Auger-vacancy satellites in the decay of 82Pb (RaD)

The L-Auger spectrum of ²¹⁰Bi from RaD (²¹⁰Pb) has been studied with a resolution of 0.18% and a very thin source but with some sacrifice in statistics. A total of 65 lines or line groups have been wholly or partially identified. The L₃-MM lines, most of which result from filling L₃ vacancies created by the L₁-L₃M_{4, 5} Coster-Kronig process, are displaced an average of −36±5 eV with respect to the energies expected from the L_{1, 2}-MM spectra. This effect is the Auger analogue of the phenomenon of X-ray satellites. The L₃-M₄M₅ and L₃-M₅M₅ displacements agree within experimental error with predictions from the displacements of the strongest L₁ and L₂ X-ray satellites. We suggest the term Auger-vacancy satellites for these displaced Auger lines to distinguish them from the weak lines of the K-LL spectrum for which we suggest the term Auger Intermediate-Coupling Satellites. The ratio (L₁-M₄M₅ Auger Line)/L₁-vacancies = R = 32.5±3.5, which may have importance in determining L₁ capture as distinct from L-capture, was also measured for the first time. The end-point of the low-energy beta spectrum of ²¹⁰Pb was found to be 17.0±0.5 keV.     

Why are the band-like states suppressed in the M3–M4,5M4,5 super Coster–Kronig electron spectrum of Cu metal compared to those in the L3–M4,5M4,5 Auger electron spectrum?

The relative spectral intensity of the band-like two M_4,5-hole state to the atomic-like localized one is much suppressed in the coincidence M₃–M_4,5M_4,5 super Coster–Kronig (sCK) electron spectrum of Cu metal compared to the one in the coincidence L₃–M_4,5M_4,5 Auger electron spectroscopy (AES) spectrum. The M₃-hole lifetime width of Cu metal is calculated by an ab initio atomic many-body theory (the extended relaxed core random phase approximation with exchange). The calculated M₃-hole lifetime width of Cu metal agrees well with the experimental one. The M₃–M_4,5M_4,5 sCK decay width of Cu metal decreases much with delocalization of the two M_4,5 holes in the sCK final state, whereas the Auger decay width is fairly independent of localization and delocalization of the two M_4,5 holes in the Auger final state. Thus, the relative spectral intensity of the band-like state is much suppressed in the coincidence M₃–M_4,5M_4,5 sCK-electron spectrum of Cu metal compared to the one in the coincidence L₃–M_4,5M_4,5 AES spectrum.     

High-resolution KLM Auger spectra of Ni metal excited by X-rays

KLM Auger spectra of Ni metal were measured with high energy resolution and high statistical accuracy using monochromatic synchrotron radiation. The spectra were corrected for the background from inelastically scattered electrons using partial intensity analysis where the electron trajectories were calculated by Monte Carlo simulation. Following background correction, the corrected spectra were fitted to model peaks taking into account intrinsic excitations. The measured transition energy of the most intense KL₂M₃ (¹D₂) Auger line is 7388.1 eV (0.4). The obtained relative intensities and energies of the Auger diagram lines are compared to published calculations as well as to experimental data for other 3d transition metals. In addition, the presence of Ni 3s, 3p photoelectron peaks in the spectra excited internally by Ni K X-rays is shown.     

Auger energy shifts in fcc AgPd random alloys from complete screening picture and experiment

We extend the complete screening picture to ab initio calculations of Auger kinetic energy and Auger parameter shifts in metallic alloys. Experimental measurements of the L(3)M(4,5)M(4,5) Auger transition in fcc AgPd random alloys are compared with first-principles calculations and the results are in excellent agreement for both the Ag and Pd Auger shifts over the whole concentration range. We discuss the Auger kinetic energy shifts in terms of single-hole states for the 2p(3/2) core level and double-hole states for the 3d(5/2) level.     

Line shape and lifetime in argon 2p electron spectroscopy

The argon 2p photoelectron spectrum and the argon L₃M₂₃M₂₃ ¹S₀ Auger spectrum have been measured at several photon energies between 6 and 80 eV above the 2p_3/2 threshold with an instrumental line width significantly smaller then the natural line width. The spectra are described well by the theory of van der Straten et al. [Z. Phys. D 8 (1988) 35] provided that allowance is made for the instrumental resolution and measurements are made at a sufficiently low pressure. The lifetime (Lorentzian) line width determined from these measurements for the core-ionized atom is 112±3 meV, in good agreement with the line width for the 2p_3/2→4s core-excited state, 114±2 meV, indicating that the 4s electron has little influence on the Auger decay rate. Remeasurement of the line width for the carbon 1s hole in carbon dioxide gives values in good agreement with the previous measurement of 99 meV.     

