Surface core level shift observed on NiAl(1 1 0)

Using high resolution core level spectroscopy, a surface core level shift towards lower binding energy of −0.13 eV is determined for the 2p level of the outwardly relaxed Al surface atoms on NiAl(1 1 0). Density functional theory based calculations with inclusion of final state effects yield a value of −0.14 eV for this shift in excellent agreement with experiment. We show that the initial state approximation yields a value of +0.09 eV, i.e. the inclusion of final state relaxation effects is vital not only to obtain the correct value but even the correct sign for this shift.     

Photoemission study of the Li/Ge(1 1 1)-3 × 1 reconstruction

In this article we report our findings on the electronic structure of the Li induced Ge(1 1 1)-3 × 1 reconstruction as determined by angle-resolved ultraviolet photoelectron spectroscopy (ARUPS) and core-level spectroscopy using synchrotron radiation. The results are compared to the theoretical honeycomb-chain-channel (HCC) model for the 3 × 1 reconstruction as calculated using density functional theory (DFT). ARUPS measurements were performed in both the and directions of the 1 × 1 surface Brillouin zone at photon energies of 17 and 21.2 eV. Three surface related states were observed in the direction. In the direction, at least two surface states were seen. The calculated band structure using the single-domain HCC model for Li/Ge(1 1 1)-3 × 1 was in good agreement with experiment, allowing for the determination of the origin of the experimentally observed surface states. In the Ge 3d core-level spectra, two surface related components were identified, both at lower binding energy with respect to the Ge 3d bulk peak. Our DFT calculations of the surface core-level shifts were found to be in fair agreement with the experimental results. Finally, in contrast to the Li/Si(1 1 1)-3 × 1 case, no double bond between Ge atoms in the top layer was found.     

A DFT + U description of oxygen vacancies at the TiO2 rutile (1 1 0) surface

Experimental observations indicate that removing bridging oxygen atoms from the TiO₂ rutile (1 1 0) surface produces a localised state approximately 0.7 eV below the conduction band. The corresponding excess electron density is thought to localise on the pair of Ti atoms neighbouring the vacancy; formally giving two Ti³⁺ sites. We consider the electronic structure and geometry of the oxygen deficient TiO₂ rutile (1 1 0) surface using both gradient-corrected density functional theory (GGA DFT) and DFT corrected for on-site Coulomb interactions (GGA + U) to allow a direct comparison of the two methods. We show that GGA fails to predict the experimentally observed electronic structure, in agreement with previous uncorrected DFT calculations on this system. Introducing the +U term encourages localisation of the excess electronic charge, with the qualitative distribution depending on the value of U. For low values of U (?4.0 eV) the charge localises in the sub-surface layers occupied in the GGA solution at arbitrary Ti sites, whereas higher values of U (?4.2 eV) predict strong localisation with the excess electronic charge mainly on the two Ti atoms neighbouring the vacancy. The precise charge distribution for these larger U values is found to differ from that predicted by previous hybrid-DFT calculations.     

Tuning the chemical functionality of a gas sensitive material: Water adsorption on SnO2(1 0 1)

Photoemission and density functional theory studies show that water adsorbs dissociatively on the SnO₂(1 0 1) surface in the presence of terminating oxygen atoms and molecularly if these surface oxygen atoms are removed. The different chemical surface responses of these two bulk terminations of SnO₂ also change the water induced band bending and consequently the conductivity of the gas sensing material.     

Effect of hydrogenation on B/Si(0 0 1)-(1 × 2)

Ab initio calculations, based on pseudopotentials and density functional theory, have been performed to investigate the effect of hydrogenation on the atomic geometries and the energetics of substitutional boron on the generic Si(0 0 1)-(1 × 2) surface. For a single B atom substitution corresponding to 0.5 ML coverage, we have considered two different sites: (i) the mixed Si-B dimer structure and (ii) boron substituting for the second-layer Si to form Si-B back-bond structure, which is energetically more favorable than the mixed Si-B dimer by 0.1 eV/dimer. However, when both of these cases are passivated by hydrogen atoms, the situation is reversed and the Si-B back-bond case becomes 0.1 eV/dimer higher in energy than the mixed Si-B dimer case. For the B incorporation corresponding to 1 ML coverage, among the substitutional cases, 100% interdiffusion into the third layer of Si and 50% interdiffusion into the second layer of Si are energetically similar and more favorable than the other cases that are considered. However, when the surface is passivated with hydrogen, the B atoms energetically prefer to stay at the third layer of the Si substrate.     

