Ion angular distributions in electron stimulated desorption: Oxygen and CO on W(111)

The ion angular distributions resulting from electron stimulated desorption (ESD) of oxygen and carbon monoxide chemisorbed on a tungsten (111) crystal have been determined. The O⁺ ions released during ESD of adsorbed oxygen exhibit three-fold symmetric angular distributions in orientational registry with the W(111) substrate. The CO⁺ and O⁺ ions released during ESD of a monolayer of CO are desorbed normal to the (111) surface. Models for both oxygen and CO adsorption are discussed. The data for CO are consistent with adsorption of CO in “standing up” carbonyl structures in the virgin and α-CO binding states.     

Desorption methods as probes of kinetics and bonding at surfaces

This paper is divided into two parts. Firstly, a review of desorption methods is presented, with emphasis on the use of temperature programmed desorption (TPD) and electron stimulated desorption (ESD) for understanding the bonding of adsorbed species to surfaces. Secondly, recent studies of the angular distribution of ESD ions from adsorbed layers on W(011) are discussed. The ESD of O⁺ ions from oxygen adsorbed on a stepped W(011) surface is shown to be sensitive to the presence of atom steps.     

多晶镍表面上氧的电子诱导脱附研究

长期暴露于大气的多晶镍样品,经700℃2小时真空退火及常温和500℃暴露氧20—60L后,发现其表面将产生两种电子诱导脱附(ESD)氧正离子。所对应的电子能量阈值分别为29eV和23eV。我们认为,两种氧正离子的产生机制为俄歇诱导脱附。29eV阈能者对应于镍表面化学吸附氧的2s能级电子向真空中电离;而23eV阈能者则对应于表面层中未与镍化合的自由氧的2s电子向体内费密能级跃迁。 关键词：     

Oxygen and carbon monoxide adsorption on W(111): An investigation with angular resolved ESD,AES and LEED

Oxygen and carbon monoxide adsorption on clean W(111) surfaces have been studied by angular resolved ESD emission (ESDIAD). In addition, the specimen could be characterized in situ with AES and LEED. Adsorption was performed at room temperature. The electron stimulated desorption yielded O⁺ ions from the two investigated adsorption layers. Upon oxygen adsorption followed by subsequent annealing at least eight different ESDIAD patterns have been obtained. However, a convincing interpretation on the basis of the surface geometry can only be presented for three patterns produced without annealing as well as for one pattern at a very high annealing temperature. The difficulties are a consequence of complex structure changes which the surface undergoes in the intermediate annealing temperature range. This may influence the little known neutralisation probability of the desorbing ions. In this special case ESDIAD probably reflects in contrast to LEED a picture of some specific adsorption sites (minority species) and therefore, no clear correlation of the two techniques can be seen. ESDIAD from carbon monoxide shows four different patterns and supports the model of linear bonded CO molecules at room temperature with oxygen in the “standing up” position. At T > 900 K, CO starts to dissociate and results in similar ESDIAD patterns as obtained from O₂ adsorption.     

The anomalous behaviour of the ESID O+ yield from a Ni(110) surface during oxygen adsorption

The behaviour of the ESID O⁺ yield is studied as a function of the exposure of a Ni(110) surface to oxygen. Measurements performed during the adsorption process reveal a contribution to the ESID O⁺ yield, which is ascribed to a precursor state. If there is a time lapse between exposure and the measurement, the precursor state is not observed. For this situation the O⁺ ions, generated by electron impact, are shown to originate from NiO islands. The disappearance of the precursor state is explained as a transition into a chemisorption state and a depletion by ESD. The behaviour of the O⁺ yield from the NiO islands during adsorption is assumed to be due to the formation of Ni₂O₃ on top of the NiO islands.     

