Initial stages of the autocatalytic oxidation of the InAs(0 0 1)-(4 × 2)/c(8 × 2) surface by molecular oxygen

The initial stages of oxidation of the In-rich InAs(0 0 1)-(4 × 2)/c(8 × 2) surface by molecular oxygen (O₂) were studied using scanning tunneling microscopy (STM) and density functional theory (DFT). It was shown that the O₂ dissociatively chemisorbs along the rows in the [1 1 0] direction on the InAs surface either by displacing the row-edge As atoms or by inserting between In atoms on the rows. The dissociative chemisorption is consistent with being autocatalytic: there is a high tendency to form oxygen chemisorption sites which grow in length along the rows in the [1 1 0] direction at preexisting oxygen chemisorption sites. The most common site size is about 21-24 Å in length at ∼25% ML coverage, representing 2-3 unit cell lengths in the [1 1 0] direction (the length of ∼5-6 In atoms on the row). The autocatalysis was confirmed by modeling the site distribution as non-Poisson. The autocatalysis and the low sticking probability (∼10⁻⁴) of O₂ on the InAs(0 0 1)-(4 × 2)/c(8 × 2) are consistent with activated dissociative chemisorption. The results show that is it critical to protect the InAs surface from oxygen during subsequent atomic layer deposition (ALD) or molecular beam epitaxy (MBE) oxide growth since oxygen will displace As atoms.     

The local structure of SO2 and SO3 on Ni(1 1 1)

The normal incidence X-ray standing wave (NIXSW) technique, supported by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS), has been used to determine the local adsorption geometry of SO₂ and SO₃ on Ni(1 1 1). Chemical-state specific NIXSW data for coadsorbed SO₃ and S, formed by the disproportionation of adsorbed SO₂ after heating from 140 K to 270 K, were obtained using S 1s photoemission detection. For adsorbed SO₂ at 140 K the new results confirm those of an earlier study [Jackson et al., Surf. Sci. 389 (1997) 223] that the molecule is located above hollow sites with its molecular plane parallel to the surface and the S and O atoms in off-atop sites; corrections to account for the non-dipole effects in the interpretation of the NIXSW monitored by S 1s and O 1s photoemission, not included in the earlier work, remove the need for any significant adsorption-induced distortion of the SO₂ in this structure. SO₃, not previously investigated, is found to occupy an off-bridge site with the C_3v axis slightly tilted relative to the surface normal and with one O atom in an off-atop site and the other two O atoms roughly between bridge and hollow sites. The O atoms are approximately 0.87 Å closer to the surface than the S atom. This general bonding orientation for SO₃ is similar to that found on Cu(1 1 1) and Cu(1 0 0) both experimentally and theoretically, although the detailed adsorption sites differ.     

Growth and structure of vanadium oxide on anatase (1 0 1) terraces

The interaction of vanadium oxide with epitaxial anatase films exposing (1 0 1) terraces was characterized. The TiO₂ films were grown on vicinal LaAlO₃ (1 1 0) substrates by oxygen plasma-assisted molecular beam epitaxy (OPA-MBE); reflection high energy and low energy electron diffraction (RHEED and LEED) indicated that the films exposed (1 0 1) terraces of the anatase TiO₂ polymorph. When a vanadium oxide monolayer was deposited onto the anatase surface by OPA-MBE at 725 K, only (1 × 1) RHEED and LEED patterns were observed. The V X-ray photoelectron spectroscopy (XPS) peak intensities indicated that the monolayer wetted the anatase surface and so the diffraction patterns were attributed to an epitaxial vanadia layer. Analysis of the vanadium oxide monolayer by X-ray and ultraviolet photoelectron spectroscopies revealed that the V was predominantly 5+. When the vanadia coverage was increased at 725 K, Auger electron spectra showed only very slow attenuation of the anatase Ti peaks while spots began to develop in RHEED patterns recorded along the LaAlO₃ direction; both indicative of 3-D cluster formation. In the orthogonal direction, the RHEED patterns showed unusual diagonal streaks. Meanwhile, the (1 × 1) LEED pattern persisted even after 30 nm of vanadia was deposited. This was attributed to gaps between the 3-D clusters exposing the epitaxial monolayer. Core level XPS spectra of the 3-D clusters revealed a broad V 2p_3/2 peak that was centered at the position expected for V⁴⁺ but could be deconvoluted into three peaks corresponding to V³⁺, V⁴⁺, and V⁵⁺. It is shown that crystallographic shear that accommodates such variations in the oxygen content of V oxides can lead to the diagonal streaks in RHEED patterns recorded along the LaAlO₃ [0 0 1] direction even as the pattern in the orthogonal direction shows sharp transmission spots. The results show that vanadia growth on anatase (1 0 1) proceeds through the Stranski-Krastanov mode with a strong vanadia-titania interaction stabilizing a dispersed vanadia monolayer. The results are compared with previous data for vanadia growth on anatase (0 0 1) where smooth, epitaxial VO₂ films grow ad infinitum.     

