Driving force for the WO3(0 0 1) surface relaxation

The optimized structure of the WO₃(0 0 1) surface with various types of termination ((1 × 1)O, (1 × 1)WO₂, and c(2 × 2)O) has been simulated using density functional theory with the Perdew-Wang 91 gradient corrected exchange-correlation functional. While the energy of bulk WO₃ depends weakly on the distortions and tilting of the WO₆ octahedra, relaxation of the (0 0 1) surface results in a significant decrease of surface energy (from 10.2 × 10⁻² eV/Ų for the cubic ReO₃-like, c(2 × 2)O-terminated surface to 2.2 × 10⁻² eV/Ų for the relaxed surface). This feature illustrates a potential role of surface relaxation in formation of crystalline nano-size clusters of WO₃. The surface relaxation is accompanied by a dramatic redistribution of the density of states near the Fermi level, in particular a transformation of surface electronic states. This redistribution is responsible for the decrease of electronic energy and therefore is suggested to be the driving force for surface relaxation of the WO₃(0 0 1) surface and, presumably, similar surfaces of other transition metal oxides.     

Reaction of O2 with the boron-terminated TaB2(0 0 0 1) surface

X-ray photoelectron spectroscopy has been used to study the clean TaB₂(0 0 0 1) surface and its reaction with O₂. In agreement with previous studies, XPS indicates that the clean surface is boron terminated. The topmost boron layer shows a chemically shifted B 1s peak at 187.1 eV compared to a B 1s peak at 188.6 eV for boron layers below the surface. The 187.1-188.6 eV peak intensity ratio and its variation with angle between the crystal normal and the detector is well described by a simple theoretical model based on an independently calculated electron inelastic mean free path of 15.7 Å for TaB₂. The dissociative sticking probability of O₂ on the boron-terminated TaB₂(0 0 0 1) surface is lower by a factor of 10⁴ than for the metal-terminated HfB₂(0 0 0 1) surface.     

Oxygen-induced p(3 × 1) reconstruction of the W(1 0 0) surface

The oxidation of the W(1 0 0) surface at elevated temperatures has been studied using room temperature STM and LEED. High exposure of the clean surface to O₂ at 1500 K followed by flash-annealing to 2300 K in UHV results in the formation of a novel p(3 × 1) reconstruction, which is imaged by STM as a missing-row structure on the surface. Upon further annealing in UHV, this surface develops a floreted LEED pattern characteristic of twinned microdomains of monoclinic WO_x, while maintaining the p(3 × 1) missing-row structure. Atomically resolved STM images of this surface show a complex domain structure with single and double W〈0 1 0〉 rows coexisting on the surface in different domains.     

Low temperature adsorption of oxygen on reduced V2O3(0 0 0 1) surfaces

Well ordered V₂O₃(0 0 0 1) films were prepared on Au(1 1 1) and W(1 1 0) substrates. These films are terminated by a layer of vanadyl groups under typical UHV conditions. Reduction by electron bombardment may remove the oxygen atoms of the vanadyl layer, leading to a surface terminated by vanadium atoms. The interaction of oxygen with the reduced V₂O₃(0 0 0 1) surface has been studied in the temperature range from 80 to 610 K. Thermal desorption spectroscopy (TDS), infrared reflection absorption spectroscopy (IRAS), high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) were used to study the adsorbed oxygen species. Low temperature adsorption of oxygen on reduced V₂O₃(0 0 0 1) occurs both dissociatively and molecularly. At 90 K a negatively charged molecular oxygen species is observed. Upon annealing the adsorbed oxygen species dissociates, re-oxidizing the reduced surface by the formation of vanadyl species. Density functional theory was employed to calculate the structure and the vibrational frequencies of the O₂ species on the surface. Using both cluster and periodic models, the surface species could be identified as η²-peroxo () lying flat on surface, bonded to the surface vanadium atoms. Although the O-O vibrational normal mode involves motions almost parallel to the surface, it can be detected by infrared spectroscopy because it is connected with a change of the dipole moment perpendicular to the surface.     

Ab-initio investigation of Ni(Fe)/ZrO2(0 0 1) and Ni-Fe/ZrO2(0 0 1) interfaces

The atomic and electronic structures of Me/ZrO₂(0 0 1) interfaces, where Me is Ni, Fe or a Ni-Fe alloy, are investigated by the plane wave pseudopotential method within density-functional theory. The work of separation of metal films from oxide substrate for the O- and Zr-terminated Me/ZrO₂(0 0 1) interfaces is calculated. High adhesion at both Me/(ZrO₂)_O and Me/(ZrO₂)_Zr interfaces is found. The effect of oxygen vacancies on the adhesion at the metal-ceramic interfaces is also investigated. It is shown that Ni(Fe)-O interaction at the O-terminated interface weakens in the presence of interfacial oxygen vacancies. At interfaces with Ni-Fe alloys the adhesion depends strongly on the composition of the interfacial layers and their magnetic properties.     