Coadsorption of oxygen and carbon monoxide on tungsten: Desorption spectra,electron stimulated desorption and field emission microscopy

CO/W desorption spectra are characterized by an α state and multiple β states; using electron stimulated desorption (ESD) the α state was shown to comprise two sub-states, α₁ and α₂. In this paper the consecutive interactions of O₂ and CO on W are investigated using ESD, flash desorption and field emission microscopy (FEM).Desorption spectra show that the α-CO state is displaced by O₂, in two stages. The ESD probe provides an identification of the first stage with the removal of the α₁-CO state, and energy analysis of ESD ions reveals a large energy shift (～ ? 1.5 eV) during O₂ coadsorption which can be attributed to an incresae in the α₁-CO WC bond length of ～ 0.15 Å. During this O₂-induced displacement, the two β peaks converge into a single peak at the β₁ position; this is ascribed to adatom interactions in the mixed O and C adlayer. Isotope exchange experiments with ²⁸CO and ³⁶O₂ reveal (i) no exchange in the α-CO states, and (ii) complete exchange in the β-CO states, which is consistent with dissociative adsorption in the latter. The amount of coadsorbed O₂ is estimated from these results, and from FEM data: a full monolayer of O adatoms can be coadsorbed on CO-saturated W, but CO pre-adsorption inhibits the formation of W oxides. The β₁-O₂ (ESD active) state also forms on the CO-covered surface: this state is identical in population, ESD cross section and ion energy distribution to β₁-O₂ on clean W, and retains its identity in the mixed layer (it does not undergo isotopic exchange). CO₂ desorption spectra from the mixed layer were also characterised, complete isotopic scrambling being observed.Pre-exposure of tungsten to O₂ inhibits CO adsorption: a monolayer of O₂ is sufficient to prevent CO adsorption, and at low O₂ coverages, every O₂ molecule preadsorbed prevents one CO molecule from adsorbing. Isotopic exchange is again complete in the β states, and a lateral interaction model for desorption kinetics, based on dissociative adsorption in the β-CO state, quantitatively describes the CO desorption spectra.     

Oxygen adsorption on a Pd(111) surface

The interaction of oxygen with Pd(111) has been studied by means of AES, ELS, thermal desorption (TD), electron stimulated desorption (ESD) and work function measurements. It was found that a very small part ( ～ 2–3%) of the available adsorption sites are contributing to the O⁺ electron stimulated yield, the population of the latter being accompanied by enormously large work function changes (up to ～ 0.9 eV). A mechanism of adsorption and depopulation of these sites involving oxygen bulk and surface diffusion has been proposed.     

Electron stimulated desorption of oxygen from nickel

Electron Stimulated Desorption (ESD) of O⁺ ions from oxygen-covered Ni(100) has been investigated at 390 K and 500 eV primary energy. The ion energy distribution is found to peak at 7.5 eV and to extend to 11 eV, over our whole exposure range (0–1000 L). The 7.5 eV peak height as a function of exposure shows that desorption takes place both in the chemisorption and the oxidation region. Emission of O⁺ occurs preferentially along the surface normal, with a base width of ≈ 60°. No azimuthal structure is observed. Additional electron energy dependent measurements clearly show a threshold near the oxygen 2s level.     

Adsorption and coadsorption of carbon monoxide and hydrogen on Pd(111)

The adsorption and coadsorption of CO and H₂ have been studied by means of thermal desorption (TD) and electron stimulated desorption (ESD) at temperatures ranging from 250 to 400 K. Three CO TD states, labelled as β₂, β₁, and β₀ were detected after adsorption at 250 K. The population of β₂ and β₁ states which are the only ones observed upon adsorption at temperatures higher than 300 K was found to depend on adsorption temperature. The correlation between the binding states in the TD spectra and the ESD O⁺ and CO⁺ ions observed was discussed. Hydrogen is dissociatively adsorbed on Pd(111) and no ESD H⁺ signal was recorded following H₂ adsorption on a clean Pd surface. The presence of CO was found to cause an appearance of a H⁺ ESD signal, a decrease of hydrogen surface population and an arisement of a broad H₂ TD peak at about 450 K. An apparent influence of hydrogen on CO adsorption was detected at high hydrogen precoverages alone, leading to a decrease in the CO sticking coefficient and the relative population of CO β₂ state. The coadsorption results were interpreted assuming mutual interaction between CO and H at low and medium CO coverages, the “cooperative” species being responsible for the H⁺ ESD signal. Besides, the presence of CO was proved to favour hydrogen penetration into the bulk even at high CO coverage when H atoms were completely displaced from the surface.     

