 0 1)-p(2 × 1) surface which is observed in experimental data. We have considered the connection between thermal fluctuation of this surface structure and its metallic properties. To this end we have performed long-time MD-DFT simulations. The obtained results show that thermal fluctuation of the Ge(0 0 1)-p(2 × 1) structure may cause its metallization which in not necessary connected with a flip-flop motion of dimer atoms. It was shown that the metallization of the Ge(0 0 1)-p(2 × 1) surface takes place when the dimer buckling angle is reduced to around 11°. In the case of our simulations the considered surface system remained in the metallic state for 25% of the simulation time. We have also found that the metallic state of the fluctuating Ge(0 0 1)-p(2 × 1) surface is built up by dangling bonds of the dimer atoms shifted up (D_up) and down (D_down).     

First-principles study of small palladium clusters on NiAl(1 1 0) alloy surface

Theoretical calculations focused on the geometry, stability, electronic and magnetic properties of small palladium clusters Pd_n (n=1–5) adsorbed on the NiAl(1 1 0) alloy surface were carried out within the framework of density functional theory (DFT). In agreement with the experimental observations, both Ni-bridge and Al-bridge sites are preferential for the adsorption of single palladium atom, with an adsorption energy difference of 0.04 eV. Among the possible structures considered for Pd_n (n=1–5) clusters adsorbed on NiAl(1 1 0) surface, Pd atoms tend to form one-dimensional (1D) chain structure at low coverage (from Pd₁ to Pd₃) and two-dimensional (2D) structures are more stable than three-dimensional (3D) structures for Pd₄ and Pd₅. Furthermore, metal-substrate bonding prevails over metal–metal bonding for Pd cluster adsorbed on NiAl(1 1 0) surface. The density of states for Pd atoms of Pd/NiAl(1 1 0) system are strongly affected by their chemical environment. The magnetic feature emerged upon the adsorption of Pd clusters on NiAl(1 1 0) surface was due to the charge transfer between Pd atoms and the substrate. These findings may shade light on the understanding of the growth of Pd metal clusters on alloy surface and the construction of nanoscale devices.     

Synthesis and characterization of layered Li1−x(Ni0.5Co0.5)1−yFeyO2(0 ≤ (1 − x) ≤ 1 and 0 ≤ y ≤ 0.2) cathodes

Layered Li(Ni_0.5Co_0.5)_1−yFe_yO₂ cathodes with 0 ≤ y ≤ 0.2 have been synthesized by firing the coprecipitated hydroxides of the transition metals and lithium hydroxide at 700 °C and characterized as cathode materials for lithium ion batteries to various cutoff charge voltages (up to 4.5 V). While the y = 0.05 sample shows an improvement in capacity, cyclability, and rate capability, those with y = 0.1 and 0.2 exhibit a decline in electrochemical performance compared to the y = 0 sample. Structural characterization of the chemically delithiated Li_1−x(Ni_0.5Co_0.5)_1−yFe_yO₂ samples indicates that the initial O3 structure is maintained down to a lithium content (1 − x) ≈ 0.3. For (1 − x) < 0.3, while a P3 type phase is formed for the y = 0 sample, an O1 type phase is formed for the y = 0.05, 0.1 and 0.2 samples. Monitoring the average oxidation state of the transition metal ions with lithium contents (1 − x) reveals that the system is chemically more stable down to a lower lithium content (1 − x) ≈ 0.3 compared to the Li_1−xCoO₂ system. The improved structural and chemical stabilities appear to lead to better cyclability to higher cutoff charge voltages compared to that found before with the LiCoO₂ system.     

