苝四甲酸二酐薄膜电子结构的同步辐射共振光电子能谱研究

利用基于同步辐射的近边X射线吸收精细结构谱(NEXAFS)和共振光电子谱(RPES)研究了苝四甲酸二酐分子(PTCDA)薄膜的电子结构.碳K边NEXAFS谱中能量小于290 eV的四个峰对应于PTCDA分子不同化学环境碳原子1s电子到未占据分子轨道的共振跃迁.RPES谱中观察到共振光电子发射和共振俄歇电子发射导致的共振峰结构,以及二次谐波激发的碳1s信号.根据电子动能对入射光能量的依赖性分别对三类峰结构进行了归属.同时,发现PTCDA分子轨道共振光电子峰的强度具有光子能量依赖性.这种能量选择性共振增强效应是由于PTCDA分子轨道空间分布差异导致的.共振俄歇峰主要源于高结合能(4.1 eV)分子轨道能级电子参与的退激发过程.明确RPES实验谱图中各个峰结构的起源有助于准确利用基于RPES的芯能级空穴时钟谱技术定量估算有机分子/电极异质界面处电子从分子未占据轨道到电极导带的超快转移时间.     

Study of the occupied and unoccupied electronic states of the Y-substituted (Bi,Pb)-2223 high temperature superconductor

Spectra for the filled and unfilled electronic states of the (Bi,Pb)-2223 high temperature superconductor were recorded by photoemission and fluorescence X-ray absorption in the entire doping range achieved by substitution of bivalent Ca ions with trivalent Y. In photoemission these samples show diminishing spectral intensity near E _F and at 1.5 eV binding energy with increasing Y content. Parallel to the observations for the filled states the O1s X-ray absorption spectra show a decrease and a shift to higher energies of the empty states just above E_F The spectral structures are identified in the framework of the Hubbard model.     

A study of core and valence levels in β-PbO2 by hard X-ray photoemission

The core and valence levels of β-PbO₂ have been studied using hard X-ray photoemission spectroscopy (hν = 6000 eV and 7700 eV). The Pb 4f core levels display an asymmetric lineshape which may be fitted with components associated with screened and unscreened final states. It is found that intrinsic final state screening is suppressed in the near-surface region. A shift in the O 1s binding energy due to recoil effects is observed under excitation at 7700 eV. It is shown that conduction band states have substantial 6s character and are selectively enhanced in hard X-ray photoemission spectra. However, the maximum amplitude in the Pb 6s partial density of states is found at the bottom of the valence band and the associated photoemission peak shows the most pronounced enhancement in intensity at high photon energy.     

Electronic structure of dendrimer-encapsulated Au nanocluster

We have carried out optical and X-ray photoemission studies of the dendrimer-encapsulated Au nanoclusters. The dendrimer-encapsulated Au nanoclusters are prepared by the chemical reduction of Au ions loaded within the dendrimer templates. Photoluminescence spectrum of the dendrimer-encapsulated Au nanoclusters with diameter of about 1.0 nm shows the visible luminescence centered at about 2.8 eV. In addition, we have measured the nanocluster-size dependent photoemission spectra in the valence-band region. From line shape analysis of Au 4f X-ray photoemission spectra, Au 4f core-level spectra of the dendrimer-encapsulated Au nanoclusters reflect the size dependent chemical-states. From these results, we discuss electronic structures and chemical states of the dendrimer-encapsulated Au nanoclusters.     

Threshold photoemission spectroscopy in solids

Threshold photoemission spectroscopy (TPES) is used to measure the Fe 2p spectrum of a stainless steel sample. The obtained spectrum is compared with analogous spectra measured by X-ray photoemission and absorption spectroscopies. The results of this comparison suggest that resonant two-electron autoionization processes, rather than direct photoemission from the core level, are the main mechanisms contributing to the signal. Limits and applicability of this experimental approach to investigate bulk electronic properties in solids are discussed.     

Electronic structure of Sr2FeMoO6

We have used electron spectroscopies to investigate the electronic structure of the double perovskite Sr₂FeMoO₆. The valence-band photoemission spectra present a well-defined cut-off at the Fermi level, indicative of the metallic character of the material. The O 1s X-ray absorption spectrum presents three peaks, which are in good correspondence with the main structures in the unoccupied density-of-states of DF-LDA calculations. The electron energy-loss spectra present two structures which are also interpreted in terms of transitions between the bands obtained in the DF-LDA calculations.     