The local structure of SO2 and SO3 on Ni(1 1 1): A scanned-energy mode photoelectron diffraction study

O 1s and S 2p scanned-energy mode photoelectron diffraction (PhD) data, combined with multiple-scattering simulations, have been used to determine the local adsorption geometry of the SO₂ and SO₃ species on a Ni(1 1 1) surface. For SO₂, the application of reasonable constraints on the molecular conformation used in the simulations leads to the conclusion that the molecule is centred over hollow sites on the surface, with the molecular plane essentially parallel to the surface, and with both S and O atoms offset from atop sites by almost the same distance of 0.65 Å. For SO₃, the results are consistent with earlier work which concluded that surface bonding is through the O atoms, with the S atom higher above the surface and the molecular symmetry axis almost perpendicular to the surface. Based on the O 1s PhD data alone, three local adsorption geometries are comparably acceptable, but only one of these is consistent with the results of an earlier normal-incidence X-ray standing wave (NIXSW) study. This optimised structural model differs somewhat from that originally proposed in the NIXSW investigation.     

Scanning tunnelling microscopy studies of growth morphology in highly epitaxial c-axis oriented Pt thin film on (0 0 1) SrTiO3

A noble metal Pt thin film was successfully grown on (0 0 1) SrTiO₃ substrate by using a DC-sputtering technique. The surface morphology and growth features of the as-grown Pt films were investigated by scanning tunnelling microscopy. Growth conditions, such as pre-sputtering, deposition ambience, and oxygen ratio are found to greatly affect the orientation, the crystallinity, and the epitaxial behavior of Pt films on (0 0 1) SrTiO₃. Single-crystalline Pt films have been achieved by introducing a few percentage oxygen into the sputtering ambient. The in-plane-relationship of the c-axis oriented Pt thin films on (0 0 1) SrTiO₃ was determined to be (0 0 1)_Pt∥(0 0 1)_SrTiO3 and [0 0 1]_Pt∥[0 0 1]_SrTiO3. Oxygen in the sputtering ambient was found to be a key factor to achieve the epitaxial Pt films.     

RAIRS studies of CO adsorption on Pd/CeO2−x(1 1 1)/Pt(1 1 1)

Reflection absorption infrared spectroscopy (RAIRS) has been used to investigate the adsorption of CO on CeO_2−x-supported Pd nanoparticles at room temperature. The results show that when CeO_2−x is initially grown on Pt(1 1 1), a small proportion of the surface remains as bare Pt sites. However, when Pd is deposited onto CeO_2−x/Pt(1 1 1), most of the Pd grows directly on top of the CeO_2−x(1 1 1). RAIR spectra of CO adsorption on 1 ML Pd/CeO_2−x/Pt(1 1 1) show a broad CO-Pd band, which is inconsistent with a single crystal Pd surface. However, the 5 ML and 10 ML Pd/CeO_2−x/Pt(1 1 1) spectra show vibrational bands consistent with the presence of Pd(1 1 1) and (1 0 0) faces, suggesting the growth of Pd nanostructures with well defined facets.     

