Secondary electron spectroscopy of platinum and carbon surfaces

The surfaces of platinum single crystals, of carbon deposits on platinum and of pyrographite are examined by secondary electron spectroscopy under 100 eV electron excitation. The spectra contain characteristic peaks in the range 0–30 eV, which are interpreted as band-like in origin. The effects of gas adsorption, of the reconstruction at Pt(100), of the temperature and of ion bombardment induced disorder are reported. The secondary electron spectrum provides a criterion for distinguishing between amorphous and graphitic carbon surfaces. By contrast with the Auger spectrum, it is sensitive to the degree of crystalline order at the surface over distances of 10–100Å.     

Auger electron spectroscopy of cesium adsorbed on clean and oxygen covered (100) tungsten

Auger electron spectroscopy of cesium adsorbed on clean W(100) shows that the well known N_4,5O_2,3O_2,3 peak can be resolved into three peaks at 43–45.8 and 48.4 eV. Simultaneously as well defined peak appears at 62 eV and it is shown that this transition involves ionization of the N₄N₅ cesium level. An additional peak appears at 56.5 eV as cesium adsorbs on a previously oxygen-covered W(100) surface. Its existence is discussed and might indicate that oxygen valence electrons are involved in this new transition.     

The adsorption of nitric oxide on a silicon (100) 2 × 1 surface studied with Auger electron spectroscopy

We present an Auger electron spectroscopy (AES) study of the adsorption of nitric oxide (NO) on a clean Si(100)2 × 1 surface at 300 and 550 K. Accurate measurement reeveal well resolved fine structure at Auger SiL_2.3VV transitions at 62 and 83 eV. These peaks can be attributed to SiO and SiN bonds. Furthermore, it is argued that the broadening in the SiLi_2.3VV Auger transition at 83 eV at 300 K may be composed of two nearby peaks, which could be attributed to two different kinds of chemical bonding, SiN and SiO. The absence of a peak at 69 eV at room temperature strongly suggests the NO adsorption on a Si(100)2 × 1 surface to be molecular. Dissociation of NO on the Si(100)2 × 1 surface is observed at 550 K.     

Characteristic energy losses on carbon contaminated layers correlated with secondary electron,auger electron emission and contrasts in scanning microscope

The secondary electron (SE) spectrum (0 < E < 50 eV) has been analysed by means of a CMA. Samples were clean aluminum, aluminum becoming carbon contaminated, sintered graphite powder, electro chemically deposited polymer on platinum and monocrystals of silicon carbon contaminated. When the clean Al surface is becoming carbon contaminated a quick decrease of surface plasmon and bulk plasmon losses is observed whereas a main characteristic energy loss peak (ELS) at 20 eV and a secondary electron peak at 20 eV appear simultaneously. Both peaks are very sensitive general features of carbon contaminated surfaces. The main loss peak is attributed to the excitation of the carbon-carbon bounds (σ → σ¹) as already proposed in the transmission ELS. The few eV change of the loss peak energy of various carbon compounds may correspond to slightly different carbon-carbon distances. The 20 eV secondary electrons could be produced by the relaxation of the excited state (σ¹ → σ transition) via an Auger process. The cross section for molecular electronic excitation is higher than that of atomic ionization for inner level. The loss peak is as intense as the SE peak and higher by more than two orders of magnitude than the C KLL Auger peak. The modification of secondary emission under carbon contamination has been observed on a silicon sample by Scanning Electron Microscopy (SEM) in the Secondary Electron Image (SEI) mode.     

A study of the charging and dissociation of SiO2 Surfaces by AES

AES is used to determine the initial spectrum of a vacuum-broken SiO₂ surface and to follow its dissociation under the electron beam probe. Both Auger peaks heights and energies are affected by the irradiation. The change in stoichiometry is accompanied by a decrease of the surface charge by 5–8 V. The relation between stoichiometry and charge is explained by the influence of radiation-induced defects on secondary electron emission. The reduction of SiO₂ is characterized in terms of irradiation dose, dissociation cross-section and electron impact efficiency. Resistance to radiation damage is increased by surface carbon contamination. The chemical contribution to the Auger peak energy can be distinguished from the charging effect leading to a shift between element and compound of 12 eV for the silicon peak.     

