Valence of “divalent” rare earth metals

It is generally recognized that light rare earths change their valence from 2 to 3 when forming a bulk metal while remaining divalent at the surface. However, performed DFT calculations ultimately indicate that the higher-binding-energy peaks in photoemission spectra (like the −5.3 eV peak for Sm), characteristic of the trivalent 4fⁿ⁻¹5d¹ configuration, correspond not to the ground state, but to excited states induced by radiation. This means that the trivalent state is not inherent for the bulk of divalent rare earths, and therefore they do not become trivalent.     

Resonant inelastic x‐ray scattering from highly correlated dysprosium compounds

Dy₂O₃ and Dy metal's resonant inelastic x‐ray scattering (RIXS) spectra were measured in the Beijing Synchrotron Radiation Facility. As a bulk sensitive probe and two‐photon process, RIXS provides more information on the electronic structure of matter. In this full RIXS experiment, the 2p⁶4fⁿ→ 2p⁵4fⁿ5d¹ (2p⁵4f^{n + 1}5d⁰) → 2p⁶3d⁹4fⁿ5d¹ (2p⁶3d⁹4f^{n + 1}5d⁰) channel of two samples (Dy₂O₃ and Dy metal) was studied. Further comparison shows that there are many differences in the RIXS spectra. Dy metal has only a single resonance and its 5d band is broader than that of Dy₂O₃. In the resonant regime, it has a lower final state energy, whereas in the non‐resonant regime it exceeds Dy₂O₃. This causes a broader bandwidth of the main final state B and a narrower bandwidth in the resonant and non‐resonant regime. The pre‐edge structure in Dy L₃ absorption spectra was also resolved using RIXS, which cannot be seen in conventional XAS owing to 2p core hole lifetime broadening. Copyright © 2005 John Wiley & Sons, Ltd.     

Under-coordinated atoms induced local strain, quantum trap depression and valence charge polarization at W stepped surfaces

We have explored the effects of atoms under-coordination on surface structure relaxation, binding energy shift of W stepped surfaces and valence charge polarization by the method of incorporating bond order-length-strength (BOLS) correlation mechanism into high-resolution X-ray photoluminescence spectra (XPS) measurements as well as density functional theory (DFT) calculations. Results show that the 4f_7/2 energy levels of bulk, surface skin and step edge W atoms shift deeper from 2.17 to 2.69 eV with respect to that of the isolated W (28.91±0.01 eV) atoms, while the valence charge energy shift upper from inner to outer layer and from bulk to stepped edge. The surface bond contraction occurs around under-coordinated atoms after geometry relaxation calculation. Consistency among BOLS calculations, DFT calculation and experimental measurements clarifies that the surface bond contraction and consolidation due to the effects of under-coordination atoms induce potential trap depression, which provides perturbation to the Hamiltonian and hence contributes to the surface core level shift deeper, and that the surface valence charge are polarized by the densely trapped core-level electrons to upper energy.     

4f-surface binding energy shift for Eu and Gd metals

Synchrotron radiation excited photoemission spectra of Eu and Gd are presented. For Eu a 4f-surface component is resolved with 0.63 eV binding energy shift. For Gd the comparison with XPS data gives strong evidence for a surface shifted 4f-component (ΔE=0.48 eV). The mean free path of photoelectrons is determined.     

Underestimating the width of the bandgap in the electronic spectra of La2CuO4

It is shown that the width of the bandgap determined by the simultaneous analysis of the experimental photoelectron and inverse photoemission spectra of the surface of La₂CuO₄ using a common energy scale is underestimated by 1 eV. The electronic and satellite structures of the spectra of La₂CuO₄ are calculated on the basis of the multiband p-d model and the sudden perturbation approximation. It is shown that shakedown processes shift the one-electron contour of the final two-hole configuration of the photoelectron spectrum 1 eV down the energy scale and shift the contour of the final d ¹⁰ configuration of the inverse photoemission spectrum downward by 2 eV; these shifts cause the energy splitting between the filled and empty bands to be underestimated. Fiz. Tverd. Tela (St. Petersburg) 39, 449–451 (March 1997)     

X-ray photoelectron spectra and atom valency distribution in oxide BaPb1−xBixO3 superconductor

