The electronic structure of ordered Cu3Au(001)

The electronic structure of the (001) face of ordered Cu₃Au was studied using synchrotron radiation at BESSY, in the photon energy range 22–80 eV. The Cu 3d-derived bands in Cu₃Au look like the foldedd-bands of fcc Cu metal. Three Au 5d-derived bands were observed at 5.0, 6.1 and 7.0 eV below the Fermi level, which showed no dispersion with change in photon energy. The Cu 3d- and the Au 5d-derived bands are found to be separated in energy. We have calculated self-consistent energy bands along the (001) direction using the fully relativistic LMTO method. Comparison of these bands with those experimentally determined shows good agreement. From the calculated bands along –X the direction dependent densities of states were determined, which give a consistent account for the non-dispersive Au-bands.     

Electronic band structure of Cu3Au: An angle-resolved photoemission study along the [111]-direction

High-resolution normal photoemission (ARPE) spectra have been recorded for Cu₃Au(111) with the use of polarized synchrotron and rare-gas resonance radiation in the photon energy range from 9 to 27 eV. It is for the first time that dispersions of the gold-like bands have been found experimentally. Using a fully relativistic layer-KKR photoemission formalism, occupied and unoccupied bands as well as one-step-model photoemission spectra have been calculated. The comparison of calculated spectra with experimental ones and the observation of direct-transition resonances upon photon energy near the Brillouin zone-center reveal a shift of the unoccupied ground-state bands by about +2.5 eV (self-energy shift). The direct-transition structures in the experimental spectra have been exploited to determine the dispersions of the occupied bands along the [111] direction (A line in k space). In order to determine the wave vector of the experimental direct transitions we used as final state that calculated unoccupied band along [111], which also exists in pure copper and gold up to about 20 eV above the Fermi energy (“unfolded” band structure), shifted by + 2.5 eV. The experimental occupied bands with Cu character are in very good agreement with theory after shifting the latter by about 0.3 eV to lower energy, whereas somewhat bigger discrepancies exist for the gold-like bands.     

Au(110)表面结构和氧原子吸附的第一性原理研究

用密度泛函理论(DFT)研究了金属Au(110)表面结构以及氧原子的吸附状态.计算得到Au(110)-(1×2)缺列再构表面原子的弛豫分别是-15.0%(Δd₁₂/d₀)和-1.1%(Δd₂₃/d₀),表面能为52.7 meV/²,功函数Φ=5.00 eV;Au(110)-(1×3)缺列再构表面的Δd_{1 关键词： 缺列再构Au(110)表面 STM图像 氧原子吸附}     

A new spin effect in photoemission with unpolarized light: Experimental evidence of spin polarized electrons in normal emission from Pt(111) and Au(111)

Unpolarized light ejects spin polarized electrons from Pt(111) and Au(111) even if the electron emission occurs normal to the surface. For off normal incidence of 11.8 eV, 16.9 eV, and 21.2 eV radiation, and for the main peaks in the photoemission spectra, a degree of spin polarization of up to 30% or more is found for the spin polarization component P _y perpendicular to the reaction plane. A crystal rotation about its surface normal does not change P _y . P _y is largest for transitions from bands with symmetry ₆ ³ . All these experimental findings agree with a recent theoretical prediction [1] of a new spin effect by Tamura and Feder.     

Low energy electron diffraction and electron spectroscopy studies of the clean (110) and (100) titanium dioxide (rutile) crystal surfaces

Low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), electron energy loss (ELS) and ultraviolet photoemission spectroscopies (UPS) were used to study the structures, compositions and electron state distributions of clean single crystal faces of titanium dioxide (rutile). LEED showed that both the (110) and (100) surfaces are stable, the latter giving rise to three distinct surface structures, viz. (1 × 3), (1 × 5) and (1 × 7) that were obtained by annealing an argon ion-bombarded (100) surface at ~600,800 and 1200° C respectively. AES showed the decrease of the $\text{O(510 eV)}\text{Ti(380 eV)}$ peak ratio from ~1.7 to ~1.3 in going from the (1 × 3) to the (1 × 7) surface structure. Electron energy loss spectra obtained from the (110) and (100)?(1 × 3) surfaces are similar, with surface-sensitive transitions at 8.2, 5.2 and 2.4 eV. The energy loss spectrum from an argon or oxygen ion bombarded surface is dominated by the transition at 1.6 eV. UPS indicated that the initial state for this ELS transition is peaked at ?0.6 eV (referred to the Fermi level E_F in the photoemission spectrum, and that the 2.4 eV surface-sensitive ELS transition probably arises from the band of occupied states between the bulk valence band maximum to the Fermi level. High energy electron beams (1.6 keV 20 μA) used in AES were found to disorder clean and initially well-ordered TiO₂ surfaces. Argon ion bombardment of clean ordered TiO₂ (110) and (100)?(1 × 3) surfaces caused the work function and surface band bending to decrease by almost 1 eV and such decrease is explained as due to the loss of oxygen from the surface.     