Use of film thickness and Cu additive to improve (0 0 1) texture in MgO/FePtCu(C) bilayers

A multilayer structure has been proposed that demonstrates improved (0 0 1) texture for FePt-based L1₀ perpendicular media. Achieving a strong perpendicular magnetic anisotropy requires aligning the L1₀ crystallographic c-axis along the film normal. The ordered L1₀ FePt structure is tetragonal with a c/a ratio close to 0.965. This makes discriminating between the three crystallographic variants ([1 0 0], [0 1 0], and the desired [0 0 1]) difficult. Alloying FePt with Cu to reduce the c/a ratio and using a multilayer approach to keep the magnetic layers thin results in a structure with an adjustable M_rt and a strong (0 0 1) texture (rocking curve widths around 2°). This is a remarkable improvement in texture from pure FePt multilayered films or monolithic FePt(X) films. The proposed [MgO(2 nm)/Fe_50−xPt₅₀Cu_x(5 nm)]_×n structure limits grain size in the vertical (perpendicular) direction albeit not in the plane of the film. Carbon can be added to the FePtCu layer to reduce the grain size with minimal degradation of the (0 0 1) orientation.     

Acetaldehyde photochemistry on TiO2(1 1 0)

The ultraviolet (UV) photon induced decomposition of acetaldehyde adsorbed on the oxidized rutile TiO₂(1 1 0) surface was studied with photon stimulated desorption (PSD) and thermal programmed desorption (TPD). Acetaldehyde desorbs molecularly from TiO₂(1 1 0) with minor decomposition channels yielding butene on the reduced TiO₂ surface and acetate on the oxidized TiO₂ surface. Acetaldehyde adsorbed on oxidized TiO₂(1 1 0) undergoes a facile thermal reaction to form a photoactive acetaldehyde–oxygen complex. UV irradiation of the acetaldehyde–oxygen complex initiated photofragmentation of the complex resulting in the ejection of methyl radical into gas phase and conversion of the surface bound fragment to formate.     

Structural and magnetic properties of BCC Fe/Co (0 0 1) superlattices

In thin layered Fe/Co (0 0 1), grown on MgO (0 0 1), both Fe and Co crystallize in the body-centered cubic (BCC) structure, as seen in a series of superlattices where the layer thickness of the components is varied from two to twelve atomic monolayers. These superlattices have novel magnetic properties as observed by magnetization and polarized neutron reflectivity measurements. There is a significant enhancement of the magnetic moments of both Fe and Co at the interfaces. Furthermore, the easy axis of the system changes from [1 0 0] for films of low cobalt content to [1 1 0] for a Co content exceeding 33%. No indication of a uniaxial anisotropy component is found in any of the samples. The first anisotropy constant (K₁) of BCC Co is found to be negative with an estimated magnitude of 110 kJ/m³ at 10 K. In all cases, the magnetic moments of Fe and Co have parallel alignment.     

Preparation and characterization of Fe3O4(1 1 1) nanoparticles and thin films on Au(1 1 1)

Fe₃O₄ nanoparticles and thin films were prepared on the Au(1 1 1) surface and characterized using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Fe₃O₄ was formed by annealing α-Fe₂O₃(0 0 0 1) structures on Au(1 1 1) at 750 K in ultrahigh vacuum (UHV) for 60 min. Transformation of the α-Fe₂O₃(0 0 0 1) structures into Fe₃O₄ nanoparticles and thin films was supported by XPS. STM images show that during the growth procedure used, Fe₃O₄ initially appears as nanoparticles at low coverages, and forms thin films at ～2 monolayer equivalents (MLE) of iron. Two types of ordered superstructures were observed on the Fe₃O₄ particles with periodicities of ～50 and ～42 Å, respectively. As the Fe₃O₄ particles form more continuous films, the ～50 Å feature was the predominant superstructure observed. The Fe₃O₄ structures at all coverages show a hexagonal unit cell with a ～3 Å periodicity in the atomically resolved STM images.     

