Oxygen adsorption and oxide formation on Cr(100) and Cr(110) surfaces

The adsorption of oxygen on (100) and (110) clean chromium surfaces was studied by electron diffraction (LEED and RHEED) and scanning microscopy. The beginning of the oxidation process was investigated using LEED technique. The successive patterns, observed with increasing oxidizing atmosphere, allow us to propose an oxidation mechanism for these chromium surfaces. For both orientations, rhombohedral chromium oxide grows on the surface, as shown by RHEED diagrams. The behaviour of the two planes is markedly different: the oxide film is polycrystalline on the (100) surface, while the pseudo six-fold symmetry of the (110) plane permits a parallel oriented growth.     

The effects of temperature upon NiO formation and oxygen removal on Ni(110)

Oxygen chemisorption and NiO nucleation and growth on Ni(110) have been studied with low energy electron diffraction and Auger electron spectroscopy. Changes in the Auger peak energies and shapes were shown to occur only upon NiO formation. The effects of step-changes in temperature upon NiO nucleation and growth were studied and it was shown that temperature steps or annealing during the chemisorption regime did not significantly affect either chemisorption or NiO formation. During NiO growth, temperature steps to a higher temperature caused reduced growth rates, while steps to lower temperature caused increased growth rates. The reaction rate constant from the island growth model was calculated and shown to agree with literature data. The values obtained from temperature step measurements agreed within a factor of two with those obtained for reactions without temperature steps. Therefore, no systematic temperature effect upon the NiO nuclei density was observed for Ni(110). The activation energy for growth of NiO was found to be 5.5 kcal/mole. Dissolution of oxygen into bulk nickel was also studied and it was shown that bulk diffusion of oxygen in nickel was not rate controlling. Rather, surface phase transitions were observed which allowed incorporation of oxygen over the temperature range of 150°C to greater than 800°C, depending on the quantity of oxygen already incorporated.     

ELS study on chemisorbed state of CO on Cr(110)

The chemisorbed state of CO on a Cr(110) surface has been investigated at 300 K by electron energy loss spectroscopy (ELS) with the in-situ combined supplementary techniques. The ELS spectrum of the Cr(110) surface after CO adsorption is characterized by the peaks at 2, 4.4, 6–7, 9, 11, 14.5, 19 and 23 eV, and is found to be practically the same as that of the oxygen covered surface. The C-KLL Auger spectra obtained in the range 0.1–900 L CO agree with those of metal carbides. These results are considered to indicate that CO is dissociatively chemisorbed on the Cr(110) surface throughout the whole exposure region examined. The average sticking probability of CO on Cr(110) is 0.7 at below 0.5 L, and the maximum work function increase at 1 L is ~0.1 eV. The adsorbed state of O atoms produced from dissociative adsorption of CO is also discussed.     

Vibrational characterization of carbon monoxide oxidation on the Pt(111) surface

The surface reaction between coadsorbed carbon monoxide and atomic oxygen has been characterized using high resolution electron energy loss spectroscopy, coupled with temperature programmed reaction spectroscopy on a Pt(111) surface characterized using Auger electron spectroscopy and low energy electron diffraction. Preferential oxidation of bridge bonded CO is not observed despite the fact that bridge bonded CO is adsorbed less vigorously than linearly bound CO. Saturation of the Pt(111) surface with one quarter of a monolayer of atomic oxygen completely suppresses the adsorption of bridge bonded CO. However, substantial coverages of bridge bonded CO can be coadsorbed if the Pt(111) surface is only partially saturated with atomic oxygen. The vibrational data for reaction of coadsorbed CO and atomic oxygen is consistent with a reaction mechanism involving reaction of mobile CO along oxygen island perimeters.     

