Untersuchung über den einfluss von adsorbierten gasen auf die elektronen-energieverlust-spektren einer Ni(110)-oberfläche

Electron energy loss spectra on a (110) nickel surface exhibit characteristic changes upon adsorption of H₂, CO and O₂. The clean surface shows only the surface and bulk plasmon losses at 8 eV and 18 eV respectively. Adsorption of CO produces two new loss peaks at 13.5 eV and 5.5 eV. Loss peaks due to hydrogen adsorption at 15 eV and 7.5 eV show a strong correlation with the well known adsorption characteristics of this system. The oxygen induced losses are different for chemisorbed O on Ni and NiO. In any case the chemisorption-induced losses are well established for primary energies below 120eV. In the loss spectra with higher excitation energies only a drastic decrease of the surface plasmon loss peak-height is visible. If the new losses can be attributed to one-electron excitations from molecular orbital levels due to the chemisorption bond, with assumptions of the final state of the excited electron a determination of the postition of these levels can be made. In case of CO and H₂ reasonable results are evaluated.     

Electron energy-loss spectra of clean and gas-covered Ni(100) surfaces

Electron energy-loss spectra have been measured on Ni(100) surfaces, clean and following oxygen and carbon monoxide adsorption, at primary energies of 40–300 eV. The observed 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 electron, respectively, and the weak but sharp peak at 33 eV is tentatively attributed to the localized many-body effect in the final state. Assignments of the loss structures on the gas-covered surfaces have been attempted.     

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.     

Scandium and lutetium surfaces studied by reflection electron energy-loss spectroscopy

The reflection electron energy-loss spectra of the (1 0 0) and (0 0 1) surfaces of Sc single crystals and the (0 0 1) surface of a Lu single crystal have been studied with primary energies in the range 50–2000 eV. Scandium is congeneric with lutetium and the loss spectra of the two elements are very similar in both the collective excitations and the interband transitions. Strong excitations observed at around 41 eV are attributed to 3p → 3d and 5p → 5d transitions in Sc and Lu, respectively. The loss data of Sc fit the characteristic energy-loss data of the other elements of the first group of transition metals. Oxygen adsorption and nitrogen adsorption on the (1 0 0) surface of Sc influence the loss spectra. The observed differences are correlated with density-of-states calculations for Sc, ScO and ScN.     

Plasmon effects in electron energy loss and gain spectra in aluminium

Oberservations of the low energy secondary and Auger electron spectra and the electron energy loss spectra from a clean aluminium surface have been made and the results are compared with other recent studies including that of Jenkins and Chung (1971). Low energy emissions at 5.7 eV and 10.3 eV are associated with the creation of single electron excitations in the valence band by plasmon decay. An apparent anomaly in the plasmon loss and gain peaks associated with the Auger spectrum is discussed.     

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.     

Electron energy loss spectroscopic investigation of palladium metal and palladium(II) oxide

Electron energy loss spectra (ELS) obtained from polycrystalline Pd metal and PdO powder using primary electron energies ranging from 100 to 1150 eV have been obtained and examined in an attempt to gain a better understanding of the origins of the loss features and to assess the utility of ELS in investigations of Pd catalysts. The two sets of ELS spectra differ significantly. The ELS spectra from Pd metal exhibit a predominant peak at 6.5 eV, shown to arise from a surface plasmon excitation, and two broad features at 25.1 and 31.9 eV, which originate from bulk loss processes. The broad features consist of several overlapping losses due mainly to interband transitions from the d-band, though a bulk plasmon excitation is believed to produce a feature near 24 eV. Two distinct peaks are present at 3.7 and 7.6 eV in the ELS spectra obtained from PdO, while a broad region of intensity appears over the range from 20 to 40 eV. The peak at 3.7 eV is attributed to a transition between the top of the valence band and the bottom of the conduction band. The feature at 7.6 eV is broad and arises from several overlapping features that are most likely caused by interband transitions rather than collective excitations. Furthermore, the ELS spectra obtained from PdO and oxidized Pd are also quite different indicating that ELS can provide useful information for determining the bonding states of oxygen on Pd-containing catalysts.     

