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.     

Observation of hydrogen adsorption on 6H-SiC(0 0 0 1) surface

We have used coaxial impact-collision ion scattering spectroscopy (CAICISS) and time-of-flight elastic recoil detection analysis (TOF-ERDA) to investigate the adsorption of atomic hydrogen on the 6H-SiC(0 0 0 1)√3×√3 surface. It has been found that the saturation coverage of hydrogen on the 6H-SiC(0 0 0 1)√3×√3 surface is about 1.7 ML. Upon saturated adsorption of atomic hydrogen, the √3×√3 surface structure changes to the 1×1 structure. The data of the CAICISS measurements have indicated that as a result of the hydrogen adsorption, Si adatoms on the √3×√3 surface move from T₄ to on-top sites.     

Structural and dynamical properties of Ru(0 0 0 1) surface

I performed density functional theory (DFT) calculations combined with MD simulations to study the structural relaxation of Ru(0001) surface. The surface relaxation of the topmost layer is found to be about ?4% at absolute zero temperature. Using MD simulations in the temperatures range of 50 K and 900 K, the effect is found to be minor on the surface relaxation as compared to Pd (1 1 1) clean surface. The effect of surface vibration is also investigated using a LEED code and shows no effect of the vibrational level on the IV curves, which rules out any disagreement between proper theory and LEED results of well prepared surfaces.     

Density functional calculations for Ni adsorption on Al(1 1 0)

The adsorption of 0.25, 0.5 and 1 monolayer (ML) of the transition metal Ni on the metal substrate Al(1 1 0) was studied using first-principles calculations at the level of density functional theory. The metal–metal system was analyzed with the generalized gradient approximation. Four stable atomic configurations were considered, and the optimized geometries and adsorption energies of different Ni adsorption sites on the Al(1 1 0) surface at selected levels of coverage were calculated and compared. The four-fold hollow site was determined to be the most stable adsorption site with adsorption energy of 5.101 eV at 0.25 ML, 3.874 eV at 0.5 ML and 3.665 eV at 1 ML. The adsorption energies of the four sites slightly decreased as the Ni coverage increased. Work function analysis showed that when Ni is adsorbed on the Al(1 1 0) surface, the work function decreased as the coverage increased due to depolarization. The Mulliken population and density of states were calculated to determine the charge distribution of the adsorption site, confirming that a chemisorption interaction exists between the adsorbed Ni atom and Al(1 1 0) surface atoms.     

Investigation on the microscopic features of layered oxide Li[Ni1 / 3Co1 / 3Mn1 / 3]O2 and their influences on the cathode properties

Three kinds of samples of Li[Ni_1 / 3Co_1 / 3Mn_1 / 3]O₂ were prepared respectively from direct solid-state reaction method, combustion method and co-precipitation route and their microscopic structural features have been investigated using Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), magnetic susceptibility measurement and X-ray photoelectron spectroscopy (XPS). The microscopic features such as uniform distribution of transition metal ions at 3b-site and the site-exchange ratio between lithium and nickel were found to be significantly dependent on the synthetic routes. The electrochemical properties of three samples were monitored using 2016 coin-cell by galvanostatic charge–discharge cycling test and cyclic voltammetry, which showed that the microscopic structural features are deeply related with the electrochemical performance. The obtained results also suggested that the combustion method may become a much simple alternative synthetic route to the complicate co-precipitation method.     

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.     

Transition of magnetic anisotropy in Ni/GaAs (0 0 1) observed by magnetization and ferromagnetic resonance

Polycrystalline thin Ni films deposited onto GaAs (0 0 1) show a transition of the magnetic anisotropy depending on its thickness. The anisotropy is perpendicular to the film plane for the thicknesses of the film ⩽12 nm. This becomes in-plane in the films having thicknesses ⩾15 nm. The films are deposited onto the n-type GaAs (0 0 1) substrate by the usual thermal evaporation method and also by the electron beam evaporation in ultra high vacuum onto a GaAs epilayer in the standard molecular beam epitaxy system. The magnetization and ferromagnetic resonance (FMR) are observed in the temperature range from 4.2 to 300 K. For the discussion of the microscopic origin of the anomalous properties in magnetization and FMR experiments, the experimental results are reviewed by introducing a uniaxial anisotropy, which is calculated from the easy-axis and hard-axis magnetization data. This calculated anisotropy is able to explain the temperature and angle dependency of the FMR spectra of the Ni films. Hence the magnetization and FMR spectra are in agreement with the type of the anisotropy and its temperature dependency. In addition to these, the temperature dependence of the in-plane magnetic anisotropy is able to explain the previously reported anomalous effect of reducing the squareness at low temperatures in Ni/GaAs.     