Charging effects on the vibrational properties of Au and Au2 on MgO(100)

Vibrational spectra of charge-neutral and charged Au and Au₂ on MgO(100) were investigated using ab-initio density functional perturbation theory. The calculated vibrational spectra showed vibrational features associated with the charge states of Au and Au₂ on MgO(100). Further analyses of surface in-plane and normal phonon modes of Au and Au₂ on MgO(100) were performed to extract vibrational features involving the Au modes. These features provide important information for experimentally explaining the charge states of Au and Au₂ on MgO(100).     

Photoemission from Co on Pt(111) using synchrotron radiation in the range 40 eV ω 150 eV

Photoelectron spectra for CO adsorbed on the (111)-face of Pt have been measured using synchrotron radiation of energy 40 eV ω 150 eV. A dramatic increase of the molecular orbital (MO) intensity relative to the intensity of the Pt 5d valence band (VB) is observed for ω > 100 eV, to a ratio at that is a factor of three higher than at . The energy variation of the Pt 5d VB photoemission peak intensity has been derived independently in the 40–200 eV range from measurements on clean Pt. The 5d peak intensity is found to decrease steeply (by more than an order of magnitude) between 100 and 150 eV. The observed increase of the MO peak intensity relative to that of the 5d VB is attributed to this cross-section effect. The Pt VB peak nearest the Fermi energy which is mainly t_2g in character, is found to decrease in intensity on adsorption of CO. In the present case synchrotron radiation in the ω > 100 eV range appears to be especially valuable for studies of adsorbates.     

Electronic structure and ordering of multilayers of Co and Ag on Cu(111) investigated by photoelectron spectroscopy

The growth and the electronic structure of multilayers of Co and Ag on Cu(111) at room temperature have been studied with photoelectron spectroscopy and low-energy electron diffraction (LEED). The coverage range spans from Co and Ag layers between one monolayer (ML) to stacking of several monolayers. Surface states and ordered structures have been identified at room temperature. A Ag-related surface state with a binding energy of 0.30 eV is identified in normal emission in the ultraviolet photoelectron spectra when silver constitutes the top layer. Core-level binding energy shifts of Ag 3d_5/2 reflect the changing surroundings of Ag. Hexagonal diffraction patterns are observed for sandwiches of consecutive layers of Co and Ag up to 5 layers. Since no interlayer diffusion is observed in the layer-by-layer formation of the films, multilayers of consecutive silver and cobalt on Cu(111) offer preparation of sandwiched magnetic–non-magnetic structures.     

Critical wetting and surface-induced continuous phase transition on Cu3Au(001)

In the bulk Cu₃Au is known to undergo adiscontinuous order-disorder phase transition atT ₀=663 K. Spin polarized low-energy-electron diffraction (SPLEED) reveals acontinuous surface-induced order-disorder phase transition-equivalent to a critical wetting transition—on the surface of Cu₃Au. The results indicate that nearT ₀ the observed singularity is related to the surface order parameter which can be described by a functional dependence of the formt ¹ with ¹=0.77±0.06.     

Electronic properties of clean and oxygen exposed GaAs (100) surfaces

Both Photoemission Yield Spectroscopy (PYS) and Auger Electron Spectroscopy (AES) have been used in the study of the electronic properties of the clean GaAs(100) surface prepared by IBA procedure and subsequently exposed to oxygen. For the clean GaAs(100)c(8 × 2) surface, the values of the work function and the absolute band bending were 4.20 ± 0.02 eV and −0.23 ± 0.06 eV, respectively, which confirms the pinning of the Fermi level E_F, and two filled electronic surface state bands localized in the band gap below the Fermi level were observed. After exposition of this surface to 10³ L of oxygen, the electronic surface state band localized just below the Fermi level E_F disappeared, and the work function and the absolute band bending increased by only 0.12eV, whereas for the higher oxygen exposures of 10⁴L and 10⁵L, only small increases in the values of the work function and the absolute bending by 0.04 eV and 0.03 eV, respectively, were observed.     

Photoemission via bloch states and evanescent band gap states for Cu(110)

Normal emission photoelectron spectra from Cu(110) using polarized synchrotron radiation (hv < 35 eV) can be explained with a direct transition model using realistic final state bands. Prominent surface photoemission via evanescent final states is observed in the large X′₅-X₁ conduction band gap. Accurate valence band eigenvalues at K and X have been determined.     

Determination of the E(k6 relation for a surface state on Au(111)

Angle-resolved photoemission measurements have been used to determine the energy versus parallel wave vector (k₆) relations for the surface state on Au(111). The state has its minimum energy 0.5 eV below the Fermi level, and disperses upward with increasing k₆     

In situ photoemission study of the contact formation of (Ba,Sr)TiO3 with Cu and Au

The contact formation of (Ba,Sr)TiO₃ thin films and SrTiO₃ single crystals with Cu and Au have been studied using X-ray and ultraviolet photoelectron spectroscopy with in situ sample preparation. During metal deposition a partial reduction of the substrate occurs. The Fermi level at the interface is found to be close to the conduction band minimum, indicating small Schottky barrier heights (< 0.2 eV).     

