Variation of electron energy loss spectra of Ni (100) with increasing primary energy

Electron energy loss spectra of clean Ni(1 0 0) show for the first time a 17 eV peak, which is attributed to an interband transtiion. All the observed peaks are shifted to higher energies as the primary electron energy E_p increases from 102 to 2045 eV. This shift is explained by a continuous decay in energy of the primary electrons inside the crystal. At E_p ? 700 eV, the decay takes place in the surface region of the crystal, while at E_p > 700 eV it takes place mainly in the bulk. The rate of decay increases with increasing temperature of the crystal between 300 and 900 K.     

The adsorption of CO on Cu surfaces studied by electron energy loss spectroscopy

Electron energy loss spectroscopy (ELS) in the energy range of electronic transitions (primary energy 30 < E₀ < 50 eV, resolution ΔE ≈ 0.3 eV) has been used to study the adsorption of CO on polycrystalline surfaces and on the low index faces (100), (110), (111) of Cu at 80 K. Also LEED patterns were investigated and thermal desorption was analyzed by means of the temperature dependence of three losses near 9, 12 and 14 eV characteristic for adsorbed CO. The 12 and 14 eV losses occur on all Cu surfaces in the whole coverage range; they are interpreted in terms of intramolecular transitions of the CO. The 9 eV loss is sensitive to the crystallographic type of Cu surface and to the coverage with CO. The interpretation in terms of d(Cu) → 2π¹(CO) charge transfer transitions allows conclusions concerning the adsorption site geometry. The ELS results are consistent with information obtained from LEED. On the (100) surface CO adsorption enhances the intensity of a bulk electronic transition near 4 eV at E₀ < 50 eV. This effect is interpreted within the framework of dielectric theory for surface scattering on the basis of the Cu electron energy band scheme.     

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.     

Energy loss mechanisms in low energy electron scattering from W(100) and their use as a surface sensitive spectroscopy

The energy loss spectrum of low energy (0 < E_p < 200 eV) electrons scattered from W(100) has been experimentally investigated, and mechanisms giving rise to the fine structure analyzed using a dielectric response formalism. The dielectric medium is characterized by available optical data and energy band calculations for tungsten. All of the structure for loss energies, w, less than 18 eV is attributed to intra- and interband transitions involving the bulk valence and conduction bands. The surface and bulk plasmon excitations are observed at w = 21 eV and w = 25.5 eV respectively which is in reasonable agreement with the optical data. A very narrow peak in the density of conduction d-band states apparently functions strongly in well defined excitations involving the $\text{5p}\text{3}\text{2}$ and 4f tungsten orbitais and the 2s and 2p orbitais of adsorbed oxygen. These conduction band states form a “window” with which to measure the electronic orbital structure of both the substrate and adsorbate during adsorption and reaction. We demonstrate this for the room temperature adsorption of oxygen on W(100) in which we observe the sequential filling of two electronically inequivalent binding states. The stability of the “d-band window” during thermally activated reaction, and the likelihood of its existence in other transition metals makes this an attractive surface sensitive spectroscopy.     

Evaluation of plasmon-loss spectra of molybdenum using elastic-peak electron spectroscopy

Plasmon-loss spectra of clean polycrystalline molybdenum surfaces have been determined in the primary energy range E_p = 50–3000 eV. Spectra a distributions (nonderivative mode). A simplified model is described for evaluating plasmon-loss spectra using elastic-peak electron spectroscopy, as de of elastically reflected electrons is determined by integrating the N(E) spectrum of secondary and backscattered electrons. The ratio of the ar (23–24 eV) to that of the elastic peak is Pλ, the product of the probability for creating a volume plasmon loss and the inelastic mean free pat second plasmon-loss peak is (Pλ)². Evaluation of our experimental plasmon-loss spectra gives Pλ = 0.4–0.5 for E_p > 500 eV. Th constitutes ～50% of all losses determining the IMFP, interband loss processes being important in the remainder. For the low energy range, E_p found. For E_p < 100 eV, no volume plasmon-loss peak could be detected in our N(E) spectra. The simplified model proves to be valid fo plasmon-loss peak (11–12 eV), i.e., such that N_pls/N_e ? 10^?2. Some results are presented concerning surface plasmon losses as molybdenum surface.     

Secondary electron emission yield behaviour of polymers

The secondary electron emission yields of highly-insulating, thin polymer foils have been measured for incident primary beam energies, 50 ? E_p ? 2500 eV. The results follow closely a ‘universal’ reduced yield curve determined by the energy loss law, dE_p/dx = -A/E_p^n-1, where n = 2 and A is a constant proportional to the density of the solid, as predicted by the elementary theory of Lye and Dekker (1957). This behaviour remains true up to high primary beam energies and, as such, is unique to these low density solids.     

