CHaracterization of CO binding sites on Rh{111} and Rh{331} surfaces by XPS and LEED: Comparison to EELS results

Changes in the nature of the binding site of chemisorbed CO on the Rh{111} and Rh{331} single crystal surfaces during adsorption and desorption have been monitored by X-ray Photoelectron Spectroscopy (XPS) and Low Energy Electron Diffraction (LEED). Two bonding states of molecular CO have been identified from the O 1s photoemission line. These states are assigned as atop and bridge-bonded species and are observed to be coverage and temperature dependent. On both surfaces atop sites are populated first and at higher CO coverages bridge sites are filled. On Rh{111} the bridge sites are filled at a CO coverage of θ_CO ～ 0.50 and their presence is correlated with a change in the LEED pattern. The presence of the step atoms on the Rh{331} surface markedly influenced the sequential filling of binding sites in comparison to that observed on the Rh{111} surface. A comparison of our data to previous Electron Energy Loss Spectroscopy (EELS) work on Rh{111} is in remarkable quantitative agreement with EELS peak heights.     

HREELS investigation of hydrogenated and deuterated GaN{0001} surfaces

The vibrational properties of clean, H- and D-covered GaN{0001} surfaces were investigated by high-resolution electron energy-loss spectroscopy. Auger electron spectroscopy and low-energy electron diffraction were utilized to monitor the surface cleanliness and structure, respectively. At the clean surface the Fuchs-Kliewer surface phonon frequency was determined to 700 cm^-1 (86.8 meV). For the adsorbate-covered surfaces current structure models predict only Ga-H vibrations for surfaces of either polarity. Despite of this, the HREEL-spectra of the hydrogenated sample show a new loss structure at 3255 cm^-1 (403.6 meV) and a shoulder at 1900 cm^-1 (235.6 meV) which are attributed to N-H and Ga-H stretching vibrations, respectively. After deuterium exposure an isotope shift occurs. Again, a N-adsorbate vibration is clearly resolved. A Ga-D bending mode is observed at 390 cm^-1 (48.4 meV), indicating that vibrations of both species are present. Received 1 February 2000     

Structure and energetics changes during hydrogenation of 4H-SiC{0001} surfaces: a DFT study

The changes in the atomic and electronic structure of Si- and C-terminated hexagonal SiC{0001} surfaces resulting from on-surface and subsurface hydrogen adsorption have been studied within the density functional theory framework. Hydrogen coverages ranging from a submonolayer to one monolayer were considered. Our results show that a monolayer of adsorbed H almost completely suppresses the relaxation of the SiC surface atomic layers. On both terminations H binds strongly to the surface and the binding is about 2?eV stronger in on-surface sites than subsurface. Hydrogen binding to the C-terminated surface varies very little with coverage and is distinctly stronger than to the Si-terminated surface.     

A combined XPS/AES study of Cu segregation to the high and low index surfaces of a Cu-Ni alloy

Quantitative information was obtained regarding the equilibrium segregation of Cu to the high index surfaces (cut 5° off the (100) plane in the [001] and [011] directions) and low index surfaces ((100), (111) and (110)) of a Cu: Ni, 5: 95% alloy crystal. Data regarding segregation to the (111) surface of a Cu: Ni, 50: 50% alloy crystal was also obtained. Equilibrium surfaces were obtained by careful annealing in the temperature range 850–920 K to avoid Cu loss by evaporation. The surface composition profile was calculated using data from the combination of the X-ray Photo-electron Spectroscopy and Auger Electron Spectroscopy techniques. Using these techniques, a wide range of electron kinetic energies and associated electron escape depths can be probed, yielding information about the topmost layer concentration and about the concentration profile into the bulk. Extensive Cu segregation was observed for the 5% and 50% Cu alloys. Topmost layer compositions of 85–100% Cu were found for both the high and low index surfaces of the 5% Cu alloy. In the next two or three atomic layers the composition was found to drop swiftly to near bulk Cu levels. For atomic layers deeper than this, some experimental evidence suggested a rise in Cu composition over three or four layers to 8–17% Cu before bulk levels were finally regained. For the 50% Cu alloy sample, a topmost layer composition was found of 95–100% Cu. Bulk levels of Cu were regained in about four atomic layers. These results are discussed in relation to other theoretical and experimental studies of segregation in these Cu-Ni alloys. The significance of the measured composition in relation to an equilibrium surface is also considered.     