Comparing inverse photoemission and X-ray absorption spectroscopies

The comparison of inverse photoemission with X-ray absorption spectra is possible. We discuss some of the similarities and differences that must be considered in both techniques. Two examples of such comparison are given: the NiMnSb half-Heusler alloy and the La_0.65Pb_0.35MnO₃ perovskite. We briefly present the dipole and symmetry selection rules which can be used for the interpretation of inverse photoemission as well as the absorption spectra. Due to the symmetry constraints imposed by the initial state, the selection rules in inverse photoemission are more restrictive than in the case of X-ray absorption.     

Photoemission study of the density of valence states of amorphous As2S3 and Sb2S3

The densities of valence states of amorphous As₂S₃ and Sb₂S₃ have been investigated by means of X-ray photoemission and ultraviolet photoemission spectroscopy. The spectra are interpreted on the basis of existing band structure calculations.     

The adsorption of adenine on mineral surfaces: Iron pyrite and silicon dioxide

The adsorption of the nucleobase adenine on surfaces of the minerals iron pyrite and silica has been studied by photoemission and soft X-ray photoabsorption spectroscopy. Pyrite samples were prepared by fracture under nitrogen followed by transfer to ultrahigh vacuum, or by cleavage in vacuum. By comparing data with multilayer spectra, adenine was found to chemisorb on pyrite, with small changes in the valence band spectrum, and stronger changes in the NEXAFS spectrum. The molecules were bonded with the molecular plane at a steep angle to the surface plane. On silica the molecule was found to adsorb at a reduced angle to the surface. The C and N 1s photoemission spectra on this surface suggest chemisorption, although the nitrogen NEXAFS spectra are similar to multilayer spectra.     

Density of valence states of As2O3 and Sb2O3

The densities of valence states of As₂O₃ and Sb₂O₃ have been measured by means of X-ray photoemission, ultraviolet photoemission, and soft X-ray emission spectroscopy. The spectra can be interpreted on the basis of existing models for the As and Sb chalcogenides.     

Generalized mechanism of plasmon excitations in nondiagram X-ray spectra

In the present work, we have studied a plasmon model for the specific contributions of intrinsic as well as extrinsic plasmon effects. The interference ‘plasmon-coupling’ have been obtained theoretically in terms of non-diagram line to diagram X-ray line for the low and high energy satellite profiles in the X-ray photoemission spectra. It is found that our results demonstrate generalized mechanism for the origin of X-ray photoemission satellite spectra.     

X-ray photoelectron spectroscopy of core states in some magnetic virtual bound state alloys

The X-ray photoelectron spectra of the 2p levels of Mn in AgMn 20 at%, Fe in AuFe 20 at%, RhFe 25 at% and 20 at% and Co in RhCo 20 at% have been measured. The Mn and Fe spectra show features which are attributed to excitation of electrons from the 3d to higher energy states during photoemission, while the Co spectra do not.     

Electronic structure of cerium and light rare-earth intermetallics

We give an overview of the use of the impurity Anderson Hamiltonian to describe the spectroscopic and low-energy thermodynamic properties of cerium intermetallics, with emphasis on interpreting 4f photoemission spectra. We show Ce valence-band resonant photoemission, Bremsstrahlung isochromat and 3d X-ray photoemission spectra for CeRu₂, CeNi₂, CeIr₂ and CeAl, and give a complete theoretical analysis of the spectra. We summarize the relation between the large and small energy scale properties. For each system, all the spectra, as well as the static magnetic susceptibility and Kondo temperature, can be described by the model using essentially the same parameters. We also present details of resonant photoemission spectra for five other cerium compounds, CeSi₂, CeOs₂, CePd₃, CeCo₂ and CeNi₅, and discuss generally the problem of obtaining the experimental 4f spectrum. Alternative theories of 4f photoemission are examined critically and we give applications of the Anderson Hamiltonian theory to CeAl₂, PrAl₂, and NdAl₂.     

Thickness dependence of X-ray absorption and photoemission in Fe thin films on Si(0 0 1)

To investigate the initial growth of Fe films on Si(0 0 1) and the Fe/Si interface, Fe films at various thicknesses have been systematically studied by soft X-ray absorption spectroscopy (XAS) and X-ray photoemission spectroscopy (XPS). The Fe L edge XAS spectrum shows a strong thickness dependence with broader line-width for thinner films. Detailed analysis of the Fe absorption signal as a function of the thickness shows that the broad linewidth of Fe L edge XAS spectra is mostly contributed by the first Fe layer at the Fe/Si interface. In contrast to XAS, Fe 2p photoemission spectra for these films are identical. However, valence band photoemission also shows a strong thickness dependence. Comparing the valence band photoemission spectra of the thin Fe/Si(0 0 1) films with that of pure Si and the thickest Fe film, the difference spectra at all thicknesses show almost identical shape indicating the same origin: the Fe/Si interface. Thus, it is mainly the first Fe layer at Fe/Si layer that is reactive with the Si substrate changing its electronic structure.     