Photoemission study of the Ba core levels in YBa2Cu3O7-x

Angle dependent X-ray photoemission spectra of epitaxial thin YBa₂Cu₃O_7-x films show characteristic differences after various heat and oxygen pretreatments. The component with the lowest binding energy in Ba 3d _5/2 and 4d _5/2 peaks results from bulk Ba in YBa₂Cu₃O_7-x . A component with 2 eV higher binding energy results from Ba in the surface unit cell with different bonding if compared with the bulk superconductor. This surface structure is observed for all YBa₂Cu₃O_7-x surfaces which have been exposed to oxygen. It is not observed for UHV prepared surfaces after mechanical scraping or fracturing.     

The electron energy loss spectrum of Br on Au (100)

The electron energy loss spectrum of Br on Au (100) shows a sharp loss at 2.5 eV accompanied by a weaker broader feature at 5.5 eV and a broad enhancement centred at 16 eV. It is suggested that an adsorbate resonance lies above the top of the d-band allowing adsorbate → free metal state transitions without appreciable coupling to or competition from metal excitations.     

Time-resolved luminescence spectroscopy of pure and doped with Ce3+ ions SrAlF5 crystals

The results of a study of time-resolved photoluminescence (PL) and energy transfer in both pure and doped with Ce³⁺ ions SrAlF₅ (SAF) single crystals are presented. The time-resolved and steady-state PL spectra in the energy range of 1.5–6.0 eV, the PL excitation spectra and the reflectivity in the energy range of 3.7–21 eV, as well as the PL decay kinetics were measured at 8.8 and 295 K. The lattice defects were revealed in the low temperature PL spectra (emission bands at 2.9 and 4.5 eV) in the undoped SAF crystals. The luminescence spectra of the doped Ce³⁺:SAF crystals demonstrate a new selective emission bands in the range of 3.7–4.5 eV with the exponential decay kinetics (τ ≈ 60 ns at X-ray excitation). These bands correspond to the d-f transitions in Ce³⁺ ions, which occupy nonequivalent sites in the crystal lattice.     

Infrared reflection absorption spectra of Fe(CO)5 adsorbed on Au surfaces

Infrared reflection absorption spectroscopy (IRAS) shows that the CO stretching bands of Fe(CO)₅ adsorbed on Au surfaces are significantly different in band shape as well as in frequency from the bands observed in a transmission mode. This difference has been observed for other metal substrates and explained in terms of the anomalous dispersion of the refractive index in the region of the observed bands. The refractive indices of Fe(CO)₅ are calculated using the Kramers-Kronig relation from the transmission spectra of Fe(CO)₅ adsorbed on a sapphire plate, an SiO₂-coated sapphire plate, and an Au film evaporated on a sapphire plate, and the IRA spectra of Fe(CO)₅ adsorbed on Au are calculated using Fresnel's formula. The results show that the ν₁₀ band of Fe(CO)₅ becomes very sharp and shifts to higher frequencies by more than 10 cm⁻¹, while the ν₆ band becomes a shoulder of the v₁₀ band, in good agreement with the observed IRA spectra. The IRAS calculation also shows that the weak band observed at 2114 cm⁻¹ for the Au film remains unchanged in position, in agreement with the observed IRAS.     

Oxygen adsorption on Cu3Au(100) above 350 K

The initial stage of oxygen adsorption on Cu₃Au(100) above 350 K has been investigated using Auger electron spectroscopy. In the temperature range 350–550 K the adsorption isotherms tend to saturate at levels which increase with temperature. Initial sticking coefficients in this temperature range are at least an order of magnitude less than those on Cu(100) and saturation levels vary from ? 5% of a monolayer at 350 K to ? 15% of a monolayer at 550 K. As the temperature is increased to within 100 K of the bulk order-disorder transformation, the rate of adsorption increases dramatically accompanied by apparent adsorption-induced rearrangement of the alloy surface. The degree of annealing following Ar⁺ bombardment is observed to affect the initial uptake of oxygen throughout the entire temperature range.     

SrTiO3(100) step sites as catalytic centers for H2O dissociation

Features arising from surface Sr(Ti) atoms on the SrO(TiO₂) terraces of SrTiO₃ (100) have been resolved in core-level photoemission spectra, which provides new insights into the surface electronic structure and reactivity of transition metal oxides. The surface Sr 3d (Ti3s) features lie to lower (higher) initial energy of the bulk-derived peaks by ca. 1.0 eV (1.7 eV), being consistent with the expected enhancement of covalent bonding in the TiO₂-terrace surface. Step-sites, which connect the two types of terrace, are found to act as catalytic centers for H₂O dissociation.