A model for the oxidation of Mg(0001) based upon LEED,AES, ELS and work function measurements

The Mg(0001) face is subjected to oxygen adsorption from 0 to 10³ L. Three characteristic stages of oxygen adsorption are detected from 0 to 10 L. The AES signal of clean Mg decays exponentially against exposure with slopes α _ai such that α_A2 (0.75 → 3 L) >α_A1 (0 → 0.75 L)>α_A3 (3 → 10 L). For increasing exposures, they correspond to: (1) a clear (1 × 1)-Mg(0001), (2) a diffuse (1 × 1)-Mg(0001) and (3) a (1 × 1) with a weaker (1 × 1)-R30°-MgO(111) LEED patterns, respectively. At the end of the third stage, a supplementary ($\text{7}\text{×}\text{7}\text{2}\text{)?R19°?MgO(111)}$ pattern is observed. In ELS, a very fast intensity decrease of energy loss peaks due to surface and bulk plasmon excitations of the clean metal is recorded during the first stage. The energy loss peak due to the oxidized surface plasmon excitation reaches a maximum intensity at the end of the second stage. Energy loss peaks to be attributed to excitations in bulk MgO appear during the third stage. The work function of the sample decreases and shows a minimum around 6 L, and then slowly increases. Beyond 10 L, a logarithmic relation between oxide thickness and exposure seems to exist. These results are interpreted by the following sequential processes: stage 1: random oxygen chemisorption followed by oxygen incorporation (α_A1); stage 2: assembling into islands and lateral island growth (α_A2); stage 3: oxide formation (α_A3) and stage 4: oxide thickening. Lattice models describing these processes are proposed and discussed. The influence of surface roughness on the results is emphasized.     

A LEED inquiry into the question of reconstruction of {001} Nb

We have examined the structure of the {001} surface of Nb by LEED and have found that a (1 × 1) diffraction pattern prevails over the entire range of temperature investigated, that is 15–1000 K. This is the first observation of an unreconstructed {001} surface of a bcc metal over such a temperature range. This result is consistent with a reconstruction mechanism requiring the coupling of occupied surface states and is expected to further theoretical development of the mechanism of surface reconstruction.     

Coverage-dependent molecular tilt of carbon monoxide chemisorbed on Pt{110}: A combined LEED and DFT structural analysis

The adsorption of carbon monoxide on the Pt{110} surface at coverages of 0.5 ML and 1.0 ML was investigated using quantitative low-energy electron diffraction (LEED IV) and density-functional theory (DFT). At 0.5 ML CO lifts the reconstruction of the clean surface but does not form an ordered overlayer. At the saturation coverage, 1.0 ML, a well-ordered p(2 × 1) superstructure with glide line symmetry is formed. It was confirmed that the CO molecules adsorb on top of the Pt atoms in the top-most substrate layer with the molecular axes tilted by ± 22° with respect to the surface normal in alternating directions away from the close packed rows of Pt atoms. This is accompanied by significant lateral shifts of 0.55 Å away from the atop sites in the same direction as the tilt. The top-most substrate layer relaxes inwards by ? 4% with respect to the bulk-terminated atom positions, while the consecutive layers only show minor relaxations. Despite the lack of long-range order in the 0.5 ML CO layer it was possible to determine key structural parameters by LEED IV using only the intensities of the integer-order spots. At this coverage CO also adsorbs on atop sites with the molecular axis closer to the surface normal (< 10°). The average substrate relaxations in each layer are similar for both coverages and consistent with DFT calculations performed for a variety of ordered structures with coverages of 1.0 ML and 0.5 ML.     

