Solid-state shifts in the L3M4,5M4,5 Auger spectra of the elements Cu TO Se

The kinetic-energy shifts between atomic and solid-state L₃M_4,5M_4,5 Auger electron spectra of Cu, Zn, Ga, Ge, As, and Se are determined with the aid of semiempirically calculated atomic and experimental solid-state Auger energies. The shift values are calculated by applying the thermochemical model to the Auger process. Good agreement is found between the calculated and experimental values.     

Investigating the structure of the Tin M45N45N45 auger spectrum using auger photoelectron coincidence spectroscopy

Auger photoelectron coincidence spectroscopy (APECS) data were collected for the M₄₅N₄₅N₄₅ Auger peak in coincidence with the 3p_3/2, 3d_3/2 and 3d_5/2 photoelectron lines of Tin. Model spectra were created to fit the APECS data from sets of Gaussian curves defined by Parry-Jones et al., J. Phys. C: Solid State Physics, 12 (1979) 1587. These models were then combined using information about the relative intensities of the peaks from the aforementioned paper to produce a model of the Auger peak which proved a good comparison to high resolution AES spectra. The APECS data revealed satelite structure in the M₅N₄₅N₄₅ peak in coincidence with the 3d_5/2 photoelectron line (M₅N₄₅N₄₅:3d_5/2) due to the Mg Kα₃ line of the X-ray source. There was evidence of a small Coster–Kronig component in the M₄N₄₅N₄₅:3d_3/2 data and the M₄₅N₄₅N₄₅:3p_3/2 data showed intensity in the M₄N₄₅N₄₅ and M₅N₄₅N₄₅ regions also arising from Coster–Kronig processes. The contribution of the M₄N₄₅N₄₅ plasmon was included in each of the APECS models and was reflected in the high resolution AES spectra. Slight oxidation of the surface of the sample during each 24-h period produced a 0.7 eV shift of the singles Auger peak to lower kinetic energies. The shift was not reflected in the coincidence peak which produced a spectrum of a clean surface due to the nature of the coincidence experiment.     

M4,5N4,5N4,5 auger electron spectrum of Ba metal

The Al Kα excited M_4,5N_4,5N_4,5 Auger spectrum of Ba has been measured from the metallic sample evaporated on a Ag substrate. The spectrum has been decomposed into individual line components after the background subtraction. The decomposed spectrum has been compared with the theoretical spectrum calculated for the 4d^?2 final state configuration in the mixed coupling scheme applying jj-coupling for the initial state and intermediate coupling for the final state. The most prominent structure of the spectrum shows the two 4d-hole coupling, but the structure which is caused by the Auger transitions M_,45N_2,3V has also been observed. The screening of the core holes in Ba metal seems to be produced by (5d6s) electrons. The simple excited atom model HF-calculations give an Auger kinetic energy shift (metal-free atom) of 16.7 eV, which is comparable to the experimental value 14–18 eV.     

Complete breakdown of the one-electron picture of auger spectra of solids

The very broad M₄₅?N₂₃N₄₅ (3d^-1 → 4p^-14d^-1) Auger spectra for metals in the range Pd to Te arise from complete breakdown of the one-electron picture of the final state double vacancy due to 4p^-14d^-1 ? 4d^-3?f giant Coster-Kronig fluctuation and decay processes. This is an example of atomic-like effects giving rise to level shifts and broadening which are large in comparison with typical widths of d-bands in solids. The 4p^-14d^-1 two-hole spectral function can be approximated by a 4p^-1 single-hole spectral function perturbed by a static, sharp 4d^-1 hole. The resulting Auger line-shapes are different from single-hole 4p^-1 line-shapes from XPS and XES. Analogous effects also occur for double vacancies involving one or two 4s-holes.     

Study of L2,3M4,5M4,5 Auger spectra of Zn and Cu in molecular ZnCl2 and (CuCl)3 vapours

L_2,3M_4,5M_4,5 Auger electron spectra of Zn and Cu have been measured in molecular ZnCl₂ and (CuCl) ₃ vapours. The spectra have been analyzed and compared with the corresponding free-atom spectra. It is found that the main features of the spectra are atomic-like. The energies are shifted by 0.55 eV in ZnCl₂ and by 3.2 eV in (CuCl)₃ towards higher kinetic energy compared with the corresponding free-atom spectra. For the intensity ratios between the L₃ and L₂ groups, the values 2.8 and 3.7 are obtained for Zn and Cu, respectively. These intensity ratio, together with energy considerations based on free-atom Dirac—Fock calculations and observed Auger shifts, indicate that the L₂L₃M_4,5 Coster—Kronig process is energetically possible in (CuCl)₃ molecular clusters but not in ZnCl₂. The satellite structure in the spectra studied also supports this conclusion.     