N incorporation and electronic structure in N-doped TiO2(1 1 0) rutile

We describe the growth and properties of well-defined epitaxial TiO_2−xN_x rutile for the first time. A mixed beam of atomic N and O radicals was prepared in an electron cyclotron resonance plasma source and Ti was supplied from a high-temperature effusion cell or an electron beam evaporator, depending on the required flux. A very high degree of structural quality is generally observed for films grown under optimized anion-rich conditions. N substitutes for O in the lattice, but only at the ∼1 at.% level, and is present as N³⁻. Epitaxial growth of TiO₂ and TiO_2−xN_x rutile prepared under anion-rich conditions is accompanied by Ti indiffusion, leading to interstitial Ti (Ti_i), which is a shallow donor in rutile. Our data strongly suggest that Ti_i donor electrons compensate holes associated with substitutional N²⁻ (i.e., Ti(III) + N²⁻ → Ti(IV) + N³⁻), leading to highly resistive or weakly n-type, but not p-type material. Ti 2p core-level line shape analysis reveals hybridization of N and Ti, as expected for substitutional N. Ti-N hybridized states fall in the gap just above the VBM, and extend the optical absorption well into the visible.     

Epitaxial growth of bcc-FexCo100-x thin films on MgO(1 1 0) single-crystal substrates

Fe_xCo_100-x (x=100, 65, 50 at%) epitaxial thin films were prepared on MgO(1 1 0) single-crystal substrates heated at 300 °C by ultra-high vacuum molecular beam epitaxy. The film structure and the growth mechanism are discussed. FeCo(2 1 1) films with bcc structure grow epitaxially on MgO(1 1 0) substrates with two types of variants whose orientations are rotated around the film normal by 180° each other for all compositions. Fe_xCo_100-x film growth follows the Volmer Weber mode. X-ray diffraction analysis indicates the out-of-plane and the in-plane lattice spacings are in agreement with the values of respective bulk Fe_xCo_100-x crystals with very small errors less than ±0.4%, suggesting the strains in the films are very small. High-resolution cross-sectional transmission electron microscopy shows that periodical misfit dislocations are preferentially introduced in the film at the Fe₅₀Co₅₀/MgO interface along the MgO[1 1¯ 0] direction. The presence of such periodical dislocations decreases the large lattice mismatch of about −17% existing at the FeCo/MgO interface along the MgO[1 1¯ 0] direction.     

Epitaxial growth of Co(0 0 0 1)hcp/Fe(1 1 0)bcc magnetic bi-layer films on SrTiO3(1 1 1) substrates

Co(0 0 0 1)_hcp/Fe(1 1 0)_bcc epitaxial magnetic bi-layer films were successfully prepared on SrTiO₃(1 1 1) substrates. The crystallographic properties of Co/Fe epitaxial magnetic bi-layer films were investigated. Fe(1 1 0)_bcc soft magnetic layer grew epitaxially on SrTiO₃(1 1 1) substrate with two type variants, Nishiyama–Wasserman and Kurdjumov–Sachs relationships. An hcp-Co single-crystal layer is obtained on Ru(0 0 0 1)_hcp interlayer, while hcp-Co layer formed on Au(1 1 1)_fcc or Ag(1 1 1)_fcc interlayer is strained and may involve fcc-Co phase. It has been shown possible to prepare Co/Fe epitaxial magnetic bi-layer films which can be usable for patterned media application.     