AES and LEED study of the activation of GaAsCsO negative electron affinity surfaces

Gallium arsenide epitaxial layers have been activated to negative electron affinity by a two-stage process. This consisted of a heat clean in vacuum and activation with caesium and oxygen, followed by a second heating, to partially desorb the caesium, and re-activation with caesium and oxygen. AES measurements during the first activation indicated that the oxygen/caesium ratio increased as the photoemission increased to a maximum. This ratio was always less than the nearly constant ratio during the second activation which gave greater photoemission. After both the first and second activations desorption studies showed that, whereas the caesium Auger peak height decreased monotonically over a wide range of temperature, the oxygen peak height passed through a maximum as the temperature was increased, before decreasing rapidly to zero as the caesium desorption was completed. This temperature of desorption was slightly higher after the second activation. LEED showed that the caesium-oxygen layer was amorphous.     

LEED,AES and work function measurements on clean and cesium covered polar faces of GaP

After argon bombardment and annealing both the (111) and (1&#x0304;1&#x0304;1&#x0304;) faces of GaP show a (1 × 1) LEED pattern. The stabilization of the polar termination is probably obtained by charging of surface states. Measurements of the work function, the Auger spectrum and the LEED pattern during cesium deposition at room temperature suggest disordered cesium adsorption limited to a monolayer.     

Potassium and potassium oxide monolayers on the platinum (111) and stepped (755) crystal surfaces: A LEED,AES, and TDS study

The adsorption of potassium and the coadsorption of potassium and oxygen on the Pt(111) and stepped Pt(755) crystal surfaces were studied by AES, LEED, and TDS. Pure potassium adlayers were found by LEED to be hexagonally ordered on Pt(111) at coverages of θ = _K0.9–;1. The monolayer coverage was 5.4 × 10¹⁴K atoms/cm² (0.36 times the atomic density of the Pt(111) surface). Orientational reordering of the adlayers, similar to the behavior of noble gas phase transitions on metals, was observed. The heat of desorption of K decreased, due to depolarization effects, from 60 kcal/mole at θ_K <0.1, to 25 kcal/mole at θ_K = 1 on both Pt(111) and Pt(755). Exposure to oxygen thermally stabilizes a potassium monolayer, increasing the heat of desorption from 25 to 50 kcal/mole. Both potassium and oxygen were found to desorb simultaneously indicating strong interactions in the adsorbed overlayer. LEED results on Pt(111) further indicate that a planar K₂O layer may be formed by annealing coadsorbed potassium and oxygen to 750 K.     

The condensation of gold onto tantalum (100) single crystal surfaces: LEED,AES analysis

The condensation of gold onto clean and contaminated, single crystal, tantalum (100) surfaces has been followed by using LEED and AES. On a contaminated surface gold condenses as crystallites in a (211) surface orientation with some degree of preferred, azimuthal orientation. On a clean surface gold condenses in an ordered overlayer. Up to approximately $\text{3}\text{4}$ monolayer the structure conforms to the (1 × 1) tantalum surface. Beyond this, the observed LEED structure may be interpreted initially in terms of a TaAu overlayer made up of 90° rotated domains with (001)TaAu//(100)Ta and 〈 10 〉 TaAu// 〈 11 〉 Ta, and then in terms of a gold overlayer in a “distorted (111)” orientation. Annealing of these gold films always results in the formation of a (1 × 1) TaAu overlayer of small crystallite size.     

Background subtraction: I. General behaviour of Tougaard-style backgrounds in AES and XPS

An analysis is made of Tougaard-style backgrounds for homogeneous materials to show how parameters interact together and comprise the general inelastic scattering background in electron spectroscopy. It is shown that insight is usefully gained by rewriting the Tougaard universal loss function in terms of two parameters, the characteristic energy, E₁, of the exponential decay observed in multiple self-convolutes of the Tougaard universal single loss function, and the centroid energy of the single loss function. Close fits to the measured background may be made over a wide energy range for only one value of E₁ which defines a unique relation between Tougaard’s B and C values but does not give the unique values themselves. For the single value of E₁, the centroid energy may be varied such that the background subtracted spectra range from those shown by Tougaard, where the intrinsic shake-up and losses may constitute two thirds of the peak intensity, to spectra similar to those of Jo in which all of the intrinsic losses are removed. Studies of Al X-ray excited Sc, Cu, Sm and Au photoelectron spectra, each of which has an extensive range of peaks, show that the relative intensities of the peaks are unaffected by the choice of the value of even though the absolute peak areas may change by a factor of 3.     

