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.     

Structures of sulfur on TiO2(1 1 0) determined by scanning tunneling microscopy, X-ray photoelectron spectroscopy and low-energy electron diffraction

The temperature dependent adsorption of sulfur on TiO₂(1 1 0) has been studied with X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and low-energy electron diffraction (LEED). Sulfur adsorbs dissociatively at room temperature and binds to fivefold coordinated Ti atoms. Upon heating to 120°C, 80% of the sulfur desorbs and the S 2p peak position changes from 164.3±0.1 to 162.5±0.1 eV. This peak shift corresponds to a change of the adsorption site to the position of the bridging oxygen atoms of TiO₂(1 1 0). Further heating causes little change in S coverage and XPS binding energies, up to a temperature of 430°C where most of the S desorbs and the S 2p peak shifts back to higher binding energy. Sulfur adsorption at 150°C, 200°C, and 300°C leads to a rich variety of structures and adsorption sites as observed with LEED and STM. At low coverages, sulfur occupies the position of the bridging oxygen atoms. At 200°C these S atoms arrange in a (3×1) superstructure. For adsorption between 300°C and 400°C a (3×3) and (4×1) LEED pattern is observed for intermediate and saturation coverage, respectively. Adsorption at elevated temperature reduces the substrate as indicated by a strong Ti³⁺ shoulder in the XPS Ti 2p_3/2 peak, with up to 15.6% of the total peak area for the (4×1) structure. STM of different coverages adsorbed at 400°C indicates structural features consisting of two single S atoms placed next to each other along the [0 0 1] direction at the position of the in-plane oxygen atoms. The (3×3) and the (4×1) structure are formed by different arrangements of these S pairs.     

Interactions of HCOOH with stoichiometric and defective TiO2(110) surfaces

Interactions of HCOOH with stoichiometric (nearly defect-free) and defective TiO₂(110) surfaces have been studied experimentally using X-ray photoelectron spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS), and theoretically using electronic structure calculations. The HCOOH saturation coverages were 0.58 ML, 0.77 ML, and 0.92 ML (1 ML ≈ 5.2 × 10¹⁴ cm⁻²) for nearly defect-free surfaces, for electron-beam exposed surfaces, and for Ar⁺ ion bombarded surfaces, respectively. The excess formic acid adsorption quantitatively corresponds to the number of newly exposed sites created by electron-beam exposure. Electronic structure calculations show a strong adsorptive interaction for formate on cation sites on both stoichiometric and defective TiO₂ surfaces, consistent with the experimental observations. In spite of adsorption at defect sites, little or no defect healing (defect healing means a reduction in defect signal observed by the photoemission measurements) was observed for either electron-beam exposed or Ar⁺ bombarded surfaces by HCOOH exposure up to 10⁴L at room temperature. However, some healing will occur if extra energy provided by electrons is introduced to breakdown formate species. In contrast to water adsorption, electronic structure calculations on defective TiO₂ have found that formate is located in an asymmetric position with respect to the Ti³⁺ sites with a potential additional interaction with the Ti⁴⁺ site.     

Growth of β-MnO2 films on TiO2(110) by oxygen plasma assisted molecular beam epitaxy

We have used oxygen plasma assisted MBE to grow epitaxial films of pyrolusite (β-MnO₂) on TiO₂(110) for thicknesses of one to six bilayers (BL). We define a bilayer to be a layer of Mn and lattice O and an adjacent layer of bridging O within the rutile structure. The resulting surfaces have been characterized in situ by reflection high-energy electron diffraction, low-energy electron diffraction, X-ray photoelectron spectroscopy and diffraction, and atomic force microscopy. Well-ordered, pseudomorphic overlayers form for substrate temperatures between 400 and 500°C. Mn–Ti intermixing occurs over the time scale of film growth (1 BL/min) for substrate temperatures in excess of 500°C. Films grown at 400–500°C exhibit island growth, whereas intermixed films grown at temperatures of 500–600°C are more laminar. 1 BL films grown at 450°C are more laminar than multilayer films grown at the same temperature, and form a well-ordered surface cation layer of Mn on the rutile structure with at most 10% indiffusion to the second cation layer.     