Ultrathin ZrO2 films on Si-rich SiC(0 0 0 1)-(3 × 3): Growth and thermal stability

The growth and thermal stability of ultrathin ZrO₂ films on the Si-rich SiC(0 0 0 1)-(3 × 3) surface have been explored using photoelectron spectroscopy (PES) and X-ray absorption spectroscopy (XAS). The films were grown in situ by chemical vapor deposition using the zirconium tetra tert-butoxide (ZTB) precursor. The O 1s XAS results show that growth at 400 °C yields tetragonal ZrO₂. An interface is formed between the ZrO₂ film and the SiC substrate. The interface contains Si in several chemically different states. This gives evidence for an interface that is much more complex than that formed upon oxidation with O₂. Si in a 4+ oxidation state is detected in the near surface region. This shows that intermixing of SiO₂ and ZrO₂ occurs, possibly under the formation of silicate. The alignment of the ZrO₂ and SiC band edges is discussed based on core level and valence PES spectra. Subsequent annealing of a deposited film was performed in order to study the thermal stability of the system. Annealing to 800 °C does not lead to decomposition of the tetragonal ZrO₂ (t-ZrO₂) but changes are observed within the interface region. After annealing to 1000 °C a laterally heterogeneous layer has formed. The decomposition of the film leads to regions with t-ZrO₂ remnants, metallic Zr silicide and Si aggregates.     

The structure of the V2O3(0 0 0 1) surface: A scanned-energy mode photoelectron diffraction study

Scanned-energy mode photoelectron diffraction (PhD), using the O 1s and V 2p photoemission signals, together with multiple-scattering simulations, have been used to investigate the structure of the V₂O₃(0 0 0 1) surface. The results support a strongly-relaxed half-metal termination of the bulk, similar to that found in earlier studies of Al₂O₃(0 0 0 1) and Cr₂O₃(0 0 0 1) surfaces based on low energy electron and surface X-ray diffraction methods. However, the PhD investigation fails to provide definitive evidence for the presence or absence of surface vanadyl (VO) species associated with atop O atoms on the surface layer of V atoms. Specifically, the best-fit structure does not include these vanadyl species, although an alternative model with similar relaxations but including vanadyl O atoms yields a reliability-factor within the variance of that of the best-fit structure.     

Sn interaction with the CeO2(1 1 1) system: Bimetallic bonding and ceria reduction

A tin layer 0.8 nm thick was deposited onto the CeO₂(1 1 1) surface by molecular beam deposition at a temperature of 520 K. The interaction of tin with cerium oxide (ceria) was investigated by X-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS) and resonant photoelectron spectroscopy (RPES). The strong tin-ceria interaction led to the formation of a homogeneous bulk Ce-Sn-O mixed oxide system. The bulk compound formation is accompanied by partial Ce⁴⁺ → Ce³⁺ reduction, observed as a giant 4f resonance enhancement of the Ce³⁺ species. CeO₂ and SnO₂ oxides were formed after oxygen treatment at 520 K. The study proved the existence of strong Ce-Sn interaction and charge transfer from Sn to the Ce-O complex that lead to a weakening of the cerium-oxygen bond, and consequently, to the formation of oxygen deficient active sites on the ceria surface. This behavior can be a key for understanding the higher catalytic activity of the SnO_x/CeO_x mixed oxide catalysts as compared with the individual pure oxides.     

Au/TiO2/Ru(0 0 0 1) model catalysts and their interaction with CO

Au/TiO₂/Ru(0 0 0 1) model catalysts and their interaction with CO were investigated by scanning tunneling microscopy and different surface spectroscopies. Thin titanium oxide films were prepared by Ti deposition on Ru(0 0 0 1) in an O₂ atmosphere and subsequent annealing in O₂. By optimizing the conditions for deposition and post-treatment, smooth films were obtained either as fully oxidized TiO₂ or as partly reduced TiO_x, depending on the preparation conditions. CO adsorbed molecularly on both oxidized and reduced TiO₂, with slightly stronger bonding on the reduced films. Model catalyst surfaces were prepared by depositing submonolayer quantities of Au on the films and characterized by X-ray photoelectron spectroscopy and scanning tunneling microscopy. From X-ray photoelectron spectroscopy, a weak interaction between the Au and the TiO₂ substrate was found. At 100 K CO adsorption occurred on both the TiO₂ film and on the Au nanoparticles. CO desorbed from the Au particles with activation energies between 53 and 65 kJ/mol, depending on the Au coverage. If the Au deposit was annealed to 770 K prior to CO exposure, the CO adsorption energy decreased significantly. STM measurements revealed that the Au particles grow upon annealing, but are not encapsulated by TiO_x suboxides. The higher CO adsorption energy observed for smaller Au coverages and before annealing is attributed to a significantly stronger interaction of CO with mono- and bilayer Au islands, while for higher particles, the adsorption energy becomes more bulk-like. The implications of these effects on the known particle size effects in CO oxidation over supported Au/TiO₂ catalysts are discussed.     