Auger-spectrum simulation techniques for surface analysis of alloys with overlapping peaks: sputtered and annealed W—Mo alloys

The surface composition of a 50% W—Mo alloy has been investigated using Auger electron spectroscopy. Problems arising from carbon contamination and the strong overlap of the intense, surface-sensitive low-energy Auger peaks have been solved. Spectra for the alloy were collected digitally and could be simulated satisfactorily using pure-element spectra. The steady-state surface composition under 500 V Ar⁺ ion bombardment shows an enrichment of the surface in W, caused by preferential Mo sputtering. It is observed that the surface composition is uniform over the range of escape depths of the Auger electrons. This is consistent with enhanced diffusion and mixing over the penetration depth of the bombarding Ar⁺ ions. On annealing, the W-enriched sputtered surface becomes Mo-enriched, consistent with surface segregation of the more weakly bonded Mo atoms. However, in contrast with the sputtered surface, it is observed that a single simulation over the range of Auger-electron energies is not possible. The Mo enrichment indicated is largest for the 120 eV peak and decreases with increasing energy (escape depth), becoming a minimum at 220 eV. This is consistent with a monolayer segregation model, which is tested using published values for electron inelastic mean free paths. The calculated monolayer composition is x_Mo 0.94, in agreement with the predicted ideal-solution values of 0.98 ± 0.02 for different orientations.     

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.     

High resolution Auger electron spectroscopy of metallic copper

Part of the LMM Auger spectrum from metallic copper has been studied in a high resolution X-ray photoelectron spectrometer. Fine structure not earlier reported has been observed. The main L₃M_4,5M_4,5 peak is very narrow, 1.0 eV, although the valence band is involved in the transition. The agreement between experimental and calculated Auger electron energies is very good. Since fine structure is found to be an intrinsic property in Auger spectra the interpretation of “satellite” peaks as due to electron—plasmon interactions should be used with care. The L₃M_4,5M_4,5 peak is very sensitive to the copper surface conditions. Surface oxygen affects the peak in a characteristic way.     

Study of the chemical bonding of titanium with silicon and oxygen by AES and SEELS

Auger electron Spectroscopy (AES) and slow electron energy loss Spectroscopy (SEELS) have been employed to study the electronic structure of Ti, TiSi₂ and TiO₂. The changes in the Auger and loss spectra when Ti chemically binds with silicon to form TiSi₂ and with oxygen to form TiO₂ have been understood as manifestations of changes in electronic participation. AES spectra show distinct changes in line shapes of transitions involving the Ti valence electrons. The SEELS spectra provide information regarding shallow core levels, valence band and the collective excitation energies of the volume and surface plasmons. By monitoring the changes in the Auger peak at 387 eV and the 3p→ 3d quasiatomic transition (at about 45 eV), the role of d-orbital occupancies are studied in Ti and its compounds. The SEELS studies in the 0-80 eV range have enabled the authors to observe the behaviour of the 3p → 3d quasiatomic transition in Ti, which persists after oxidation but almost disappears during TiSi₂ formation. The values of the plasmon losses are related to the collective behaviour of conduction electrons.     

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 gold-palladium binary alloy system

The surface composition of the AuPd alloy system has been determined by Auger electron spectroscopy. Measurements were performed on polished polycrystalline alloy foils. After cleaning, the intensities of the 71 eV and 2024 eV gold Auger transitions, and the intensity of the 330 eV palladium transition were measured, and then converted to atom concentrations in the surface layer. The surfaces of the annealed samples were found to be significantly enriched in gold with respect to the bulk. This result disagrees with the regular solution theory prediction. After extensive sputtering of the AuPd alloys with 1.5 keV Ar⁺ ions, a slight surface enrichment with palladium was found, as predicted by the simple theoretical model for sputtering.     

Observation of extrinsic surface states on (112&#x0304;0) CdS

Surface states have been detected by surface photovoltage spectroscopy on (112&#x0304;0) CdS surfaces subjected to various treatments in UHV and studied by Auger electron spectroscopy and LEED. All surface electronic features can be related to chemical contamination or lattice nonstoichiometry. Energy level spectra of air-exposed CdS exhibit a set of discrete states due to adsorption of C, O, and Cl. Ion bombardment generates a pair of states 2.35 eV and ~0.8 eV above the valence band edge due to S interstitials and vacancies, respectively. Oxygen adsorption produces a broad continuum of states. Changes in surface atomic order show no direct effect on these electronic features. No intrinsic surface states, filled or empty, are observed by surface photovoltage spectroscopy on clean, stoichiometric (112&#x0304;0) faces of CdS.     

Stability of ZnO{0 0 0 1} against low energy ion bombardment

The steady-state surface compositions of the polar (O and Zn terminated) faces of ZnO{0 0 0 1} produced by low energy (0.3-2 keV) Ar⁺ ion bombardment were studied by Auger electron spectroscopy and electron energy loss spectroscopy. The alterations produced by the ion bombardment using different ion energies were monitored by calculating the intensity ratios of the low and high energy Zn Auger peaks (59 eV and 994 eV, respectively); Zn and O Auger peaks (59 eV and 510 eV, respectively). Based on the dependence of these ratios on the ion energy and termination of the surface, we could conclude that the stability of the Zn face is higher against the low energy argon ion bombardment-induced compositional changes than that of the O face.     

