Energy calculation of (0 1 1) twist grain boundary in noble metals

With modified analytical embedded atom method (MAEAM), the energy of (0 1 1) twist grain boundary (GB) has been calculated for three noble metals Cu, Ag and Au. The results show that the unrelaxed energy keeps almost constant with twist angle θ except several cusps at low Σ boundaries. The GB energies drop significantly after expansion perpendicular to the boundary. In-boundary translation results in a periodic energy variation and the rectangular period is 1/Σ of their own CSL smallest unit cell. Three specific positions, the corners or centre of the periodic rectangle, or the midpoints of the sides, are preferable in GB translation.     

The periodicity in translation of Ag (0 0 1) and (1 1 0) twist grain boundary

The energies of Ag (0 0 1) and (1 1 0) twist grain boundary (GB) in translation have been calculated with the modified analytical embedded atom method (MAEAM). The energy period corresponds exactly to the DSC lattice unit cell and the area of the energy period referred to the CSL unit cell is 1/Σ². The ‘energy grooves’ are parallel to the sides of the CSL or DSC lattice unit cell. The most preferable sliding direction is parallel to identical sides of the square CSL unit cell for (0 0 1) boundaries and to the short side of the rectangular CSL unit cell for (1 1 0) boundaries. From energy minimization, the stable configuration appears when two adjacent grains are translated relatively to the corners, centre or sides’ midpoint of the DSC lattice unit cell.     

Adsorption site preference of CO2 on the Pt(1 0 0) surface by ab initio calculations

This paper investigates the adsorption sites and electronic structure of the adsorption of CO₂ on the Pt(1 0 0) surface by ab initio periodic density functional theory (DFT) methods. Several parallel and vertical adsorption sites are examined in detail. The results show that the adsorption energy for the atop hollow horizontal (thh) site is 0.34 eV. However, other sites only have small binding energies and these values are very close. For an atop hollow horizontal site, the calculated elecronic interaction is contributed to not only the Pt-O atoms, but also Pt-C atoms. So the results indicate that the thh site is the most favorable and stable.     

Analysis of the first triad of interacting states (0 2 0), (1 0 0), and (0 0 1) of D2O from hot emission spectra

The far-infrared and middle-infrared emission spectra of deuterated water vapour were measured at temperatures 1370, 1520, and 1940 K in the ranges 320-860 and 1750-3400 cm⁻¹. The measurements were performed in an alumina cell with an effective length of hot gas of about 50 cm. More than 3550 new measured lines for the D₂¹⁶O molecule corresponding to transitions from highly excited rotational levels of the (0 2 0), (1 0 0), and (0 0 1) vibrational states are reported. These new lines correspond to rotational states with higher values of the rotational quantum numbers compared to previously published determinations: J_max = 29 and K_a(max) = 22 for the (0 2 0) state, J_max = 29 and K_a(max) = 25 for the (1 0 0) state, and J_max = 30 and K_a(max) = 23 for the (0 0 1) state. The extended set of 1987 experimental rotational energy levels for the (0 2 0), (1 0 0), and (0 0 1) vibration states including all previously available data has been determined. For the data reduction we used the generating function model. The root mean square (RMS) deviation between observed and calculated values is 0.004 cm⁻¹ for 1952 rovibrational levels of all three vibration states. A comparison of the observed energy levels with the best available values from the literature and with the global predictions from molecular electronic potential energy surfaces of water isotopic species [H. Partridge, D.W. Schwenke, J. Chem. Phys. 106 (1997) 4618] is discussed. The latter confirms a good consistency of mass-dependent DBOC corrections in the PS potential function with new experimental rovibrational data.     

