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.     

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.     

Oxygen chemisorption and initial oxidation of Cr(110)

The initial stages of the interaction of oxygen with a Cr(110) surface have been investigated at 300 K by LEED, AES, electron energy loss spectroscopy (ELS), secondary electron emission spectroscopy (SES) and work-function change measurement (Δφ). In the exposure region up to 2 L, the clean-surface ELS peaks due to interband transition weakened and then disappeared, while the ～5.8 and 10 eV loss peaks attributed to the O 2p → Cr 3d transitions appeared, accompanied with a work-function increase (Δφ = +0.19 eV at2L). In the region 2–6 L the work function decreased to below the original clean-surface value (Δφ_min = ?0.24 eV at6L), and five additional ELS peaks were observed at ～2, 4, 11, 20 and 32 eV: the 2 and 4 eV peaks are ascribed to the ligand-field d → d transitions of a Cr³⁺ ion, the 11 eV peak to the O 2p → Cr 4s transition, the 20 eV peak to the Cr 3d → 4p transition of a Cr³⁺ ion and the 32 eV peak probably to the Cr 3d → 4f transition. A new SES peak at 6.1 eV, being attributed to the final state for t he 11 eV ELS peak, was observed at above 3 L and identified as due to the unfilled Cr 4s state caused by charge transfer from Cr to oxygen sites in this region. In the region 6–15 L the work function increased again (Δφ_max = +0.32 eV at15 L), the 33 and 46 eV Auger peaks due to respectively the M_2,3(Cr)L_2,3(O)L_2,3(O) cross transition and the M_2,3VV transition of the oxide appeared and the 26 eV ELS peak due to the O 2s → Cr 4s transition was also observed. Above 10 L, the ELS spectra were found to be practically the same as that of Cr₂O₃. Finally, above 15 L, the work function decreased slowly (Δφ = +0.13 eV at40L). From these results, the oxygen interaction with a Cr(110) surface can be classified into four different stages: (1) dissociative chemisorption stage up to 2 L, (2) incorporation of O adatoms into the Cr selvedge between 2–6 L, (3) rapid oxidation between 6–15 L leading to the formation of thin Cr₂O₃ film, and (4) slow thickening of Cr₂O₃ above 15 L. The change in the Cr 3p excitation spectrum during oxidation was also investigated. The oxide growth can be interpreted on the basis of a modified coupled current approach of low-temperature oxidation of metals.     

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.     

Distribution d'énergie des électrons secondaires émis par InP et GaP soumis à un bombardement d'ions Ar de 40 keV

The energy distributions N(E) of secondary electrons emitted from GaP and InP samples bombarded with 40 keV Ar⁺ ions have been studied by a retarding potential method and an electronic derivation. The spectra show beyond an intensive peak developed at 2 eV, a detailed spectrum between 80 and 140 eV. The analysis of this spectrum reveales Auger electrons corresponding to L₂₃(P) VV and L₂₃M_IV–V(Ga) V [or L₂₃(P) N_IV-V(In) V] transitions; moreover, peaks due to plasmon excitations and d band excitations can be distinguished.     

SrTiO3(100) step sites as catalytic centers for H2O dissociation

Features arising from surface Sr(Ti) atoms on the SrO(TiO₂) terraces of SrTiO₃ (100) have been resolved in core-level photoemission spectra, which provides new insights into the surface electronic structure and reactivity of transition metal oxides. The surface Sr 3d (Ti3s) features lie to lower (higher) initial energy of the bulk-derived peaks by ca. 1.0 eV (1.7 eV), being consistent with the expected enhancement of covalent bonding in the TiO₂-terrace surface. Step-sites, which connect the two types of terrace, are found to act as catalytic centers for H₂O dissociation.     

Adsorption and reaction of bromine with Ag(110): A photoemission study

The adsorption of bromine on the (110) surface of silver has been studied by ultraviolet (hυ = 21.2 and 40.8 eV) photoelectron spectroscopy in the temperature range of 100–300 K. Four different adsorption and reaction states could be detected. For fractional monolayer coverages Br₂ adsorbs dissociatively on the Ag(110) surface. The chemisorption of bromide leads to new emission features at about 3 and 5.2 eV below E_F, which are assigned as occupied antibonding structures (3 eV) and as bonding Br4p_{x, y} orbitals (5.2 eV). At 100 K, further bromide adsorption leads to the formation of an AgBr layer with molecular adsorbed bromine on top of this corrosion layer. The He I spectrum is dominated by structures at 3.5, 5.8 and 7.5 eV which are due to emission from the π_g, π_u and σ_g molecular orbitals of Br₂. The buildup of the AgBr layer is clearly demonstrated by desorbing the molecular bromine at about 150 K. The resulting spectrum of the AgBr layer shows peaks at 2.5 and 3.4 eV with p- and mixed-in d-character and peaks at 4.1, 5.2 and 6.1 eV which are primarily d-like. Heating of the AgBr layer up to 300 K results in a transformation from a 2D layer into a 3D agglomeration of larger AgBr clusters on top of a Br/Ag(110) chemisorption layer.     