Design of an Auger Electron Mössbauer Spectrometer (AEMS) using a modified cylindrical mirror analyzer

We have designed and built an Auger Electron Mössbauer Spectrometer (AEMS) for the detection of resonant ⁵⁷Fe Auger electrons using a modified commercial cylindrical mirror analyzer (CMA). The CMA final aperture was modified intentionally in order to increase electron transmission at the expense of reducing its energy resolution, from an original value of 0.5 % to a value of 11 % after the modification. The Channeltron detector electronics and the pre-amplifier were also modified in order to increase the counting efficiency. The electron energy analyzer is selective in energy in the 30 eV–3000 eV range, so the spectrometer can be used to detect MNN (45 eV) and LMM (600–700 eV) Fe Auger signals, what gives it a high surface sensitivity for Fe containing samples. We have used it to acquire the Fe LMM Auger signals generated from the de-excitation process after γ-Ray resonant nuclear absorption. The spectrometer can be used to study samples non-enriched in ⁵⁷Fe, with acquisition times from 5 to 7 days, what is a big advantage. From electron trajectory Monte Carlo simulations in metallic iron, the mean-escape-depth of the detected Auger signals has been estimated in approximately 1 nm. Fe K conversion electrons and KLL Auger electrons with mean escape depths of 129 nm and 78 nm respectively also contribute to the detected signal although in a lesser proportion.     

Some aspects of auger electron spectra of 3d transition metal oxides

Auger electron spectra of the transition metals Cr, Mn, Fe, Co and Ni as well as their oxides have been investigated in the energy range between 0–100 eV. In each case of the clean metal surface the observed spectrum consists essentially of one Auger line identified asM _2,3 VV transition. After oxidation a line doublet is observed revealing two transitions instead of one. Additional new Auger peaks appear in the low energy range between 0–30 eV. The “splitting” of the Auger line can be explained as resulting from aM _2,3 V _dV_d and aM _2,3 V _pV_p transition. The latter is characteristic for the compound and can in a simple way be interpreted as a cross transition.     

LEED and Auger investigations of Cu (111) surface

After ultrahigh vacuum bake-out, electropolished Cu (111) surfaces were shown by Auger analysis to be contaminated by C, N, O, S and Cl. Other than C and S, which were contained in the bulk, the impurities were introduced by surface preparation; but all were easily removed by light Ar ion bombardment. Heating to ≈ 750°C caused diffusion of C and S from the bulk to the extent that a clear diffraction pattern corresponding to a √7 × √7 structure was produced by S on the surface. At ≈ b 900°C evaporation of Cu occurred to an observable degree, and S and C could no longer be detected on the surface. Auger analysis of clean Cu surfaces showed many details of the LMM and MMM types of transitions. Kinetic energies of all observed Auger electrons were in excellent agreement with calculated values. Also, the ≈ 62 eV MMM peak was resolved into two components related to the small differences in the M₂ and M₃ energy levels. The LMM transitions were classified according to their intensities, which could be rationalized on the basis of Coster-Kronig transitions and transition probabilities, as L₃MM > L₂MM > L₁MM.     

Auger and direct electron spectra in X-ray photoelectron studies of zinc,zinc oxide,gallium and gallium oxide

Auger and direct electron spectra from Zn, ZnO, Ga and Ga₂O₃ have been studied with X-ray photoelectron spectroscopy (ESCA). The chemical shift between zinc electron binding energies in Zn and ZnO is very small, whereas the zinc Auger electron signals are separated by 4.3 eV. In gallium, the oxide and metal signals are separated by 1.9 eV, but the Auger electron energy shift is three times as large. Thus the Auger signals are more sensitive to the chemical environment than the direct electron signals, which is the same relation as earlier observed for copper and copper oxides.     

