High resolution analysis of the rotational levels of the (0 0 0), (0 1 0), (1 0 0), (0 0 1), (0 2 0), (1 1 0) and (0 1 1) vibrational states of SO2

A high resolution (0.0018 cm⁻¹) Fourier transform instrument has been used to record the spectrum of an enriched ³⁴S (95.3%) sample of sulfur dioxide. A thorough analysis of the ν₂, 2ν₂ − ν₂, ν₁, ν₁ + ν₂ − ν₂, ν₃, ν₂ + ν₃ − ν₂, ν₁ + ν₂ and ν₂ + ν₃ bands has been carried out leading to a large set of assigned lines. From these lines ground state combination differences were obtained and fit together with the existing microwave, millimeter, and terahertz rotational lines. An improved set of ground state rotational constants were obtained. Next, the upper state rotational levels were fit. For the (0 1 0), (1 1 0) and (0 1 1) states, a simple Watson-type Hamiltonian sufficed. However, it was necessary to include explicitly interacting terms in the Hamiltonian matrix in order to fit the rotational levels of the (0 2 0), (1 0 0) and (1 0 1) states to within their experimental accuracy. More explicitly, it was necessary to use a ΔK = 2 term to model the Fermi interaction between the (0 2 0) and (1 0 0) levels and a ΔK = 3 term to model the Coriolis interaction between the (1 0 0) and (0 0 1) levels. Precise Hamiltonian constants were derived for the (0 0 0), (0 1 0), (1 0 0), (0 0 1), (0 2 0), (1 1 0) and (0 1 1) vibrational states.     

On the Mixing of K0-K0,D0-D0 and B0-B0

Systematically, we study the long-range contribution to the mixing effects based on the potential model while the QCD correction in Hamiltonian being taken into account. We have found that the long-distance effects are important to K⁰-K⁰ and D⁰-D⁰, but B⁰-B⁰. The QCD correction causes a change to the results, enhances the mixing, for K⁰-K⁰, by a factor of 1.3, whereas for D⁰-D⁰ it is a suppression of about 0.7. The absorptive parts which give rise to ΔΓ have also been discussed and the diquark-intermediate-state contributions to D and B systems are included.     

Oxidation of epitaxial Y(0 0 0 1) films

We have investigated the oxidation behavior of MBE grown epitaxial Y(0 0 0 1)/Nb(1 1 0) films on sapphire substrates at elevated temperatures under atmospheric conditions with a combination of experimental methods. At room temperature X-ray diffraction (XRD) reveals the formation of a 25 Å thick YO_xH_x layer at the surface, while simultaneously oxide growth proceeds along defect lines normal to the film plane, resulting in the formation of a single crystalline cubic Y₂O₃ (2 2 2) phase. Furthermore, nuclear resonance analysis (NRA) reveals that hydrogen penetrates into the sample and transforms the entire Y film into the hydride YH₂ phase. Additional annealing in air leads to further oxidation radially out from the already existing oxide channels. Finally material transport during oxidation results in the formation of conically shaped oxide precipitations at the surface above the oxide channels as observed by atomic force microscopy (AFM).     

Half-metallicity characteristic at zincblende CrSb(0 0 1) surfaces and its interfaces with GaSb(0 0 1) and InAs(0 0 1)

Electronic and magnetic properties of the zincblende CrSb(0 0 1) surfaces and its interfaces with GaSb(0 0 1) and InAs(0 0 1) semiconductors are studied within the framework of the density-functional theory using the FPLAPW+lo approach. We found that the Cr-terminated surfaces retain the half-metallic character, while the half-metallicity is destroyed for the Sb-terminated surfaces due to surface states, which originate from p electrons. The phase diagram obtained through the ab-initio atomistic thermodynamics shows that at phase transition has occurred. Also the half-metallicity character is preserved at both CrSb/GaSb and CrSb/InAs interfaces. The conduction band minimum (CBM) of CrSb in the minority spin case lies about 0.63 eV above that of InAs, suggesting that the majority spin can be injected into InAs without being flipped to the conduction bands of the minority spin. On the other hand the CrSb/GaSb interface has a greater valence band offset (VBO) compared with the CrSb/InAs interface and the minority electrons have lower contribution in the injected currents and hence more efficient spin injection into the GaSb semiconductor. Thus the CrSb/GaSb and CrSb/InAs heterojunctions can be useful in the field of spintronics.     