Stable atomic structure and magnetism of Pt–Cr binary surface alloys on Pt(0 0 1): First-principle calculations

The possibility of Pt–Cr surface alloys formation on Pt(0 0 1) was investigated and their magnetism was calculated by the full-potential linearized augmented plane wave (FLAPW) method with eight different atomic configurations. The most stable structure was calculated to be the Pt-segregated L1₂ ferromagnetic surface alloy. A₃B types (L1₂ or D0₂₂) were more stable compared to AB types (L1₀). It implies that the A₃B type surface alloys may be formed when depositing a monolayer of Cr on Pt(0 0 1). It was found from the total energy calculations that there exists a strong tendency of the Pt segregation. The segregation further stabilizes the surface alloy significantly. The work function of the most stable surface alloy was calculated to be 6.02 eV and the magnetic moment of the surface Cr was much enhanced to 3.3 μ_B. It is a quite interesting finding that the coupling between Cr and Pt atoms on the surface plane is ferromagnetic in the Pt-segregated L1₂ ferromagnetic surface alloy, while the coupling is antiferromagnetic in the bulk.     

CO2 adsorption on Cr(1 1 0) and Cr2O3(0 0 0 1)/Cr(1 1 0)

We attempt to correlate qualitatively the surface structure with the chemical activity for a metal surface, Cr(1 1 0), and one of its surface oxides, Cr₂O₃(0 0 0 1)/Cr(1 1 0). The kinetics and dynamics of CO₂ adsorption have been studied by low energy electron diffraction (LEED), Aug er electron spectroscopy (AES), and thermal desorption spectroscopy (TDS), as well as adsorption probability measurements conducted for impact energies of E_i = 0.1-1.1 eV and adsorption temperatures of T_s = 92-135 K. The Cr(1 1 0) surface is characterized by a square shaped LEED pattern, contamination free Cr AES, and a single dominant TDS peak (binding energy E_d = 33.3 kJ/mol, first order pre-exponential 1 × 10¹³ s⁻¹). The oxide exhibits a hexagonal shaped LEED pattern, Cr AES with an additional O-line, and two TDS peaks (E_d = 39.5 and 30.5 kJ/mol). The initial adsorption probability, S₀, is independent of T_s for both systems and decreases exponentially from 0.69 to 0.22 for Cr(1 1 0) with increasing E_i, with S₀ smaller by ∼0.15 for the surface oxide. The coverage dependence of the adsorption probability, S(Θ), at low E_i is approx. independent of coverage (Kisliuk-shape) and increases initially at large E_i with coverage (adsorbate-assisted adsorption). CO₂ physisorbs on both systems and the adsorption is non-activated and precursor mediated. Monte Carlo simulations (MCS) have been used to parameterize the beam scattering data. The coverage dependence of E_d has been obtained by means of a Redhead analysis of the TDS curves.     

Low-temperature STM/STS studies on boron-doped (1 1 1) diamond films

We have performed scanning tunneling microscopy/spectroscopy (STM/STS) experiments on (1 1 1)-oriented epitaxial films of heavily boron-doped diamond (T_c∼5.4 K). We present that tunneling conductance spectra show temperature-dependent spatial variations. In the low-temperature region (T=0.47 K), the tunneling spectra do not show strong spatial dependence and a superconducting energy gap is observed independent of the surface morphology. In the high-temperature region (T=4.2 K), on the other hand, the tunneling conductance spectra show significant spatial dependence, indicating the inhomogeneous distribution of the superconducting property due to the distribution of boron atoms.     

Atomic structure of Cs layer grown on Si(0 0 1)(2 × 1) surface at room temperature

The atomic structure of Cs atoms adsorbed on the Si(0 0 1)(2 × 1) surface has been investigated by coaxial impact collision ion scattering spectroscopy. When 0.5 ML of Cs atoms are adsorbed on Si(0 0 1) at room temperature, it is found that Cs atoms occupy a single absorption site on T3 with a height of 3.18 ± 0.05 Å from the second layer of Si(0 0 1)(2 × 1) surface, and the bond length between Cs and the nearest Si atoms is 3.71 ± 0.05 Å.     

