Disorder broadening of alloy Auger spectra

Auger spectroscopy promises the means to separate initial and final state contributions to the disorder broadening of core XPS spectra in disordered alloys. Auger disorder broadening, deduced from recent ab initio results, is predicted to be greater than XPS disorder broadening for Cu₅₀Pd₅₀ and Ag₅₀Pd₅₀ alloys. Simulations are used to assess whether this effect is observable experimentally despite the greater lifetime broadening of Auger spectra. A number of cases where narrow core–core–core Auger transitions should allow clear experimental identification of this effect are identified. The prospects for determining environment-resolved Auger spectra using APECS have been investigated.     

Many-body effect in the coincidence L3 and M3 photoelectron spectroscopy spectra of Cu metal

The coincidence L₃ and M₃ photoelectron spectroscopy (PES) main lines of Cu metal are calculated by a many-body theory. There is no peak-energy shift between the singles PES main line and the coincidence one. The asymmetric narrowing of the coincidence PES main line on the low kinetic energy (KE) side is very small. This is in accord with recent experimental findings. In Cu metal, the shakeup satellite intensity is small and the main-line satellite separation energy is much larger than the core–hole lifetime width. The interference via the final-state interaction is negligible. In the PES main line, the imaginary part of the self-energy by shakeup excitations, which is very small compared to the core–hole lifetime width, decreases very slowly in linear with photoelectron KE. The branching ratio of Auger decay of a single hole state then increases very slowly in linear with photoelectron KE so that the deviation of the coincidence PES main line from the singles one is very small. The 939 eV structure seen only in the coincidence L₃ PES spectrum of Cu metal is attributed to the enhancement of the inelastic peak of a smaller energy loss due to electrons of a smaller average emission depth measured in coincidence with the elastic Auger peak. The structure will not be enhanced in the singles PES spectrum. The background subtraction in the coincidence spectrum cannot be the same as that in the singles one. Such consideration is necessary before we can conclude about the asymmetric narrowing on the low KE side. A unique capability of APECS by which one can determine the photoelectron KE dependent part of the imaginary part of the self-energy is pointed out.     

Many-body effect in the M45–N23N45–N45N45N45 coincidence spectroscopy spectra of metallic elements around Cd

The quasi-particle approximation for the 4p4d state of the metallic elements around Cd breaks down because of very rapid 4p4d–4d³ super Coster–Kroning (sCK) decay of the 4p hole in the presence of the spectator 4d hole. Here the underbar is a hole. As a result, the 4p4d multiplet coupling breaks down. We can examine the presence or absence of the 4p4d multiplet by Auger-electron sCK-electron coincidence spectroscopy measurement of the 3d–4p4d–4d³ Auger-preceded sCK transitions. We collect the sCK-electrons in coincidence with the Auger-electrons of a selected kinetic energy (KE) and vice versa. If the multiplet coupling breaks down and does not exist, the coincidence sCK-electron (or Auger-electron) lines shift as much as the Auger-electron (or sCK-electron) analyzer's selected KE is varied. We can determine not only the three 4d-hole sCK final-state energy but also the presence or absence of the 4p4d multiplet by Auger-electron sCK-electron coincidence spectroscopy. The unique capability of the coincidence measurement by which one can determine the correlation between an Auger-electron and a sCK electron generated, respectively, by creation and annihilation of the same Auger two-hole final state is very useful, even when the quasi-particle approximation of the two-hole state breaks down.     

Many-body effect in the N23-VV Auger-photoelectron coincidence spectroscopy (APECS) spectra of Ag metal

The coincidence N23-VV Auger-electron spectroscopy (AES) spectra and N23 photoelectron spectroscopy (PES) spectra of Ag metal are analyzed. Here NX is the notation for atomic shell Nx (X = 2, 3). The band-like feature in the coincidence N23-VV AES spectra is much more intense than that in the coincidence M45-VV ones because the potential in the delocalized two-hole state is less attractive than that in the localized one. The partial N23-VV super Coster–Kronig (sCK) transition rate depends critically on both the final-state potential and the sCK-electron kinetic energy (KE) because the KE is low, whereas the partial M45-VV Auger-transition rate is fairly independent of them because the KE is very high. As a result, the partial sCK-transition rate to the band-like state is enhanced compared to that to the atomic-like localized state. The low KE tail in the coincidence N23-VV AES spectra which is likely due to the sCK transition involving more than two electrons, is more enhanced than that in the coincidence M45-VV ones. This is due to the enhancement of the partial sCK-transition rate by the presence of extra holes in the final state. The sharp peaks of small intensity on the lower KE side of the main line in the coincidence N2 PES spectrum are tentatively attributed to the shakeup satellites.     