Quasi-atomic fine structure in the Auger spectra of solid silver and indium

High resolution M₄,₅N_4,5N_4,5 Auger spectra of Ag and In reveal fine structure, which may be interpreted in terms of spin-orbit splitting of the initial state and multiplet structure in the final state. Interaction between d holes in Ag is an important factor in determining the shape of the Auger spectrum, and so the Auger profile is not related in any simple way to the one-particle density of states.     

High resolutionMNN auger spectra of Ag,Cd, In,Sb, Te,and I

The strongest lines (M ₅ N _4,5 N _4,5 andM ₄ N _4,5 N _4,5) in theMNN Auger spectra of Ag, Cd, In, Sb, Te, and I have been investigated with high resolution by means of an electrostatic cylindrical spectrometer. The measured spectra have been found to have a fine structure corresponding to the splitting of the final states of the Auger transitionsM ₅ N _4,5 N _4,5 andM ₄ N _4,5 N _4,5. This has not been observed for these elements in spectra measured by the retarding field method. The line profiles are discussed.     

Esca studies of Ga,As, GaAs,Ga2O3, As2O3 and As2O5

The binding energies of Ga 3d, As 3d, Ga L₃M₄,₅M₄,₅ and O 1s in Ga, As, GaAs, Ga₂O₃, As₂O₃ and As₂O₅ are reevaluated by means of ESCA. The calibration lines of the C 1s and the Au 4f_{$\text{7}\text{2}$} gave different binding energies for the compound materials. In order to determine the absolute binding energies, the chemical shifts in Auger and photoelectron lines from a layered structure composed of thin layer oxide and substrate of a defined material were used. An energy calibration curve, E(Ga 3d) vs. ΔE(GA LMM - Ga 3d), was found to be useful for determination of binding energies in the material which contains gallium. In the case of the GaAs sample, both the chemical etching and the ion bombardment effects on the chemical structure of the GaAs surface are also discussed.     

Interpretation of Auger satellites in Co,Ni, and Cu compounds

X-ray photoelectron spectra of the 2p levels of Co, Ni, and Cu compounds are examined concurrently with their L₃M_4,5M_4,5 Auger spectra. A correlation is established between the presence or absence of Auger satellites with the presence or absence of photoelectron shake-up satellites for Co and Ni compounds. The correlation is less clear for cupric compounds. We propose the mechanism of Auger shake-up as a plausible interpretation for the observed behavior of these Auger satellites.     

Vapour phase M4,5N4,5N4,5 Auger electron spectra of antimony and tellurium

High resolution M_4,5N_4,5N_4,5 Auger electron spectra from Sb₄ and Te₂ vapours have been measured using electron impact excitation. The spectra have been decomposed into line components and relative intensities and energies of the components are compared with calculated intensities and energies. The calculations have been done for these molecular samples using the free-atom calculation model involving initially filled shells. The calculations have been treated in the mixed coupling scheme using jj coupling for initial state and intermediate coupling for the final state. The experimental results agree well with the calculated values, indicating that the molecular effects on the relative intensities and energies are very small for these core level transitions. The clear molecular effects are found in the broadening of lines and in the kinetic energy shifts due to extra-atomic relaxation effects.     

Electron-induced KLL Auger electron spectroscopy of Fe,Cu and Ge

KLL Auger spectra excited by electrons with energies in the 30–35 keV range of Fe, Cu and Ge films were measured, using thin free-standing films. It was possible to obtain spectra with an energy resolution of about 1 eV. The observed spectra can not be described satisfactorily by just the multiplet splitting of the final state as calculated for an isolated atom. Additional features, due in part to intrinsic (shake satellites) and in part to extrinsic (energy loss of the escaping electron) processes formed a large fraction on the observed intensities. In particular a number of distinct satellite structures that are not predicted by the atomic Auger process are observed. For Fe and Cu the satellite peaks can be explained in terms of shake-up processes from the 3d_5/2–4d_5/2 states. Similar satellite structures observed in Ge are partly attributed to plasmon creation and partly to shake-up processes. It is demonstrated that both the thickness dependence of the observed intensity distributions and transmission electron energy loss measurements contain invaluable information for the interpretation of these spectra.     

Comparison of site-specific valence band densities of states determined from Auger spectra and XPS-determined valence band spectra in GeS (001) and GeSe (001)

Auger lineshapes of the Ge M₁M_4,5V and M₃M_4,5V and Se _M1M_4,5V transitions in GeS (001) and GeSe (001) are measured and compared to XPS valence band spectra. Distortions in both types of spectra due to inelastic scattering, analyzer and source broadening, and core level lifetime broadening are removed by deconvolution techniques. The valence band consists of three main peaks at ?2 eV, ?8 eV, and ?13 eV. There is excellent agreement of peak positions in AES and XPS spectra. The Auger lineshapes can be interpreted in terms of site-specific densities of states. They indicate that the states at ～?8 eV and at ～?13 eV are associated with the cation and anion sites respectively. The bonding p-like states at the top of the valence band have both cation and anion character. The Auger lineshapes indicate that the states closest to the valence band maximum are preferentially associated with Ge.     