Photoluminescence investigation of ferromagnetic Ga1−xMnxN layers with GaN templates grown on sapphire (0 0 0 1) substrates

We have investigated the temperature and composition dependent photoluminescence (PL) spectra in Ga_1−xMn_xN layers (where x ≈ 0.1-0.8%) grown on sapphire (0 0 0 1) substrates using the plasma-enhanced molecular beam epitaxy technique. The efficient PL is peaked in the red (1.86 eV), yellow (2.34 eV), and blue (3.29 eV) spectral range. The band-gap energy of the Ga_1−xMn_xN layers decreased with increasing temperature and manganese composition. The band-gap energy of the Ga_1−xMn_xN layers was modeled by the Varshni equation and the parameters were determined to be α = 2.3 × 10⁻⁴, 2.7 × 10⁻⁴, 3.4 × 10⁻⁴ eV/K and β = 210, 210, and 230 K for the manganese composition x = 0.1%, 0.2%, and 0.8%, respectively. As the Mn concentration in the Ga_1−xMn_xN layers increased, the temperature dependence of the band-gap energy was clearly reduced.     

Energy calculation for symmetrical tilt grain boundaries in iron

An atomic study of [0 0 1] symmetrical tilt grain boundary (STGB) in iron has been made with modified analytical embedded atom method (MAEAM). The energies of two rigid-body crystals joined together directly are unrealistically high due to very short distance between atoms near grain boundary (GB) plane in either crystal. For each of 27 (h k 0) GB planes, a relative slide between grains could result in a decrease in GB energy and a minimum value could be obtained at specific translation distance L_min/L_(h k 0). Three lowest minimum-energies are corresponding to (3 1 0), (5 3 0) and (5 1 0) boundary successively, from minimization of GB energy, these boundaries should be preferable in (h k 0) boundaries. In addition, the minimum energy increases with increasing ∑, but decreases with increasing interplanar spacing.     

Ruthenium adsorption and diffusion on the GaN(0 0 0 1) surface

We report first principles calculations to analyze the ruthenium adsorption and diffusion on GaN(0 0 0 1) surface in a 2×2geometry. The calculations were performed using the generalized gradient approximation (GGA) with ultrasoft pseudopotential within the density functional theory (DFT). The surface is modeled using the repeated slabs approach. To study the most favorable ruthenium adsorption model we considered T₁, T₄ and H₃ special sites. We find that the most energetically favorable structure corresponds to the Ru- T₄ model or the ruthenium adatom located at the T₄ site, while the ruthenium adsorption on top of a gallium atom (T₁ position) is totally unfavorable. The ruthenium diffusion on surface shows an energy barrier of 0.612 eV. The resultant reconstruction of the ruthenium adsorption on GaN(0 0 0 1)- 2×2 surface presents a lateral relaxation of some hundredth of Å in the most stable site. The comparison of the density of states and band structure of the GaN(0 0 0 1) surface without ruthenium adatom and with ruthenium adatom is analyzed in detail.     

Theoretical study of the electronic structure of the Si3N4(0 0 0 1) surface

Density functional theory has been applied to a study of the electronic structure of the ideally-terminated, relaxed and H-saturated (0 0 0 1) surfaces of β-Si₃N₄ and to that of the bulk material. For the bulk, the lattice constants and atom positions and the valence band density of states are all in good agreement with experimental results. A band gap of 6.7 eV is found which is in fair accord with the experimental value of 5.1-5.3 eV for H-free Si₃N₄. Using a two-dimensionally-periodic slab model, a π-bonding interaction is found between threefold-coordinated Si and twofold-coordinated N atoms in the surface plane leading to π and π* surface-state bands in the gap. A surface-state band derived from s-orbitals is also found in the gap between the upper and lower parts of the valence band. Relaxation results in displacements of surface and first-underlayer atoms and to a stronger π-bonding interaction which increases the π-π* gap. The relaxed surface shows no occupied surface states above the valence band maximum, in agreement with recent photoemission data for a thin Si₃N₄ film. The π* band, however, remains well below the conduction band minimum (but well above the Fermi level). Adsorbing H at all dangling-bond sites on the ideally-terminated surface and then relaxing the surface and first underlayer leads to smaller, but still finite, displacements in comparison to the clean relaxed surface. This surface is more stable, by about 3.67 eV per H, than the clean relaxed surface.     