X-ray photoelectron spectra of valent regions and inner atomic levels for BaPb_0.8Bi_0.2O₃, PbO, PbO₂, BaPbO₃, BaBiO₃, NaBiO₃, Bi₂O₃ have been measured. On the basis of the comparison of bond energy values 4f_7/2 Pb for PbO (137.9 eV), PbO₂ (136.9 eV), BaPbO₃ (137.8 and 136.6 eV) and bond energy values 4f_7/2 Bi for BaBiO₃ (158.4 and 157.5 eV), NaBiO₃ (157.6 eV), Bi₂O₃ (158.2 eV) with analogous values 4f_7/2 Pb (137.7 and 136.9 eV) and 4f_7/2 Bi (158.2 and 157.4 eV) for studied BaPb_0.8Bi_0.2O₃ it is strictly shown that two valent forms of lead atoms Pb^IV, Pb^II and two valent forms of bismuth atoms Bi^V, Bi^III are simultaneously present in the structure of the high temperature oxide superconductor BaPb_0.8Bi_0.2O₃. The parameters of X-ray photoelectron spectra of valent regions of all studied compounds do not contradict this conclusion about the valent states of lead and bismuth atoms in the BaPb_0.8Bi_0.2O₃ structure.     

Chemisorption-induced Pt 4f surface core level shifts

Soft X-ray photoemission experiments have led to the unambiguous observation of a metal surface core level ($\text{Pt}\text{4}\text{f}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$) shift, due to an adsorbate (CO), to a binding energy larger than the bulk binding energy. The $\text{4}\text{f}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ clean (110) surface component, with a binding energy 0.35 ± 0.02 eV lower than the bulk, is shifted by 1.06 ± 0.04 eV towards higher binding energy upon CO chemisorption. The lack of significant changes in the bulk component indicates the localized nature of the CO-Pt surface bonding.     

Ce(Ⅳ)和Ce(Ⅲ)化合物系列的X射线光电子能谱研究

用XPS研究了标称四价铈盐系列:硫酸铈铵、硫酸铈、二苯基羟乙酸铈、碘酸铈、过氧化铈、二氧化铈以及三价铈盐系列:草酸亚铈、硫酸亚铈、二苯基羟乙酸亚铈、碘酸亚铈和氯化亚铈.结果表明,上述标称四价铈盐都属于混合价化合物,其Ce3d电子能谱呈现Ce⁴⁺和Ce³⁺的二组谱线结构的混合.在真空中加热后CeO₂的Ols电子能谱有两个氧峰,这说明 Ce(4f⁰)O(2p^π)←→Ce(4f¹)O(2p^n-1) 类型价态波动的可能性较大.三价铈盐的3d谱线的低结合能端约3.5—4eV处则存在摔落伴峰.     

Isotope shift and configuration mixing in dysprosium II

The isotope shift in the spark spectrum of dysprosium was studied by means of a photoelectric recording Fabry-Perot spectrometer with digital data output. For 29 lines the isotope shift of¹⁶²Dy and¹⁶⁴Dy was measured in order to check the mixing of the three configurations 4f ⁹5d6s, 4f ⁹5d ², and 4f ¹⁰6p calculated by Wyart. By means of the sharing rule the configuration mixing could be confirmed as a whole. In the ground state configuration the influence of relativistic effects was demonstrated and explained by theory. The order of magnitude of crossed-second-order effects contributing to the isotope shift of 4f ¹⁰6s⁶ I and⁴ I could be estimated. In three lines the isotope shift of all stable Dy isotopes was measured. Mass shift and field shift were separated by comparison with results obtained in the arc spectrum.     

Surface electron accumulation in indium nitride layers grown by high pressure chemical vapor deposition

Surface termination and electronic properties of InN layers grown by high pressure chemical vapor deposition have been studied by high resolution electron energy loss spectroscopy (HREELS). HREEL spectra from InN after atomic hydrogen cleaning show N-H termination with no indium overlayer or droplets and indicate that the layer is N-polar. Broad conduction band plasmon excitations are observed centered at 3400 cm⁻¹ in HREEL spectra with 7 eV incident electron energy which shift to 3100 cm⁻¹ when the incident electron energies are 25 eV or greater. The shift of the plasmon excitations to lower energy when electrons with larger penetration depths are used is due to a higher charge density on the surface compared with the bulk, that is, a surface electron accumulation. These results indicate that surface electron accumulation on InN does not require excess indium or In-In bonds.     

