Metal (Cu; Pd) adsorption on MgO: investigations with MIES and UPS

MgO films (2-nm thick) were grown on W(110) while metastable impact electron (MIES) and photoelectron (UPS(HeI)) spectra were collected in situ; apart from the valence-band emission no additional spectral features could be detected. The oxide surface was exposed to metal atoms (Cu; Pd) (substrate at 300 K). For Cu, but not for Pd/MgO, a characteristic initial decrease of the surface work function by about 0.4 eV is observed for small exposures. Metal-induced intensity develops above the top of the O2p valence band in UPS caused by 3dCu (4dPd) emission. The emission seen for Cu/MgO in the MIES spectra above the 2pO valence band is attributed to the ionization of Cu4s states of neutrally adsorbed Cu species; the shape of the MIES spectra suggests island growth even at the lowest studied exposures. For Cu/MgO the critical coverage for the transition from 2D to 3D island growth, as determined with MIES, is estimated as 0.15 monolayers. PACS 79.20; 79.60.Dp; 73.22.-f; 82.80.Pv     

Infrared reflection absorption study of carbon monoxide adsorption on Pd/Cu(1 1 1)

Pd-Cu bimetallic surfaces formed through a vacuum-deposition of Pd on Cu(1 1 1) have been discussed on the basis of carbon monoxide (CO) adsorption: CO is used as a surface probe and infrared reflection absorption (IRRAS) spectra are recorded for the CO-adsorbed surfaces. Low energy electron diffraction (LEED) patterns for the bimetallic surfaces reveal six-fold symmetry even after the deposition of 0.6 nm. The lattice spacings estimated by the separations of reflection high-energy electron diffraction (RHEED) streaks increase with increasing Pd thickness. Room-temperature CO exposures to the bimetallic surfaces formed by the Pd depositions less than 0.3 nm thickness generate the IRRAS bands due to the three-fold-hollow-, bridge- and linear-bonded CO to Pd atoms. In particular, on the 0.1 nm-thick Pd surface, the linear-bonded CO band becomes apparent at an earlier stage of the exposure. In contrast, the bridge-bonded CO band dominates the IRRAS spectra for CO adsorption on the 0.6 nm-thick Pd surface, at which the lattice spacing corresponds to that of Pd(1 1 1). A 90 K-CO exposure to the 0.1 nm-thick Pd surface leads to the IRRAS bands caused not only by CO-Pd but also by CO-Cu, while the Cu-related band is almost absent from the spectra for the 0.3 nm-thick Pd surface. The results clearly reveal that local atomic structures of the outermost bimetallic surface can be discussed by the IRRAS spectra for the probe molecule.     

Electronic properties of thin Zn layers on Pd(1 1 1) during growth and alloying

The growth and alloying of thin Zn layers on Pd(1 1 1) was investigated using X-ray and ultraviolet photoelectron spectroscopy as well as low energy electron diffraction and correlated with density functional calculations. At 105 K, the formation of a pseudomorphic Zn monolayer is observed. Upon heating this layer to 550 K or upon deposition of 1 ML at 550 K, an ordered p(2 × 1) PdZn surface alloy with a Pd:Zn ratio of ∼1:1 is formed, with a characteristic Pd 3d_5/2 peak at a binding energy of ∼335.6 eV. For deposition of 3 ML Zn at 550 K or by heating 3 ML, deposited at low temperature, to 500 or 600 K, a PdZn alloy with a Pd:Zn ratio of again ∼1:1 is found in the surface region, with a Pd 3d_5/2 peak at ∼335.9 eV; the direct preparation at 550 K leads to a more homogeneous and better ordered alloy. The valence band spectrum of this alloy with a low density of states at the Fermi level and pronounced maxima due to the “Pd 4d” band at ∼2.4 and 3.9 eV closely resembles the spectrum of Cu(1 1 1), in good agreement with the calculated density of states for a PdZn alloy of 1:1 stoichiometry. The shift of the “Pd 4d” band to higher binding energies as compared to Pd(1 1 1) indicates a charge transfer from Zn to the Pd 4d levels. Overall, the similarity between the ultraviolet photoelectron spectra for the PdZn alloy and for Cu(1 1 1) is taken as explanation for the similar chemical activity of both systems in methanol steam reforming.     

