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．     

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.     

Inelastic effects in X-ray photoelectron spectroscopy

Inelastic scattering of excited electrons and deep holes in X-ray photoemission, and especially the problem of electron attenuation lengths and escape     

Shake-up satellites in X-ray photoelectron spectroscopy

Shake-up satellite peaks have been reported in the core electron spectra of various types of molecules. The specific valence excitation(s) giving rise to this extra structure has been assigned largely as a result of the application of the sudden approximation coupled with other considerations, e.g. transition energies. Satellite peaks appearing in the core electron spectra of first row transition metal complexes appear to be particularly interesting since existing data indicate that their positions and intensities convey information regarding some important properties of the complex.In this work reported shake-up satellite peaks are described and analyzed. In addition, some areas requiring more experimental work are pointed out, and a few potential applications of satellite peak data are mentioned.     

X-ray photoelectron spectroscopy of rare-earth compounds

A variety of rare-earth (RE) compounds (oxides, sulfates and oxalates) have been studied by X-ray photoelectron spectroscopy. Except for Eu, the binding energies (BE's) of the RE 3d and 4d peaks for the sulfates and oxalates are respectively almost equal to and 1.3–3.1 eV higher than those for the oxides. In the Eu 3d spectrum of europium(II) oxalate, distinct shake-down satellite peaks are present, and the BE's of these peaks are 1̃0 eV lower than the parent ones. For the oxides, appreciable differences are found in the BE's of the O 1s peaks, and a specific “inclined W” form is observed in plots of BE versus 1/R (where R is the mean distance from the oxygen atom to the neighboring RE atom) and versus the RE oxidation-reduction potential (ORP). No characteristic differences are seen in the BE's (C 1s, S 2s and S 2p) of the other ligands.     

X-ray photoelectron spectroscopy of FeP phosphide

The structure of the outer and inner electron spectra of iron (2p, 3p, 3s, and 3d) and phosphorus (3s and 3p) atoms in FeP monophosphide is studied in detail by the X-ray photoelectron spectroscopy (XPS) method. On the basis of the analysis of the binding energy of electrons, as well as the parameters characterizing the structure of experimental spectra, a conclusion is made that Fe³⁺ (d ⁵) cations in FeP are stabilized in a state with intermediate value of the total spin (IS, S = 3/2). The range of values of intra-atomic parameters (10Dq, J _H ) is established in which the consideration of the high degree of covalence of Fe–P bonds may lead to the stabilization of (FeP₆)^15– clusters in the IS state.     

X-ray photoelectron spectroscopy of copper compounds

The X-ray photoelectron spectra of some forty-six copper compounds and complexes have been measured. The chemical shifts obtained from accurate determinations of the binding energies have been qualitatively explained on the basis of the Pauling electronegativity concept using the group electronegatives of Huheey for the polyatomic counter anions. The chemical shifts of the copper atoms as well as the atoms in the ligands were found to be dependent not only on the oxidation state but also on the kind and number of ligand atoms.

Intense satellite lines were found in the 2p and 2s bands of the cupric compounds; the number and splitting of the satellites were found to be sensitive to the chemical environment. A correlation was found between the satellite splitting and the binding energies and this is explained by a 3d→4s, 4p ‘shake-up’ mechanism.     

Surface sensitivity of Auger-electron spectroscopy and X-ray photoelectron spectroscopy

A convenient measure of surface sensitivity in Auger-electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) is the mean escape depth (MED). If the effects of elastic-electron scattering are neglected, the MED is equal to the electron inelastic mean free path (IMFP) multiplied by the cosine of the emission angle with respect to the surface normal, and depends on the material and electron energy of interest. An overview is given here of recent calculations of IMFPs for 50–2000 eV electrons in a range of materials. This work has led to the development of a predictive formula based on the Bethe equation for inelastic electron scattering in matter from which IMFPs can be determined. Estimates show, however, that elastic-electron scattering can significantly modify the MED. Thus, for AES, the MED will be reduced by up to about 35%. For XPS, however, the MED can be changed by up to ±30% for common measurement conditions although it can be much larger (by up to a factor of 2) for near-grazing emission angles. Ratios of MED values, calculated with elastic scattering considered and neglected for XPS from the 3s, 3p, and 3d subshells of silver with Mg Kα X-rays are approximately constant (to about 10%) over a range of emission angles that varies from 40° to 60° depending on the subshell and the angle of X-ray incidence. Recommendations are given on how to determine the optimum range of emission angles for satisfactory analysis of angle-resolved XPS (ARXPS) data. Definitions are included of three terms often used for describing surface sensitivity (IMFP, MED, and effective attenuation length (EAL)), and examples are given of the varying magnitudes of these quantities for different analytical conditions.     