Characteristic energy loss and Auger electron spectra of GaP (110)

The characteristic energy loss and Auger electron spectra of clean GaP (110) have been measured with a four grid retarding field analyser. A peak in the loss spectrum has been found at 11.2 eV which is probably due to a surface plasma loss. The remaining structure has been assigned to direct interband transitions, to single and double bulk plasma losses and to d-band transitions by analogy with previous optical and electron transmission studies. Suggestions are made as to the origin of the peaks in the Auger spectrum and changes in the spectrum in the presence of oxygen are discussed.     

W(110)面二维氧化的低能电子显微镜研究

应用低能电子显微术对W（110）面二维氧化结构进行了初步研究．随着氧暴露量的增加，低能电子衍射图样由清洁表面（1×1）结构转变成p（2×1），再变为带有复杂衍射卫星点的p（2×2）结构．利用低能电子显微术的暗场像模式，对（00）束附近的分数衍射斑点进行了放大成像，发现表面由两种对比度相差很大的区域组成，它们就是具有不同方位取向的氧超结构畴区．两种畴区的分布与衬底表面缺陷特别是表面台阶有一定的关系，而且温度对这种钨表面的二维氧化起着重要作用 关键词：     

Oxygen adsorption on (110) silver

The adsorption of oxygen on a (110)Ag surface is investigated by means of Auger electron spectroscopy, LEED and low energy helium ion scattering (IS). With LEED two ordered structures, i.e. (3×1) and (2×1) were observed at oxygen exposures of 1700 L and 7000 L respectively. The oxygen signal observed by AES and IS increases monotonically with oxygen exposure. The signals can be related to absolute coverage by comparison with Δφ measurements and by the use of the LEED data. With this calibration and with theoretical scattering cross-sections the IS measurements allow the position of the adsorbed oxygen to be estimated. The observation of a strong azimuthal anisotropy of the IS signal, e.g. a large oxygen signal if the plane of scattering is parallel to the [110] direction and a relatively small oxygen signal in the [100] direction, leads to the conclusion that the oxygen is adsorbed in a bridge position between two Ag atoms of the [110] surface channels, its centre being slightly below the centres of the Ag atoms.     

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.     

Initial oxidation of the Mg(0001) surface,an electron spectroscopy study

The initial oxidation of Mg(0001) has been studied using AES (Auger electron spectroscopy), LEED (low energy electron diffraction), and EELS (electron energy loss spectroscopy). The oxidation proceeds through different stages; first oxygen atoms are incorporated to chemisorption sites below the top layer magnesium. This chemisorption phase is followed by the formation of an oxide layer. The oxide layer covers the Mg surface after an oxygen exposure of ～ 10 L O₂. After this exposure the bulk-like MgO formation slowly increases the oxide thickness. The oxide layer formed for exposures up to ≤ 10 L O₂ gives rise to a diffuse LEED pattern of the same symmetry as the original “clean” LEED pattern; the possibility of an epitaxial oxide formation at this stage is discussed.     

Oxidation of the (100) surface of a NiFe alloy

The initial stages of oxidation of the (100) surface of a single crystal alloy specimen of approximate atomic composition Ni 59, Fe 41 (at%) have been studied by Auger spectroscopy and electron diffraction techniques. The clean alloy surface shows only a slight iron enrichment over the temperature range of the oxidation studies (373–873 K). Oxidation studies were performed over the O₂ pressure range 5 × 10^?9 to 1 × 10^?6 Torr. Within these experimental conditions the rate of oxygen uptake was found to be linear in pressure and essentially independent of temperature. LEED studies showed that a chemisorbed c(2 × 2) structure preceded the formation of surface oxides. The interaction of oxygen with the surface induced a marked segregation of iron and this was particularly pronounced at elevated temperatures. Chemical shifts were observed in the low energy Ni and Fe Auger spectra during oxidation; these were similar to those previously observed in separate studies of the oxidation of pure Ni and of pure Fe. At the higher temperatures the initial oxide layer grew epitaxially apparently as a (111) cubic oxide on the (100) substrate. The Ni to Fe concentration ratio in oxides several layers thick was found to depend on the temperature of the reaction; at higher temperatures the oxide were more Fe-rich. The Fe to Ni ratio in oxides produced at lower temperatures could be increased by annealing. At large O₂ exposures (about 5000 L) a transition was observed in the structure of the oxide layer.     