Spatially resolved dynamics of the TiO2(1 1 0) surface reconstruction

We use low-energy electron microscopy to image the reversible transformation of the TiO₂(1 1 0) surface between a high-temperature 1 × 1 structure and a low-temperature 1 × 2 structure. The reconstruction dynamics are novel: 1 × 2 bands nucleated during cooling at the steps of the starting 1 × 1 surface and then grew laterally from the steps. The transformation kinetics are dominated by mass flow from the surface to the bulk, a process that facilitates converting the high-density 1 × 1 phase to the lower-density 1 × 2 phase. We have also imaged how the 1 × 1 surface reconstructs to 1 × 2 phase after sufficient oxygen is removed from the crystal’s bulk during vacuum annealing. 1 × 2 bands also nucleated and grew laterally from the initial 1 × 1-surface’s steps. However, because this isothermal 1 × 1-to-1 × 2 transition occurs largely by mass redistribution on the surface, the steps of the initial 1 × 1 surface and final 1 × 2 surface are offset. We propose models of mass redistribution during the 1 × 1/1 × 2 phase transition to explain this effect. We conclude that the phase transition is first-order because it always occurred by the nucleation and growth of discrete phases. Finally, we show that quenching can roughen TiO₂’s surface by forming pits and that changing temperature causes step motion on 1 × 2 surfaces.     

Study of the interactions between the overlayer and the substrate in the early stages of palladium growth on TiO2(1 1 0)

The interaction between palladium and the (1 1 0) surface of a TiO₂ single crystal and the electronic properties of the system were studied by means of photoelectron spectroscopy (core levels and valence band) and resonant photoemission for Pd coverage in the sub- and monolayer range. We performed the metal depositions at room temperature. Similarly to copper, platinum and rhodium, palladium does not reduce titanium, has metallic character already from a quite early deposition, grows with a 3D-island mode and the interactions between palladium and TiO₂ are very weak. Annealing treatments at 400 °C provoke a change in the morphology of the palladium clusters and the formation of islands characterized by a higher ratio between volume and area in contact with the substrate.     

X-ray and electron beam modification of thiophene overlayers on TiO2(100)1 × 1 and 1 × 3

The effects of electron and X-ray beams on thiophene overlayers on TiO₂(100) 1 × 1 and 1 × 3 surfaces have been investigated using AES, UPS and XPS. Mg K X-rays were found to polymerise a thiophene multilayer condensed at 120 K. The evidence points to a substrate-secondary-electron mediated process. A 3 keV electron beam also modifies a condensed thiophene overlayer, probably by polymerisation.     

A surface X-ray diffraction study of TiO2(1 1 0)(3 × 1)-S

Surface X-ray diffraction has been used to investigate the structure of TiO₂(1 1 0)(3 × 1)-S. In concert with existing STM and photoemission data it is shown that on formation of a (3 × 1)-S overlayer, sulphur adsorbs in a position bridging 6-fold titanium atoms, and all bridging oxygens are lost. Sulphur adsorption gives rise to significant restructuring of the substrate, detected as deep as the fourth layer of the selvedge. The replacement of a bridging oxygen atom with sulphur gives rise to a significant motion of 6-fold co-ordinated titanium atoms away from the adsorbate, along with a concomitant rumpling of the second substrate layer.     

In situ XPS study of Pd(1 1 1) oxidation. Part 1: 2D oxide formation in 10 mbar O2

The oxidation of the Pd(1 1 1) surface was studied by in situ XPS during heating and cooling in 3 × 10⁻³ mbar O₂. A number of adsorbed/dissolved oxygen species were identified by in situ XPS, such as the two dimensional surface oxide (Pd₅O₄), the supersaturated O_ads layer, dissolved oxygen and the R 12.2° surface structure.Exposure of the Pd(1 1 1) single crystal to 3 × 10⁻³ mbar O₂ at 425 K led to formation of the 2D oxide phase, which was in equilibrium with a supersaturated O_ads layer. The supersaturated O_ads layer was characterized by the O 1s core level peak at 530.37 eV. The 2D oxide, Pd₅O₄, was characterized by two O 1s components at 528.92 eV and 529.52 eV and by two oxygen-induced Pd 3d_5/2 components at 335.5 eV and 336.24 eV. During heating in 3 × 10⁻³ mbar O₂ the supersaturated O_ads layer disappeared whereas the fraction of the surface covered with the 2D oxide grew. The surface was completely covered with the 2D oxide between 600 K and 655 K. Depth profiling by photon energy variation confirmed the surface nature of the 2D oxide. The 2D oxide decomposed completely above 717 K. Diffusion of oxygen in the palladium bulk occurred at these temperatures. A substantial oxygen signal assigned to the dissolved species was detected even at 923 K. The dissolved oxygen was characterised by the O 1s core level peak at 528.98 eV. The “bulk” nature of the dissolved oxygen species was verified by depth profiling.During cooling in 3 × 10⁻³ mbar O₂, the oxidised Pd²⁺ species appeared at 788 K whereas the 2D oxide decomposed at 717 K during heating. The surface oxidised states exhibited an inverse hysteresis. The oxidised palladium state observed during cooling was assigned to a new oxide phase, probably the R 12.2° structure.     

