Many-electron contributions in the auger spectrum of CO

The CO Auger electron spectrum has been re-investigated by means of ab initio MO LCAO calculations using a combined SCF CI procedure. The CI comprises internal and semi-internal contributions to the final double-hole Slate wave-functions. In particular, the latter contributions are found to be highly significant both with respect to energies and intensities of the Auger transitions. In order to compare with the experimental spectra, the intensities of the transitions have also been calculated using a simple one-center model.     

Study of electron states of solids by techniques of electron spectroscopy

Studies of valence bands and core levels of solids by photoelectron spectroscopy are described at length. Satellite phenomena in the core level spectra have been discussed in some detail and it has been pointed out that the intensity of satellites appearing next to metal and ligand core levels critically depends on the metal-ligand overlap. Use of photoelectron spectroscopy in investigating metal-insulator transitions and spin-state transitions in solids is examined. It is shown that relative intensities of metal Auger lines in transition metal oxides and other systems provide valuable information on the valence bands. Occurrence of interatomic Auger transitions in competition with intraatomic transitions is discussed. Applications of electron energy loss spectroscopy and other techniques of electron spectroscopy in the study of gas-solid interactions are briefly presented.     

Experimental auger electron spectrum of ammonia

The first electron excited Auger electron spectrum for gas-phase ammonia has been obtained and is compared with an existing theoretical prediction. Decomposition of the spectrum using a gaussian approximation reveals close agreement in both intensity and energy for the higher energy components provided the theoretical data is shifted toward lower energies by ≈ 2.7 eV. As the transitions involve progressively deeper final state levels there is a general trend of increasing widths and increasing discrepancy towards lower energy with respect to their predicted positions. Such behavior has been seen in other experimental—theoretical comparisons of gas-phase Auger results and while the variation in widths is interpreted in terms of transitions to a manifold of final state vibrational levels, the nature of the differential shift in the lower energy components is unclear.     

Monte Carlo simulation of full energy spectrum of electrons emitted from silicon in Auger electron spectroscopy

A Monte Carlo simulation including surface excitation, Auger electron‐ and secondary electron production has been performed to calculate the energy spectrum of electrons emitted from silicon in Auger electron spectroscopy (AES), covering the full energy range from the elastic peak down to the true‐secondary‐electron peak. The work aims to provide a more comprehensive understanding of the experimental AES spectrum by integrating the up‐to‐date knowledge of electron scattering and electronic excitation near the solid surface region. The Monte Carlo simulation model of beam–sample interaction includes the atomic ionization and relaxation for Auger electron production with Casnati's ionization cross section, surface plasmon excitation and bulk plasmon excitation as well as other bulk electronic excitation for inelastic scattering of electrons (including primary electrons, Auger electrons and secondary electrons) through a dielectric functional approach, cascade secondary electron production in electron inelastic scattering events, and electron elastic scattering with use of Mott's cross section. The simulated energy spectrum for Si sample describes very well the experimental AES EN(E) spectrum measured with a cylindrical mirror analyzer for primary energies ranging from 500 eV to 3000 eV. Surface excitation is found to affect strongly the loss peak shape and the intensities of the elastic peak and Auger peak, and weakly the low energy backscattering background, but it has less effect to high energy backscattering background and the Auger electron peak shape. Copyright © 2014 John Wiley & Sons, Ltd.     

Auger photoelectron coincidence spectroscopy using synchrontron radiation

The technique of Auger-photoelectron coincidence spectroscopy (APECS) is described and illustrated with a case study of the Cu(100) 3p and M₂₃VV spectra. APECS offers many advantages over the conventional singles spectroscopy such as isolating overlapping spectral features, reducing secondary electron background, and revealing new decay modes. In the coincidence Cu Auger spectra discussed here, the multiplet structure of the quasi-atomic 3d⁸ Auger final state is clearly observed, as well as different intensities for the multiplet components for the p_1/2 and p_3/2 transitions. Furthermore, the spectra reveal evidence for a Coster-Kronig decay channel for 3p_1/2 core holes, and illustrate that the sum of the Auger electron and photoelectron kinetic energies is conserved. Possible technical improvements that can increase the counting efficiency are also discussed.     

SCF discrete-variational Xα calculations of the NH4Cl Auger spectrum

Formalism for calculations of the singlet and triplet Auger energies within the Xα model is presented. Using this method the KVV Auger spectrum of NH₄Cl is calculated and the theoretical intensities are determined within a one-center approximation. The calculated spectrum reproduces quite well all the main features observed for solid NH₄Cl. A new interpretation of the spectrum is suggested.     

The change of the LMM auger spectra in 3d-metals due to oxidation and its correlation with the change of the atomic magnetic moment.