First-principles calculations of hydrogen molecule adsorption on Ti (0 0 0 1)-(2 × 1) surface

Adsorption of H₂ molecule on the Ti (0 0 0 1)-(2 × 1) surface was studied by density functional theory with generalized gradient approximation (GGA). The parallel and vertical absorption cases were investigated in detail by adsorption energy and electronic structure analysis, we obtained three stable configurations of FCC-FCC (the two H atoms adsorption on the two adjacent fcc sites of Ti (0 0 0 1) surface, respectively), HCP-HCP (the two H atoms adsorption on the two adjacent hcp sites of Ti (0 0 0 1) surface, respectively) and FCC-HCP (the one H atom adsorption on the fcc site and the other adsorption on the near hcp site) based on the six different parallel adsorption sites after the H₂ molecule dissociates. However, all the end configurations of four vertical adsorption sites were unstable, H₂ molecule was very easy to desorb from Ti surface. The H-H bond breaking and Ti-H bond forming result from the H₂ molecule dissociation. H-H bond breaking length ranges from 1.9 Å to 2.3 Å for different adsorption configurations due to the strong Ti-H bond forming. The H₂ dissociative approach and the end stable configurations formation in parallel adsorption processes are attributed to the quantum mechanics steering effects.     

Atom geometry of nanostructured Fe films grown on c(2 × 2)-N/Cu(1 0 0) surface: An investigation by X-ray absorption spectroscopy with multishell analysis

We investigated the growth of Fe nanostructured films on c(2 × 2)-N/Cu(1 0 0) surface with Fe K-edge X-ray absorption fine structure (XAFS) in the near edge and in the extended energy region. The high photon flux of the incident X-rays allowed us to perform multishell analysis of the XAFS oscillations for Fe coverage Θ_Fe < 1 ML. This data analysis yields a detailed investigation of the atom geometry and some insights in the film morphology. At Θ_N < 0.5 ML (N saturation coverage) there is absence of contribution to XAFS from N atoms. First shell analysis of linearly polarized XAFS gives Fe-Fe (or Fe-Cu) bond length values varying between R₁ = 2.526 ± 0.006 Å at the highest Fe coverage (3 ML ) and R₁ = 2.58 ± 0.01 Å at Θ_Fe = 0.5 ML, Θ_N = 0.3 ML, with incidence angle Θ = 35°. These values are different from the case of bcc Fe (R = 2.48 Å), and compatible with fcc Fe (R₁ = 2.52 Å) and fcc Cu (R₁ = 2.55 Å). At the Fe lowest coverage (Θ_Fe = 0.5 ML) the dependence of R₁ on the incidence angle indicates expansion of the outmost layer. Near edge spectra and multishell analysis can be well reproduced by fcc geometry with high degree of static disorder. At N saturation pre-coverage (Θ_N = 0.5 ML) the XAFS analysis has to keep into account the Fe-N bonding. The results suggest two different adsorption sites: one with Fe in a fcc hollow site, surrounded by other metal atoms as nearest neighbours, and one resulting from an exchange with a Cu atom underneath the N layer.     

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.     