Molecular and atomic oxygen adsorption on the kinked Pt(321) surface

Oxygen adsorption and desorption were characterized on the kinked Pt(321) surface using high resolution electron energy loss spectroscopy, thermal desorption spectroscopy and Auger electron spectroscopy. Some dissociation of molecular oxygen occurs even at 100 K on the (321) surface indicating that the activation barrier for dissociation is smaller on the Pt(321) surface than on the Pt(111) surface. Molecular oxygen can be adsorbed at 100 K but only in the presence of some adsorbed atomic oxygen. The dominance of the v(OO) molecular oxygen stretching mode in the 810 to 880 cm^?1 range indicates that the molecular oxygen adsorbs as a peroxo-like species with the OO axis parallel or nearly parallel to the surface, as observed previously on the Pt(111) surface [Gland et al., Surface Sci. 95 (1980) 587]. The existence of at least two types of peroxo-like molecular oxygen is suggested by both the unusual breadth of the v(OO) stretching mode and breadth of the molecular oxygen desorption peak. Atomic oxygen is adsorbed more strongly on the rough step sites than on the smooth (111) terraces, as indicated by the increased thermal stability of atomic oxygen adsorbed along the rough step sites. The two forms of adsorbed atomic oxygen can be easily distinguished by vibrational spectroscopy since oxygen adsorbed along the rough step sites causes a v(PtO) stretching mode at 560 cm^?1, while the v(PtO) stretching mode for atomic oxygen adsorbed on the (111) terraces appears at 490 cm^?1, a value typical of the (111) surface. Two desorption peaks are observed during atomic oxygen recombination and desorption from the Pt(321) surface. These desorption peaks do not correlate with the presence of the two types of adsorbed atomic oxygen. Rather, the first order low temperature peak is a result of the fact that about three times more atomic oxygen can be adsorbed on the Pt(321) surface than on the Pt(111) surface (where only a second order peak is observed). The heat of desorption for atomic oxygen decreases from about 290kJ/mol (70 kcal/mol) to about 196 kJ/mol (47 kcal/mol) with increasing coverage. Preliminary results concerning adsorption of molecular oxygen from the gas phase in an excited state are also briefly discussed.     

A study of the adsorption of oxygen on Ni(111) using auger electron spectroscopy: Chemical shifts and valence spectra

Auger electron spectra have been recorded when oxygen is adsorbed on a Ni(111) single crystal surface. For the coverage range θ < 1, an analysis of the plot of the peak to peak height (H) of the oxygen KVV (516 eV) transition versus the total number of molecules cm^2? impinging on the surface (molecular beam dosing) shows agreement with the kinetic mechanism proposed by Morgan and King [Surface Sci. 23 (1970) 259] for the adsorption of oxygen on polycrystalline nickel films. In this coverage range, no energy shifts of the nickel or oxygen Auger peaks were recorded.At coverages θ > 1 (standard dosing procedure) shifts in the valence spectra M_{2, 3}VV (61 eV) and L₃M_{2, 3}V (782 eV) of ?2.3 eV and ?1.8eV respectively are recorded at 1.4 × 10^?2 torr-sec. Up to these coverages no shift of the L₃VV transition (849 eV) is observed. A chemical shift of ?2.1 eV is recorded in the L₃M_{2, 3}M_{2, 3} Auger transition (716 eV) at 1.4 × 10^?2 torr-sec.In the coverage range θ > 1, shifts in the energy of the oxygen Auger peaks are observed. At 5.8 × 10^?3 torr-sec. the KVV (516 eV) and KL₁V (495.2 ± 0.3 eV) transitions show shifts of ?1.5 eV and ?(1.0 ±0.3) eV respectively. No shift up to this coverage is recorded in the KL₁L₁ (480.6 ± 0.3 eV) transition.     

An Auger and X-ray photoelectron spectroscopic study of sodium metal and sodium oxide

Photoelectron and Auger electron measurements have been made on polycrystalline films of sodium metal evaporated in ultra high vacuum, and on Na₂O produced by in-situ oxidation by dry oxygen. Most of the spectra were recorded using Mg Kα (1254 eV) radiation but excitation by 5 keV electrons or monochromatized Al Kα (1487 eV) X-rays was used for specific purposes. Core and valence electron binding energies, photoionization cross-sections relative to Na 1s, KLL and KLV Auger energies and transition probabilities are reported. Energy losses in the metal and oxide are discussed and the relative intensities of surface and bulk plasmon losses have been used to calculate mean electron escape depths in the metal. When corrections were made for experimental geometry, escape depths of 10 Å at 180 eV and 31 Å at 1200 eV were obtained. An escape depth of 23 Å at 980 eV was obtained by Na 1s-Na K-Auger intensity correlation and this is consistent with the plasmon data. Data on Auger satellite lines are presented and, in particular, evidence has been obtained which indicates that a high energy satellite should not be attributed to a plasmon gain mechanism. Valence band influences on the KLV Auger spectra are discussed with reference to the XPS spectrum and other sources of valence band information. Unexpected structure was found in the KLV spectra of the metal which, pending thorough interpretation, offsets the sensitivity and resolution advantages which these spectra otherwise offer for valence band studies.