Coverage effects on the adsorption of sulfur on Co(0 0 0 1): A DFT study

The adsorption of sulfur on Co(0 0 0 1) was studied using density functional theory calculations at coverage from 0.11 ML to 1.0 ML. Calculated results indicate that atomic S favors in hollow sites with bond S–Co dominated at lower coverage and at higher coverage the strong adsorbate S–S interaction leads to the formation of S₂ species. It was shown that the adsorption energy generally increases (gets weaker) with the coverage in a near linear fashion for the most stable configurations. In addition, modification of the surface electronic properties has been discussed and some discrepancy are found between our calculations and the findings of O adsorption on Au(1 1 1) and Pt(1 1 1) surfaces.     

ZnO nanocubes with (1 0 1) basal plane photocatalyst prepared via a low-frequency ultrasonic assisted hydrolysis process

The crystallographic plane of the ZnO nanocrystals photocatalyst is considered as a key parameter for an effective photocatalysis, photoelectrochemical reaction and photosensitivity. In this paper, we report a simple method for the synthesis of a new (1 0 1) high-energy plane bounded ZnO nanocubes photocatalyst directly on the FTO surface, using a seed-mediated ultrasonic assisted hydrolysis process. In the typical procedure, high-density nanocubes and quasi-nanocubes can be grown on the substrate surface from a solution containing equimolar (0.04 M) zinc nitrate hydrate and hexamine. ZnO nanocubes, with average edge-length of ca. 50 nm, can be obtained on the surface in as quickly as 10 min. The heterogeneous photocatalytic property of the sample has been examined in the photodegradation of methyl orange (MO) by UV light irradiation. It was found that the ZnO nanocubes exhibit excellent catalytic and photocatalytic properties and demonstrate the photodegradation efficiency as high as 5.7 percent/μg mW. This is 200 times higher than those reported results using a relatively low-powered polychromatic UV light source (4 mW). The mechanism of ZnO nanocube formation using the present approach is discussed. The new-synthesized ZnO nanocubes with a unique (1 0 1) basal plane also find potential application in photoelectrochemical devices and sensing.     

Ellipsometric detection of GaAs(0 0 1) surface hydrogenation in H2 atmosphere

Optical properties of MBE-grown GaAs(0 0 1) surfaces have been studied by spectroscopic ellipsometry under dynamic conditions of ramp heating and cooling after desorption of passivating As-cap-layer with low pressure H₂ atmosphere (14 Torr) applied to the surface. The temperature dependence of GaAs pseudo-dielectric function with atomically smooth (0 0 1) surface carrying the fixed Ga-rich (4 × 2) reconstruction was obtained for the temperature range of 160–600 °C. It is shown ellipsometrically that GaAs(0 0 1) heating in the molecular hydrogen atmosphere results in the formation of hydrogenated layer on the surface.     

The effect of SixNy interlayer on the quality of GaN epitaxial layers grown on Si(1 1 1) substrates by MOCVD

In the present paper, the effects of nitridation on the quality of GaN epitaxial films grown on Si(1 1 1) substrates by metal–organic chemical vapor phase deposition (MOCVD) are discussed. A series of GaN layers were grown on Si(1 1 1) under various conditions and characterized by Nomarski microscopy (NM), atomic force microscopy (AFM), high resolution X-ray diffraction (HRXRD), and room temperature (RT) photoluminescence (PL) measurements. Firstly, we optimized LT-AlN/HT-AlN/Si(1 1 1) templates and graded AlGaN intermediate layers thicknesses. In order to prevent stress relaxation, step-graded AlGaN layers were introduced along with a crack-free GaN layer of thickness exceeding 2.2 μm. Secondly, the effect of in situ substrate nitridation and the insertion of an Si_xN_y intermediate layer on the GaN crystalline quality was investigated. Our measurements show that the nitridation position greatly influences the surface morphology and PL and XRD spectra of GaN grown atop the Si_xN_y layer. The X-ray diffraction and PL measurements results confirmed that the single-crystalline wurtzite GaN was successfully grown in samples A (without Si_xN_y layer) and B (with Si_xN_y layer on Si(1 1 1)). The resulting GaN film surfaces were flat, mirror-like, and crack-free. The full-width-at-half maximum (FWHM) of the X-ray rocking curve for (0 0 0 2) diffraction from the GaN epilayer of the sample B in ω-scan was 492 arcsec. The PL spectrum at room temperature showed that the GaN epilayer had a light emission at a wavelength of 365 nm with a FWHM of 6.6 nm (33.2 meV). In sample B, the insertion of a Si_xN_y intermediate layer significantly improved the optical and structural properties. In sample C (with Si_xN_y layer on Al_0.11Ga_0.89N interlayer). The in situ depositing of the, however, we did not obtain any improvements in the optical or structural properties.     