Giant Coster-Kronig transitions and intrinsic line shapes of the anomalous Pd M45VV Auger spectrum of Pd/Ag(100) dilute surface alloys

The Pd M4VV and M5VV Auger spectra of the 0.1 ML Pd/Ag(100) dilute surface alloy have been measured using Auger-photoelectron coincidence spectroscopy. The M4VV spectrum indicates that Pd 3d(3/2) core holes have a Coster-Kronig decay rate that is approximately 10 times that of Pd metal. Our calculations show that this giant enhancement arises from the local electronic structure of excited Pd atoms at the surface. Anomalous features in the Auger line shape are similar to those seen in dilute bulk PdAg alloys, and these features in the M5VV and M4VV lines are in good agreement with theoretical predictions.     

Effects of metal-support interactions on the electronic structures of metal atoms adsorbed on the perfect and defective MgO(1 0 0) surfaces

The electronic structures of Ni, Pd, Pt, Cu, and Zn atoms adsorbed on the perfect MgO(1 0 0) surface and on a surface oxygen vacancy have been studied at the DFT/B3LYP level of theory using both the bare cluster and embedded cluster models. Ni, Pd, Pt, and Cu atoms can form stable adsorption complexes on the regular O site of the perfect MgO(1 0 0) surface with the binding energies of 19.0, 25.2, 46.7, and 17.3 kcal/mol, respectively, despite very little electron transfer between the surface and the metal atoms. On the other hand, adsorptions of Ni, Pd, Pt, and Cu atoms show strong interaction with an oxygen vacancy on the MgO(1 0 0) surface by transferring a significant number of electron charges from the vacancy to the adsorbed metal atoms and thus forming ionic bonds with the vacancy site. These interactions on the vacancy site for Ni, Pd, Pt, and Cu atoms increase the binding energies by 25.8, 59.7, 85.2, and 19.1 kcal/mol, respectively, compared to those on the perfect surface. Zn atom interacts very weakly with the perfect surface as well as the surface oxygen vacancy. We observed that the interaction increases from Ni to Pt in the same group and decreases from Ni to Zn in the same transition metal period in both perfect and vacancy systems. These relationships correlate well with the degrees of electron transfer from the surface to the adsorbed metal atom. The changes in the ionization potentials of the surface also correlate with the adsorption energies or degrees of electron transfers. Madelung potential is found to have significant effects on the electronic properties of metal atom adsorptions on the MgO(1 0 0) surface as well as on an oxygen vacancy, though it is more so for the latter. Furthermore, the Madelung potential facilitates electron transfer from the surface to the adsorbed metal atoms but not in the other direction.     

Angle resolved photoemission study of the Ce/Pd(1 1 1) interface

X-ray and UV excitation angle resolved photoemission spectroscopy of ultra-thin films of cerium deposited on a Pd(1 1 1) single-crystal surface has been carried out. Both core level and valence band spectra show a formation of a surface alloy exhibiting d- and f-electron orbital hybridization. An azimuth and polar angle mapping of X-ray excited photoemission intensities results in a surface-geometrical structure information. Mapping of ultra-violet photoelectron intensities as a function of emission angles is used for a band mapping and an electronic structure determination. The d-, f-hybridization occurs even for 0.7 ML of Ce deposited at room temperature. The surface annealing at 260 °C enhances this behavior. A shift of Pd 4d-derived states to higher binding energy in the Ce-Pd systems is observed.     