Electron energy loss spectroscopy study of the initial stage of lanthanum oxidation

The electron energy loss spectra (EELS) of a pure metallic lanthanum surface and variations in these spectra at the initial stages of surface oxidation were studied. The measurements were performed at primary-electron beam energies E _p from 200 to 1000 eV. A very pronounced peak at a loss energy of about 7.5 eV arises due to transitions from the La4d electronic states of the valence band into the empty La4f electronic states of the conduction band at 5.0–5.5 eV above the Fermi level. Marked changes are observed in the EELS during the oxidation of lanthanum: the peak at an energy of 7.5 eV disappears, and the peak at 13.5 eV corresponding to bulk collective energy loss in lanthanum oxide becomes more pronounced. The results obtained are discussed in terms of the electronic structure of lanthanum and lanthanum oxide.     

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.     

An electronic and structural interpretation of tin oxide ELS spectra

In this study electron energy-loss spectroscopy (ELS) is used to examine polycrystalline tin oxide films which have been annealed, ion sputtered and oxygen treated. The major features in the N(E) loss spectrum are interpreted as due to collections of optically allowed interband transitions. It is demonstrated that depth profile information may be obtained by varying the primary electron beam energy. Combined ELS and valence-band XPS results indicate that a significant amount of structural information may be inferred from the size, shape and/or position of the N(E) ELS features. Core-level features are found to be quite sensitive to the presence of defects in an SnO₂ lattice with some specificity as to the type of defect.     

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.     

Comparison of the electron energy loss spectrum of erbium metal with ErO2andErH2

Electron energy loss spectra of metallic erbium, Er under different exposures of oxygen at room temperature, and Er deposited in an atmosphere of H₂ are presented in both N(E) and $\text{dN}\text{dE}$ form for primary energies in the range 100–1000 eV. Resonant excitations associated with the 5p and 4d levels in Er show little environmental dependence, and are largely intraatomic in character. In contrast the main plasmon peak shifts to higher energy on exposure to oxygen or hydrogen, and the spectrum of one electron excitations at low energies alters with a decrease in metal losses around 3.5 eV accompanied by a build up of valence band transitions at 8–9 eV. There is no evidence of a stable chemisorption phase under oxygen exposure, but the results are consistent with rapid oxygen incorporation into subsurface layers and oxide formation.     

Identification of Cu(I) and Cu(II) oxides by electron spectroscopic methods: AES,ELS and UPS investigations

The externally prepared black-coloured copper oxide (T? 700 K, P_O2 ? 100 torr) on a Cu(100) surface is identified by electron spectroscopy as CuO. Compared to the red-coloured Cu(I) oxide (in situ oxidation at T ? 400 K, P_O2 ? 0.5 torr, ～ 10⁹ L), the He(I)- excited photoemisson from CuO reveals characteristic shake-up satellites 10–12 eV below E_F and a broadened emission from overlapping oxygen-induced 2p and Cu 3d states. From the AES and ELS results, in correlation with the data from core electron spectroscopy, chemical shifts of Cu 2p, Cu 3s and Cu 3p in CuO to higher binding energy and decreases in binding energy of the oxygen-induced states were deduced. The unoccupied electron states of Cu at 5 and 7.5 eV above E_F — postulated from the ELS results — are preserved in Cu₂O and CuO compounds. Annealing of the Cu(II) oxide at 670 K is accompanied by decomposition into Cu₂O due to the solid-state reaction following the scheme: 2CuO → 1/2 O₂ + Cu₂O.     

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.     

Study of the initial stage of yttrium oxidation using characteristic electron-energy-loss spectroscopy

The characteristic electron-energy-loss (EEL) spectra of the pure surface of metallic yttrium and of this surface in the initial stages of oxidation are recorded. The energy of the primary electron beam E _p is 200–1000 eV. The spectra exhibit high-and low-frequency peaks. During oxidation, the positions of the basic peaks in the EEL spectra are significantly shifted. The peaks corresponding to the bulk energy loss shift toward higher energies upon oxidation. The peak corresponding to the low-frequency surface oscillations also shifts, but toward lower energies, and its intensity monotonically decreases with increasing oxygen dose. The differences between the spectra recorded at different E _p are explained as resulting from an increase in the electron escape depth with E _p .     