Effects of UV photon irradiation on SiOx (0 < x < 2) structural properties

Thin films of a-SiO_x (0 < x < 2) were prepared by reactive r.f. magnetron sputtering from a polycrystalline-silicon target in an Ar/O₂ gas mixture. The oxygen partial pressure in the deposition chamber was varied so as to obtain films with different values of x. The plasma was monitored, during depositions, by optical emission spectroscopy (OES) system. Energy dispersive X-ray (EDX) measurements and infra-red (IR) spectroscopy were used to study the compositional and structural properties of the deposited layers.Structural modifications of SiO_x thin films have been induced by UV photons’ bombardment (wavelength of 248 nm) using a pulsed laser. IR spectroscopy and X-ray photoemission spectroscopy (XPS) were used to investigate the structural changes as a function of x value and incident energy. SiO_x phase separation by spinodal decomposition was revealed. The IR peak position shifted towards high wavenumber values when the laser energy is increased. Values corresponding to the SiO₂ material (only Si⁴⁺) have been found for laser irradiated samples, independently on the original x value. The phase separation process has a threshold energy that is in agreement with theoretical values calculated for the dissociation energy of the investigated material.For high values of the laser energy, crystalline silicon embedded in oxygen-rich silicon oxide was revealed by Raman spectroscopy.     

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.     

A structural study of disordered sulfur overlayers on Cu(1 1 1)

The structure of disordered chemisorbed sulfur overlayers on Cu(1 1 1) have been investigated using normal incidence X-ray standing wavefield absorption (NIXSW). The NIXSW data indicates that within the coverage range studied, 0.13 < θ < 0.30 ML, all the disordered layers contain the same structural sub-units. The NIXSW data are consistent with a previously proposed model, which suggests that at room temperature the disordered layers contain both sulfur adatoms and mobile Cu₃S₃ clusters.     

The interplay between molecular orientation, film morphology and luminescence properties of tetracene thin films on epitaxial AlOx/Ni3Al(1 1 1)

We report a systematic study of the interplay between molecular orientation, film morphology and luminescence properties of tetracene thin films on epitaxial alumina films on Ni₃Al(1 1 1), employing high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), and photoluminescence spectroscopy (PL). If deposited at low temperatures, tetracene forms laterally disordered and compact films in which at least the first monolayer is oriented parallel to the substrate. For thicknesses in the range of 10 Å or below, these as-deposited films show no luminescence, while thicker films exhibit weak luminescence from higher layers. On annealing to 210 K, tetracene films dewet the AlO_x/Ni₃Al(1 1 1) surface and transform into an island morphology. At the same time, molecules tend to re-orient into a more upright configuration. In this island configuration, even thin films show luminescence. We can thus conclude that in spite of the insulating nature of the surface, the interaction of flat-lying tetracene molecules with AlO_x/Ni₃Al(1 1 1) is strong enough to provide at least one efficient non-radiative decay channel.     

Photoemission studies of initial oxidation for ultra-thin zinc film on 6H-SiC(0 0 0 1) surface with synchrotron radiation

The thermal oxidation process of metallic zinc on 6H-SiC(0 0 0 1) surface has been investigated by using atomic force microscopy (AFM), synchrotron radiation photoelectron spectroscopy (SRPES) and XPS methods. The AFM images characterize the surface morphology of ZnO film formed during the thermal oxidation and SRPES record the valence band, Si 2p and Zn 3d spectra at different stages. The O 1s peak is recorded by XPS because of the energy limit of the synchrotron radiation. Our results reveal that the silicon oxides layer of SiC substrate can be reduce by hot metallic zinc atom deposition. The oxygen atoms in the silicon oxides are captured by the zinc atoms to form ZnO_x at the initial stage and as a result, the oxidized SiC surface are deoxidized. After the zinc deposition with the final thickness of 2.5 nm, the sample is exposed in oxygen atmosphere and annealed at different temperatures. According to the evolution of peaks integrated intensities, it is considered that the Zn/SiC system will lose zinc atoms during the annealing in oxygen flux at high temperature due to the low evaporation temperature of pure zinc. After further annealing in oxygen flux at higher temperature, the substrate is also oxidized and finally the interface becomes a stable SiC-SiO_x-ZnO sandwich structure.     