The surface structure of Fe3O4(1 1 1) films as studied by CO adsorption

We have studied adsorption of CO on Fe₃O₄(1 1 1) films grown on a Pt(1 1 1) substrate by temperature programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS) and high resolution electron energy loss spectroscopy (HREELS). Three adsorption states are observed, from which CO desorbs at ∼110, 180, and 230 K. CO adsorbed in these states exhibits stretching frequencies at ∼2115-2140, 2080 and 2207 cm⁻¹, respectively. The adsorption results are discussed in terms of different structural models previously reported. We suggest that the Fe₃O₄(1 1 1) surface is terminated by 1/2 ML of iron, with an outermost 1/4 ML consisting of octahedral Fe²⁺ cations situated above an 1/4 ML of tetrahedral Fe³⁺ ions, in agreement with previous theoretical calculations. The most strongly bound CO is assigned to adsorption to Fe³⁺ cations present on the step edges.     

Nanoclusters of TiO2 wetted with gold

We combined scanning tunneling microscopy and density functional theory to establish the structure-functionality relationship for nanometer-sized defects on TiO₂(1 1 0). Three-angstrom high topographically distinct dots are ascribed to stoichiometric TiO₂ nanoclusters with low coordination numbers. The under-coordinated O atoms of the nanocluster, with surface O atoms, provide exceptionally strong binding sites for Au nanoparticles. Our atomistic model elucidates a number of characteristics salient to low temperature CO oxidation by Au nanoparticles.     

Aromatic interactions in the close packing of phenyl-imides at Cu(1 1 0) surfaces

The oxidation of aniline at Cu(1 1 0) surfaces at 290 K has been studied by XPS and STM. A single chemisorbed product, assigned to a phenyl imide (C₆H₅N(a)), is formed together with water which desorbs. Reaction with preadsorbed oxygen results in a maximum surface concentration of phenyl imide of 2.8 × 10¹⁴ mol cm⁻² and a surface dominated by domains of three structures described by , and unit meshes. However, concentrations of phenyl imide of up to 3.3 × 10¹⁴ mol cm⁻² were obtained from the coadsorption of aniline and dioxygen (300:1 mixture) resulting in a highly ordered biphasic structure with and domains. Comparison of the STM and XPS data shows that only half the phenyl imides at the surface are imaged. Pi-stacking of the phenyl rings is proposed to account for this observation.     

Photoemission study of the modification of the electronic structure of transition-metal overlayers on TiO2 surfaces II. Cr on TiO2(0 0 1)

The electronic states of the Cr overlayers on TiO₂(0 0 1) surfaces have been investigated using angle-resolved and resonant photoemission spectroscopy with synchrotron radiation. At lower coverages, Cr deposition on TiO₂(0 0 1) creates two well separated in-gap emissions due to the formation of surface Ti³⁺ (3d¹) ions and Cr³⁺ (3d³) ions. At higher coverages, the in-gap emission is developed into the 2-peak-structure emission of Cr 3d character. The corresponding state is considered to be of metallic nature from the viewpoint of the high ability of oxygen adsorption, but has no Fermi edge, indicating a possibility of forming small Cr clusters on TiO₂(0 0 1) at this stage.     

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.     

Solar light decomposition of DFP on the surface of anatase and rutile TiO2 prepared by hydrothermal treatment of microemulsions

The photocatalytic decomposition of diisopropylfluorophosphate (DFP) over nanostructured anatase and rutile TiO₂ powder was investigated by FTIR and XPS. Upon irradiation with artificial solar light DFP decomposed on both polymorphs as evidenced by FTIR. For both crystalline structures acetone and subsequently coordinated formate and carbonate were observed on the surface during the photocatalytic reaction as the isopropyl groups dissociated from DFP. XPS revealed that small amounts of phosphates and inorganic fluoride (TiF) gradually built up on both TiO₂ surfaces, while organic F was present only on the rutile phase. From repeated cycles of intermittent DFP adsorption and irradiation measurements, the decomposition rates and formation of residuals on the surface were deduced. It was found that the overall oxidation yield is higher on anatase than rutile. The oxidation rate decreases with increasing irradiation time, an effect that is more pronounced on rutile. We find that both the difference between the polymorphs and the initial decrease of the oxidation yield can largely be explained by variations in surface area rather than poisoning by PO_x or F species. In particular, we observe a dramatic decrease of the specific area of rutile as a function of photocatalytic oxidation cycle.     