Electron energy-loss spectra of clean and hydrogen-covered Cr(110) surfaces

Electron energy-loss spectra of clean and hydrogen-covered Cr(110) surfaces have been investigated in the spectral range of 0–80 eV for primary energies of 60–500 eV. The observed peaks for the clean surface are at the loss energies of 2, 3.5, 5.5, 9.6, 23, 35, 42, 48 and 55 eV. The 3p-excitation spectra for high primary energies (> 250 eV) are in good agreement with the corresponding optical spectrum. The edge at & 42 eV observed for low primary energies is tentatively attributed to the onset of the transition from the 3p subshell to the local 4s-band in the vicinity of the core hole. A characteristic energy-loss at ≈ 15.5 eV is observed after hydrogen adsorption. The 3p-spectrum is not influenced by hydrogen adsorption, indicating that the excitation is of a localized character.     

Reflectometric study of surface states and oxygen adsorption on clean Si(100) and (110) surfaces

External differential reflection measurements were carried out on clean Si(100) and (110) surfaces in the photon energy range of 1.0 to 3.0 eV at 300 and 80 K. The results for Si(100) at 300 K showed two peaks in the joint density of states curve, which sharpened at 80 K. One peak at 3.0 ± 0.2 eV can be attributed to optical transitions from a filled surface states band near the top of the valence band to empty bulk conduction band levels. The other peak at 1.60 ± 0.05 eV may be attributed to transitions to an empty surface states band in the energy gap. This result favours the asymmetric dimer model for the Si(100) surface. For the (110) surface at 300 K only one peak was found at 3.0 ± 0.2 eV. At 80 K the peak height diminished by a factor of two. Oxygen adsorption in the submonolayer region on the clean Si(100) surface appeared to proceed in a similar way as on the Si(111) 7 × 7 surface. For the Si(110) surface the kinetics of the adsorption process at 80 K deviated clearly. The binding state of oxygen on this surface at 80 K appeared to be different from that on the same surface at 300 K.     

Low-energy electron energy-loss spectroscopy with Ge:GaAs (110) heterostructures

Electronic properties and chemical composition of Ge films grown by molecular beam epitaxy on GaAs (110) surfaces were studied in situ by electron energy-loss spectroscopy. The loss peaks involving core-level excitations proved that As atoms segregate at the surface of the growing film. The well known 20 eV loss peak of the clean GaAs (110) surface, being attributed to transitions from Ga(3d) to Frenkel-type excitons of dangling-bond surface states, was found to persist, slightly shifted to 19.7 eV, with the growing Ge (110) film. Since the Ga coverage amounts to below approximately 0.05 of a monolayer this transition seems to contain a strong intraatom contribution.     

Interaction of oxygen and CO with thin Ag films at AgTi2 substrates

Clean Ag overlayers with a thickness of about three atomic layers are prepared at polycrystalline AgTi₂ surfaces. Adsorption of oxygen and CO at these overlayers is studied with AES, UPS, and TDS methods. UP spectra reveal that oxygen adsorbs dissociatively on the surface of the Ag overlayers at 120 K, similar as at the surfaces of bulk Ag crystals. At higher temperatures, O atoms diffuse into the overlayer and get trapped at Ti at the interface underneath the Ag layer. Unlike at bulk Ag, oxygen adsorption proceeds with high sticking probability, which is attributed to a reduced activation barrier. CO adsorbs at the Ag overlayers in a weakly chemisorbed state with an adsorption energy of ca. 9 kcal/mol, whereas at bulk Ag true physisorption has been observed. Accordingly, UP spectra of CO adsorbed at 120 K exhibit well separated 4σ, 1π and 5σ emission peaks at energetic positions which are essentially different from the CO/Ag physisorption system. This observation is interpreted as a demonstration of the ligand effect, i.e., the activation of weak CO bonding at Ag by strong bonding Ti.     