Angular distributions of auger electron emission: Clean and gas-adsorbed polycrystalline Ni surfaces

The excitation angle (β) and emission angle (θ) dependences of the Ni M₂,₃VV (61 eV) and Ni L₃VV (850 eV) Auger emissions from clean polycrystalline Ni surfaces, and the S L₂, ₃ M₂, ₃M₂, ₃ (150 eV) Auger emission from S-adsorbed poly-Ni surfaces have been investigated. In the case of Ni (61 eV) and S Auger emissions, the β-dependence shows the $\text{1}\text{cos β}$ distribution, while a significant deviation from $\text{1}\text{cos β}$ is observed for Ni (850 eV) Auger emission. The cosθ distribution and the intermediate between isotropic and cosθ distributions are observed for Ni (61 eV), and for Ni (850 eV) and S Auger emissions, respectively. Those results have been found to be in fairly good agreement with the calculations based on the simple continuum model without consideration of the diffraction effect and the inherent anisotropic emission.     

Photoelectron spectra of adsorbed carbonates

In order to provide photoelectron spectra for analytical purposes, X-ray and ultraviolet photoelectron spectra for known surface species have been measured. The surface carbonate on Ag(110), formed by reacting gaseous CO₂ with pre-adsorbed atomic oxygen, yields C 1s and O 1s peaks at 287.7 and 529.9 eV, respectively. The UPS results show features due to surface CO₃ which scale well with those for bulk carbonates. These observations, coupled with the increase in work function that accompanies carbonate formation, suggest strongly that this surface species is negatively charged.     

Characteristic electron energy loss structure for clean and oxidized chromium surfaces

AES and EELS spectra have been measured on clean and oxidized chromium surfaces. Auger peaks at 31.0 and 44.0 eV of the oxide are attributed to cross transitions between chromium and oxygen: {M_2,3(Cr)V(Cr)V(O)} and {M₁(Cr)L₁(O)V(Cr)} respectively. Core loss features are consistent with valence band structure with a newly observed loss peak at 41.1 eV for the oxidized surface being ascribed to a core exciton with binding energy E_b = 1.6 eV.     

Anomalous Auger-electron spectra of metallic calcium

A1Kα-excited L_{2, 3}MM and L_{2, 3}MV Auger-electron spectra of Ca have been measured in ultrahigh vacuum from a metallic sample evaporated onto an Ag substrate. An interpretation of the spectra is made by applying a line-fitting procedure. The lineshape and the solid-state—free-atom kinetic-energy shift are also studied. The extrinsic loss structure in the L_{2, 3}MM Auger-electron emission is found to be similar to that in 2p photoelectron emission. Spin—density-functional (SDF) calculations for the singularity index describing the intrinsic lineshape give a value of ～ 0.35 for both processes. Thus the experimental 2p_3/2 photoelectron line broadened from 1.2 to ～ 5 eV FWHM has been used as a standard line in the line fitting of the L_{2, 3}MM transitions. The term splitting of the L_{2, 3}M_{2, 3}M_{2, 3} transition is larger than in the corresponding free-atom spectrum. This result is also supported by the SDF calculations. The L_{2, 3}M_{2, 3}V spectrum is anomalously sharp, probably both because of the structure of the local density of states at the site of the core-ionized atom and because of differences in the transition probabilities into the different parts of the band. The experimental solid-state shift is 20.3 eV for the L_{2, 3}M_2,3M_{2, 3}:¹D transition, and the binding-energy shifts are 8.3 and 6.1 eV for the 2p and 3p levels, respectively. The SDF shifts for the above transitions are 19.9 (configurational average), 9.4 and 8.0 eV, consecutively, in agreement with the experimental values. The calculations also show a localized d-type (atomic-like) structure for the screening of the initial- and final-state core hole (s). This is the origin of the large values of both the singularity index and the solid-state shift.     

