The influence of core hole relaxation on the main-line intensities in X-ray photoelectron spectra

The main photoelectron line spectroscopic factors that are currently used in photoelectron spectroscopy for quantitative analysis are calculated for a broad set of atoms. General trends of the behaviour of the spectroscopic factors of core atomic levels are discussed. The influence of the spectroscopic factors on the main line intensities and on concentrations of the elements, that are obtained using X-ray photoelectron spectra, is analysed.     

Relative intensities in X-ray photoelectron spectra

An experimental determination of the relative intensities of X-ray photoelectron lines corresponding to the inner levels of elements with Z ? 20, and calculations of the total photo-ionization cross-sections for all shells of these elements with the Hartree—Fock—Slater potential are reported. The experimental and theoretical values agree well for the 1s levels while marked discrepancies are revealed for the 2p levels. The theoretical values of the cross sections for the atomic valence levels are used to calculate the relative intensities of molecular levels in CF₄, BF₄^?, BeF₄^2?, LiF, NO₃^?, CO₃^2?, CO, N₂, CO₂, H₂O and C₄H₅N. The results of the calculations agree satisfactorily with experiment.     

Relative intensities in X-ray photoelectron spectra.: Part VIII

The photoionization cross-sections for the 3s and 3p shells of atomic Si, P, S, and Cl and the S²⁺ ion, and for the 2s and 2p shells of atomic F have been calculated using the random-phase approximation with exchange (RPAE) for the average-configuration term. Using the theoretical atomic cross-section values, the partial cross-sections for photoionization of the SF₆ molecule have been calculated for hv ? 54 eV and the photoelectron spectra have been interpreted. The calculation of relative intensities in the photoelectron spectra of H₂S is presented. The influence of the effective charge of an atom on the photoionization cross-section value for a molecular level is shown.     

Effects of epitaxial films of nanometric thickness on the X-ray photoelectron diffraction intensities from substrates

The effects on the X-ray photoelectron diffraction intensities from the substrate produced by epitaxial NiO(0 0 1) films of various thickness deposited on Ag(0 0 1) were investigated. The variations in the Ag XPD curves induced by the NiO films can be explained in terms of multiple scattering of the electrons emitted by the substrate atoms along the close-packed rows of the overlayer. Intensity minima in the XPD curves from the substrate in correspondence to intensity maxima in the XPD curves from the overlayer are observed when the thin film is commensurate with the substrate. For films of suitable thickness, the analysis of XPD curves from the substrate allows one to get information about the structure of the film and of the film–substrate interface.     

Quantitative XPS: I. Analysis of X-ray photoelectron intensities from elemental data in a digital photoelectron database

An analysis of the correlation of theoretical predictions for photoelectron intensities is made with experimental data from an XPS digital database for 46 solid elements measured using a spectrometer with calibrated intensity and energy scales. This analysis covers single element samples measured for Al and Mg K X-rays. The spectral data are for widescans at 1 eV energy intervals with kinetic energies from 200 to 1506 eV using Al X-rays and to 1273 eV using Mg X-rays. In addition are narrow scans around the photoelectron peaks at 0.1 eV energy intervals. All spectra have the instrument intensity/energy response function removed so that the peak areas are proportional to the number of electrons emitted per steradian per incident K photon. Correlations are made for the ionisation cross sections of Scofield and the inelastic mean free paths given by the TPP-2M formula. The correlations are excellent, apart from a factor which may be associated with the background removal arising from the use of the Tougaard Universal cross section. These correlations lead directly to pure element relative sensitivity factors suitable for quantitative analysis. General equations are also provided to extract values for a new form of relative sensitivity factor for an average matrix. These average matrix relative sensitivity factors lead to simpler equations involving matrix factors that are effectively unity instead of the traditional values in the range 0.3 to 3.0.     

The influence of elastic scattering of electrons on measured X-ray photoelectron signals

The basic equations for quantitative X-ray photoelectron spectroscopy (XPS) of uncovered and covered solid surfaces have to be corrected regarding the effect of elastic scattering processes of photoelectrons in matter. We propose two correction terms which were quantified on an empirical basis from the results of Monte Carlo calculations.     