Low energy electron diffraction and electron spectroscopy studies of the clean (110) and (100) titanium dioxide (rutile) crystal surfaces

Low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), electron energy loss (ELS) and ultraviolet photoemission spectroscopies (UPS) were used to study the structures, compositions and electron state distributions of clean single crystal faces of titanium dioxide (rutile). LEED showed that both the (110) and (100) surfaces are stable, the latter giving rise to three distinct surface structures, viz. (1 × 3), (1 × 5) and (1 × 7) that were obtained by annealing an argon ion-bombarded (100) surface at ~600,800 and 1200° C respectively. AES showed the decrease of the $\text{O(510 eV)}\text{Ti(380 eV)}$ peak ratio from ~1.7 to ~1.3 in going from the (1 × 3) to the (1 × 7) surface structure. Electron energy loss spectra obtained from the (110) and (100)?(1 × 3) surfaces are similar, with surface-sensitive transitions at 8.2, 5.2 and 2.4 eV. The energy loss spectrum from an argon or oxygen ion bombarded surface is dominated by the transition at 1.6 eV. UPS indicated that the initial state for this ELS transition is peaked at ?0.6 eV (referred to the Fermi level E_F in the photoemission spectrum, and that the 2.4 eV surface-sensitive ELS transition probably arises from the band of occupied states between the bulk valence band maximum to the Fermi level. High energy electron beams (1.6 keV 20 μA) used in AES were found to disorder clean and initially well-ordered TiO₂ surfaces. Argon ion bombardment of clean ordered TiO₂ (110) and (100)?(1 × 3) surfaces caused the work function and surface band bending to decrease by almost 1 eV and such decrease is explained as due to the loss of oxygen from the surface.     

The surface composition of the nickel-copper alloy system as determined by Auger electron spectroscopy

The Ni-Cu alloys were prepared by evaporation of the specpure metals in UHV onto a quartz substrate. Spectra were obtained from clean as well as from gas covered surfaces. The Auger signal intensity of a monolayer of both metals was determined for the low energy electrons (102–105 eV) and for the high energy electrons (716–920 eV). The overlapping peaks of Cu and Ni in the low energy region (102–105 eV) were evaluated by comparing them with computer simulated alloy spectra. The results of the sintered alloys are interpreted by means of a model by Gallon and Jackson, using the experimentally determined signal intensity of a monolayer. Several surface enrichment data were used to predict the experimentally observed Auger signal intensities. A clear indication of surface enrichment of Cu was obtained; this is in good agreement with previous conclusions based upon hydrogen adsorption and work function measurements. An explanation is suggested why previous work with AES and CO chemisorption did not reveal any surface enrichment.     

Quantitative Auger electron spectroscopy analysis with co-evaporated AuCu films

A method for the quantitative Auger electron spectroscopy (AES) analysis by using a co-evaporation technique is extended to the AuCu system following the previous work. The calibration curves for lower Auger energy have peaks at 60 eV for Cu and at 69 eV for Au, and for higher Auger energy peaks at 239 eV for Au and at 920 eV for Cu. It is found that a simple linear relation does not exist in the results for AES measurements and the bulk analysis by atomic absorption spectroscopy (AAS) because of the back-scattering effect and the overlap of the spectra at lower energies in the Au-Cu system. It is also found that the adsorption of oxygen caused by electron beam bombardment has a significant influence on the AES results. The calibration curves obtained after a correction for oxygen adsorption are successfully applied to the determination of the composition at the surface of a sputtered AuCu alloy.     

Valence band of molybdenum by photoelectron spectroscopy

Experimental photoelectron spectra of a clean polycrystalline Mo surface excited by monochromatized Al K _α X-rays are presented. The spectra are compared with valence bands obtained by UPS and by band structure calculations within the 5 eV region below the Mo Fermi level. All results mentioned above display peaks at 0.3, 1.7, 2.8 and 4 eV belowE _F. The energy distribution of the valence band does not vary with photon energy and electron emission angle for the four different polycrystalline Mo surfaces compared. It is concluded that the four peaks representing the Mo valence band are predominantly of bulk origin.     