The 2 × 1 reconstruction of the rutile TiO2(0 1 1) surface: A combined density functional theory, X-ray diffraction, and scanning tunneling microscopy study

An extensive search for possible structural models of the (2 × 1)-reconstructed rutile TiO₂(0 1 1) surface was carried out by means of density functional theory (DFT) calculations. A number of models were identified that have much lower surface energies than the previously-proposed ‘titanyl’ and ‘microfaceting’ models. These new structures were tested with surface X-ray diffraction (SXRD) and voltage-dependent STM measurements. The model that is (by far) energetically most stable shows also the best agreement with SXRD data. Calculated STM images agree with the experimental ones for appropriate tunneling conditions. In contrast to previously-proposed models, this structure is not of missing-row type; because of its similarity to the fully optimized brookite TiO₂(0 0 1) surface, we call it the ‘brookite (0 0 1)-like’ model. The new surface structure exhibits two different types of undercoordinated oxygen and titanium atoms, and is, in its stoichiometric form, predicted to be rather inert towards the adsorption of probe molecules.     

Interaction of CO with atomically well-defined PtxRuy/Ru(0 0 0 1) surface alloys

The interaction of CO with structurally well-defined Pt_xRu_y surface alloys supported on Ru(0 0 0 1) was investigated by thermal desorption spectroscopy and infrared reflection-absorption spectroscopy. The surface composition and the distribution of the surface atoms were controlled by high resolution scanning tunneling microscopy. On these surfaces, which have a nearly random distribution of the two surface species, the adsorption (and desorption) of CO is strongly modified compared to the pure elemental surfaces, by strain effects and electronic ligand effects. CO adsorbs exclusively in a linear configuration on Pt and Ru atoms for all surfaces investigated. The adsorption energy of CO is lowered on the alloy surfaces with respect to both Pt(1 1 1) and Ru(0 0 0 1), similar as for pseudomorphic monolayer Pt films. For both Pt and Ru sites the adsorption strength decreases with increasing Pt concentration.     

Reduction of FeO/Pt(1 1 1) thin films by exposure to atomic hydrogen

Using scanning tunneling microscopy (STM), X-ray photoemission spectroscopy (XPS) and density functional theory (DFT) calculations we have studied the reduction of ultra-thin films of FeO(1 1 1) grown on Pt(1 1 1) after exposure to atomic hydrogen at room temperature. A number of new ordered, partly-reduced FeO_x structures are identified and as a general trend we reveal that all the reduced FeO_x structures incorporate 2-fold coordinated Fe atoms as opposed to the original 3-fold coordinated Fe atoms in the FeO film. We find that when all the Fe atoms are 2-fold O-coordinated the FeO_x surface structure is resistant to further reduction at room temperature. We observe that water easily dissociates on the most heavily reduced FeO_x, structure in contrast to the initially inert FeO film, and reveal that it is possible to partially re-oxidize the FeO_x film by heating the surface slightly in the presence of water.     

Dissociation of water molecule at three-fold oxygen coordinated V site on the InVO4 (0 0 1) surface

Water molecule adsorption properties at the surface of InVO₄ have been investigated using an ab initio molecular dynamics approach. It was found that the water molecules were adsorbed dissociatively to the three-fold oxygen coordinated V sites on the (0 0 1) surface. The dissociative adsorption energy was estimated to be 0.8-0.9 eV per molecule. The equilibrium distance between V and O of the hydroxyl -OH was almost the same as the V-O distance of tetrahedra VO₄ in the InVO₄ bulk crystal (1.7-1.8 Å).     

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.     

Methylthiolate-induced reconstruction of Ag(1 1 1): A medium energy ion scattering study

Medium energy ion scattering (MEIS), using 100 keV H⁺ incident ions, has been used to investigate the structure of the Ag(1 1 1)(√7 × √7)R19° -CH₃S surface phase. The results provide the first direct evidence that this structure does involve substantial reconstruction of the Ag surface layer. The measured absolute scattered ion yields and blocking curves are in generally good agreement with a specific structural model of the surface based on a reconstructed layer containing 3/7 ML Ag atoms, previously suggested on the basis of scanning tunnelling microscopy (STM) and normal incidence X-ray standing wave (NIXSW) studies. However, the MEIS data indicate that any rumpling of the thiolate layer, is small, and probably ?0.2 Å. This value is smaller than the amplitude suggested in the STM and NIXSW studies, but could be entirely consistent with the earlier experimental data.