X-ray photoelectron spectroscopy of tin oxide nanolayers

X-ray photoelectron spectra of 30- and 100-nm nanolayers, recorded in the energy range 0–35 eV, show a strong dependence of both the distribution of the density of Sn 5s, p+ O₂ p valence states and the change in the intensity ratio for the Sn 4d and O 2s subvalence states on the annealing temperature and nanolayer thickness. In the nanolayers fabricated at an annealing temperature of 450°C, an unusually strong band of O 2s states of unbound oxygen is observed, which is retained for nanolayers doped with palladium and disappears for nanolayers doped with gold and silver.     

X-ray photoelectron spectroscopy study of magnetic films

Ta/NiO_x/Ni₈₁Fe₁₉/Ta films were prepared by rf reactive and dc magnetron sputtering. The exchange coupling field H_ex and the coercivity H_c of NiO_x/Ni₈₁Fe₁₉ as a function of the ratio of Ar to O₂ during the deposition process were studied. The composition and the chemical states in the interface region of NiO_x/NiFe were also investigated using X-ray photoelectron spectroscopy (XPS) and the peak decomposition technique. The results show that the ratio of Ar to O₂ has a great effect on the chemical states of nickel in NiO_x films. The exchange coupling field H_ex and the coercivity H_c of Ta/NiO_x/Ni₈₁Fe₁₉/Ta are thus seriously affected. XPS is shown to be a powerful tool for characterizing magnetic films. Received: 18 July 2001 / Accepted: 21 December 2001 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-010/6232-7283, E-mail: guanghua_yu@263.net     

Electronic structure of carbyne studied by X-ray photoelectron spectroscopy and X-ray emission spectroscopy

The electronic structure of amorphous carbyne has been investigated by X-ray photoelectron spectroscopy and X-ray emission spectroscopy. Carbyne band structure has been calculated semiempirically and the experimental data have been interpreted on the basis of the calculation results. The valence band width was found to be about 20 eV which is the same as that in all other condensed carbon structures. The fine satellite structure near the 1s line of carbon has been studied. It is shown that the energy bands in carbyne are arranged in a mirror-like way relative to the Fermi level. The real carbyne structure is susceptible to conformations which affect primarily the π-subband structure.     

Elastic photoelectron-scattering effects in quantitative X-ray photoelectron spectroscopy

We present improved formulae for the correction parameters Q_x and β_eff that are used to account for elastic scattering of photoelectrons in quantitative X-ray photoelectron spectroscopy (XPS). The new formulae are based on new Monte Carlo simulations for 584 photoelectrons in 39 elemental solids that could be excited by Mg Kα and Al Kα X-rays in 315 different XPS configurations. The new simulations differed from similar earlier calculations in that differential elastic-scattering cross sections calculated from the Dirac–Hartree–Fock potential were utilized rather than those from the Thomas–Fermi–Dirac potential, a smaller analyzer acceptance angle was chosen, and the number of trajectories in each simulation was an order of magnitude larger. New values of Q_x and β_eff were obtained for each photoelectron line, each X-ray source, and each XPS configuration. These Q_x and β_eff values could be fitted to simple two-parameter expressions, each a function of the single-scattering albedo and the photoelectron emission angle. Values of Q_x from the new predictive formula differed from the previous expression by less than 1%. Larger deviations in the values of β_eff, up to 2.5%, were found from the new fit to the β_eff parameter. The new expressions for Q_x and β_eff provide a convenient means for correction of elastic-scattering effects in XPS.     

Electron energy loss processes in X-ray photoelectron spectroscopy

A technique is established in X-ray photoelectron spectroscopy (XPS), using spectra emitted from successively evaporated metallic films, to distinguish between electron energy loss mechanisms identified as, respectively, extrinsic and intrinsic to the photoelectron excitation process. It is demonstrated that tailing on the high kinetic energy side of many XPS peaks is due to intrinsic processes, while the background emission at energies generally some 30 eV below the peaks arises from extrinsic processes. Plasmon energy-loss peaks are believed to contain contributions from both intrinsic and extrinsic processes.     

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.     

Secondary electron emission control in X-ray photoelectron spectroscopy

Secondary electron emission (SEE) is a major player in surface charging during X-ray photoelectron spectroscopy (XPS); its characteristics and applicability as a current source for electrical measurements are studied. We employ sample biasing and a top retarding grid to control the photoelectron current, and further compare their I–V characteristics with direct spectroscopy of the secondary electrons. Using silica-coated gold substrates, the effect of sample work function on the emitted secondary electrons is shown and fine control over the surface potential gradients, in the range of 10–100 meV, is achieved. XPS-based chemically resolved electrical measurements (CREM) can thus be extended to the positive current regime.     

A new charge-correction method in X-ray photoelectron spectroscopy

The 2p_{$\text{3}\text{2}$} binding energy (242.3 eV) of Ar implanted in insulating materials is available to correct for charging shifts. Argon ions hav materials SiO₂ and soda glass. In each case the charging shift for Ar 2p_{$\text{3}\text{2}$} electrons agrees exactly with those for core-level elec The charge-corrected binding energies of the insulating materials permit the identification of atomic chemical states. Ion-induced reduction of the ins investigations.