The adsorption of oxygen and carbon monoxide on cleaved polar and nonpolar ZnO surfaces studied by electron energy loss spectroscopy

Electron energy loss spectroscopy (ELS) with primary energies e₀ ? 80 eV has been performed on ultrahigh vacuum (UHV) cleaved nonpolar (11?00) and polar zinc (0001) and oxygen (0001?) surfaces of ZnO to study the adsorption of oxygen and carbon monoxide. Except for CO on the nonpolar surface where no spectral changes in ELS are observed a surface transition near 11.5 eV is strongly affected at 300 K on all surfaces by CO and O₂. At 300 K clear evidence for new adsorbate characteristic transitions is found for oxygen adsorbed on the Zn polar surface near 7 and 11 eV. At 100 K on all three surfaces both CO and O₂ adsorb in thick layers and produce loss spectra very similar to the gas phase, thus indicating a physisorbed state.     

Probing the electronic structure of ZnO nanowires by valence electron energy loss spectroscopy

Valence electron energy loss spectroscopy in a transmission electron microscope is employed to investigate the electronic structure of ZnO nanowires with diameter ranging from 20 to 100 nm. Its excellent spatial resolution enables this technique to explore the electronic states of a single nanowire. We found that all of the basic electronic structure characteristics of the ZnO nanowires, including the 3.3 eV band gap, the single electron interband transitions at approximately = 9.5, approximately = 13.5,and approximately = 21.8 eV, and the bulk plasmon oscillation at approximately 18.8 eV, resemble those of the bulk ZnO. Momentum transfer resolved energy loss spectra suggest that the 13.5 eV excitation is actually consisted of two weak excitations at approximately = 12.8 and approximately = 14.8 eV, which originate from transitions of two groups of the Zn 3d electrons to the empty density of states in the conduction band, with a dipole-forbidden nature. The energy loss spectra taken from single nanowires of different diameters show several size-dependent features, including an increase in the oscillator strength of the surface plasmon resonance at approximately = 11.5 eV, a broadening of the bulk plasmon peak, and splitting of the O 2s transition at approximately = 21.8 eV into two peaks, which coincides with a redshift of the bulk plasmon peak, when the nanowire diameter decreases. All these observations can be well explained by the increased surface/volume ratio in nanowires of small diameter.     

Anomalous oxidation properties of the ZnSe (100) surface

We have observed a unique, pressure-dependent adsorption isotherm of oxygen on the ZnSe (100) surface, which consists of an unmeasurable uptake followed by an irreversible, step-like uptake for pressures exceeding a critical value of ～ 0.08 torr at room temperature. A partial depletion of Se accompanies this adsorption process. For incomplete oxidation, oxygen induced (2 × 1) and (3 × 1) surface reconstructions may be generated, the first such structures to be observed for semiconductors. The electron-energy-loss spectra for these surfaces and for the clean ZnSe (100)c(2 × 2) surface are presented. The clean surface exhibits a dangling-bond-derived empty surface state ～ 1 eV above the conductor band edge, and filled surface states near 3.2, 6.5, and 15 eV below the valence band edge.     

Electronic transitions on UHV-cleaved Si (111) adsorbed with oxygen

The electron energy loss spectra have been measured of oxygen-adsorbed Si (111) surfaces at the primary energies of 10–200 eV. The observed peaks are at the loss energies of 2.9, 3.6, 4.8, 5.7, 6.9, 8.2, 9.6, 12.0, and 13.0 eV. All the peaks are attributed to the one-electronic transitions related to the adsorbed oxygen, except for the 9.6 eV peak which could possibly be due to the relaxed surface plasmon excitation. It is shown that the “splitting” of surface plasmon reported by Ibach and Rowe does not exist.     

Reaction of oxygen with gallium surfaces

The adsorption of oxygen molecules on evaporated gallium films has been studied by UV photoelectron spectroscopy between 10 and 300 K. In addition to the oxygen levels, the chemical shift of the Ga 3d core level has been investigated using monochromatized light from a He discharge lamp at ?ω = 40.8 eV. Four different states of oxygen have been found depending on temperature. At 10 K the molecules of the first layer are physisorbed onto which several additional layers can be condensed. The rigid relaxation shifts to smaller binding energies are 2.7 eV for physisorbed and 1.3 eV for condensed oxygen. During warming-up the oxygen reacts with the gallium surface. Between 70 and 130 K an oxygen species develops which is interpreted as chemisorbed molecular oxygen. This is concluded from the valence band UP spectra, the chemical shift of the Ga 3d level, and the work function change. At 300 K oxygen is dissociatively bound and the bulk oxide grows.