Sulphur adsorption on Au{1 1 0}: DFT and LEED study

The adsorption of sulphur on clean reconstructed Au{1 1 0}-(1 × 2) surface was studied using density functional theory (DFT) and quantitative low energy electron diffraction (LEED) calculations. The results show that the sulphur atoms form a (4 × 2) ordered structure which preserves the missing row reconstruction of the clean surface. The sulphur atom is found to adsorb on threefold hollow sites, on the {1 1 1} microfacets that border the trenches of the missing rows.     

The growth and chemisorptive propertles of Ag and Au monolayers on platinum single crystal surfaces: An AES,TDS and LEED study

The growth and chemisorptive properties of monolayer films of Ag and Au deposited on both the Pt(111) and the stepped Pt(553) surfaces were studied using Auger electron spectroscopy (AES), thermal desorption spectroscopy (TDS), and low energy electron diffraction (LEED). AES studies indicate that the growth of Au on Pt(111) and Pt(553) and Ag on Pt(111) proceeds via a Stranski-Krastanov mechanism, whereas the growth of Ag on the Pt(553) surface follows a Volmer-Weber mechanism. Au dissolves into the Pt crystal bulk at temperatures > 800 K, whereas Ag desorbs at temperatures > 900 K. TDS studies of Ag-covered Pt surfaces indicate that the AgPt bond (283 kJ mol^?1) is ～25 kJ mol^?1 stronger than the AgAg bond (254 kJ mol^?1). On the Pt(553) surface the Au atoms are uniformly distributed between terrace and step sites, but Ag preferentially segregates to the terraces. The decrease in CO adsorption on the Pt crystal surfaces is in direct proportion to the Ag or Au coverage. No CO adsorption could be detected for Ag or Au coverages above one monolayer at 300 K and 10^?8 Torr. The heat of adsorption of CO on Pt is unaltered by the presence of Ag or Au.     

Initial interaction of oxygen with aluminium single crystal faces: A LEED,AES and work function study

Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and work function (Kelvin probe) measurements have been used to study the initial interaction of clean Al(111), (100) and (110) surfaces with oxygen at room temperature. The oxidation process was found to be surface orientation dependent, but a common feature has been always observed on the three low-index surfaces: they show two distinct phases, i.e. a chemisorbed phase followed then by an oxidized phase. From analysis of AES, LEED and Kelvin probe results, an adsorption mechanism of O on Al for each surface orientation is proposed.     

The reactivity of the clean and contaminated (0001&#x0304;) polar and the (101&#x0304;0) prism ZnO surfaces to chlorine

The reactivities of the (0001&#x0304;) and (101&#x0304;O) surfaces of zinc oxide to chlorine gas have been studied by a range of techniques. In the case of the (0001&#x0304;) oxygen polar surface investigations were made with the surface both atomically clean and with a known level of carbon and calcium contamination. Comparison is made with our earlier results on the (0001) surface which showed a high level of reactivity due to the increased electrostatic stability on adsorption of the electronegative gas. Both the oxygen polar and the prism surface showed a much lower reactivity to chlorine than the zinc face: contamination by carbon and calcium on the former surface reduced the reactivities still further. This result conflicts with comparable data for oxygen adsorption where previous work has shown a greater take-up of oxygen on the oxygen face than the zinc face. Unlike the zinc face, no LEED superstructures were observed on any of, the three surfaces, but in common with the (0001) there were significant electron beam desorption effects. Two states could be identified: one was rapidly removed in ~10 μA min exposure to the beam, the other in much longer periods. Work function and ELS data were consistent with atomic adsorption of chlorine on all surfaces. An exception was the (101&#x0304;O) at high exposures where a work function decrease took place following the initial increase: this may indicate a second molecular state.