Layer-resolved photoelectron diffraction from Si(0 0 1) and GaAs(0 0 1)

Photoelectron diffraction in the layer-resolved mode brings more detailed information about local atomic arrangement than is obtained in the standard mode. This is demonstrated in crystals with diamond and zinc-blende structures, both for unpolarized photon excitation as well as for circularly polarized excitation. The full angular distributions of photoemission intensities are evaluated for large atomic clusters representing ideally truncated surfaces of Si(0 0 1) and GaAs(0 0 1). Highly structured layer-resolved patterns enable a more detailed understanding of the standard mode outcomes. Photoelectron intensities from atomic layers placed at different depths under the crystal surface provide direct evidence about electron attenuation and its anisotropy in crystals.     

Observation of B0 -->D0K0 and B0 -->D0K*0 decays

We report on a search for B(0)-->D(*0)K(*0) decays based on 85 x 10(6) BB events collected with the Belle detector at KEKB. The B(0)-->D0K(0) and B(0)-->D0K(*0) decays have been observed for the first time with the branching fractions B(B(0)-->D0K(0))=(5.0(+1.3)(-1.2)+/-0.6)x10(-5) and B(B(0)-->D0K(*0))=(4.8(+1.1)(-1.0)+/-0.5)x10(-5). No significant signal has been found for the B(0)-->D(*0)K*0) and B(0)-->D(*0)K(*0) decay modes, and upper limits at 90% C.L. are presented.     

Fourfold in-plane magnetic anisotropy in epitaxial Fe(1 1 0)/Cu(0 0 1) and Fe(1 1 0)/Ni(0 0 1) bilayers

Epitaxial Fe(1 1 0) films with thicknesses of 100-800 nm on Cu(0 0 1) and Ni(0 0 1) buffer layers grown on MgO(0 0 1) substrates have been fabricated. These films contain Fe(1 1 0) crystallites which are in the Pitsch orientation relationship. Magnetization and the fourfold in-plane magnetic anisotropy constants of these films have been determined by torque measurements. All the samples under study are characterized by a fourfold magnetic anisotropy with easy axes parallel to the [1 0 0] and [0 1 0] directions of Cu(0 0 1) and Ni(0 0 1) layers. The measured values of the constant for Fe(1 1 0)/Cu(0 0 1) are found to depend on deposition temperature; a maximum value of (2.5±0.1)×10⁵ erg/cm³ is reached after annealing at 600 °С. The in-plane torque measurements on Fe(1 1 0)/Ni(0 0 1) bilayers obtained at 300 °С, on the other hand, exhibit a constant value of (2.7±0.1)×10⁵ erg/cm³. Assuming an exchange interaction between the Fe(1 1 0) crystallites, which are in the Pitsch orientation relationship, the fourfold in-plane magnetic anisotropy has been calculated as 2.8×10⁵ erg/cm³. The deviations of the experimental values from the predicted one may be explained by the formation of a polycrystalline phase within the Fe(1 1 0) layer and a partial disorientation of the epitaxial crystallites.     

Olefin metathesis reaction on GaN (0 0 0 1) surfaces

Proof-of-concept reactions were performed on GaN (0 0 0 1) surfaces to demonstrate surface termination with desired chemical groups using an olefin cross-metathesis reaction. To prepare the GaN surfaces for olefin metathesis, the surfaces were hydrogen terminated with hydrogen plasma, chlorine terminated with phosphorous pentachloride, and then terminated with an alkene group via a Grignard reaction. The olefin metathesis reaction then bound 7-bromo-1-heptene. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and water contact angle measurements following each step in the reaction scheme. The XPS data was used to qualitatively identify surface chemical species and to quantitatively determine molecular surface coverage. The bromine atom in 7-bromo-1-heptene served as a heteroatom for identification with XPS. The reaction scheme resulted in GaN substrates with a surface coverage of 0.10 monolayers and excellent stability towards oxidation when exposed to oxygen plasma.     

