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.     

A study of the orientation dependence of the electron energy loss spectra for single crystal films of copper and silver

Apart from two peaks caused by bulk and surface plasmons, four or five peaks (depending on the crystal type) of electron energy losses due to inter- and intraband electron transitions are observed in the investigation of the electron energy loss spectra for metals (Cu, Ag). A comparative analysis of the spectra for Cu or Ag films reveals a shift of bulk plasmon loss peaks to higher values for polycrystals, as in the case of transition metals and semiconductors. In a study concerning the orientation dependence of the energy loss spectra (ELS) for electrons scattered from the copper and silver surface, the anisotropy of the bulk plasmon peak is found when the incident beam’s polar angle or the sample’s azimuthal angle are altered. The anisotropy of the primary electron energy loss for plasmon excitation is also observed, depending on the sample orientation relative to the direction incident electrons. The energy losses are found to increase with an increasing atomic packing density of planes and crystal transparency relative to the incident beam.     

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.     

Electron energy loss and secondary emission mechanisms in BaO

Electron Loss Spectroscopy (ELS), X-ray Photoemission (XPS), Secondary Emission Energy Distribution, and Secondary Electron yield data have been obtained on both evaporated films and sprayed-on coatings of BaO. Using the ELS correlated with the XPS data, bulk and surface plasmon losses as well as excitonic and interband transition electron loss mechanisms have been identified. It was found that at low primary beam energies (<100 eV), structure in the secondary emission energy distribution could be correlated with a conduction band energy structure. This structure was consistent with the model used to explain the loss transitions. The structure in the energy distribution curves shows little, if any, correlation with plasmon decay mechanisms and other two-step electron emission processes. On the contrary, for the case of BaO (at least at low primary energies), the energy distribution data and structure in the secondary yield vs. primary beam energy data indicate that most secondaries are produced by direct excitation of secondaries by the primary electrons.     

Electron energy loss spectra from polycrystalline Cr and Cr2O3 before and after surface reduction by Ar bombardment

Electron energy loss spectra (ELS) have been obtained from polycrystalline Cr and Cr₂O₃ before and after surface reduction by 2 keV Ar⁺ bombardment. The primary electron energy used in the ELS measurements was systematically varied from 100 to 1150 eV in order to distinguish surface versus bulk loss processes. Two predominant loss features in the ELS spectra obtained from Cr metal at 9.0 and 23.0 eV are assigned to the surface and bulk plasmon excitations, respectively, and a number of other features arising from single electron transitions from both the bulk and surface Cr 3d bands to higher-lying states in the conduction band are also present. The ELS spectra obtained from Cr₂O₃ exhibit features that originate from both interband transitions and charge-transfer transitions between the Cr and O ions as well as the bulk plasmon at 24.4 eV. The ELS feature at 4.0 eV arises from a charge-transfer transition between the oxygen and chromium ions in the two surface layers beneath the chemisorbed oxygen layer, and the ELS feature at 9.8 eV arises from a similar transition involving the chemisorbed oxygen atoms. The intensity of the ELS peak at 9.8 eV decreases after Ar⁺ sputtering due to the removal of chemisorbed oxygen atoms. Sputtering also increases the number of Cr²⁺ states on the surface, which in turn increases the intensity of the 4.0 eV feature. Furthermore, the ELS spectra obtained from the sputtered Cr₂O₃ surface exhibit features characteristic of both Cr⁰ and Cr₂O₃, indicating that Ar⁺ sputtering reduces Cr₂O₃. The fact that neither the surface- nor the bulk-plasmon features of Cr⁰ can be observed in the ELS spectra obtained from sputtered Cr₂O₃ while the loss features due to Cr⁰ interband transitions are clearly present indicates that Cr⁰ atoms form small clusters lacking a bulk metallic nature during Ar⁺ bombardment of Cr₂O₃.     

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.     

Angular dependence of the electron energy loss spectra from a clean and adsorbate covered W(001) surface

A dispersion analysis of the EELS from a W(001) surface in the range 1 < ΔE < 35 eV has been performed and compared with recent and complete optical data for tungsten. The non-dispersive (k ～ 0) EELS correlated well with a combination of the surface and bulk loss functions calculated from the optical data. Losses at 1–5 eV and a pair at 32 and 34.5 eV were assigned to interband and N_6,7 core ionization excitations respectively. The principal bulk and surface plasmon losses were identified at 24.0 and 20.3 eV respectively. Two further losses at 14.0 and 9.6 eV were also observed and assigned to subsidiary plasmon losses. All four plasmon losses showed only minimal energy dispersion, never exceeding 1.5 eV. A momentum selectivity for separating bulk and surface interband losses was demonstrated with the non-dispersive losses arising from excitations within the bulk even with incident energies as low as 88 eV, whereas their dispersive counterparts were extremely sensitive to the chemical state of the surface. New adsorbate derived losses which develop during adsorption were associated with excitations from the new deep lying adsorbate levels to final state levels at or near the Fermi level. It was concluded that this final state was also responsible for the N_6,7 ionization losses.     