Face centered cubic cobalt layer on Au(1 1 1): a magneto-optical study

It has been recently shown that Co can grow epitaxially on an Au(1 1 1) layer with a face centered cubic (FCC) structure, the Co[1 1 1] and Au[1 1 1] axes being oriented along each other. First magneto-optical studies of the FCC Co film structure are reported here. The differences in magnetic behavior for FCC and HCP-type Co films as a function of the layer thickness are underlined and interpreted in the framework of a phenomenological model.     

A precise first-principles study on the non-existence of ferromagnetism in V monolayer on the Nb(001) surface

We report the non-existence of ferromagnetism in V monolayer on the Nb(0 0 1) surface, based on the result obtained by a precise all-electron full-potential linearized augmented plane wave (FLAPW) method within the generalized gradient approximation (GGA). Precisely calculated total energy displays that the paramagnetic state is more stable than the ferromagnetic one. The calculated density of states reveals the microscopic origin of the non-existence of ferromagnetism in the V/Nb(0 0 1) system. The paramagnetic result of our precise calculation contradicts to those of the recent tight-binding calculation using Hubbard-type Hamiltonian by J. Khalifeh [J. Magn. Magn. Mater. 168 (1997) 25] that predicted magnetism of the V overlayers on the Nb(0 0 1) surface.     

Potential-induced structure transitions in self-assembled monolayers: II. Propanethiol on Au(1 0 0)

The structure of propanethiol self-assembled monolayers (SAMs) on Au(1 0 0) in 0.1 M H₂SO₄ has been investigated as a function of electrode potential by in situ scanning tunnelling microscopy (STM). These studies reveal a potential-induced, reversible transition between an in essence quadratic and a distorted hexagonal structure. We suggest that a thiolate-driven surface reconstruction, similar to Au(1 0 0)-(hex), is responsible for the hexagonal SAM structure, whereas the quadratic one refers to the unreconstructed substrate.     

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.     

The effect of spacer layer thickness on vertical alignment of InGaAs/GaNAs quantum dots grown on GaAs(3 1 1)B substrate

We fabricated multiple stacked self-organized InGaAs quantum dots (QDs) on GaAs (3 1 1)B substrate by atomic hydrogen-assisted molecular beam epitaxy (H-MBE) to realize an ordered three-dimensional QD array. High quality stacked QDs with good size uniformity were achieved by using strain-compensation growth technique, in which each In_0.35Ga_0.65As QD layer was embedded by GaNAs strain-compensation layer (SCL). In order to investigate the effect of spacer layer thickness on vertical alignment of InGaAs/GaNAs QDs, the thickness of GaNAs SCL was varied from 40 to 20 nm. We observed that QDs were vertically aligned in [3 1 1] direction when viewed along [0 1 −1], while the alignment was inclined when viewed along [−2 3 3] for all samples with different SCL thickness. This is due to their asymmetric shape along [−2 3 3] with two different dominant facets thereby the local strain field around QD extends further outward from the lower-angle facet. Furthermore, the inclination angle of vertical alignment QDs became monotonously smaller from 22° to 2° with decreasing SCL thickness from 40 to 20 nm. These results suggest that the strain field extends asymmetrically resulting in vertically tilted alignment of QDs for samples with thick SCLs, while the propagated local strain field is strong enough to generate the nucleation site of QD formation just above lower QD in the sample with thinner SCLs.     

Optical characterization of methanol adsorption on the bare and oxygen precovered Cu(1 1 0) surface

We have studied the adsorption and reaction of methanol on the bare and oxygen precovered Cu(1 1 0) surface at 200 K using reflectance difference spectroscopy (RDS). On the bare and fully oxygen covered surface, the sticking coefficient is close to zero. In contrast, on the partially oxygen covered surface, a sticking coefficient close to unity is obtained. This observation suggests a high mobility of methanol on both bare and oxygen covered Cu(1 1 0) and of methoxy on Cu(1 1 0). Two reaction regimes, an oxygen supply limited and an adsorption site limited regime are identified. The transition between these two regimes occurs for an oxygen coverage of about 0.2.     

Adsorption behaviors of CO on W(1 1 0) and Mo(1 1 0) surfaces in the β-state are still not clear

Adsorption structure of CO on W and Mo at above ～800 K (β-CO) has been extensively studied in the history of surface science. Most of the previous studies concluded that CO is dissociated in the β-CO, and a tilted structure plays a role as a precursor state of the dissociation. We have recently studied valence band spectra of the β-CO on W(1 1 0), oxygen-precovered W(1 1 0) and Mo(1 1 0) using synchrotron radiation. CO-derived states with binding energies close to those of the 4σ-CO can be observed, implying a non-dissociative chemisorption in this high-temperature state. We suggest that still some additional works need to be done in order to understand adsorption structure of β-CO completely.     

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).