Adsorption of water on thin V2O3(0 0 0 1) films

V₂O₃(0 0 0 1) films have been grown epitaxially on Au(1 1 1) and W(1 1 0). Under typical UHV conditions these films are terminated by a layer of vanadyl groups as has been shown previously [A.-C. Dupuis, M. Abu Haija, B. Richter, H. Kuhlenbeck, H.-J. Freund, V₂O₃(0 0 0 1) on Au(1 1 1) and W(1 1 0): growth, termination and electronic structure, Surf. Sci. 539 (2003) 99]. Electron irradiation may remove the oxygen atoms of this layer. H₂O adsorption on the vanadyl terminated surface and on the reduced surface has been studied with thermal desorption spectroscopy (TDS), vibrational spectroscopy (IRAS) and electron spectroscopy (XPS) using light from the BESSY II electron storage ring in Berlin. It is shown that water molecules interact only weakly with the vanadyl terminated surface: water is adsorbed molecularly and desorbs below room temperature. On the reduced surface water partially dissociates and forms a layer of hydroxyl groups which may be detected on the surface up to T ∼ 600 K. Below ∼330 K also co-adsorbed molecular water is detected. The water dissociation products desorb as molecular water which means that they recombine before desorption. No sign of surface re-oxidation could be detected after desorption, indicating that the dissociation products desorb completely.     

Characterization of ZrB2(0 0 0 1) surface prepared by ex situ HF solution treatment toward applications as a substrate for GaN growth

ZrB₂(0 0 0 1) crystals grown by the rf-floating zone technique were characterized by X-ray photoelectron spectroscopy, reflection high-energy electron diffraction, and atomic force microscopy. These characteristics were investigated as a function of thermal cleaning temperature up to 1000 °C in vacuum for as-received substrates as well as substrates treated ex situ in HF aqueous solution. The HF treatment process removed the ZrO₂ native oxide layer present on as-received substrates and resulted in ZrB₂(0 0 0 1) surfaces exhibiting long-range order. Upon annealing the HF-treated surface in high vacuum, two types of reconstructions were observed: an incommensurate reconstruction from 650 to 900 °C related to residual H₂ gas, and n × n reconstructions at 1000 °C, possibly related to oxygen.     

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.     

Formamide reactions on rutile TiO2(0 1 1) surface

The reaction of formamide over the (0 1 1) faceted TiO₂(0 0 1) surface has been studied by Temperature Programmed Desorption (TPD) and X-ray Photoelectron Spectroscopy (XPS). Two main reactions were observed: dehydration to HCN and H₂O and decomposition to NH₃ and CO. The dehydration reaction was found to be three to four times larger than the decomposition at all coverages. Each of these reactions is found to occur in two temperature domains which are dependent upon surface coverage. The low temperature pathway (at about 400 K) is largely insensitive to surface coverage while the high temperature pathway (at about 500 K) shifts to lower temperatures with increasing surface coverage. These two temperature pathways may indicate two adsorption modes of formamide: molecular (via an η¹(O) mode of adsorption) and dissociative (via an η²(O,N) mode of adsorption). C1s and N1s XPS scans indicated the presence of multiple species after formamide absorption at 300 K. These occurred at ca. 288.5 eV (-CONH-) and 285 eV (sp³/sp² C) for the C1s and 400 eV-(NH₂), 398 eV (-NH) and 396 eV (N) for the N1s and result from further reaction of formamide with the surface.     

Electron surface states in short-period superlattices: (GaAs)2/(AlAs)2(1 0 0)-c(4 × 4)

The electronic structure of (GaAs)₂/(AlAs)₂(1 0 0)-c(4 × 4) superlattice surfaces was studied by means of angular-resolved photoelectron spectroscopy (ARUPS) in the photon energy range 20-38 eV. Four samples with different surface termination layers were grown and As-capped by molecular beam epitaxy (MBE). ARUPS measurements were performed on decapped samples with perfect c(4 × 4) reconstructed surfaces. An intensive surface state was, for the first time, observed below the top of the valence band. This surface state was found to shift with superlattices’ different surface termination in agreement with theoretical predictions.     