Positron trapping at quantum-dot-like particles on metal surfaces

Measurements of the positron annihilation-induced Auger electron (PAES) spectra from the Fe-Cu alloy surfaces with quantum-dot-like Cu nanoparticles embedded in Fe reveal a decrease of the Fe M_2,3VV positron annihilation-induced Auger signal intensity and an enhancement of the Cu one for surfaces created by enriching the Cu content of the Fe-Cu alloy. These experimental results are analyzed by performing calculations of positron surface states and annihilation characteristics at the Fe(1 0 0) surface with quantum-dot-like Cu nanoparticles embedded in the top atomic layers of the host substrate. Estimates of the positron binding energy and annihilation characteristics reveal their strong sensitivity to the nanoparticle coverage. Theoretical core annihilation probabilities are compared with experimental ones estimated from the measured Auger peak intensities. The observed behavior of the Fe and Cu PAES signal intensities is explained by theoretical calculations as being due to trapping of positrons in the regions of Cu nanoparticles embedded in the top atomic layers of Fe.     

Electron excited Auger line shape study of ion-beam-mixed Pd–Au alloys

The electronic structure of the ion-beam-mixed Pd–Au alloys have been studied using valence band spectra of XPS and electron excited CVV–Auger spectra. To show the relationship between the electronic structure changes and the Auger spectral line shape, the data of the self-convolution of the partially weighted valence band spectra was compared with the Auger spectra of Pd–Au alloys. The Pd–Au alloy is one of the systems which both atomic and band-like contributions are evident in the Auger spectral line shape. Since the self-convolution of PDOS’s relates to the band-like part of Auger spectra, in Pd–Au alloys, the band-like structure in the Auger line shape can be classified by the self-convolution of the partially weighted valence band spectra. Finally, we found that the increase in peak size at ∼80 eV with the increase in Pd content is due to the band-like contribution in the Au N_6,7VV Auger line shape.     

The valence band of free K clusters studied by photoelectron and Auger spectroscopies

The valence states of free neutral potassium clusters produced by a gas aggregation source were probed by synchrotron radiation based photoelectron spectroscopy. The first ionization energy (IE) of the clusters was determined to be 10% larger than the work function of bulk potassium. Using electrostatic concepts and the IE, the mean size of the clusters was estimated to be ≈2000 atoms. Further information about the valence band was provided by investigation of the Auger process initiated by the ionization of the 3p level with a subsequent emission of an Auger electron from the valence band (M_2,3VV). Plasmon satellites were observed in Auger spectra of free metal clusters.     

Carbon monoxide adsorption on Pd-deposited Cu(1 1 0) surface: Infrared reflection absorption and temperature programmed desorption studies

We investigated carbon monoxide (CO) adsorption and desorption behaviors on 0.1-nm-, 0.15-nm-, and 0.3-nm-thick-Pd-deposited Cu(1 1 0) surfaces using infrared reflection absorption (IRRAS) and temperature-programmed desorption (TPD) spectroscopic methods. CO was exposed to the 0.1-nm-thick-Pd/Cu(1 1 0) surface at the substrate temperature of 90 K. The IR band attributable to CO bonded to Cu atoms emerged at 2092 cm⁻¹: the band was located at 2100 cm⁻¹ at saturation coverage, with a shoulder at 2110 cm⁻¹. In addition to these bands, weak absorptions attributable to the PdCO bonds appeared at 2050 and 1960 cm⁻¹. With increasing Pd thickness, the Pd related-bands became increasingly prominent. Particularly at the early stage of exposure, the band at 2115 cm⁻¹ became visible. The band at 2117 cm⁻¹ dominated the spectra all through the exposures for the 0.3-nm-thick-Pd surface. The TPD spectra of the surfaces showed two remarkable features at around 220-250 and 320-390 K, ascribable ,respectively, to CuCO and PdCO. The desorption peaks shifted to higher temperatures with increasing Pd thickness. Based on the TPD and IRRAS results, we discuss the adsorption-desorption behaviors of CO on the Pd/Cu(1 1 0) surfaces.     