Manganese silicide single crystal and films deposited on Si(1 1 1): A comparative spectroscopic study

A comparative experimental study is presented of the electronic properties of MnSi films grown on Si(1 1 1) and of MnSi single crystals, using X-ray absorption spectroscopy (XAS), and core level and valence band photoemission spectroscopy (PES). No significant differences in the electronic structure of the two systems can be found.Absorption measurements on the Mn 2p threshold show a mixed valence ground state, where the multiplet structure is washed out by the hybridisation of the Mn 3d states with the Si sp states. These results are also confirmed by photoemission (PE) spectra from the valence band and the Mn 3s, 3p and 2p core levels.Strong attention has been paid to the effect of contamination. The occurrence of multiplet effects in the absorption spectra indicates unambiguously the localisation of the Mn 3d electrons in Mn-O bonds, which strongly influences the electronic properties of these systems.     

Effects of band structure on the X-ray spectra of metals

Using the change-of-mean-field model, the X-ray absorption, emission, and photoemission spectra of electrons in a one-dimensional nearest-neighbor tight-binding crystal are calculated and compared with the spectra of a corresponding free-electron model. Multi-electron recoil, and shake-off and replacement transitions, are included. The effects of band structure on the spectra are discussed.     

Electron energy loss spectroscopy and ultraviolet photoemission of TmSe

Intraionic Tm²⁺ and Tm³⁺ ? → d and p → d charge transfer transitions are identified in the energy loss spectra of 100eV electrons of TmSe by comparison with X-ray photoemission data. In contrast the ultraviolet photoemission spectra with photon energies up to 21.2 eV do not show any evidence for the intermediate valence character of TmSe due to matrix element effects.     

A detailed analysis of the photoemission spectra of basic thioaromatic monolayers on noble metal substrates

Analysis of photoemission spectra of complex thioaromatic self-assembled monolayers (SAMs) requires the knowledge and understanding of such spectra for the basic systems. Keeping this goal in mind, synchrotron-based high-resolution X-ray photoelectron spectroscopy was used to characterize SAMs formed from the simplest thioaromatic compounds, namely thiophenol, 1,1′-biphenyl-4-thiol and 1,1′;4′,1″-terphenyl-4-thiol on evaporated Au(1 1 1) and Ag(1 1 1) substrates. The acquired S 2p and C 1s spectra were analyzed in terms of fine structure and initial and final state effects in the photoemission process. The assignment of the individual spectral features was considered in detail. Conclusions on quality and chemical and structural homogeneity of the investigated SAMs were derived.     

Electron spectrometer calibration. consistency between magnesium- and aluminum-excited spectra

Analysis of a variety of Auger and photoemission spectra leads to the conclusion that the value given by Bearden for the MgKα_1,2 X-ray energy is not the best value for use in photoemission spectroscopy. The reported value is the energy at the maximum of the X-ray spectrum. Use of this can lead to inconsistencies in measured energies. These are removed if one uses the centroid of the magnesium X-ray spectrum (1253.53 eV). Use of this value also resolves a disagreement between values reported by different laboratories for the Nels ionization energy.     

Electronic structure of Yb/H－Si (111) interface

Photoemission spectra are measured for Yb covered surface of wet-chemically-etched H－Si (111). The results reveal that the lattice structure of the H－Si (111) surface is stable against the deposition of Yb atoms. X-ray photoemission spectra indicate the formation of a polarized (dipole) surface layer, with the silicon negatively charged. Ultraviolet photoemission spectra exhibit the semiconducting property of the interface below one monolayer coverage. Work function variation during the formation of the Yb/H－Si (111) interface is measured by the secondary-electron cutoff in the ultraviolet photoemission spectral line. The largest decrease of work function is ～1.65eV. The contributions of the dipole surface layer and the band bending to the work function change are determined to be ～1.15eV and ～0.5eV, respectively. The work function of metal Yb is determined to be ～2.80±0.05eV.