Water adsorption and dissociation on BeO(0 0 1) and (1 0 0) surfaces

Plateaus in water adsorption isotherms on hydroxylated BeO surfaces suggest significant differences between the hydroxylated (1 0 0) and (0 0 1) surface structures and reactivities. Density functional theory structures and energies clarify these differences. Using relaxed surface energies, a Wulff construction yields a prism crystal shape exposing long (1 0 0) sides and much smaller (0 0 1) faces. This is consistent with the BeO prisms observed when beryllium metal is oxidized. A water oxygen atom binds to a single surface beryllium ion in the preferred adsorption geometry on either surface. The water oxygen/beryllium bonding is stronger on the surface with greater beryllium atom exposure, namely the less-stable (0 0 1) surface. Water/beryllium coordination facilitates water dissociation. On the (0 0 1) surface, the dissociation products are a hydroxide bridging two beryllium ions and a metal-coordinated hydride with some surface charge depletion. On the (1 0 0) surface, water dissociates into a hydroxide ligating a Be atom and a proton coordinated to a surface oxygen but the lowest energy water state on the (1 0 0) surface is the undissociated metal-coordinated water. The (1 0 0) fully hydroxylated surface structure has a hydrogen bonding network which facilitates rapid proton shuffling within the network. The corresponding (0 0 1) hydroxylated surface is fairly open and lacks internal hydrogen bonding. This supports previous experimental interpretations of the step in water adsorption isotherms. Further, when the (1 0 0) surface is heated to 1000 K, hydroxides and protons associate and water desorbs. The more open (0 0 1) hydroxylated surface is stable at 1000 K. This is consistent with the experimental disappearance of the isotherm step when heating to 973 K.     

The thermodesorption mechanism of ammonia from Ru(0 0 0 1)

Thermodesorption rates for the desorption of ammonia from Ru(0 0 0 1) are calculated by Transition State Theory including small curvature tunneling corrections. The potential energy surface is derived on a model cluster employing hybrid density functional theory (B3LYP). Two desorption pathways can be identified, just distinguished by the orientation of the leaving ammonia entity. It is found that the rate dominating mechanism comprises an umbrella-like flipping movement of the hydrogen atoms during the desorption. Nevertheless tunneling does not play any significant role in the reaction as the hydrogen movements are shown to occur at the low energy regions of the barrier.     

Vibrational entropy-driven dealloying of Mo(1 0 0) and W(1 0 0) surface alloys

The formation and stability of Cu, Ag and Au-induced c(2 × 2) alloys at the Mo(1 0 0) and W(1 0 0) surfaces have been investigated with low-energy electron microscopy and diffraction. The ordered alloys transform to disordered overlayer structures at elevated temperature. Comparison of the transformation temperatures with energetics obtained from first principles calculations reveals the vibrational entropic contribution to the system free energy that defines alloy thermal stability. Effective Debye temperatures for metal adatoms are determined that exhibit the expected mass and bond strength dependence.     

Electronic structure study of reconstructed Au-SiC(0 0 0 1) surfaces

A study of surface and interface properties of reconstructed Au-SiC(0 0 0 1) surfaces is reported. Two reconstructions were prepared on SiC(0 0 0 1), a √3 × √3R30° and a Si-rich 3 × 3, before Au deposition and subsequent annealing at different temperatures. For the Si-rich 3 × 3 surface the existence of three stable reconstructions 2√3 × 2√3R30°, 3 × 3 and 5 × 5 are revealed after deposition of Au layers, 4-8 Å thick, and annealing at progressively higher temperatures between 500 and 950 °C. For the 2√3 surface two surface shifted Si 2p components are revealed and the Au 4f spectra clearly indicate silicide formation. The variation in relative intensity for the different core level components with photon energy suggests formation of an ordered silicide layer with some excess Si on top. Similar core level spectra and variations in relative intensity with photon energy are obtained for the 3 × 3 and 5 × 5 phases but the amount of excess Si on top is observed to be smaller and an additional weak Si 2p component becomes discernable.For the √3 surface the evolution of the core level spectra after Au deposition and annealing is shown to be distinctly different than for the Si-rich 3 × 3 surface and only one stable reconstruction, a 3 × 3 phase, is observed at similar annealing temperatures.     