ELS study on initial oxidation of Ni(100) surfaces

Electron energy loss spectra of clean and oxygen-covered Ni(100) surfaces were observed with concomitant measurements of LEED, work function change, and Auger peak height ratio O(KL_{2, 3}L_{2, 3})/Ni(L_{2, 3}VV). The observed electronic transitions are interpreted on the basis of primary election energy dependence, and of comparison with the loss spectrum for a UHV-cleaved NiO(100) surface and optical data of Ni. The observed loss peaks at 9.1, 14, and 19 eV in the clean surface spectrum are ascribed to the bulk plasmon of the 4s electrons, the surface plasmon, and the bulk plasmon of the coupled 3d + 4s electrons, respectively, and the weak but sharp peak at 33 eV is tentatively attributed to the localized many-body effect in the final state. Three oxygen-derived peaks at 6.0, 8.0, and 10.3 eV in the low oxygen exposure region (?4 L) are ascribed to the O 2p(e) → Ni 3d, O 2p(a₁) → Ni 3d, and O 2p → Ni 4s transitions, respectively. In the high oxygen exposure region (?50 L), the spectra become quite similar to that of the UHV-cleaved NiO(100) surface. The oxidation process consistent with LEED, Auger peak height ratio and work function change measurements is discussed.     

Initial oxidation stages on FeCr(100) and FeCr(110) surfaces

Simultaneous LEED and AES are used to follow early stages of oxidation of monocrystalline FeCr(100) and (110) between 700 and 900 K in the oxygen pressure range 10^?9–10^?6 Torr. A chromium-rich oxide region at the alloy/oxide interface is observed, which exhibits different surface structures on oxidized FeCr(100) and FeCr(110). The chromium concentration in this initially formed oxide film is found to be enhanced by low oxygen pressures or high temperatures. During further oxidation different behaviours are observed on FeCr(100) and FeCr(110), which are explained by assuming different ion permeabilities through the initial chromium rich oxide regions on the two surface planes. On FeCr(110) surfaces oxidation is initiated on chromium enriched (100) facets at 800 K or below. At 900 K a film consisting of rhombohedral Cr₂O₃ or (Fe, Cr)₂O₃ is epitaxially growing with its (001) plane parallel to the alloy (110) face. On FeCr(100) surfaces the chromium rich oxide region next to the substrate is of fcc type. As soon as the diffusion of iron from the alloy to the gas/oxide interface is observable, a spinel type oxide is formed and connected with the location of iron in tetrahedral lattice sites. Closer to the fcc lattice the spinel oxide consists of FeCr₂O₄ or a solid solution of FeCr₂O₄ and Fe₃O₄ whereas next to the gas phase the oxide is pure Fe₃O₄.     

Electron loss spectroscopy of clean and oxygen covered GaAs(110) surfaces

Electron energy loss spectra of clean and oxygen covered GaAs(110) surfaces have been measured with a four grid retarding field analyser. Loss spectra of clean cleaved p- and n-type surfaces are slightly different and different states of adsorption for the oxygen on the two surfaces are found. The loss peaks which are common in the spectra obtained from clean surfaces of both types of material have been interpreted in terms of bulk and surface excitations. The data associated with the bulk excitations are in good agreement with previous optical and electron transmission data while loss peaks at 11.5 and 18.5 eV are interpreted as the surface plasma loss and a surface state transition respectively. For n-type material extra loss peaks were observed. In the case of oxygen adsorption on these surfaces new loss peaks were found at 13.5, 17.2 and 28.1 eV in both spectra and are assumed to be characteristic of the oxygen. Further, for n-type material an extra peak occurs at 8.2 eV.     