Isochromat spectroscopy on CePd3

Isochromat spectra from CePd₃ recorded at quantum energies of 9.7 and 72.7 eV are presented. The data obtained at 9.7 eV show three different peaks and are by and large identical to previously published data for a quantum energy of 1486 eV. Only two of those three peaks are present in the 72.7 eV spectrum. We conclude that the missing peak is bulk in origin and derives from a Ce5d-Pd4d hybridization leading to a Ce5d split off level from the filled Pd d-band.     

Delayed onset of 4d photoemission relative to the giant 4d photoabsorption of La

For the giant 4d photoabsorption of La, both the total photoabsorption spectrum and the N_4.5-derived Auger emission intensity spectrum increase significantly above hν ? 112 eV, with spectral peaks at hν = 118 and 119 eV, respectively. However, the predominant 4d photoemission partial cross section shows a delayed onset of ～ 4 eV, with a peak at hν = 121 eV, while the 5s, 5p, and 5d partial cross sections all show a strong resonant enhancement at lower energies, with spectral peaks at hν = 116.6 eV. These results are compared with a recent many-body calculation for Ce. The photon energy dependence of the La 4d_{$\text{5}\text{2}$}/4d_{$\text{3}\text{2}$} photo-emission branching ratio is consistent with a “final-state model.”     

Auger- und Coster-Kronig-Übergänge der M-Schale von Krypton

The Auger spectra of theM ₂,M ₃,M ₄,M ₅ subshells of krypton and the Coster-Kronig spectra of theM ₁,M ₂,M ₃ subshells of krypton were measured with an electrostatical spectrometer. The ionization in theM shells was caused by electron impact. The use of a gaseous target made it possible to measure the Auger lines even at energies as low as 25 eV. The absolute energies and relative intensities of a great number of transitions were determined: 22 of theM _{4, 5} spectrum, 14 of theM _{2, 3} spectrum and 2 of theM ₁ spectrum. Only in the case of theM _{2, 3} spectrum a comparison between the relative intensities, determined experimentally, and those calculated byRubenstein forZ=47 was possible. The agreement is only qualitatively. Moreover, from the Auger electron energies measured, the following binding energies were calculated:E(M ₁)=(292,1±1,0) eV,E(M ₂)=(222,1±0,6) eV,E(M ₃)=(214,6±0,6)eV,E(N ₁ N ₁)=(62,81±0,05) eV.     

Surface chemistry of Fe2O3 nanoparticles on ultrathin oxide layers on Si and Ge

In this paper, we report on a comparative study of the effect of Fe₂O₃ nanoparticles (NP), introduced onto a thin oxide layer formed on silicon and germanium surfaces, on the thermal decomposition pathway of the individual oxide layers. On both the surfaces, NP of Fe₂O₃ undergo a reduction reaction through a bonding partner change reaction, where the oxygen atoms change from Fe to Si or Ge. On both the surfaces, annealing results in the conversion of the suboxide-like species to dioxide-like species (SiO_x to SiO₂ and GeO_x to GeO₂ respectively for Si and Ge surfaces), until the oxide layer decomposes following the desorption of the respective monoxide species (SiO and GeO). Both the Si and Ge corelevels show a larger chemical shift (4.1 and 3.51 eV in Si 2p and Ge 3d corelevels, respectively) for the as-prepared oxide samples with the NP, at room temperature compared to that without the NP (3.7 and 3.4 eV), indicating a catalytic enhancement of the dioxide formation. Selective formation of silicon oxides leads to encapsulation of the nanoparticles and acts like a protective layer, preventing the oxidation of Fe.     

Electron energy-loss spectroscopy study of oxygen chemisorption and initial oxidation of Fe(110)

The initial stages of the interaction of oxygen with an Fe(110) surface have been studied at 300 K by electron energy-loss spectroscopy with in-situ combined low energy electron diffraction, Auger electron spectroscopy and work-function change measurement. From all the results, four different stages of the oxygen interaction are distinguished: (I) a first dissociative chemisorption up to 3 L, characterized by the c(2×2)-O structure, (II) a second dissociative chemisorption between 3 and 7 L, characterized by the c(3×1)-O structure, (III) incorporation of O adatoms into the selvage between 7 and 30 L, and (IV) oxidation above 30 L leading to the formation of FeO(111), characterized by the diffuse hexagonal diffraction pattern. The sticking probability was found to be initially near unity and fall off rapidly to a minimum value of ≈0.05 at ≈1 L. Particular emphasis was placed upon the investigation of the change in surface electronic properties from those characteristic of them metal to those of the oxide. In stage (I) an energy-loss peak, being attributed to the transition from the 2p orbital of the chemisorbed oxygen, was observed at 6.0 eV, while in stage (II) two additional peaks of the same origin appeared at 7.5 and 9.3 eV due to the formation of the O 2p band. The energy-loss spectrum in the oxide phase was characterized by the peaks at 4.8 and 7.5 eV due to the O²⁻ 2p → Fe²⁺3d charge-transfer transitions and by a peak at 2.4 eV due to the ligand-field d → d transitions of an Fe²⁺ ion in FeO. It is shown that the Fe 3d_yz,zx and 4sp electrons play a major role in the chemisorption bond (O adatoms located in the long-bridge site), and that for the incorporation process the Fe 3d_y² electrons are also involved in bonding by the symmetry breaking. The change in the Fe 3p-excitation spectrum during oxidation was also investigated. The differences between the experimental results on Fe(100) and (110) surfaces are summarized.     