Study of He bubbles in Al by electron energy loss spectroscopy

High energy electron energy loss spectroscopy (ELS) has been used to study He bubbles in Al, which were obtained by irradiation of He ions or α-particles of energy ranging from 500 eV to 8 keV and fluences 1x10²⁰m^?2 and 5x10²⁰m^?2. ELS reveals surface plasmon losses of the Al cavities as well as pressure shifts of the He-resonance lines as large as 1 eV. This is viewed as evidence for the existence of a so-called super-dense He in the bubbles. ELS is therefore a promising tool for obtaining information on the He pressure within the bubbles.     

Characteristic energy loss spectra of copper crystals with surfaces described by LEED

Energy distributions of electrons back-scattered from copper (100) and (110) surfaces have been obtained for incident electron energies in the range 30 to 350 eV. The relations between optical measurements and the characteristic energy losses, as well as the effect of interband transitions on the bulk and surface plasmon frequencies in metals which do not have ideally free electron plasmas are discussed. By chemisorbing increasing amounts of oxygen on the clean surface, the surface plasmon loss peak was identified in the copper energy loss spectrum from its intensity dependence on the dielectric constant at the surface. This peak has been identified by previous authors as the bulk plasmon loss of a single s-electron plasma oscillation. Our identification of the surface plasmon loss peak implies that the d-electrons in copper do participate in the plasma oscillation and that the bulk plasmon frequency is shifted from its free electron value because of interband transitions.     

Interface effects for metal oxide thin films deposited on another metal oxide I. SnO deposited on SiO2

The growing mode of SnO overlayers deposited on SiO₂ has been studied by ISS and XPS. This study has shown that SnO spreads on the surface of SiO₂. The oxidation state of tin under different experimental conditions of preparation has been characterized by XPS and ELS and a procedure has been found to produce pure SnO. For comparison, SnO has been evaporated on highly oriented pyrolytic graphite (HOPG). In this case, independent of the deposited amount of SnO, XPS and ELS did not show any significant difference in the photoemission and loss features of this material as a function of coverage (i.e. there are no size effects). On the contrary, at low coverages of SnO deposited on SiO₂ XPS showed a shift of 1 eV in the BE of the Sn 3d_5/2 peak another of 1.7 eV in the values of the Auger parameter with respect to the values found for the bulk material. These shifts, very common on deposited metal particles, have been previously reported by us for TiO₂/SiO₂, and are tentatively attributed to t of the interaction of small deposits of SnO with the surface of SiO₂. The characterization by ELS and valence band photoemission of SnO completes the set of results reported in this paper.     

Investigation of intrinsic plasmon energy losses associated with the Fe 1s core level in metallic iron

A recently developed Cu Kα₁ (hν = 8047.8 eV) X-ray source/ESCA300 electron spectrometer combination has been used to investigate the intrinsic plasmon energy losses associated with the Fe 1s core level (binding energy = 7111 eV) in metallic iron. The surface and bulk intrinsic plasmon energy losses were separated and it was found that using the theoretically calculated extrinsic energy loss cross-section to represent the bulk intrinsic energy loss cross-section gave an overall intrinsic loss probability which is approximately the same as if a Lorentzian type cross-section is used. However, this approach does not separate the surface and bulk intrinsic losses properly and is not a good approximation for peak shape analysis in the near peak region. A more realistic approximation is provided by using a Lorentzian type energy loss cross-section to represent the bulk intrinsic energy losses. It has also been shown that for the Fe 1s core level of metallic iron the probability that a photoelectron will suffer an intrinsic energy loss is higher at the surface than in the bulk. Also for this core level the excitation probability for the intrinsic plasmons is greater than that of the extrinsic plasmons. Hence ignoring the intrinsic plasmons would cause considerable error in peak shape analysis in the near peak region.     