The surfaces of crystalline samples of 3d-metals (Mn, Fe, Co, Ni, and Cu) and their stoichiometric oxides have been studied by Auger spectroscopy. A correlation between the change in the LVV (L-inner level-valence-valence electron transition) Auger intensities and the change of the squares of the corresponding atomic-magnetic moments has been observed. This is because of the complicated nature of the Auger process. That is, the Auger electron emission is a result of the inner atomic level excitation by electron impact and Auger annihilation of the inner-level hole. Therefore, the Auger process has been considered a second-order process, and spin polarization of the valence states has been taken into account for the LMM (L-inner level-M-inner level-M-inner level electron transition) Auger spectra of 3d-metals.     

Calculated Auger emission spectrum of ammonia

Doubly ionized states of ammonia are calculated with Roothaan's symmetry-restricted open-shell SCF method. A GTO basis of double-ζ quality is used. Calculated energies compare well with previous calculations for the lowest doubly ionized states. Auger emission intensities are estimated using an analogy with the experimental Auger spectrum of neon.     

Quantitative surface analysis by Auger and x-ray photoelectron spectroscopy

Recent developments in quantitative surface analysis by Auger (AES) and x-ray photoelectron (XPS) spectroscopies are reviewed and problems relating to a more accurate quantitative interpretation of AES/XPS experimental data are discussed. Special attention is paid to consideration of elementary physical processes involved and influence of multiple scattering effects on signal line intensities. In particular, the major features of core-shell ionization by electron impact, Auger transitions and photoionization are considered qualitatively and rigorous approaches used to calculate the respective transition probabilities are analysed. It is shown that, in amorphous and polycrystalline targets, incoherent scattering of primary and signal Auger and photoelectrons can be described by solving analytically a kinetic equation with appropriate boundary conditions. The analytical results for the angular and energy distribution, the mean escape depth, and the escape probability as a function of depth of origin of signal electrons as well as that for the backscattering factor in AES are in good agreement with the corresponding Mote Carlo simulation data. Methods for inelastic background subtraction, surface composition determination and depth-profile reconstructions by angle-resolved AES/XPS are discussed. Examples of novel techniques based on x-ray induced photoemission are considered.     

Resonant Auger spectroscopy at the carbon and nitrogen K-edges of pyrimidine

The resonant Auger electron spectra obtained after photoexcitation below the C and N 1s ionization thresholds in the pyrimidine molecule have been measured at several photon energies. The results show the relevance of the localization of the inner hole and of the matching between the symmetries of the intermediate and final states in the decay spectra via participator transitions. The comparison with the Auger electron spectra suggests some assignment for the two-hole-one-particle states reached via spectator transitions. The analysis of the participator decay is supported by state-of-the art density functional theory calculations.     

Directional elastic peak and directional Auger electron spectroscopies — New tools for investigating surface-layer atomic structure

Intensities of elastically scattered electrons and Auger electrons emitted from a crystalline sample depend strongly on the direction of the primary electron beam with respect to the sample. Namely, distinct maxima of those intensities appear when the primary beam is parallel to one of the close-packed rows of atoms in the sample,

In an RFA analyzer, the angular distribution of the elastically scattered electrons or Auger electrons is integrated over a large scattering angle and does not influence the dependence of intensities mentioned above on the primary beam incidence angle (DEPES or DAES polar profiles). Those profiles can be obtained simply by rotation the sample positioned in front of the RFA analyzer around the axis parallel to the sample surface,

Maxima in DEPES and DAES polar profiles connected with the close-packed atom rows can be easily recognized because their position does not depend on the primary electron energy. Those maxima are the evidence for presence of the crystalline structure in the surface layer. They also enable characterization of this structure even for a crystalline layer composed of very small islands or maintained at temperatures too high to observe LEED patterns. This was shown for the Ag/Cu(111), Ag/Cu(011), and Ag/Ni(111) adsorption systems.

DEPES and DAES profiles are sensitive to the disorder in the surface layer. For example, the surface roughening transitions on the Ni(O11) and Cu(O11) faces was clearly demonstrated and the temperatures of these transitions in both cases were determined with the use of those methods.

A background on which maxima of the DAES and DEPES profiles appear is calculated using a simplified model. It is indicated that the shape of this background should contain information about the sample composition profile.     

Chemical shifts of auger electron lines and electron binding energies in free molecules. Sulfur compounds

The first paper describing a series of systematic investigations of the chemical shifts in Auger electron spectra from various free molecules is presented. Excitation is performed by means of a fine focus electron beam. The Auger electrons are retarded in a four component lens system and recorded at high resolution in a new multidetector system placed in the focal plane of the ESCA instrument. A calibration procedure against the KL₂L₃ Auger electron line of Ne is described. The first study concerns Auger electron line shifts for sulfur in some small molecules and the results are compared to the corresponding chemical shifts in the core photoelectron spectra. A formalism based on a transition potential model is briefly presented which takes account of the relaxation energies involved in Auger transitions as well as in single photoionization.     