The kinetics of vacancy annihilation and short range order formation in Ni 11.4 at % Cr

In Ni-Cr alloys annealing after quenching from high temperatures leads to an increase of electrical resistivity which is attributed to a short range order state often denoted as K-state. Here the kinetics of the formation of the K-state in a Ni 10% Cr alloy is investigated by resistivity measurements for different quenching and annealing temperatures. The measurements are analyzed by an extended Schulze-Lücke method [22] which assumes that the rate of resistivity change is proportional to the vacancy concentration and that this rate as well as the rate of vacancy annihilation is described by a chemical rate equation.This analysis allowed a quantitative determination of the parameters determining the kinetics of short range order formation under different vacancy concentrations as well as the kinetics of annealing out of the quenched-in surplus vacancies. Among other quantities this treatment yielded the activation energies for vacancy formation H_F = 1.16 eV, for vacancy migration H_M = 1.56 eV and, as an independent cross check, for self diffusion H_D = 2.73 eV in good agreement with H_F + H_M = 2.72 eV.     

Untersuchung über den einfluss von adsorbierten gasen auf die elektronen-energieverlust-spektren einer Ni(110)-oberfläche

Electron energy loss spectra on a (110) nickel surface exhibit characteristic changes upon adsorption of H₂, CO and O₂. The clean surface shows only the surface and bulk plasmon losses at 8 eV and 18 eV respectively. Adsorption of CO produces two new loss peaks at 13.5 eV and 5.5 eV. Loss peaks due to hydrogen adsorption at 15 eV and 7.5 eV show a strong correlation with the well known adsorption characteristics of this system. The oxygen induced losses are different for chemisorbed O on Ni and NiO. In any case the chemisorption-induced losses are well established for primary energies below 120eV. In the loss spectra with higher excitation energies only a drastic decrease of the surface plasmon loss peak-height is visible. If the new losses can be attributed to one-electron excitations from molecular orbital levels due to the chemisorption bond, with assumptions of the final state of the excited electron a determination of the postition of these levels can be made. In case of CO and H₂ reasonable results are evaluated.     

The influence of pressure on the electrical conductivity of molten zinc chloride and its Mixtures with potassium chloride

Abstract

The electrical conductivities of molten ZnCl₂ and its mixtures with KCl were measured as functions of pressure, temperature, and composition. The measuremkents were performed in an internally heated pressure vessel in which the melts were contained in open quartz glass cells. The addition of KCl to molten ZnCl₂ causes a large increase of the conductivity at all pressures and temperatures. With increasing pressure the conductivity increases in pure molten ZnCl₂ and in mixtures rich in ZnCl₂ and decreases in mixtures with more than 30 mol% of KCl.     

Structure electronique des oxydes de cobalt CoO et Co3O4

The total density of occupied states in the valence band of CoO and Co₃O₄ is determined by XPS and UPS. From variations of excitation probability of the bands, the 4 e V wide O2_p band is shown to be located around 5 eV for both oxides, while structures obtained from photoionisation of the localized 3d band spread over 10 eV range below the Fermi level overlapping with O2_p band. The 3d peaks located at binding energy <3 eV correspond to the calculated energy of the d_n ?1 manifold final state in the octahedral and tetrahedral crystal field of CoO and Co₃O₄. The 3d levels at higher binding energy are shown to occur from configuration interaction in both final and initial states. These last peaks are higher in intensity for CoO relative to Co₃O₄. A superior limit for the width of the 3d initial band in a one electron energy diagram is given to be <3 eV. This value associated to the Coulomb correlation energy measured equal to ~3 eV. This value associated to the Coulomb correlation energy measured equal to ~3 eV from shake-up and Auger energy confirms the Mott insulator nature of CoO.