Photoemission studies of initial oxidation for ultra-thin zinc film on 6H-SiC(0 0 0 1) surface with synchrotron radiation

The thermal oxidation process of metallic zinc on 6H-SiC(0 0 0 1) surface has been investigated by using atomic force microscopy (AFM), synchrotron radiation photoelectron spectroscopy (SRPES) and XPS methods. The AFM images characterize the surface morphology of ZnO film formed during the thermal oxidation and SRPES record the valence band, Si 2p and Zn 3d spectra at different stages. The O 1s peak is recorded by XPS because of the energy limit of the synchrotron radiation. Our results reveal that the silicon oxides layer of SiC substrate can be reduce by hot metallic zinc atom deposition. The oxygen atoms in the silicon oxides are captured by the zinc atoms to form ZnO_x at the initial stage and as a result, the oxidized SiC surface are deoxidized. After the zinc deposition with the final thickness of 2.5 nm, the sample is exposed in oxygen atmosphere and annealed at different temperatures. According to the evolution of peaks integrated intensities, it is considered that the Zn/SiC system will lose zinc atoms during the annealing in oxygen flux at high temperature due to the low evaporation temperature of pure zinc. After further annealing in oxygen flux at higher temperature, the substrate is also oxidized and finally the interface becomes a stable SiC-SiO_x-ZnO sandwich structure.     

The bΣ(b0) → XΣ(X10,X21) and aΔ(a2) → X21 transitions of AsBr

Emission spectra of the b¹Σ⁺(b0⁺) → X³Σ⁻(X₁0⁺,X₂1) and a¹Δ(a2) → X₂1 transitions of AsBr have been measured in the near-infrared spectral region with a Fourier-transform spectrometer. The arsenic bromide radicals were generated in fast-flow systems by reaction of arsenic vapor (As_x) with bromine and were excited by microwave-discharged oxygen. The most prominent features in the spectrum are the Δv = +1,0,−1, and −2 band sequences of the b¹Σ⁺(b0⁺) → X³Σ⁻(X₁0⁺) transition in the range 11 700-12 700 cm⁻¹. With lower intensities, the Δv = 0 and −1 sequences of the b¹Σ⁺(b0⁺) → X³Σ⁻(X₂1) sub-system show up in the same range. Further to the red, between 6000 and 6700 cm⁻¹, the Δv = 0, +1, and −1 sequences of the hitherto unknown a¹Δ(a2) → X₂1 transition are observed. Analyses of medium- and high-resolution spectra have yielded improved molecular constants for the X₁0⁺, X₂1, and b0⁺ states and first values of the electronic energy and the vibrational constants of the a2 state.     

Hydrocarbon film growth by energetic CH3 molecule impact on SiC (0 0 1) surface

Classic molecular dynamics (MD) calculations were performed to investigate the deposition of thin hydrocarbon film. SiC (1 0 0) surfaces were bombarded with energetic CH₃ molecules at impact energies ranging from 50 to 150 eV. The simulated results show that the deposition yield of H atoms decreases with increasing incident energy, which is in good agreement with experiments. During the initial stages, with breaking Si-C bonds in SiC by CH₃ impacting, H atoms preferentially reacts with resulting Si to form Si-H bond. The C/H ratio in the grown films increases with increasing incident energy. In the grown films, CH species are dominant. For 50 eV, H-Csp3 bond is dominant. With increasing energy to 200 eV, the atomic density of H-Csp2 bond increases.     

An ordered surface ternary alloy of a c(6 × 4) structure formed on Cu(0 0 1) by substitutional coadsorption of Mg and Bi

A c(6 × 4) structure formed on Cu(0 0 1) by the coadsorption of Mg and Bi atoms at room temperature has been determined by a tensor low energy electron diffraction analysis. It is an ordered surface ternary alloy with a thickness of single layer, in which Mg, Bi and Cu atoms are mixed in the top layer. In the primitive unit cell, there are one Mg, four Bi, six Cu atoms and one vacancy in the top layer, and substituted Mg and Bi atoms form MgBi₄ plane clusters being arranged in the c(6 × 4) order. Structural parameters show that Mg-Bi bond distances in the MgBi₄ cluster are 3.01 and 3.07 Å, which are shorter than the summation of metallic radii of Mg and Bi. It is concluded that a direct, attractive interaction between Mg and Bi atoms plays critical role in the formation of the c(6 × 4) structure.