Interaction of atomic H and CO with Cu(1 1 0) and bimetallic Ni/Cu(1 1 0)

Co-adsorption of hydrogen and CO on Cu(1 1 0) and on a bimetallic Ni/Cu(1 1 0) surface was studied by thermal desorption spectroscopy. Hydrogen was exposed in atomic form as generated in a hot tungsten tube. The Ni/Cu surface alloy was prepared by physical vapor deposition of nickel. It turned out that extended exposure of atomic hydrogen leads not only to adsorption at surface and sub-surface sites, but also to a roughening of the Cu(1 1 0) surface, which results in a decrease of the desorption temperature for surface hydrogen. Exposure of a CO saturated Cu(1 1 0) surface to atomic H leads to a removal of the more strongly bonded on-top CO (α₁ peak) only, whereas the more weakly adsorbed CO molecules in the pseudo threefold hollow sites (α₂ peak) are hardly influenced. No reaction between CO and H could be observed. The modification of the Cu(1 1 0) surface with Ni has a strong influence on CO adsorption, leading to three new, distinct desorption peaks, but has little influence on hydrogen desorption. Co-adsorption of H and CO on the Ni/Cu(1 1 0) bimetallic surface leads to desorption of CO and H₂ in the same temperature regime, but again no reaction between the two species is observed.     

Nonlinear magnetoelastic effects in ultrathin epitaxial FCC Co(0 0 1) films:: an ab initio study

Those linear and nonlinear magnetoelastic coupling coefficients which determine the magnetostrictive stress and the strain-induced out-of-plane magnetic anisotropy in epitaxially grown FCC Co(0 0 1) films are calculated by the ab initio density functional electron theory. The nonlinear couplings have a strong effect on the change Δσ₁^m of the in-plane magnetostrictive stress resulting from a change of the magnetization direction from [0 1 0] to [1 0 0], but a negligibly small effect on the out-of-plane anisotropy e_MCA. The calculations confirm the experimental result that the measured out-of-plane anisotropy cannot be totally attributed to volume magnetoelastic effects. Estimates are given for the nonlinear magnetoelastic coupling coefficients m₁^γ,2 and m₂^γ,2.     

Ab initio study of structural and magnetic properties of cubic Fe4N(0 0 1) surface

First-principles calculations are employed to study the structural and magnetic properties of fully-relaxed cubic Fe₄N(0 0 1) surfaces with both Fe₂- and Fe₂N-termination. The results of surface stability calculations show that the (0 0 1) surface of Fe₄N is most possibly existing with Fe₂N-termination. Slab structures have more localized features in the density of states especially for the Fe₂N-terminated surface due to structure relaxation. The average magnetic moments of Fe atoms increase with increasing thickness of slabs. The calculated interlayer distances indicate that the decreases of d₁₂ and d₂₃ result in stronger hybridization and shorter bond distances between Fe2 atom in the second layer and other atoms in surface or the third layers, which lead to variation of magnetic moments with different slab thicknesses.     

Magnetic anisotropy of epitaxial Fe layers grown on Si(0 0 1)

The magnetic properties of epitaxial iron films up to 80 monolayers (ML) thickness grown on Si(0 0 1) by using a template technique were investigated by means of superconducting quantum interference device and magneto-optic Kerr effect techniques. The thinnest films investigated (∼3 ML) exhibit a composition close to Fe₃Si with a Curie temperature below room temperature (RT) and strong out-of-plane remanent magnetization that reflects the presence of a dominant second order surface anisotropy term. Thicker films (⩾4 ML) are ferromagnetic at RT with remanent magnetization in film-plane and a composition closer to pure Fe with typically 8–10% silicon content. When deposited at normal incidence such films show simple in-plane fourfold anisotropy without uniaxial contribution. The relevant fourth-order effective anisotropy constant K₄^eff was measured versus film thickness and found to change its sign near 18 ML. The origin of this remarkable behavior is investigated by means of a Néel model and mainly traced back to fourth-order surface anisotropy and magneto-elastic effects related to the large biaxial in-plane compressive strain up to 3.5% in the thinnest (⩽25 ML) films.     