A core level and valence band photoemission study of the (1 1 1) and ( ) surfaces of 3C–SiC

A core level and valence band photoemission study of thick 3C–SiC(1 1 1) and 3C–SiC( ) epilayers grown by sublimation epitaxy is reported. The as introduced samples show threefold 1×1 low-energy electron diffraction patterns. For the Si face and reconstructed surfaces develop after in situ heating to 1100°C and 1300°C, respectively. For the C face a 3×3 reconstruction form after heating to 980°C. A semiconducting behavior is observed for the and 3×3 reconstructed surfaces while the reconstruction show a Fermi edge and thus a metallic-like behavior. The surface state on the surface is investigated and found to have Λ₁ symmetry and a total band width of 0.10 eV within the first surface Brillouin zone. For the Si 2p and C 1s core levels binding energies and surface shifted components are extracted and compared to earlier reported results for 6H– and 4H–SiC.     

Resonant Auger spectroscopy study of charge transfer phenomena in N 1s core-excited acetonitrile adsorbates on Si(0 0 1)-2 × 1

Acetonitrile (CH₃CN) adsorbs on Si(0 0 1)-2 × 1 at room temperature under two forms, a cycloaddition-like adduct (Si-CN-Si) and a pendent cyano (Si-CH₂-CN) resulting from the decomposition of the molecule. Resonant Auger spectroscopy has been used to study the excited-state-dependent electron transfer from the N 1s core-excited molecular adsorbate to the silicon substrate, using the core-hole lifetime (∼6 fs) as an internal clock. It is shown that the π_CN^∗ NEXAFS state lies within the silicon bandgap because of a core-excitonic effect. Therefore no charge transfer of the excited electron to the substrate is observed. On the other hand the π_CN^∗ NEXAFS state is placed within the silicon conduction band. Excitation to this orbital leads to valence/Auger spectra in which both resonant and normal Auger contributions are observed. Therefore there is evidence for a charge transfer from the pendent CN to the silicon surface, on a timescale estimated to tens of femtoseconds.     

A comparative study of ethylene oxide and diethylene dioxide adsorption on silicon (0 0 1)

The adsorption of ethylene oxide (oxirane) and diethylene dioxide (1,4-dioxane) on the Si(0 0 1) surface was investigated using the first-principles pseudopotential method within a generalised gradient approximation to the density functional theory. Our results indicate that oxirane adsorption on the silicon surface probably occurs via C-C bond. This interaction induces the breaking of the C-C bond and the formation of a Si-C-O-C-Si ring. The 1,4-dioxane interaction with the silicon (2 × 2) surface, on the other hand, results in the decomposition of the considered molecule in different radicals, depending on the original adsorbed structure. In order to disregard the possible influence of the slab considered, we suggest that high order reconstruction surfaces, i.e. (4 × 2) or (4 × 4), should be investigated.     

Electronic surface states of Cu(1 1 0) surface

Surface states are a unique and important class of quantum states that shave an important effect on the electronic properties of Cu(1 1 0) surface. The Cu(1 1 0) surface has been studied using ultraviolet photoemission spectroscopy (PES), inverse photoemission spectroscopy (IPES), and reflection anisotropy spectroscopy (RAS), and shows a resonance in the RAS spectra at 2.1 eV due to a transition between occupied and unoccupied surface states. The unoccupied surface state involved in the RAS transition at an energy of 1.7 eV at the point of the surface Brillouin zone has been investigated using IPES and the occupied surface state is seen in PES spectra at 0.45 eV below the Fermi level. The energy difference of the surface states, 2.15 eV, is a good match to the transition energy found in the RAS experiments.     

Topologically induced surface electron state on Si(1 1 1) surfaces

First-principle electronic structure calculation reveals the appearance of a new class of surface state on hydrogenated and clean Si(1 1 1) surfaces. The states are found to exhibit different characteristics to conventional surface electron states in terms of the peculiar distribution of the wavefunction depending on the wavenumber. In addition, the state results in flat dispersion bands in a part of the surface Brillouin zone having energy of about 8 eV below the top of the valence band. An analytic expression based on the tight-binding approximation corroborates the surface electron state results from the delicate balance of the electron transfer among the atoms situated near the surface. The obtained results give a possible extension and generalization of the edge state in graphite ribbons with zigzag edges.     

Surface resonance transition of roughened Cu(1 1 0)

The temperature dependence of the reflection anisotropy spectroscopy (RAS) of a Cu(1 1 0) surface has been studied over the temperature range 700-1000 K. Because of the roughening transition at 900 K, the bimodal feature at 4.2 eV for a clean surface shifted to 4.3 eV on annealing. A significant decrease in intensity of the same energy level was also observed with increasing annealing temperature. In the annealing temperature range 700-1000 K, anharmonic behavior is expected to be the predominant process of atomic disordering at the surface. Changes in the RAS of Cu(1 1 0) as a result of thermal processing can be understood in terms of the associated changes in surface states. The RAS signal for a surface resonance transition at 4.2 eV is associated with monoatomic [0 0 1] steps.     