Development of a miniature double-pass cylindrical mirror electron energy analyzer (DPCMA), and its application to Auger photoelectron coincidence spectroscopy (APECS)

We have developed a miniature double-pass cylindrical mirror electron energy analyzer (DPCMA) with an outer diameter of 26 mm. The DPCMA consists of a shield for the electric field, inner and outer cylinders, two pinholes with a diameter of 2.0 mm, and an electron multiplier. By assembling the DPCMA in a coaxially symmetric mirror electron energy analyzer (ASMA) coaxially and confocally we developed an analyzer for Auger photoelectron coincidence spectroscopy (APECS). The performance was estimated by measuring the Si-LVV-Auger Si-1s-photoelectron coincidence spectra of clean Si(1 1 1). The electron-energy resolution of the DPCMA was estimated to be E/ΔE = 20. This value is better than that of the miniature single-pass CMA (E/ΔE = 12) that was used in the previous APECS analyzer.     

X-ray photoelectron and X-ray Auger electron spectroscopy studies of heavy ion irradiated C60 films

The influence of 200 MeV Au ion irradiation on the surface properties of polycrystalline fullerene films has been investigated. The X-ray photoelectron and X-ray Auger electron spectroscopies are employed to study the ion-induced modification of the fullerene, near the surface region. The shift of C 1s core level and decrease in intensity of shake-up satellite were used to investigate the structural changes (like sp² to sp³ conversion) and reduction of π electrons, respectively, under heavy ion irradiation. Further, X-ray Auger electron spectroscopy was employed to investigate hybridization conversion qualitatively as a function of ion fluence.     

Study of ion desorption induced by a resonant core-level excitation of condensed NH3 using Auger-electron photo-ion coincidence (AEPICO) spectroscopy combined with synchrotron radiation

Photostimulated ion desorption at the 4a₁ ← N 1s resonant transition of condensed NH₃ was studied using electron emission spectroscopy and Auger-electron photoion coincidence (AEPICO) spectroscopy. The total ion yield divided by the Auger-electron yield exhibited a threshold peak at hν = 399 eV which is ascribed to the resonant transition from the N 1s to the N---H antibonding 4a₁ orbital. The electron emission spectrum at the 4a₁ ← N 1s resonance is decomposed into three components: a valence photoelectron emission spectrum, and normal- and resonant-Auger-electron emission spectra. We ascribe the resonant-Auger-electron emission spectrum mainly to spectator-Auger transitions on the basis of the peak assignment. A series of AEPICO spectra at the 4a₁ ← N 1s resonance was also measured as a function of the Auger-electron kinetic energy. The electron kinetic energy dependence of the H⁺ AEPICO yield displays a shape approximately similar to that of the mixed spectrum of normal- and spectator-Auger-electron emission spectra. Based on this result the H⁺ desorption at the 4a₁ ← N 1s resonance is concluded to originate from the spectator-Auger transitions and from the normal-Auger transitions following the delocalization of the excited electron.     

Many-electron effect in the angle resolved L3-M23M23 Auger-photoelectron coincidence spectroscopy (APECS) spectrum of metallic Zn

The many-body effect in the L₃-M₂₃M₂₃ Auger-electron spectroscopy (AES) spectrum of metallic Zn is discussed. The lifetime width and residual relaxation energy shift of the two M₂₃-hole state are governed by the (super) Coster-Kronig (sCK) transitions of two M₂₃-hole state. The residual relaxation energy shift and decay width of the two M₂₃-hole state are calculated in an average configuration by an ab initio atomic many-body theory. The agreement with experiment is good. To elucidate the many-body effect in the two-hole states, it is necessary to be able to discriminate individual components of the multiplet-split AES spectrum. We discuss how to discriminate individual components of the multiplet-split L₃-M₂₃M₂₃ AES spectrum of metallic Zn by angle-resolved Auger-photoelectron coincidence spectroscopy (AR-APECS) in order to determine accurately their line shapes, multiplet splitting energies, and spin states (singlet etc.).     