KLL Auger resonant Raman transition in metallic Cu and Ni

High energy resolution KL₂₃L₂₃ Auger spectra of polycrystalline Cu and Ni were measured using photon energies up to about 50 eV above the K-absorption edge and down to 5 eV (Cu KLL) and 4 eV (Ni KLL) below threshold. The spectra show strong satellite structures varying considerably as a function of the photon energy. In the sub-threshold region the linear dispersion of the diagram line energy positions and a distortion of the line shape as a function of photon energy, attributable to the Auger resonant Raman process, is clearly observed, indicating the one-step nature of the Auger emission. These changes in the resonant spectra are interpreted using a simple model based on resonant scattering theory in combination with partial density of states obtained from cluster molecular orbital (DV-Xα) calculations.     

Ab initio study of rumpled relaxation and core-level shift of barium titanate surface

The rumpled relaxation and the core-level shift of full-relaxed BaTiO₃ (0 0 1) surface have been investigated by first-principles calculation. Based on the work function and the electric-field gradient, the right size of vacuum and the slab have been evaluated. The large displacements of ions deviated from their crystalline sites to lead to the formation of the surface rumples have been found. Some fully occupied surface oxygen p states at the top M point of the valance band and the empty surface titanium d states at the edge of the bulk conduction band are observed on the TiO₂-terminated surface. In contrast, on the BaO-terminated surface, two different core levels of the Ba 5p states shifted about 1.29 eV are induced by the bulk perovskite Ba atoms and the relaxation of surface Ba atoms, respectively. Our calculations are consistent with the experimental data.     

Angle-resolved photoemission study of Pd(111) and Co/Pd(111)

Electronic structure of epitaxial Co films on Pd(111) has been investigated as a function of the Co overlayer thickness, by using angle-resolved photoemission spectroscopy (ARPES). It is found that experimental band structures for Pd(111) and work functions for Co/Pd(111) agree reasonably well with the results of band structure calculations. Compared to Pd(111), valence band ARPES spectra of Co/Pd(111) support the existence of the induced magnetic polarization of Pd atoms near the interface, suggesting large hybridization between Co 3d and Pd 4d states near the interface.     

Insulating properties of ultrathin KF layers on Cu(1 0 0): Resonant Auger spectroscopy

Solid-state effects in the creation and decay of K 2p core excitations in thin KF films on Cu(1 0 0) surface have been studied in resonant Auger spectra, excited using synchrotron radiation. The spectra of films of various thickness starting from a single monolayer were measured.The photoabsorption spectra reveal crystal field splitting already at film thickness of about 1 monolayer. The Auger decay spectra of the K 2p⁻¹3d core excitations in films of thickness up to 2 monolayers exhibit a band characteristic of the decay of core ionised states, showing that the excited electron delocalises into substrate before the core hole decays. In thicker films the coexistence of the decay of excited states in the bulk of the KF crystalline film and of ionised states at the KF-metal interface is observed, indicating that the charge transfer probability from the upper layers of the film into the metallic substrate is strongly reduced.     

Mechanism of Cu deposition on the alpha-Al(2)O(3) (0001) surface

The growth mechanism of the Cu/alpha-Al(2)O(3) (0001) interface is studied by first-principles molecular-dynamics simulations as a function of the transition-metal coverage (theta) and the temperature of the system. On the anhydrous surface growth of Cu(0) 3D clusters is predicted. On the partially hydroxylated surface, a Cu(I) monolayer, relatively stable upon the temperature rising, is first observed (theta<1/3 ML). Increasing Cu loading leads to Cu(I)/Cu(0) mixed phases that when heated aggregate into 3D particles increasing the number of Cu(0) atoms, in agreement with the Auger spectra of Kelber et al.     