A density functional theory study of formaldehyde adsorption and oxidation on CeO2(1 1 1) surface

The effects of different oxygen species and vacancies on the adsorption and oxidation of formaldehyde over CeO₂(1 1 1) surface were systematically investigated by using density functional theory (DFT) method. On the stoichiometric CeO₂(1 1 1) surface, the C-H bond rupture barriers of chemisorbed formaldehyde are much higher than that of formaldehyde desorption. On the reduced CeO₂(1 1 1) surface, the energy barriers of C-H bond ruptures are less than those on the stoichiometric CeO₂(1 1 1) surface. If the C-H bond rupture occurs, CO and H₂ form quickly with low energy barriers. When O₂ adsorbs on the reduced (1 1 1) surface (O₂/O_v species), the C-H bond rupture barriers of formaldehyde are greatly reduced in comparison with those on the stoichiometric CeO₂(1 1 1) surface. If O₂ adsorbs on oxygen vacancy at sub-layer surface, its oxidative roles on formaldehyde are much similar to that of O₂/O_v species.     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

The catalytic reduction of NO by H2 on Ru(0 0 0 1): Observation of NHads species

Adsorption of NO and the reaction between NO and H₂ were investigated on the Ru(0 0 0 1) surface by X-ray photoelectron spectroscopy (XPS). Surface composition was measured after NO adsorption and after the selective catalytic reduction of nitric oxide with hydrogen in steady-state conditions at 320 K and 390 K in a 30:1 mixture of H₂ and NO (total pressure = 10⁻⁴ mbar). After steady-state NO reduction, molecularly adsorbed NO in both the linear on-top and threefold coordinations, NH_ads and N_ads species were identified by XPS. The coverage of the NH_ads and N_ads species was higher after the reaction at 390 K than the corresponding values at 320 K. Strong destabilisation of N_ads by O_ads was detected. A possible reaction mechanism is discussed.     

Band offsets at the epitaxial anatase TiO2/n-SrTiO3(0 0 1) interface

We have used high-energy resolution X-ray photoelectron spectroscopy to measure valence band offsets at the epitaxial anatase TiO₂(0 0 1)/n-SrTiO₃(0 0 1) heterojunction prepared by molecular beam epitaxy. The valence band offsets range between −0.06 ± 0.05 and +0.16 ± 0.05 eV for anatase thicknesses between 1 and 8 monolayers and three different methods of substrate surface preparation, with no systematic dependence on film thickness. The conduction band offset (CBO) varies over a comparable range by virtue of the fact that anatase and SrTiO₃ exhibit the same bandgap (∼3.2 eV). In contrast, density functional theory predicts the VBO to be +0.55 eV. The lack of agreement between theory and experiment suggests that either some unknown factor in the interface structure or composition excluded from the modeling is influencing the band offset, or that density functional theory cannot accurately calculate band offsets in these oxide materials. The small experimental band offsets have important implications for the use of this interface for fundamental investigations of surface photocatalysis. Neither electrons nor holes are likely to become trapped in the substrate and thus be unable to participate in surface photocatalytic processes.     

Behavior of N atoms in atomic-order nitrided Si0.5Ge0.5(1 0 0)

Behavior of N atoms in atomic-order nitrided Si_0.5Ge_0.5(1 0 0) by heat treatment in Ar at 600 °C was investigated by X-ray photoelectron spectroscopy (XPS). For thermal nitridation by NH₃ at 400 °C, nitridation of surface Si atoms tends to proceed preferentially over nitridation of surface Ge atoms. It is also clear that, with the heat treatment, nitridation of Si atoms proceeds by transfer of N atoms from Ge atoms. Angle-resolved XPS results show that Ge fraction beneath the surface nitrided layer increases significantly at 600 °C compared to the initial surface. These results indicate that preferential nitridation of Si atoms at surface over Ge atoms induces Ge segregation beneath the surface nitrided layer at higher temperatures above 400 °C.     

DFT study of Pt adsorption on low index SrTiO3 surfaces: SrTiO3(1 0 0), SrTiO3(1 1 1) and SrTiO3(1 1 0)

Density Functional Theory has been used to determine the energetically preferred structures of submonolayer, monolayer, and multilayer Pt films on both ideal terminations of SrTiO₃(1 0 0), SrTiO₃(1 1 1), and SrTiO₃(1 1 0). The strength of the resulting metal/metal oxide interfaces was characterized by the adsorption energy of the film and the film’s work of separation. The two polar surfaces, SrTiO₃(1 1 1) and SrTiO₃(1 1 0), form significantly stronger interfaces than the non-polar SrTiO₃(1 0 0) surface. Approximate criteria were applied to predict the growth mode of Pt on each surface.