Resonant photoemission from SmS(100)

A strong, sharp resonance enhancement of 4f photoemission has been observed on SmS(100) surfaces for photon energies in the region of the 4d-4f transitions at about 126 eV. The discrete final state reached via the excitation hν+4d¹⁰4f⁶→4d⁹4f⁷ autoionizes primarely via a super Coster-Kronig transition of the type 4d⁹4f⁷→4d¹⁰4f⁵ + unbound electron. Other decay channels, e.g, Sm 5p emission, as well as a surface induced binding energy shift in the Sm³⁺ final state are identified and discussed.     

Mössbauer spectra of tin in float glass

Tin is not a major constituent of window glass, but is found at high concentrations in the lower surface of float glass which has been in contact with the molten tin bath. It does not extend far into the surface, but causes the physical and chemical behaviour to differ from that of the upper surface. It is important, therefore, to understand the structural role of tin in silicate glasses and thus its effect on various properties. Mössbauer spectra were taken of three series of glassy materials, namely binary glasses (SnO and SiO₂) in varying proportions, re-melted float glass containing tin, and float glass from a production plant. The binary glasses contained between 20 and 70% tin which was found to be mainly Sn²⁺, with very small amounts of Sn⁴⁺ in some of them. The spectra showed a small decrease in isomer shift with increase in tin content, which is ascribed to the change in molar volume. The re-melted samples were float glass which was mixed with stannous oxalate in appropriate conditions to try and maintain tin in the 2+ state, and contained up to 15% tin by weight. The spectra show both Sn⁴⁺ and Sn²⁺ with rather more in the 4+ oxidation state. The change in the spectra as a function of temperature revealed a large difference in thef-factor (and hence the chemical binding) of the two states. A series of spectra was taken between 17.5 and 900 K for the sample containing 15% tin. From the absorption as a function of temperature thef-factor was determined for both oxidation states, and hence enabled the relative amounts of Sn⁴⁺ and Sn²⁺ present in each sample to be estimated. Measurements of the shift as a function of temperature were also made. The float samples were surface material produced by grinding away all but 0.1 mm of the lower surface of industrially produced float glass. The Mössbauer spectra showed them to be predominantly Sn²⁺, as expected from the reducing atmosphere in the float plant. The concentration and oxidation state of the tin may be estimated from the value of thef-factors and isomer shifts.     

Time-resolved luminescence spectroscopy of pure and doped with Ce3+ ions SrAlF5 crystals

The results of a study of time-resolved photoluminescence (PL) and energy transfer in both pure and doped with Ce³⁺ ions SrAlF₅ (SAF) single crystals are presented. The time-resolved and steady-state PL spectra in the energy range of 1.5–6.0 eV, the PL excitation spectra and the reflectivity in the energy range of 3.7–21 eV, as well as the PL decay kinetics were measured at 8.8 and 295 K. The lattice defects were revealed in the low temperature PL spectra (emission bands at 2.9 and 4.5 eV) in the undoped SAF crystals. The luminescence spectra of the doped Ce³⁺:SAF crystals demonstrate a new selective emission bands in the range of 3.7–4.5 eV with the exponential decay kinetics (τ ≈ 60 ns at X-ray excitation). These bands correspond to the d-f transitions in Ce³⁺ ions, which occupy nonequivalent sites in the crystal lattice.     

Electron energy loss spectroscopy study of the initial stage of lanthanum oxidation

The electron energy loss spectra (EELS) of a pure metallic lanthanum surface and variations in these spectra at the initial stages of surface oxidation were studied. The measurements were performed at primary-electron beam energies E _p from 200 to 1000 eV. A very pronounced peak at a loss energy of about 7.5 eV arises due to transitions from the La4d electronic states of the valence band into the empty La4f electronic states of the conduction band at 5.0–5.5 eV above the Fermi level. Marked changes are observed in the EELS during the oxidation of lanthanum: the peak at an energy of 7.5 eV disappears, and the peak at 13.5 eV corresponding to bulk collective energy loss in lanthanum oxide becomes more pronounced. The results obtained are discussed in terms of the electronic structure of lanthanum and lanthanum oxide.     

Intrinsic surface binding energy shifts in Yb metal

We report on the four-peak structure observed in the region of 4f photoemission in Yb metal, using synchrotron radiation in the energy range 70–200 eV. We conclude, contrary to previous reports, that the doublet associated with surface emissions results from an intrinsic surface shift on clean regions of the surface. We also demonstrate that the observed structure is consistent with earlier XPS measurements, and we set an upper limit on the width of the bulk peaks.     