Ionic and electronic conductivities,stability and thermal expansion of La10 − x(Si,Al)6O26 ± δ solid electrolytes

Apatite-type La_10 − xSi_6 − yAl_yO_{27 − 3x/2 − y/2} (x = 0–0.33; y = 0.5–1.5) exhibit predominant oxygen ionic conductivity in a wide range of oxygen partial pressures. The conductivity of silicates containing 26.50–26.75 oxygen atoms per formula unit is comparable to that of gadolinia-doped ceria at 770–870 K. The average thermal expansion coefficients are (8.7–10.8) × 10^− 6 K^− 1 at 373–1273 K. At temperatures above 1100 K, silicon oxide volatilization from the surface layers of apatite ceramics and a moderate degradation of the ionic transport with time are observed under reducing conditions, thus limiting the operation temperature of Si-containing solid electrolytes.     

Structure and electrochemical properties of Sm0.5Sr0.5Co1 − xFexO3 − δ cathodes for solid oxide fuel cells

Crystal structure, thermal expansion coefficient, electrical conductivity and cathodic polarization of compositions in the system Sm_0.5Sr_0.5Co_1 − xFe_xO_3 − δ with 0 ≤ x ≤ 0.9 were studied as function of Co / Fe ratio and temperature, in air. Two phases, including an Orthorhombic symmetry for 0 ≤ x ≤ 0.4 and a cubic symmetry for 0.5 ≤ x ≤ 0.9, were observed in samples of Sm_0.5Sr_0.5Co_1 − xFe_xO_3 − δ at room temperature. The adjustment of thermal expansion coefficient (TEC) to electrolyte, which is one of the main problems of SSC, could be achieved to lower TEC values with more Fe substitution. High electrical conductivity above 100 S/cm at 800 °C was obtained for all specimens, so they could be good conductors as cathodes of IT-SOFC. The polarization behavior of SSCF as a function of Fe content was evaluated by means of AC impedance using LSGM electrolyte. It was discovered that the Area Specific Resistance (ASR) of SSCF increased as the amount of substitution of Fe for Co increased. When the amount of Fe reached to 0.4, the highest ASR was obtained and then the resistance started decreasing above that. The electrode with a composition of Sm_0.5Sr_0.5Co_0.2Fe_0.8O_3 − δ showed high catalytic activity for oxygen reduction operating at temperature ranging from 700 to 800 °C.     

Annealing effects on the crystal structure and physical properties of FeSe1−xTex (0.6 ≦ x ≦ 1) single crystals

Annealing effects of FeSe_1?xTe_x (0.6 ≦ x ≦ 1) single crystals have been investigated from measurements of the powder X-ray diffraction and specific heat. Through the annealing, several peaks of powder X-ray diffraction have become sharp and a clean jump of the specific-heat at the superconducting (SC) transition temperature, T_c, has been observed for x = 0.6–0.9, indicating bulk superconductivity. For annealed single-crystals of x = 0.6–0.8, the SC condensation energy, U₀, and the SC gap, Δ₀, at 0 K have been estimated as ～1.8 J/mol and 2.3–2.5 meV, respectively. The value of 2Δ₀/k_BT_c is 3.9–4.5, indicating a little strong-coupling superconductivity. Both the electronic specific-heat coefficient in the normal state, γ_n, and the residual electronic specific-heat coefficient in the SC state, γ₀, have been found to show significant x dependence. The values of γ_n are much larger than those estimated from the band calculation.     