A review of auger photoelectron coincidence spectroscopy

The application of coincidence detection techniques produces a dramatic increase in the information obtained from particle and photon scattering studies. A clear illustration of this is given by Auger Photoelectron Coincidence Spectroscopy (APECS). By coincident detection of the ejected photoelectron and the resulting Auger electron during x-ray excited Auger spectroscopy, it is possible to distinguish the true origin of peaks and satellites within the Auger spectra. For example, it becomes possible to separate standard Auger processes from those occurring in conjunction with Coster-Kronig transitions and from those either followed or preceded by shake-off or shake-up transitions. In addition, the technique often allows the separation of overlapping series of Auger peaks, thus permitting the study of individual elements within compounds and alloys. These possibilities will be illustrated primarily by reference to APECS studies of 3d transition metal elements.     

X-ray and electron induced Auger processes for I2 adsorption on uranium

The accurate determination of the kinetic energy of X-ray induced Auger electrons, which is necessary in XPS experiments, e.g. for calculating the Auger parameter, is sometimes hampered by peak interferences or by the high secondary electron background. The latter is of special importance for low kinetic energy electrons like e.g. the U(OPV) and U(OVV) Auger electrons. These problems can be circumvented by using electron induced Auger transitions (AES). However, since XPS and AES use different reference points for the energy scales, both scales have to be matched. This can be done by measuring the kinetic energy of an appropriate Auger transition in XPS and relating this value to the maximum of the second derivative of the same peak in AES.     

Studies of the Auger spectrum from the (100) surface of GaAs using positron annihilation induced Auger electron spectroscopy

Measurements of the first high-resolution positron annihilation induced Auger spectrum from GaAs(100) are presented. The spectrum displays six As and three Ga Auger peaks below 110 eV, including a strong As M_4,5VV peak at 28 eV and a less intense Ga M_2,3M_4,5M_4,5 peak at 53 eV. The Auger peak intensities are used to obtain experimental annihilation probabilities for relevant core-level electrons. Experimental results are compared with first-principles calculations of positron surface states and annihilation characteristics of surface trapped positrons.     

A fast and simple method for background removal in Auger electron spectroscopy

A purely formal method for background removal in electron beam induced Auger electron spectroscopy is presented. The method has been developed for practical purposes. It is typically used to remove the background of a complete recorded spectrum, no fit is necessary to remove the backscattered electrons background. An overcompensation of the background, resulting in negative values of the background removed spectrum is not possible, all values of the background removed spectrum are positive or zero. Since the Auger peaks are separated by zeros after background removal, the method is well suited for peak finding and identification.     

Calculation of sulphur L(S2p)-MM Auger energies of H2S

The Auger energies of the L(S2p)-MM transitions of H₂S have been computed using MC SCF methods. The results are sufficiently accurate to assign the experimental spectrum and indicate large relaxation as well as large single-triplet splitting for low energy transitions.     

Final state correlation effects on the auger transition rates of methane

The doubly ionized Auger final states of CH₄ and the corresponding states of of Ne atom are studied by semi-internal configuration interaction (Cl) calculations. Correlation redistributes dramatically the intensities between the Auger diagram states and gives rise to strong satellite peaks in the law-kinetic-energy part of the spectrum.     

A fast and simple method for background removal in Auger electron spectroscopy

A purely formal method for background removal in electron beam induced Auger electron spectroscopy is presented. The method has been developed for practical purposes. It is typically used to remove the background of a complete recorded spectrum, no fit is necessary to remove the backscattered electrons background. An overcompensation of the background, resulting in negative values of the background removed spectrum is not possible, all values of the background removed spectrum are positive or zero. Since the Auger peaks are separated by zeros after background removal, the method is well suited for peak finding and identification.Dedicated to Professor Dr. H. Seiler on the occasion of his 65th birthday     

CO inner-shell excitation studied by electron impact spectroscopy

The inner-shell excitation and decay of the CO molecule have been studied in electron impact experiments. The dipole-forbidden transition (1sσ_c)⁻¹(2pπ) ³Π has been characterized by angular resolved electron energy loss spectroscopy and its decay via the measurement of resonant Auger spectra. The contribution of the (1sσ_c)⁻¹(2pπ) ³Π state to the CO resonant Auger spectrum in the region of the “spectator transitions” has been isolated and the population of CO⁺ quartet final states has been observed.