Effectiveness of in situ NH3 annealing treatments for the removal of oxygen from GaN surfaces

An in situ NH₃ annealing procedure for the cleaning of GaN(0 0 0 1) is studied in detail using density functional theory (DFT), microkinetic modeling and X-ray photoelectron spectroscopy (XPS). The microkinetic model was calibrated and tested against published H₂ and NH₃ temperature programmed desorption (TPD) experiments on GaN(0 0 0 1). We find that an NH₃ treatment is efficient for the removal of carbon contaminants, but a complete removal of oxygen contaminants cannot be achieved. The remaining oxygen coverage after the treatment was estimated from XPS measurements to be 0.92 ML. In contrast, our microkinetic model based on DFT derived parameters predicts complete removal of OH species and a final oxygen coverage of 0.19 ML. We assign the difference between model and experiments to the formation of a surface oxide phase, which is not included in the model. DFT results also indicate strong adsorbate-adsorbate interactions for H, N, NH, NH₂, O, and OH on the GaN(0 0 0 1) surface which were incorporated into the microkinetic model to a first approximation. XPS experiments and microkinetic modeling demonstrate that the final surface composition shows little dependence on process parameters such as temperature or the time the sample is kept at an elevated temperature. Furthermore, the microkinetic model suggests that complete removal of OH from the surface can also be achieved using a NH₃/H₂ mixture, or even pure H₂ as a hydrogen source. The amount of H₂ present in the feed changes the coverage of NH_x species, but a certain amount of adsorbed oxygen is always left on the surface.     

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.     

Reaction mechanism of ammonia oxidation over RuO2(1 1 0): A combined theory/experiment approach

Combining state-of-the-art density functional theory (DFT) calculations with high resolution core level shift spectroscopy experiments we explored the reaction mechanism of the ammonia oxidation reaction over RuO₂(1 1 0). The high catalytic activity of RuO₂(1 1 0) is traced to the low activation energies for the successive hydrogen abstractions of ammonia by on-top O (less than 73 kJ/mol) and the low activation barrier for the recombination of adsorbed O and N (77 kJ/mol) to form adsorbed NO. The NO desorption is activated by 121 kJ/mol and represents therefore the rate determining step in the ammonia oxidation reaction over RuO₂ (1 1 0).     

Oxidation and thermal reduction of the Cu(1 0 0) surface as studied using positron annihilation induced Auger electron spectroscopy (PAES)

Changes in the surface of an oxidized Cu(1 0 0) single crystal resulting from vacuum annealing have been investigated using positron annihilation induced Auger electron spectroscopy (PAES). PAES measurements show a large increase in the intensity of the annihilation induced Cu M_2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 °C. The intensity then decreases monotonically as the annealing temperature is increased to ∼600 °C. Experimental probabilities of annihilation of surface-trapped positrons with Cu 3p and O 1s core-level electrons are estimated from the measured intensities of the positron annihilation induced Cu M_2,3VV and O KLL Auger transitions. Experimental PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface, surface reconstructions, and electron-positron correlations effects. The effects of oxygen adsorption on localization of positron surface state wave function and annihilation characteristics are also analyzed. Possible explanation is proposed for the observed behavior of the intensity of positron annihilation induced Cu M_2,3VV and O KLL Auger peaks and probabilities of annihilation of surface-trapped positrons with Cu 3p and O 1s core-level electrons with changes of the annealing temperature.     

The effect of controlled ion bombardment on the electronic structure of the Si(0 0 1) surface

We have studied the effects of controlled ion bombardment on the electronic structure of the Si(0 0 1) surface. The surface was exposed to various doses of Ar⁺ ions accelerated towards the surface at 500 eV. X-ray photoelectron spectroscopy (XPS) spectra of the irradiated H-terminated Si(0 0 1) surface reveal the appearance of peaks that are associated with the presence of cleaved Si bonds. Ultraviolet photoelectron spectroscopy (UPS) spectra of the irradiated Si(0 0 1)2 × 1 surface show that the dimer dangling-bond surface state decays monotonically with increasing dose. These results, coupled with previous scanning tunneling microscopy (STM) studies, indicate that the breaking of dimers, and possibly the creation of adatom-like defects, during ion irradiation are responsible for the changes in the electronic structure of the valence band for this surface.     