Transformation of auger electron spectra of ytterbium nanofilms under the action of adsorbed carbon monoxide and oxygen molecules

The transformation of the Auger electron spectra of ytterbium nanofilms as a result of chemisorption of CO and O₂ molecules on their surface has been studied. It has been shown that the adsorption of these molecules is accompanied by a radical transformation of the electronic structure of nanofilms, during which the 5d level of ytterbium drops below the Fermi level. As a consequence, one electron can transfer from the 4f level to the 5d level. In turn, this provides the conditions for a giant resonance 4d → 4f and a subsequent Coster-Kronig supertransition 4d ⁹4f ¹⁴ → 4d ¹⁰4f ¹² + Auger electron, which is accompanied by emission of one 4f electron to vacuum. The results obtained have demonstrated that molecules chemisorbed on the surface of nanofilms can cause qualitative changes in the properties of the surface and in the bulk of these films. It is obvious that this offers a means for designing nanoobjects with controlled properties.     

Hole lifetime and chemical shift of the 4f levels in Yb metal

UHV photoemission studies of Yb metal are reported using synchrotron radiation in the photon energy range 25 < hv < 180 eV, whereby maximum surface sensitivity can be reached. The 4f photoemission spectrum shows a quadruplet structure owing to a superposition of two 4f spin—orbit doublets. One doublet has a very asymmetric lineshape and an extremely narrow lifetime linewidth 2γ? 0.013 eV; this is attributed to bulk emission. The other doublet exhibits almost symmetric lines with a much larger linewidth (0.43 eV FWHM); it has also a larger binding energy by 0.6 ± 0.03 eV. This is attributed as being due to chemically bound Yb atoms located at the surface. The implications of these findings on recent high-resolution photoemission studies of rare earth (RE) metals and their analysis are considered.     

Europium luminescence in fluorite upon high-energy excitation

The reflection and luminescence excitation spectra of CaF₂ crystals containing europium ions in divalent (Eu²⁺) and trivalent (Eu³⁺) states were measured in the range from 4 to 16 eV. It was established that, in CaF₂ : Eu³⁺ crystals, luminescence of Eu³⁺ ions (the f-f transitions) is effectively excited both in the charge-transfer band (at ～8 eV) and in the region of the 4f–5d transitions (at ～10 eV) but is virtually not excited in the fundamental region of the crystal (at an energy higher than 10.5 eV). Luminescence of Eu²⁺ ions (the 427-nm band) in CaF₂ : Eu³⁺ is effectively excited in the fundamental region of the crystal; i.e., luminescence of divalent europium ions occurs through the trapping mechanism. Emission of Eu²⁺ ions in CaF₂ : Eu²⁺ crystals is characterized by the excitation band at an energy of 5.6 eV (the 4f → 5d,t _2g transitions), as well as by the exciton and interband luminescence excitations. The results obtained and data available in the literature are used to construct the energy level diagram with the basic electron transitions in the CaF₂ : Eu crystals.     

The electron energy loss spectrum of EuO(100)

Energy losses of 200 eV to 2 keV electrons reflected from a disordered EuO(100) crystal show a bulk plasmon loss consistent with just less than six “quasi free” electrons per EuO unit, and 5p → nd resonance losses above the 5p threshold. The ratio of intensity of the 4d¹⁰ 4fⁿ⁰ → 4d⁹ 4fⁿ⁺¹ “giant resonance” loss at 142 eV to the corresponding direct recombination feature varies with energy, while the direct recombination and related Auger channels show similar energy dependence.     

A self-modeling approach to the resolution of XPS spectra into surface and bulk components

A method of resolving XPS spectra into surface and bulk component spectra for cases of moderate energy resolution is designed based on an analysis of a family of spectra acquired at different polar angles from flat specimens. Assumptions about line shapes are not required, but an analytical model of the angular dependence of the bulk and surface XPS signals is needed when the component spectra overlap in the range of binding energies of interest. Recommendations are made of the error limits of experimental variables for the successful application of the self-modeling method. The method was used successfully in the separation and quantitative analysis of the O(1s) XPS spectra of surface silanols from bulk silicon dioxide of a fully hydrated silicon dioxide surface. The surface (silanol) and bulk (oxide) components were found to be separated by 0.30 eV, and the surface component was found to be broader (1.58 eV) than the bulk component (1.15 eV).