The influence of relaxation and nondipole effects on the intensity of X-ray photoelectron spectra

The photoionization cross sections; dipole and nondipole parameters of the angular distribution of photoelectrons; and the spectroscopic factors for the main X-ray photoelectron lines, which are used in quantitative analysis of the surface and most of atoms, have been calculated. It is shown that consideration of nondipole effects leads to a significant (up to 10%) change in the photoelectron angular distribution. Therefore, neglect of nondipole transitions may lead to an error above 10% when MgK _α and AlK _α X-ray lines are used for surface analysis. Consideration of the spectroscopic factors leads to a decrease in the absolute line intensity by about 20%. Calculations showed that this value weakly depends on the atomic number and quantum shell numbers.     

Relative intensities in x-ray photoelectron spectra

An experimental determination of the relative intensities of X-ray photoelectron lines corresponding to the inner levels of elements with Z ? 20, and calculations of the total photo-ionization cross-sections for all shells of these elements with the Hartree—Fock—Slater potential are reported. The experimental and theoretical values agree well for the 1s levels while marked discrepancies are revealed for the 2p levels. The theoretical values of the cross sections for the atomic valence levels are used to calculate the relative intensities of molecular levels in CF₄, BF₄^?, BeF₄^2?, LiF, NO₃^?, CO₃^2?, CO, N₂, CO₂, H₂O and C₄H₅N. The results of the calculations agree satisfactorily with experiment.     

On line shape analysis in X-ray photoelectron spectroscopy

Any solid state X-ray photoelectron spectrum (XPS) contains contributions due to multiple inelastic scattering in the bulk, surface excitations, energy losses originating from the screening of the final state hole (intrinsic losses), and, for non-monochromatized incident radiation, ghost lines originating from the X-ray satellites. In the present paper it is shown how all these contributions can be consecutively removed from an experimental spectrum employing a single general deconvolution procedure. Application of this method is possible whenever the contributions mentioned above are uncorrelated. It is shown that this is usually true in XPS to a good approximation. The method is illustrated on experimental non-monochromatized MgK spectra of Au acquired at different detection angles but for the same angle of incidence of the X-rays.     

X射线光电子能谱

X射线光电子能谱（X-ray photoelectron spectroscopy, XPS）技术也被称作用于化学分析的电子能谱（electron spectroscopy for chemical analysis,ESCA）.XPS属表面分析法,它可以给出固体样品表面所含的元素种类、化学组成以及有关的电子结构重要信息,在各种固体材料的基础研究和实际应用中起着重要的作用.文章简要介绍了XPS仪器的工作原理和分析方法,并给出了XPS在科学研究工作中的应用实例.     

X射线光电子能谱

X射线光电子能谱（X-ray photoelectron spectroscopy，XPS）技术也被称作用于化学分析的电子能谱（electron spectroscopy for chemical analysis，ESCA）．XPS属表面分析法，它可以给出固体样品表面所含的元素种类、化学组成以及有关的电子结构重要信息，在各种固体材料的基础研究和实际应用中起着重要的作用．文章简要介绍了XPS仪器的工作原理和分析方法，并给出了XPS在科学研究工作中的应用实例．     

Interpretation of intensities in electron-momentum and photoelectron spectroscopiesag

Relative intensities for the photoelectron reaction on atoms and molecules are not related to structure calculations in the same way as those for the noncoplanar symmetric (e, 2e) reaction. The photoelectron dipole matrix element is dependent on recoil momentum only through the unique relationship of recoil momentum to the photon energy and is much harder to calculate for chemically-interesting momenta. Relative intensities for binary (e, 2e) reactions are independent of total energy at high enough energies and strongly dependent on symmetry and recoil momentum, for which an intensity profile can be measured for values starting at zero. In comparing with structure calculations, binary (e, 2e) intensities for low recoil momentum may be compared directly with pole strengths in calculations of the one-electron Green's function. In the case of states within a single symmetry manifold the relative intensities will be independent of recoil momentum up to some maximum, usually at least a few atomic units.     