Electrochemical and magnetic properties of Li4 / 3Mn2 / 3O2–LiCoO2 solid solution

The compounds Li_(4−x)/3Mn_2(1−x)/3Co_xO₂ (0 < x < 0.5) were prepared by the sol–gel technique. X-ray diffraction patterns of these compounds were identified as α-NaFeO₂ type layered structure, though some super-structure lines, related to the ordered array of Li and transition metal ions in the transition metal layer, were observed. The magnetic susceptibility exhibited an antiferromagnetic transition around 40 K for x < 0.2, however the specimens with x > 0.3 had no magnetic transition. The magnetic percolation may explain these magnetic variations. The electrochemical performances were evaluated for the compound of x = 0.5, and it was seen that the electrochemical properties were sensitive to the potential window. Additionally, it was also found that the discharge capacity strongly depended on the preparation temperature; it took a maximum value at the preparation temperature of 900 °C. The discharge capacity is sensitive not only to the cation mixing degree but also to the particle size.     

Metastable helium atom scattering from Ni(1 1 0) surface

The survival probability (SP) of metastable helium atoms (He¹) during scattering from the clean, alkalated and oxygen-adsorbed Ni(1 1 0) surfaces has been examined in the kinetic energy range of 50–400 meV. The measurements were carried out using a time-of-flight technique and a pulsed-discharge type metastable helium atom source. The SP is nearly constant for a kinetic energy (E_kin) of 50–100 meV and decreases exponentially with the increase in E_kin at 100–400 meV. It has been shown that the SP at E_kin=100–400 meV depends on the repulsive part of the He¹-surface interaction potential.     

Near-surface stresses in silicon(0 0 1)

We report here on a detailed atomistic stress analysis of the near-surface stresses on the 2 × 1 surface reconstruction on Si(0 0 1). We find that the surface stresses are spatially periodic with fairly large amplitude. We additionally investigate the stresses in the neighborhood of an S_A-type step.     

In situ magneto-optical Kerr effect study of uncovered Fe films on ZnSe(0 0 1)

The magnetic properties of uncovered Fe/ZnSe/GaAs(1 0 0) ultrathin films have been determined in situ by magneto-optical Kerr effect (MOKE). Fe films up to 10 monolayers (ML) thick were deposited on c(2×2) Zn-rich ZnSe/GaAs(0 0 1) surfaces at 180 °C. We have studied the thickness dependence of the in-plane lattice parameter of the Fe films and of the MOKE hysteresis loops in the longitudinal geometry, at 150 K, under magnetic fields up to 0.1 T applied along the [1 1 0] and [1-1 0] directions of the ZnSe(0 0 1). Reflection high energy electron diffraction show that in the low thickness regime the Fe films present an in-plane structural anisotropy characterized by an expansion along the [1 1 0] direction. Hysteretic loops were obtained only starting from ∼5 ML Fe. We found the onset of an uniaxial magnetic anisotropy with [1 1 0] magnetic easy axis at 7 ML Fe.     

AC-susceptibility of Ni/W(1 1 0) ultrathin magnetic films: determination of the Curie temperature and critical behavior

The temperature dependence of the magnetic susceptibility of 6–8 ML Ni/W(1 1 0) is measured in situ in UHV by means of an AC-susceptibility mutual inductance bridge. At sufficient small driving magnetic fields ⩽11 A/m a susceptibility maximum and an interval of constant susceptibility on the high temperature side of the peak are observed. The Curie temperature is identified as the low temperature limit of this region of constant susceptibility. The appearance of the maximum at lower temperatures is interpreted as a ferro-magnetic response at T<T_C. The critical exponent γ is extracted from a power law fit at T>T_C. For the smallest field of 3 A/m, the determined γ of 1.26 (7) is consistent with γ of the three-dimensional Ising model. For larger fields, the exponent depends on the field and presents an effective value.     

A high (0 0 1)-oriented CoPt/Ag film deposited on glass substrate

The magnetic properties and structures of CoPt_15 nm/Ag_0−100 nm films deposited by DC magnetron sputtering on glass substrates have been studied. The (0 0 1) texturing was improved by introducing an Ag underlayer. As the Ag underlayer thickness was 100 nm, a nearly perfect (0 0 1)-textured CoPt film was obtained.