Photoemission study of the modification of the electronic structure of transition-metal overlayers on TiO2 surfaces: I. Fe on TiO2(1 1 0)

The electronic states of the Fe overlayers on TiO₂(1 1 0) surfaces have been investigated using normal-emission and resonant photoelectron spectroscopy with synchrotron radiation. It was found that Fe grows in a Stranski-Krastanov mode. At low coverages, Fe deposition on TiO₂(1 1 0) is supposed to create surface Ti³⁺(3d¹) ions leading to the same in-gap emission as that is produced by surface oxygen vacancies of TiO₂. At high coverages, Fe-induced in-gap emission is evolved into a bulk Fe spectrum. However, at the beginning, a Fermi edge is not observed, indicating that the small Fe clusters of non-metallic nature are formed. A sharp Fermi edge is formed at higher coverages, indicating that the cluster becomes metallic as the size increases.     

Wavelet analysis of the surface morphologic of nanocrystalline TiO2 thin films

Surface morphologies of nanocrystalline TiO₂ thin films were studied by analyzing the surface profile of AFM images using wavelet transform method. Based on characterizing the fractal feature and computing the image details at different orientations and resolutions, the surface textures of nanocrystalline TiO₂ thin films before and after chemical treatment were examined. The results reveal that titanium isopropoxide treatment leads to an increase of surface roughness. The related mechanism of modification of the microstructure by chemical treatment associated with the improvement of the photocurrent response is discussed.     

Structural study of adsorption of isonicotinic acid and related molecules on rutile TiO2(1 1 0) II: XPS

The adsorption of monolayers of the pyridine-carboxylic acid monomers (isonicotinic acid, nicotinic acid, and picolinic acid) on rutile TiO₂(1 1 0) has been studied by means of X-ray photoemission spectroscopy. An investigation of the O 1s spectra shows that the molecular carboxylic groups are deprotonated and, hence, that the molecules bind to the surface in a bidentate mode. Moreover, the binding energy of those core levels that are related to the pyridine ring atoms shift as a function of molecule relative to the substrate O 1s and Ti 3p levels, while the position of the core levels related to emission from the carboxylic group are constant relative to the substrate levels. The molecule-dependent shifts are attributed to local intermolecular interactions that determine the proximity of adjacent molecular rings and thus the core-hole screening response of the neighbouring molecules. We propose a simple molecular arrangement for each case which satisfies the known constraints.     

The adsorption and decomposition of NO on Pd(110)

The sticking probability of nitric oxide (NO) on Pd(110) and the relative selectivity of the surface to nitrogen (N₂) and nitrous oxide (N₂O) production has been measured as a function of coverage and as a function of surface and gas temperatures using a molecular beam. It is found that, at low temperatures (<440 K), molecular adsorption occurs with an initial sticking probability of 0.40 ± 0.02, rising quickly to a maximum of about 0.48 ± 0.02 as coverage increases before falling towards saturation. Following adsorption at 170 K four distinct adsorption sites can be identified by subsequent TPD. Hence, if beaming occurs at a temperature above the TPD peak due to a given site, then that site cannot be populated and the saturation coverage is found to be reduced. At higher temperatures (440–650 K) the sticking probability is seen to decrease continuously as a function of coverage. At a given NO uptake, the sticking probability falls with temperature indicating that the rate of NO desorption is significant in this temperature range. In addition, dissociation occurs leading to the desorption of nitrogen and nitrous oxide leaving only oxygen adatoms on the surface. The oxygen adatoms poison further reaction but can be cleaned off, even at the lowest temperature at which dissociation occurs, by hydrogen or carbon monoxide. At the low temperature end of this range more nitrous oxide is produced than nitrogen but this ratio falls with temperature until, above 600 K, there is 100% selectivity to the production of nitrogen which we propose is due to the low lifetime of molecular NO on the surface. However, at such high temperatures, reaction only occurs on a few sites probably located at the few step edges present on the crystal.     

A reversible reaction forming (---Cu---O---) strings and (Cu)6-clusters on Ag(110) shown by STM

An artificial new surface of (---Cu---O---) chains grown on Ag(110) surface was prepared by reacting a surface with Cu atoms, where the (---Cu---O---) chains grow in the [1 0] direction and are self-assembled on the Ag(110) surface in a (2 x 2)-p2mg structure. When the Cu---O/Ag(110) surface was heated in vacuum, the (---Cu---O---) chain decomposed to uniform cluster dots arranged along the [1 0] direction, where the cluster dots were composed of six Cu atoms. When the Ag(110) surface with the Cu---cluster dots was exposed to O₂, the (---Cu---O---) lines were redrawn along the [1 0] direction by reacting a s in the [1 0] direction with O₂. This is a reversible chemical reaction in one dimensional regime proved in atomic resolution.