Theory of multiple-pass two-photon Doppler-free spectroscopy

Electron stimulated desorption (ESD) of CO on Ru (001) leads to emission of CO⁺ and O⁺ ions from the same adsorption states. Following earlier work on this system, a correlated study of its ESD behaviour together with LEED, Δϕ, and TPD measurments has been carried out. The filling of the two states found earlier can be seen in ESD also. The dividing line between the high and low energy states is different in room temperature adsorption on the one hand, and desorption or equilibrium measurements at elevated temperatures on the other, which is explained by incomplete attainment of equilibrium in the layer under the first condition. The behaviour of the ESD ion currents with coverage showstthat part of the molecules occupying high energy sites in the ordered layer of intermediate coverage are shifted to less favourable sites at higher coverage, so that the full layer consists of a mixture of states due to the occupation of different sites in the compressed layer, possibly accompanied by lateral interactions. ESD also suggests that the high energy sites are the on-top sites rather than the threefold sites.     

Electron-stimulated desorption of positive ions from hexagonal α-SiC

Electron-stimulated desorption (ESD) of positive ions (H⁺, O⁺, ⁺OH, F⁺ and Cl⁺) from the Si- and C-terminated surfaces of hexagonal α-SiC has been observed for electron energies in the 5–105 eV range. Comparison of these results with those for the ESD of the same ions from the surfaces of Si and condensed hydrocarbons leads to a model for the H⁺, ⁺OH, F⁺ and Cl⁺ threshold desorption process based on transitions from deep valence Si and C “s-like” levels to states in the conduction band, followed by Auger decay to form a localized multiple valence-hole configuration. O⁺ desorption, on the other hand, is initiated by O 2s ionization. Evidence is found for a strong dependence of the F⁺ threshold on the local chemical bonding. The results indicate that the thresholds for ESD of these ions from SiC are determined more by the electronic excitation of the substrate than by direct excitation of the adsorbate bond.     

Electron stimulated desorption of O+ ions: Energy dependence of the desorption efficiency from adsorbed oxygen on metal surfaces and its bearing on the mechanism

Measurements of the structure in the curve of desorption yield versus electron energy for ESD of O⁺ from β₁-oxygen on polycrystalline W and W(100), and from oxidized V are reported. They show definite structure around the core ionization thresholds of the metal atoms. This may be taken as evidence for the existence of Auger mechanisms of ESD, e.g. that proposed recently by Knotek and Feibelman for oxidic oxygen.     

Study of the sputtering of adsorbates by low energy ions (O on Ni)

Sputtering or ion impact desorption of adsorbed layers has been studied by low energy ion scattering and model calculations. For adsorption of a monolayer or less (e.g. oxygen on nickel) the desorption by ions can be readily observed by He⁺ ion scattering from the development of the adsorbate and substrate signal as a function of time. Desorption cross sections for Ne⁺ and He⁺ ions in the energy range from 500 eV to 1600 eV are given. These results are compared with the model calculations and the influence of various parameters can be studied by this comparison. The contribution of different processes to the sputtering mechanism is discussed.     

Electron induced ion desorption of oxygen adsorbed on rhenium

The behavior of low energy electron-stimulated O⁺ ions desorbing from oxygen adsorbed on polycrystalline rhenium samples has been found to be significantly different from those observed desorbing from other oxygen ad layers. Oxygen initially adsorbed at 300°K has an ionic desorption cross section below the level of detectability, (< 10⁻⁹ ions/electron) in these experiments, a result in accordance with that previously observed on other metals. On continued oxygen exposure, the O⁺ signal first increases to a maximum value and then decays to a lower level; the rate of both these processes is directly proportional to the oxygen pressure in the gas phase. If the temperature of the ad layer is raised above 300°K, the adsorbed species with high ionic desorption cross section are removed at about 500°K. At higher temperatures, O⁺ ions which can be related to the oxygen initially adsorbed are detected. The possible reasons for the observed O⁺ desorption characteristics for oxygen on rhenium are 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.     