Influence of surface oxidation on the photoelectron diffraction intensities from InP single crystals

The Monte Carlo method was used to calculate the influence of amorphous overlayers on the angle-dependent intensity distribution due to photoelectron diffraction (XPD) in monocrystalline substrates. The influences of the overlayer thickness, the elastic and inelastic mean free paths in the amorphous overlayer, the shape of the initial intensity distribution, as well as the overlayer chemical composition, on XPD is discussed and some trends are formulated. The simulated P 2p intensities of oxidized InP agree with the experimental data. The effect of elastic scattering on the intensity minimum around the detection angle 18° is stronger than that of inelastic scattering. A new method for the thickness determination of thin overlayers on single ecrystals is discussed.     

Relative intensities in X-ray photoelectron spectra. Part IX. Estimates for photoelectron mean free paths taking into account elastic collisions in a solid

By means of the Monte Carlo method the angular dependences of photoelectron peak intensities have been calculated for substrates covered with films of various thicknesses D. The calculations have been carried out for several sets of parameters of the elastic and inelastic interactions of electrons with solids and for various experimental geometries. On the basis of numerical theoretical results, analytical expressions are derived for estimating the difference between the effective mean free path of photoelectrons (λ_eff) and the inelastic mean free path (λ_n) in solids. These expressions are used to analyse experimental data for the determination of thin-film thicknesses by means of ESCA. It is concluded that the values determined experimentally are apparently D/λ_eff ratios — not D/λ_n, as is usually assumed. The importance of the results obtained is discussed with reference to the determination of photoelectron mean free paths in solids and of thin-film thicknesses by means of ESCA.     

Relative intensities in photoelectron spectroscopy of atoms and molecules

The relative intensities of photoelectron lines is discussed. The relationship of observed intensities to angle of observation is considered as are the errors introduced by ignoring the fact that different lines may have different angular distributions. Tables of theoretical results for the angular distribution asymmetry parameter, β, are presented for incident Al K_α, Mg K_α, and Zr M_ζ radiation for all atomic ground state subshells of non-zero angular momentum. The application of these results to molecules is discussed.     

Study of the influence of hole concentration on high-Tc superconductivity of cuprates Bi-2212 by X-ray photoelectron spectroscopy

In this paper, we report the observation of X-ray photoelectron spectra (XPS), which were obtained from high-T_c superconducting compounds Bi-2212 with some percentage of 3d elements (Fe, Co, and Ni) substituted for copper. The changes in characteristics of XPS spectra Sr 3d and Cu 2p_3/2 with the doping content were explained in the relation to the hole concentration on CuO₂ planes, which resulted in high-T_c superconductivity.     

X-ray photoelectron spectroscopy studies on solid xanthates

Two commonly used xanthates, potassium ethyl xanthate (KEX) and sodium isopropyl xanthate (NaiPX) were characterized by comparing their bulk and surface composition. The XPS spectra were recorded using Al K and Mg K excitation and potential sources of contamination were accounted for. Sulfate and carbonate contaminations were identified, both in the bulk and on the surface of the KEX sample. NaiPX contained hydroxyl- and carbonyl-type contaminations. The earlier published XPS spectral data on xanthates were compiled and compared with the results of this work.     

Deconvolution in X-ray photoelectron spectroscopy

Published Mg and Al Kα X-ray lineshapes have been used to study the removal of the effects of X-ray broadening in XPS spectra by deconvolution. These results are compared with spectra obtained for the same specimens in the same instrument using a monochromatic X-ray source. The use of deconvolution to remove analyzer broadening from spectra has also been examined, and it has been verified experimentally that the maximum improvement in the full width at half-maximum of a peak that can be achieved is 30%. Deconvolution has also been examined as a means to remove backgrounds from XPS spectra over wide energy ranges, up to 100 eV.