Core-level shifts of the c(8 × 2)-reconstructed InAs(1 0 0) and InSb(1 0 0) surfaces

We have studied In-stabilized c(8 × 2)-reconstructed InAs(1 0 0) and InSb(1 0 0) semiconductor surfaces, which play a key role in growing improved III–V interfaces for electronics devices, by core-level photoelectron spectroscopy and first-principles calculations. The calculated surface core-level shifts (SCLSs) for the ζ and ζa models, which have been previously established to describe the atomic structures of the III–V(1 0 0)c(8 × 2) surfaces, yield hitherto not reported interpretation for the As 3d, In 4d, and Sb 4d core-level spectra of the III–V(1 0 0)c(8 × 2) surfaces, concerning the number and origins of SCLSs. The fitting analysis of the measured spectra with the calculated ζ and ζa SCLS values shows that the InSb spectra are reproduced by the ζ SCLSs better than by the ζa SCLSs. Interestingly, the ζa fits agree better with the InAs spectra than the ζ fits do, indicating that the ζa model describes the InAs surface better than the InSb surface. These results are in agreement with previous X-ray diffraction data. Furthermore, an introduction of the complete-screening model, which includes both the initial and final state effects, does not improve the fitting of the InSb spectra, proposing the suitability of the initial-state model for the SCLSs of the III–V(1 0 0)c(8 × 2) surfaces. The found SCLSs are discussed with the ab initio on-site charges.     

Identification of the vanadyl terminated V2O3(0 0 0 1) surface by NEXAFS spectroscopy: A combined theoretical and experimental study

In this work we present results from density functional theory (DFT) cluster studies to determine polarization-dependent near edge X-ray absorption fine structure (NEXAFS) spectra of the vanadyl termination of the V₂O₃(0 0 0 1) surface. The oxygen K edge spectra are calculated for the relaxed surface geometry where geometric parameters are taken from recent periodic DFT work. A detailed analysis of energetic peak positions, relative intensities, and final state orbitals allows a deep understanding of the complex angular dependence of the calculated spectra on the basis of the local binding environment of differently coordinated oxygen species. Further, our theoretical analysis can assign and explain various spectral details in the experimental NEXAFS data, in particular, those related to vanadyl oxygen. This allows us to support the experimentally suggested vanadyl surface termination.     

Structure and dynamics of the missing-row reconstruction on O/Cu(0 0 1) and O/Ag(0 0 1)

The geometry and the vibrational properties of missing row reconstructed O/Cu(0 0 1) and O/Ag(0 0 1) surfaces are investigated by means of density functional theory and density functional perturbation theory, using the local density and the generalized-gradient approximations. Our results predict very similar structural and vibrational properties for the two reconstructed surfaces. In the case of copper our calculations reproduce quite accurately the experimental results, while for the missing row reconstructed O/Ag(0 0 1) surface the agreement between theory and experiment is less satisfactory.     

High resolution XPS study of the large-band-gap semiconductor stibnite (Sb2S3): Structural contributions and surface reconstruction

Conventional X-ray photoelectron spectroscopy (XPS) and synchrotron radiation XPS (SRXPS) were used to probe the chemical state properties of stibnite (Sb₂S₃), a large-band-gap semiconductor of complex structure. The conventional spectra were obtained with a Kratos Axis Ultra XPS with magnetic confinement charge neutralization, which is very effective in minimizing both uniform charging and differential charging on this large-band-gap semiconductor. The narrow linewidths (much narrower than previously obtained) for single doublet fits (e.g. Sb 4d_5/2 of 0.57 eV and S 2p_3/2 of 0.63 eV) enabled the observation of a small peak on the low binding energy side of the Sb 3d and Sb 4d lines. With the aid of the very surface-sensitive Sb 4d SRXPS spectra, these low energy peaks are assigned to small Sb metal clusters at the surface after cleavage; the signal for these clusters increases with X-ray dose on the sample.A detailed analysis of the Sb 4d and S 2p linewidths concludes that the Sb 4d_5/2 linewidth is larger than expected based on the inherent linewidth of the instrument and the Sb 4d lifetime width, and on comparison with the As 3d linewidth (0.52 eV) for the analogous As₂S₃. Also, the S 2p_3/2 linewidth is substantially broader than the Sb 4d_5/2 linewidth. These larger than expected linewidths are due to two structurally distinct Sb atoms and three structurally distinct S atoms in the Sb₂S₃ crystal structure. Accordingly, the Sb 4d and S 2p spectra have been fitted to two and three doublets respectively, and the linewidth for all peaks is 0.53 eV. Using recent molecular orbital calculations, the doublets have been assigned to the different structural Sb and S sites.