H2O interaction with clean and oxygen precovered Ni(110)

The interaction of water vapour with clean as well as with oxygen precovered Ni(110) surfaces was studied at 150 and 273 K, using UPS, ΔΦ, TDS, and ELS. The He(I) (He(II)) excited UPS indicate a molecular adsorption of H₂O on Ni(110) at 150 K, showing three water-induced peaks at 6.5, 9.5 and 12.2 eV below E_F (6.8, 9.4 and 12.7 eV below E_F). The dramatic decrease of the Ni d-band intensity at higher exposures, as well as the course of the work function change, demonstrates the formation of H₂O multilayers (ice). The observed energy shift of all water-induced UPS peaks relative to the Fermi level (ΔE_max = 1.5 eVat 200 L) with increasing coverage is related to extra-atomic relaxation effects. The activation energies of desorption were estimated as 14.9 and 17.3 kcal/mole. From the ELS measurements we conclude a great sensitivity of H₂O for electron beam induced dissociation. At 273 K water adsorbs on Ni(110) only in the presence of oxygen, with two peaks at 5.7 and 9.3 eV below E_F (He(II)), being interpreted as due to hydroxyl species (OH)^δ? on the surface. A kinetic model for the H₂O adsorption on oxygen precovered Ni(110) surfaces is proposed, and verified by a simple Monte Carlo calculation leading to the same dependence of the maximum amount of adsorbed H₂O on the oxygen precoverage as revealed by work function measurements. On heating, some of the (OH)^δ? recombines and desorbs as H₂O at ? 320 K, leaving behind an oxygen covered Ni surface.     

Giant core-exciton effects on Si(111) 7 × 7 surfaces

We present the first direct experimental evidence for a large surface influenced core-exciton effect on silicon. The Si(111) 7 × 7 L_2,3 absorption edge has been studied with core-level electron energy loss (ELS) and X-ray photoemission spectroscopy (XPS). An excitonic shift of ～1–2 eV have been found for transitions from Si(2p) to empty surface states.     

Dissociative Excitation of the Even Quartet and Sextet Levels of the Manganese Atom by Collisions of Electrons with Manganese Diiodide Molecules

Dissociative excitation of even quartet and sextet levels of the manganese atom by electron collisions with manganese diiodide molecules was studied experimentally. Twelve excitation cross-sections for transitions from quartet levels and 23 cross-sections for transitions from sextet levels were measured at an incident electron energy of 100 eV. The optical excitation function (OEF) was recorded in the range of electron energies 0?100 eV for transitions originating at the 3d⁵4s4de⁶D_J levels. The potential channels of dissociative excitation in the range of low electron energies (E < 22 eV) were discussed.     

Optical properties of electron irradiation induced defects in InP

The optical properties of deep hole traps H₄ and H₅ in p type and of the deep electron trap E₁₁ in n type InP, introduced by electron irradiation, have been studied using deep level optical spectroscopy. Comparison of the optical threshold with the thermal activation energy of H₅ level shows that it is highly relaxed with a Frank-Condon shift d_Fc = 0.45 eV. The electron level E₁₁ is weakly relaxed and its optical cross section σ ⁰ is well accounted for by transitions to the Γ_6c minimum. The optical absorption σ_p⁰ associated to level H₄ shows two successive onsets at hν = 0.5 and hν = 1.2 eV which can be attributed to hole transitions to the Γ_7–8 and to the L_4–5 valence band extrema, respectively. The deduced Frank-Condon shift, d_Fc = 0.23 eV, agrees with the measured difference of 40 meV between its apparent activation energy E_a and its thermal activation energy E_T.     

Ionic implantation of N2+ in Ni(110) at 300 K

The present work gives results of a preliminary investigation, carried out by SES, AES, LEED and ELS, on the implantation of nitrogen ions in Ni(110) as a function of ion dose and subsequent surface heat treatment at different temperatures. The fine structure in the SES spectrum is the most sensitive to implantation: peaks at 9, 17.5 and 31.5 eV are shifted towards lower energies by E = 1 eV for the first two peaks and 2.8 eV for the last. At high nitrogen doses a disordered layer is observed by LEED. The p(2 × 3) structure is obtained when the crystal is heated to 750 K. The two electron loss peaks of 4.8 and 10 eV arise from an induced electron N_2p level situated 4.8 eV below the Fermi level.     

Measurements of double differential cross sections in electron impact ionization of helium and argon

Double differential cross sections (angular distributions and energy loss spectra) have been measured of electrons after ionizing electron collisions with helium at primary energiesE ₀ between 25 eV and about 260 eV and with argon atE ₀=75, 150 and 200 eV. The spectra have been measured with an energy analyzing collector system of constant transmission. It was found that for high collision energies (E ₀≧ 80 eV) the outgoing electrons belong to one of the two energetically well separated groups, either thefast electrons, which are scattered mainly in forward direction or theslow electrons which are distributed isotropically into all angles. At low primary energiesE ₀ no separation into groups is possible. Several findings indicate the qualitative applicability of the binary collision model.