Studies of adsorption and electron-induced dissociation of Fe(CO)5 on Si(100)

The adsorption and electron-stimulated decomposition properties of Fe(CO)₅ on Si(100) have been investigated. At substrate temperatures in the range 77–300 K, no chemisorption states are populated to a detectable extent. Physisorption at 77 K is observed, with a sticking probability of ≈ 0.2; TDS indicates that the heat of adsorption is constant at 33 ± 4 kJ mol⁻¹ both in the monolayer and multilayer regimes and the desorption kinetics are suggestive of island formation. Prominent electron-stimulated desorption (ESD) and decomposition effects have been investigated. Fe(CO)₅ multilayers decompose by rapid ESD of iron carbonyls, whilst monolayer decomposition involves the evolution of O and CO species in a stepwise manner from the parent molecule. Cross-sections for the processes occurring are evaluated; the electron stimulated rate of FeCO bond cleavage is demonstrated to be more rapid than the rate of escape of oxygen containing entities from the surface and this is explained in terms of bond orientation effects.     

Photon and electron stimulated desorption of adsorbates from W {100}

We have performed photon and electron stimulated desorption (PSD and ESD) studies of F⁺, Cl⁺ and O⁺ ions from a W {100} surface and have measured the kinetic energies for a small range of emission angles of these ions as well as the effect of different electron and photon excitation energies. We find that the PSD and ESD processes show essentially the same threshold energies and produce the same ion energy and angle distribution, and so evidently involve the same mechanism. For the case of O⁺ we also find clear evidence that substrate core-level excitation initiates the desorption process as proposed by Knotek and Feibelman for adsorbates bonded to surface atoms with a maximal valency configuration. The substrate levels are not seen to play a role in the F⁺ and Cl⁺ desorption, indicating a very different type of bonding for these species on the W surface.     

Theoretical study of the coadsorption of CO and O2 on doped cationic gold clusters MAun + (M = Ti, Fe, Au; n = 1, 6, 7)

We present a study based on first-principles calculations of the adsorption of CO on selected equilibrium configurations of MAu_nO₂ ⁺ (M = Ti, Fe; n = 1, 6, 7) complexes resulting from the adsorption of O₂ on doped cationic gold clusters MAu_n ⁺. Empirical rules for the formation of CO₂-MAu_nO⁺ complexes are outlined. The desorption energy of CO₂ is calculated. The adsorption of a second CO molecule on the residual MAu_nO⁺ complex leads in some cases to the formation of CO₂-MAu_n ⁺. The desorption of a second CO₂ molecule brings back to the initial doped gold cluster MAu_n ⁺.     

Study of lithium adsorption on the TiO2 surface by electron-stimulated desorption

This paper reports on a study of electron-stimulated desorption (ESD) of O⁺ and Li⁺ ions from titanium dioxide as a function of the preheating temperature T and of the concentration of lithium adsorbed at 300 K, which was carried out with a static magnetic mass spectrometer combined with a retarding-field energy analyzer. For T>1500 K, the TiO₂ surface undergoes irreversible rearrangement. At temperatures from 300 to 900 K and at lithium coverages Θ<1, the ESD cross sections of the O⁺ and Li⁺ ions vary in a reversible manner with temperature, while for lithium coverages Θ>1, the changes in the Li⁺ and O⁺ ESD cross sections become irreversible. For θ<1, the appearance threshold of the Li⁺ and O⁺ ions is 25 eV, whereas for θ>1, the ESD threshold of Li⁺ ions shifts to 37 eV.     

The effect of potassium on the molecular orientation of CO chemisorbed on Ni(111): An esdiad study

Using electron stimulated desorption (ESD) and electron stimulated desorption ion angular distribution (ESDIAD) techniques, we have determined that coadsorbed potassium systematically quenches the O⁺ ion yield from CO on the Ni(111) surface for 1000 eV electron excitation energies. The quenching appears to be a short range K-CO interaction; 3 or 4 CO molecules are affected for each K atom adsorbed on the surface. The quenching effect of K on CO indicates that a significant electronic perturbation of CO is caused by its local interaction with K. This effect prevents ESDIAD observation of the K-quenched CO species. In addition, the CO molecules that are not quenched at a potassium coverage of 0.02 K/Ni exhibit a normally oriented C-O bond similar to that found for CO adsorbed on a K-free Ni(111) surface.