Oxidation of the hydrogenated diamond (100) surface

The surface composition and structure of natural diamond (100) surfaces subsequently oxidized with activated oxygen at T_sub≤35°C were investigated with high-resolution electron energy loss spectroscopy (HREELS), Auger electron spectroscopy, electron loss spectroscopy (ELS) and low-energy electron diffraction (LEED). Complete surface oxidation (oxygen coverage θ=1 ML) required doses of hundreds of kilolangmuirs of O₂. HREELS vibrational spectra permitted identification of the specific surface oxygen species, and also provided information about the diamond surface states. Most surface sites lost their hydrogen at least once before becoming oxidized. The oxygen coverage θ increased quickly at first, and then more slowly as saturation was approached; different mechanisms or sites may have accounted for the decreased rate. The relative distribution of oxygen species varied with the oxidation conditions. Ether, carbonyl and hydroxyl groups appeared during the initial stages of oxidation, but the hydroxyl groups disappeared at higher coverages. Bridge-bonded ether groups dominated at saturation coverage, although smaller amounts of carbonyl and hydroxyl were still observed. The carbonyl and C---H stretch frequencies increased with oxygen dose due to formation of higher oxidation states and/or hydrogen bonding between adjacent groups. ELS revealed only a low concentration of C=C dimers on the oxidized surfaces, and no evidence of graphitization.

Surfaces generated by oxygen addition and then desorption were more reactive than surfaces generated by hydrogen desorption. Oxidized surfaces that were heated in vacuum and then rehydrogenated did not recover the sharp LEED patterns and HREELS spectra of the original plasma-smoothed surface. This effect was presumably due to surface roughening caused by oxygen desorption as CO and CO₂, and creation of reactive high-energy sites that quickly bonded to available background gases and prevented large areas of organized surface reconstruction.     

Etude par spectroscopie de photoelectrons et d'electrons auger des etapes initiales de l'oxydation du chrome polycristallin

The joint application of various techniques of surface analysis (XPS, UPS, AES and work function measurements) allowed us to pinpoint the initial stages in the oxidation of polycrystalline chromium in the temperature range 180–720 K. At weak exposures ( < 10 L) the oxygen was dissociatively adsorbed without providing any information on the amount of oxygen involved or the sites of adsorption (chemisorption vs. physical interaction due to the roughness of the surface). At stronger exposures the oxide Cr₂ O₃ is observed to form, and this is covered by a layer of chemisorbed oxygen at ordinary temperatures and below. The maximum thickness of the oxide layer depends on the temperature, as would be expected from the logarithmic oxidation kinetics. The change in shape of the Auger peaks of chromium during oxidation has been interpreted in terms of interatomic transitions made via the 2p levels of oxygen.     

Oxygen chemisorption and initial oxidation of Cr(110)