Structural properties of oxygen on InN(0 0 0 1) surface

First-principles calculations are performed to study the various structures of oxygen (O) adsorbed on InN(0 0 0 1) surfaces. It is found that the formation energy of O on InN(0 0 0 1) decreases with decreasing oxygen coverage. Of all the adsorbate induced surface structures examined, the structure of InN(0 0 0 1)-(2 × 2) as caused by O adsorption at the H₃ sites with 0.25 monolayers coverage is most energetically favorable. Meanwhile, nitrogen (N) vacancy can form spontaneously. Oxygen atoms may also substitute N atoms, or accumulate at the voids inside InN film or simply stay on the surface during growth. The oxygen impurity then acts as a potential source for the n-type conductivity of InN as well as the large energy band gap measured.     

Stability of ZnO{0 0 0 1} against low energy ion bombardment

The steady-state surface compositions of the polar (O and Zn terminated) faces of ZnO{0 0 0 1} produced by low energy (0.3-2 keV) Ar⁺ ion bombardment were studied by Auger electron spectroscopy and electron energy loss spectroscopy. The alterations produced by the ion bombardment using different ion energies were monitored by calculating the intensity ratios of the low and high energy Zn Auger peaks (59 eV and 994 eV, respectively); Zn and O Auger peaks (59 eV and 510 eV, respectively). Based on the dependence of these ratios on the ion energy and termination of the surface, we could conclude that the stability of the Zn face is higher against the low energy argon ion bombardment-induced compositional changes than that of the O face.     

Adsorption structure of germanium on the Ru(0 0 0 1) surface

Coverage-dependent adsorption energy of the Ge/Ru(0 0 0 1) growth system and the geometrical distortions of the most stable adsorption structure are investigated through first-principles calculations within density functional theory. A local minimum in adsorption energy is found to be at a Ge coverage of 1/7 monolayer with a Ru(0 0 0 1)- symmetry. Based on this stale superstructure, the scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) images are simulated by means of surface local-density of states (LDOS). The results are consistent well with the STM measurements on the phase for Ge overlayer on Ru(0 0 0 1). From this stimulation, the relations between the STM images and the lattice distortion are also clarified.     

Fabrication of rubrene nanowires on vicinal (0 0 0 1) sapphire surfaces

Morphology of high-vacuum deposited rubrene thin films on the annealed (0 0 0 1) vicinal sapphire surfaces was studied by atomic force microscopy in non-contact mode. Atomic force microscopy images of rubrene thin films indicate that a regular array of steps on the sapphire surface acts as a template for the growth of the arrays of rubrene nanosize wires. To further demonstrate that morphological features of a substrate are crucial in determining the morphology of rubrene layers we have grown rubrene on the sapphire surfaces that were characterized by the terrace-and-step morphology with islands. We have found preferential nucleation of rubrene molecules at the intersection between a terrace and a step, as well as around the islands located on terraces.     

Stable surface termination on vicinal 6H-SiC(0 0 0 1) surfaces

Ordered nanofacet structures on vicinal 6H-SiC(0 0 0 1) surfaces, consisting of pairs of a (0 0 0 1) basal plane and a facet, are investigated in terms of stable surface stacking of the (0 0 0 1) basal planes. The surface termination of S3 (or S3*), i.e., ABC (or A*C*B*), was suggested by a structural model based on quantized step-bunching, which typically gives a one-unit-cell bunched step configuration at the facet. Here, we evaluate the surface termination at basal planes covered with a layer of silicon oxynitride by means of quantitative low-energy electron diffraction (LEED) analysis combined with scanning tunneling microscopy (STM), and show the validity of the structural model proposed.     

Stoichiometry, contamination and microstructure of MnSb(0 0 0 1) surfaces

The stoichiometry, microstructure and surface composition of MnSb have been investigated using X-ray photoelectron spectroscopy, electron diffraction and microscopy. Epitaxially grown samples were exposed to ambient air for several weeks and methods for preparing clean, stoichiometric and smooth surfaces were investigated. Air-stored sample surfaces are chemically stratified but dominated by Mn oxides 4-5 nm thick. These oxides are difficult to remove by ion bombardment and annealing (IBA), but a brief etch in HCl removes them very efficiently. It leaves the surface Sb-rich, and clean, smooth and stoichiometric surfaces are then readily recovered by IBA. These surfaces exhibit a (2 × 2) surface reconstruction with atomically flat terraces. This reconstruction can be reversibly changed to a (1 × 1) by Sb deposition and annealing.     

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.