Many-body effects in l2mm auger electron spectra of Ge(CH3)4 excited by Mg Kα X-rays

The Ge:L₂MM Auger electron spectra excited by Mg Kα X-rays from Ge(CH₃)₄ free molecules have been compared with the corresponding spectra excited by Al Kα X-rays. The Al Kα excited spectra have characteristic features of the diagram Auger transitions, because the excitation energy is far above the L₂ ionization threshold. The energy of Mg Kα photons is 1.21 eV below the Ge:L₂ ionization threshold and thus the Mg Kα excited L₂MM Auger electron spectra indicate many-body effects, post collision interaction (PCI) effects and spectator Auger satellite structures. The L₂M_4,5M_4,5 type spectrum displays both these features but the L₂M_2,3M_4,5 type spectrum has only a spectator Auger satellite structure, because the (3p⁻¹3d⁻¹nl) final state interferes with the (3s) hole state.     

ESCA studies of Cu,Cu2O and CuO

Cu 2p, Cu 3d and O 1s electron spectra and Cu L₃M_4,5M_4,5 Auger electron spectra from Cu, Cu₂O and CuO have been studied at 25°C and at 400°C. The height of the Cu 2p satellite peaks from copper oxides was lowered when the temperature was raised. The intensity of the satellites also decreased if the sample stayed in vacuum for prolonged periods.Two commercial cuprous oxides were different with respect to the behaviour of the satellite peaks. One produced very weak satellites, while the other produced strong ones as previously reported in the literature for cuprous oxide. The colour of the oxides was slightly different, indicating that the stoichiometry was not the same.The change in satellite intensity is accompanied by changes in oxygen spectra, Cu L₃M_4,5 M_4,5 Auger spectra and valence band spectra.It is useful to study Auger electrons in addition to the direct electron spectrum, since Auger signals can be more sensitive to surface conditions than direct electron spectra.     

X-ray photoelectron (XPS) and Auger (XAES) spectroscopy study of rhodium dispersed on carbon substrate

Photoelectron 3d_5/2 binding and Auger M₅VV kinetic energies of dispersed rhodium have been measured. For the smallest deposition of Rh the shifts 0·6 eV and -2·5 eV of 3d_5/2 and M₅VV lines respectively have been found. Electron core level energy, Auger kinetic energy and Fermi edge shifts have been interpreted by a model based on electrostatic relaxation mechanism in metal particles and initial state contribution of surface atoms. Intensity and background height analysis indicate only surface distribution of Rh.I wish to express my gratitude to Dr. Zdenk Bastl for helpful discussions.     

Observation of resonance recombination lines in electron excited auger spectra of Gd

Combined measurements of electron excited N_4,5 Auger spectra and photoelectron emission on clean and oxidized Gd lead to a distinction between Auger lines originating from 4d → continuum and 4d → 4? resonance excitations. Several Auger structures are identified as due to the direct recombination of 4d⁹4?⁸ states with the 4f and valence electrons. The shape of the most prominent Auger line for oxidized Gd agrees perfectly with the Fano profile of the 4? photoemission intensity.     

X-ray induced photoelectron and auger spectra of Cu,CuO, Cu2O,and Cu2S thin films

Improved techniques have been used to prepare thin films of Cu, CuO, Cu₂O and Cu₂S for x-ray photoelectron spectral analysis. The Cu 2p and Cu LMM Auger spectra have been obtained. Photoelectron and Auger chemical shifts as well as qualitative spectral features are found to be useful diagnostics for valence-state characterization of unknowns.     

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.     

Impurity Auger spectra: A probe of the local impurity density of state and the impurity electron—electron interactions

We show that the local impurity density of states and the impurity electron—electron interactions can be obtained from impurity Auger spectra. For a Ag_0.95Pd_0.05 alloy we find 11% Pd(d) character in the Ag d band and Pd(4d-4d) Coulomb interactions which are much larger than the virtual bound state widths.     

The M5 photoelectron line of Ag metal measured in coincidence with the M5–N45N45 Auger-electron spectral line

The M₅ (3d_5/2) photoelectron line of Ag metal was measured in coincidence with the M₅–N₄₅N₄₅ (¹G or ³F) Auger-electron line by Auger-photoelectron coincidence spectroscopy (APECS). The M₅ photoelectron line of Ag metal measured in coincidence with either the ¹G or the ³F Auger-electron line is unshifted, within the accuracy of the experiment. As the theory [M. Ohno, J. Electron Spectrosc. Relat. Phenom. 124 (2002) 53] predicts, the energy shift and asymmetrical narrowing of the coincidence photoelectron line compared to the singles one is much smaller than that in Cu metal.