Many-electron effect in the Fe L3-M4,5M4,5 Auger electron spectrum of ultrathin Fe films grown on Cu(1 0 0)

D’Addato et al. [S. D’Addato, P. Luches, R. Gotter, L. Floreano, D. Cvetko, A. Morgante, A. Newton, D. Martin, P. Unsworth, P. Weightman, Surf. Rev. Lett. 9 (2002) 709] studied the variation with Fe coverages in the relative Fe L₃-M_4,5M_4,5 Auger electron spectroscopy (AES) spectral satellite intensity of ultrathin Fe films grown on Cu(1 0 0) by sweeping photon excitation energy through the Fe L₂-level ionization threshold. They interpreted that the M_4,5 hole in the L₃M_4,5 double-hole state created by the L₂-L₃M_4,5 Coster–Kronig (CK) decay remains localized for longer than the L₃-hole lifetime for the 0.3 and 10 ML coverages but has a lifetime comparable to the L₃-hole lifetime for the 1 ML coverages. The present many-body theory shows that when the M_4,5 hole created either by the CK decay or by the L₃M_4,5 shakeoff hops away from the ionized atomic site and becomes completely screened out prior to the L₃-hole decay, the Fe L₂-L₃M_4,5-L₃-M_4,5M_4,5 AES main line as well as the Fe L₃ M_4,5 (satellite)-L₃-M_4,5M_4,5 one, both of which are identical in line shape to the Fe L₃-M_4,5M_4,5 one, dominate in the Fe CK preceded AES spectrum. The present analysis shows that the delocalization time of the M_4,5 hole created in the 1 ML Fe/Cu(1 0 0) system by the L₂-L₃M_4,5 CK decay is much shorter than the L₃-hole lifetime so that the Fe L₃-M_4,5M_4,5 AES spectral line shape hardly changes, except for the presence of a very weak spectator L₂-L₃M_4,5-M_4,5M_4,5M_4,5 AES satellite, when the photon excitation energy is swept through the Fe L₂-level ionization threshold. For the 0.3 ML coverages the M_4,5-hole delocalization time is still shorter than the L₃-hole lifetime.     

Auger electron spectroscopic study of the surface oxidation of uranium-niobium alloy {U-6 wt.% Nb} in a UHV environment containing primarily H2, H2O and CO

Auger electron spectroscopy has been used to study the surface oxidation of a uranium-niobium alloy, U-6 wt.% Nb, in a UHV environment containing primarily H₂, H₂O and CO. For comparison, the reaction of the oxidative species with pure uranium and niobium metals has also been investigated. The observed changes of the shape and position of the Auger transition peaks for U, Nb and O following exposures this UHV environment up to 200 L, and under a continuous electron bombardment indicated that oxidation of the alloy leads, first, to the formation of a surface oxide consisting of UO_2.0. The formation of this oxide was followed by the development of Nb-oxides (NbO, NbO₂ and Nb₂O₅) at the metal-oxide interface. Pure uranium was found to exhibit faster oxidation kinetics than the alloy, while pure niobium oxidised at a much lower rate than the uranium based materials.     

The lowest 4f-to-5d and charge-transfer transitions of rare earth ions in YPO4 hosts

In order to study the high-energy optical transitions i.e. 4f-to-5d (f–d) and charge-transfer (CT) spectra of trivalent rare earth (4fⁿ-series, lanthanide) ions in crystal lattices, the luminescence excitation spectra of the series ions in YPO₄ host lattices are measured in a VUV–UV spectral region of 120–350 nm. The f–d bands are observed with all of the series ions except for the ions with the transition energy higher than the host lattice absorption edge i.e. except for Gd³⁺ and Yb³⁺, and the CT bands are observed except for Ce³⁺, Gd³⁺ and Tb³⁺ (Pm is unavailable).

Jørgensen's formulation which has elucidated the systematic variation of the energies of the f–d and CT transitions through the 4fⁿ-series is modified in a form of a single-electron scheme. The many-electron effects in the scheme are calculated and presented as a numerical table. The energies of the observed f–d and CT bands fit well with those calculated by the use of this table.     

The pure rotational spectra of the two lowest energy conformers of the asymmetric ether C4H9OC2H5

An experimental study has been performed shedding light on the conformational energies of the asymmetric ether n-butyl ethyl ether. Rotational spectroscopy between 7.8 GHz and 16.2 GHz has identified two conformers of n-butyl ethyl ether, C₄H₉OC₂H₅. In these experiments spectra were observed as the target compound participated in an argon expansion from high to low pressure causing molecular rotational temperatures to be below 4 K. For one conformer, 95 pure rotational transitions have been recorded, for the second conformer, 20 pure rotational transitions were recorded. Rotational constants and centrifugal distortion constants are presented for both butyl ethyl ether conformers. The structures of both conformers have been identified by exploring the multi-dimensional molecular potential energy surface using ab initio calculations. From the numerous low energy conformers identified using ab initio methods, the three lowest conformers were pursued at increasingly higher levels of theory, i.e. complete basis set extrapolations, coupled cluster methods, and also taking into consideration zero point vibrational energies. The two conformers observed experimentally are only revealed to be the two lowest energy conformers when high levels of quantum chemical methodologies are employed.