The initial stages of the interaction of oxygen with a Cr(110) surface have been investigated at 300 K by LEED, AES, electron energy loss spectroscopy (ELS), secondary electron emission spectroscopy (SES) and work-function change measurement (Δφ). In the exposure region up to 2 L, the clean-surface ELS peaks due to interband transition weakened and then disappeared, while the ～5.8 and 10 eV loss peaks attributed to the O 2p → Cr 3d transitions appeared, accompanied with a work-function increase (Δφ = +0.19 eV at2L). In the region 2–6 L the work function decreased to below the original clean-surface value (Δφ_min = ?0.24 eV at6L), and five additional ELS peaks were observed at ～2, 4, 11, 20 and 32 eV: the 2 and 4 eV peaks are ascribed to the ligand-field d → d transitions of a Cr³⁺ ion, the 11 eV peak to the O 2p → Cr 4s transition, the 20 eV peak to the Cr 3d → 4p transition of a Cr³⁺ ion and the 32 eV peak probably to the Cr 3d → 4f transition. A new SES peak at 6.1 eV, being attributed to the final state for t he 11 eV ELS peak, was observed at above 3 L and identified as due to the unfilled Cr 4s state caused by charge transfer from Cr to oxygen sites in this region. In the region 6–15 L the work function increased again (Δφ_max = +0.32 eV at15 L), the 33 and 46 eV Auger peaks due to respectively the M_2,3(Cr)L_2,3(O)L_2,3(O) cross transition and the M_2,3VV transition of the oxide appeared and the 26 eV ELS peak due to the O 2s → Cr 4s transition was also observed. Above 10 L, the ELS spectra were found to be practically the same as that of Cr₂O₃. Finally, above 15 L, the work function decreased slowly (Δφ = +0.13 eV at40L). From these results, the oxygen interaction with a Cr(110) surface can be classified into four different stages: (1) dissociative chemisorption stage up to 2 L, (2) incorporation of O adatoms into the Cr selvedge between 2–6 L, (3) rapid oxidation between 6–15 L leading to the formation of thin Cr₂O₃ film, and (4) slow thickening of Cr₂O₃ above 15 L. The change in the Cr 3p excitation spectrum during oxidation was also investigated. The oxide growth can be interpreted on the basis of a modified coupled current approach of low-temperature oxidation of metals.     

Changes in Auger spectra of Mg and Fe due to oxidation

Auger electron spectra of clean Mg and Fe surfaces have been investigated under UHV conditions. The main Auger peaks in the low energy Auger spectra of these elements are identified as due to L_2,3VV and M_2,3VV transitions for Mg and Fe respectively. Changes in the low energy spectra of these clean surfaces of Mg and Fe due to chemisorption of residual oxygen in the UHV system, were also studied. The results indicate that for each oxidised surface new larger Auger peaks appear at energies lower than the original main peaks in the clean spectra. The changes in the spectra are believed to be due to the energy shifts of inner energy levels and valence bands involved in the Auger transitions as an oxide is formed.     

The adsorption of sulfur on the tungsten (110) surface

The adsorption and desorption of S on a W(110) surface is studied by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), work function change (δφ) measurements and thermal desorption spectroscopy (TDS). The evolution of the structure with coverage θ is quite different from that reported for S on Mo(110) and — at low coverages — from that of Te on W(110). At low coverages the structure indicates complex lateral interactions. The bonding changes with coverage similar to S on W(100). Evidence for more complex desorption kinetics than assumed in the past is presented.     

Adsorbed state and vibrational excitation of N2 on Pd(110)

High-resolution vibrational electron energy loss spectroscopy, low-energy electron diffraction and Auger electron spectroscopy have been used to study the interactions of nitrogen with the Pd(110) surface. At 120 K, N₂ is chemisorbed molecularly on the Pd(110) surface, and the (2 × 1)-N₂ structure is formed. Most probably, the N₂ molecules are chemisorbed in the on-top sites of the bulk-like Pd(110) surface in the upright-linear structure. The Pd---N₂ bond energy is estimated to be ˜ 6 kcal/mol. The Pd---N₂ and N---N stretching vibrations of N₂ admolecules on Pd(110) are observed at 30 and 278 meV, respectively. The primary-energy dependence and angle dependence of their excitation cross sections agree reasonably well with the prediction of the dipole theory. The electron beam-induced effects are briefly discussed.     

Electron production by metastable rare gas atom impact on a molybdenum (110) surface

Electron production by impact of thermal energy metastable helium, argon, and xenon atoms on a molybdenum (110) surface was studied. The electron yield was always highest for a clean surface and decreased considerably when the surface was exposed to either oxygen or carbon monoxide. The change in electronic yield with gas coverage of the surface was most drastic for xenon and smallest for helium metastables. The similarity of the present results to earlier measurements of electron production by low energy noble gas ion impact led us to believe that metastable deexcitation proceeded via resonance ionization followed by Auger neutralization in the present cases.