A study of atomic iodine and molecular thallium iodide by X-ray photoelectron and auger electron spectroscopy

The I3d5/2 binding energy has been measured in atomic iodine, thallium iodide and cesium iodide by high temperature gas-phase photoelectron spectrscopy using Al K (1486.6 eV) X-rays. The iodine M₅N_4,5N_4,5 (¹G₄) Auger energies for TlI and CsI have also been measured and combined with binding energies to yield extra-atomic relaxation energies of 0.5 and O.3 eV, respectively, after corrections are applied to the Auger parameter. Charges were calculated using the simple potential model, which was also used to obtain an estimate of the atomic T14f binding energy. Two other estimates of the atomic T14f7/2 binding energy have also been calculated, both based on Dirac-Fock ΔSCF binding energies. The results of the three methods suggest a value of 125.3 ± 0.2 eV for T14f7/2.     

High-resolution LMN and LMM Auger spectra of Pd,Ag, In,Sn and Sb

Considerable interest in high-resolution Auger spectroscopy of the 4d metals has arisen because of the possibility of treating Auger spectroscopy as an excited state probe in order to extract new information regarding electronic structure. Auger transitions involving only core levels are interesting because current theories of line shapes and energies usually assume that the final core holes are either atomic or quasi-atomic. Comparison of the results of atomic calculations with experimental Auger spectra comprises a crucial test of the atomic theories.We present the results of high-resolution measurements of several high energy LMN and LMM Auger spectra of Pd, Ag, In, Sn and Sb excited with Ti Kα radiation. Assignments of the peaks are based upon energy and intensity considerations. We compare the experimental spectra with the results of atomic transition probability calculations, which indicates the reliability of such calculations as we proceed from open to closed 4d shell metals.     

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.     

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.     

High energy satellites in Auger spectra from metals

Auger spectra from Mg and Li suggest that the high energy satellites observed in some metals are due to double ionization rather than to a coupled plasmon-hole excitation.     

3 to 15 keV Ar+ induced Auger electron emission from Si and Ar

Ar⁺ induced Auger electrons from Si and Ar were investigated at bombardment energies between 3–15 keV and target currents of a few μA. The Auger electron yields were compared with secondary ion yields of Si and Ar by simultaneous SIMS-AES measurements. In the ion induced Auger spectra of Si five Auger peaks and in the Ar spectra three Auger peaks were observed. The ion induced Auger electron yield of Si and Ar were found to be strongly dependent upon the primary ion energy. “Bulk like” and “atomic like” Auger transitions of ion induced Auger electrons of Si were observed.     

Auger kinetic energies and electronic relaxation phenomena in atoms and solids

A semi-empirical theory has been developed to calculate the kinetic energy of Auger electrons resulting from radiationless transitions in both free atoms and metals. Experimental electron binding energies and calculated two-electron interaction and relaxation energies are used. Relaxation energies are determined by means of hyper-Hartree—Fock hole-state calculations. To account for extra-atomic relaxation phenomena in metals, it is assumed that conductionband electrons occupy free-atom-like screening orbitais. The relationship of the present theory to recent work of Shirley et al., Larkins, Kim et al. and Watson et al. is discussed. The dependence of the Auger cross-relaxation energy on the ionicity of compounds is briefly discussed.     

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.     

Resonant shake-up satellites in photoemission at the Ga 3p photothreshold in GaN

Photoemission spectra recorded near the Ga 3p photothreshold from GaN have been found to contain satellites of the main Ga 3d emission line. The intensity of these satellites resonate at this threshold, and are associated with a 3d⁸ state. The correlation energies and binding energies for the satellite multiplet have been measured for the satellite and related Auger transitions. The satellite multiplet contains additional constant binding energy features not observed in previous studies of other Ga compounds. The present results are compared with those for GaP and GaAs.     

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.     

Surface segregation in Pt-Au alloys studied using Auger electron spectroscopy

Temperature dependent surface segregation studies using Auger electron spectroscopy have been performed on three different Pt-Au alloys, containing 2, 5 and 90 wt% Au. By utilizing Auger transitions of different kinetic energies and model segregation profiles, an estimate of the in-depth variation in composition was made. Strong surface segregation of Au was observed in the three alloys.     

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.     

Photoelectron spectra of chromium tetranitrosyl

The ultraviolet and X-ray-excited photoelectron spectra of Cr(NO)₄ are reported. The electron binding energies, shake-up spectra, relative peak intensities and the Auger peak kinetic energies have been measured, and are compared to the spectra from gas-phase NO, from NO adsorbed on a transition metal surface, and to SCF-MS calculations. The theoretical calculations are utilized to obtain ionization energies and charge distributions, and consequently to discuss the bonding in nitrosyl complexes.