The growth of Au/Pd/alumina/Cu-Al system studied by SRPES

An ultra-thin alumina layer grown on Cu-9at.%Al (1 1 1) surface was studied using synchrotron radiation photoelectron spectroscopy (SRPES), X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). By deconvolving SRPES spectra of the Al 2p doublet, four components belonging to metallic as well as oxide phases were recognized. Pd-Au alloy formation was confirmed by SRPES measurement during Pd and Au deposition. The study of the system's thermal stability reveals diffusion of Pd and Au atoms through the alumina layer. While Au atoms start to diffuse under the alumina layer at 670 K, Pd atoms are forming Pd-Al surface alloy at this temperature. The diffusion of Pd atoms through alumina occurs when sample was heated over 770 K. Alumina layer was stable even after heating the sample at 870 K, but its structure was corrupted probably due to the diffusion of metal atoms.     

Fermi surface and band mapping of the cerium/palladium surface alloy

X-ray and UV excitation angle-resolved photoemission spectroscopy of ultra-thin films of cerium deposited on Pd(1 1 1) single-crystal surface has been carried out. Photoelectron diffraction pattern showed that deposition of 1 ML of Ce led to a formation of Ce-Pd substitutional alloy. Valence band spectra measured with high angular resolution permitted to plot valence band maps and Fermi surface scans and showed formation of surface alloy exhibiting d- and f-electron orbital hybridization. A shift of Pd 4d-derived states to higher binding energy in the Ce-Pd systems was observed.     

Core-hole screening effects in the initial state of Auger emission across the transition metal series

Supercell method is used to study the relaxation and screening effects on the initial state of the Auger transition in metals. Our consideration is based on the assumption that when a core-hole exists long enough before the Auger transition occurs, the occupied valence states relax to screen the core-hole which results in a redistribution of the valence electrons, in particular within the atom that contains the core-hole. In order to make the interaction between the core-holes sites at different atoms negligible, the real metal is simulated by supercells repeated periodically. In each supercell one atom is considered to have a core-hole and many others not to have one. The electronic states concerned by the Auger transition are calculated by the self-consistent full-potential linearized augmented plane wave (FLAPW) method. Different responses of the local valence band on the site of the core-hole have been shown depending on whether the d-bands are partially or completely filled. According to the final state rule, the screening to the two holes in the local valence band after the Auger transition has also been considered, as examples, for Ni and Cu metals. The result shows that, with the existence of two holes in them, the states of the local valence band of Cu relax to atomic-like impurity states, while the local valence band of Ni changes to a much narrow band at the bottom of the original band. As examples, L₃VV and M₁VV Auger spectral profiles of Cu have been calculated in reasonably good agreement with the experiment.     

Photoemission study of the electronic and chemical structure of amorphous CuxY100-x films

Valence band and core level photoelectron spectra are reported for clean Cu_xY_100-x amorphous thin films grown in situ by sputtering of targets with different stoichiometry. The density of occupied states of these amorphous metallic alloys is shown not to be a simple linear superposition of the constituent densities of states. Experimental evidence shows overlap of Cu and Y d bands with significant electron transfer from Y to Cu atoms which induce large bonding shifts, narrowing and intensity modifications of the valence band. The same conclusion is reached from the Cu core level shift and asymmetry. An estimation of the effective Coulomb interaction on Cu sites from Auger results is attempted.     

Photoemission from α and β phases of the GaAs(0 0 1)-c(4 × 4) surface

We prepared α- and β surface phases of GaAs(0 0 1)-c(4 × 4) reconstruction by molecular beam epitaxy (MBE) using As₄ and As₂ molecular beams, respectively, and examined them by angle-resolved ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS) with synchrotron radiation as an excitation source. The UPS valence band spectra and the XPS 3d core level data show pronounced differences corresponding to the surface composition and the atomic structure of the two phases, as proposed in the literature. In UPS, the β phase is characterized by an intensive surface state 0.5 eV below the top of the valence band at low photon energy, while an analogous peak in the α phase spectra is missing. The surface state is interpreted in terms of dangling bonds on As dimers. The As3d and Ga3d core level photoelectron lines exhibit phase-specific shapes as well as differences in the number, position and intensity of their deconvoluted components. The location of various atoms in the surface and subsurface layers is discussed; our photoemission results support models of the β phase and the α phase with As-As dimers and Ga-As heterodimers, respectively.