Electron spectroscopic studies of tin surface segregation on iron single crystal surfaces

AES, ELS, LEED and XPS investigations of the surface segregation of tin dissolved in a Fe-4wt%Sn alloy were performed in ultra-high vacuum at elevated temperatures. The three low indexed surface orientations (100), (110) and (111) were studied. In all cases, no dependence of the maximum tin surface coverage on temperature was detected within the temperature range from 450 to 650°C. An order-disorder transition was observed by LEED, AES and XPS for the (100) oriented surface during tin segregation. The binding state for the segregated tin atoms abruptly changes at the order-disorder transition as determined by XPS. Similar results were obtained for the (111) surface. A deviating behaviour was observed for the (110) surface orientation, where two different ordered hexagonal surface structures were detected by LEED during tin surface enrichment. The first structure is similar to the diamond structure of pure tin, and the second one corresponds to the formation of a thin layer of the intermetallic compound FeSn on the (110) surface. The electron binding energies of the segregated tin atoms determined by XPS increase with increasing tin coverage on the (110) oriented surface. ELS studies on (100) and (111) oriented surfaces saturated with segregated tin show in comparison with literature data of pure tin a surface plasmon loss peak but no signal for the corresponding bulk loss. An energy loss signal found only for the (110) surface at Sn saturation coverage seems to be characteristic of an intermetallic FeSn surface phase.     

Quantification of surface effects: Monte Carlo simulation of REELS spectra to obtain surface excitation parameter

The surface excitation effect is investigated by using the quantum mechanical frame work of complex self-energy of electrons which interact with a bounded semi-infinite medium. In the self-energy formalism, differential inverse inelastic mean free path (DIIMFP) has contributions from bulk and surface plasmons. Monte Carlo simulation of the interaction of electrons with a solid medium and surface has been performed. The surface excitation parameter (SEP) is then obtained from the simulated reflection electron energy loss spectroscopy (REELS) spectra. The calculated SEP results by Monte Carlo simulation are compared with the previous calculations of total surface excitation probability, which was estimated by a numerical integration of surface term of DIIMFP. The contribution merely due to surface excitations towards REELS spectra is extracted by subtracting the two Monte Carlo simulated REELS spectra that based on the two models of electron inelastic scattering, i.e. a full surface model (SM) and a pure bulk model (BM). The surface excitations found to be significant at low energy losses and diminish at higher energy losses whereas the bulk plasmon contributions show opposite behavior and are negligible at lower energy losses. The average number of surface excitations is then evaluated by the computation of ratio of the integrated surface contribution to the elastic peak. The calculated results for Ag are found to be reasonably in agreement with our previous results for total probability of surface excitations and other reported experimental data for SEP. Surface correction factor (SCF) is calculated using SEP for several metals and is compared with the reported ratio of SCF with Ni sample as reference.     

Anregung von Volumen- und Oberflächenplasmaschwingungen in Al und Mg durch mittelschnelle Elektronen

Dispersion and scattering cross section of the bulk plasma losses of Al and Mg are compared with plasma theory. The low lying Mg loss shows an asymmetric intensity distribution for non-normally incident electrons and an angular dependence of intensity as expected from the theory of surface losses. In very thin Al films, coupling effects between the two opposite surfaces are found, causing some new properties of the surface losses. Especially a thickness dependent dispersion of the surface loss is measured which is quite different from that of the bulk losses and characteristic for surface excitation.     

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.     

The growth mode of aluminium on silver (111)

The geometric and electronic structures occuring during the growth of Al on a single crystal Ag(111) surface have been studied using a combination of low energy electron diffraction (LEED), Auger electron spectroscopy (AES), energy loss spectroscopy (ELS) and work function measurements. The Auger signal versus deposition time plots, which were used to monitor the growth mode, are shown to behave in an identical fashion to that expected for layer-by-layer (Frank-van der Merwe) growth. LEED was used to determine the lateral periodicity of thin Al films and shows that Al forms, at very small coverages, 2D islands which have the same structure as the Ag(111) substrate and which grow together to form the first monolayer. At substrate temperatures of 150 K a well defined (1 × 1) structure with the same orientation as the underlying Ag(111) can be seen up to at least 12 ML. After completion of the third monolayer the ELS spectrum approached that observed for bulk aluminium. At a coverage of 3 ML the work function decreases by 0.4 eV from the clean silver value.     

Electron energy-loss spectroscopy of tetracyanoquinodimethane,TCNQ, tetrathiafulvalene,TTF, and the salt TTF-TCNQ

Energy loss spectra of low energy electrons (ELS) have been obtained for thin solid films of tetracyanoquinodimethane (TCNQ), tetrathiafulvalene (TTF), and the charge transfer salt TTF-TCNQ as a function of incident energy (20 to 100 eV). The incident energy dependence of energy loss features allows the identification of triplet and symmetry forbidden excitations in TCNQ and TTF. The ELS spectrum of TTF-TCNQ is compared with high energy electron loss data to show that the surface of evaporated films of TTF-TCNQ contains 20–50% neutral TCNQ molecules.     

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.     

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.     

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.