Very low-energy electron diffraction as a method of band structure investigations: Applications in photoelectron spectroscopy

This review presents the theoretical and experimental foundations of very low-energy electron diffraction (VLEED) spectroscopy, which is the most direct method of studying the band structure E(k) of unoccupied higher-lying electronic states. The experimental results presented here indicate that, contrary to the generally accepted point of view, these states may differ significantly from free-electron dispersion and may experience considerable many-electron effects. It is shown that the higher-lying states observed in the experiment can be used directly in photoelectron spectroscopy, which is the basic method for studying valence states. This makes it possible to solve the basic problem of resolving the band structure in the three-dimensional quasi-wave vector.     

An analysis of the structure of the iridium (111) surface by low-energy electron diffraction

Elastic low-energy electron diffraction (LEED) intensity versus voltage (I-V) measurements for the clean Ir(111) surface have been obtained. Seven specular I-V spectra were measured from 15 to 975 eV at incident angles from 7° to 62.5° relative to the surface normal. The outermost atomic layer spacing of the unreconstructed Ir(111) surface was determined both by the convolution-transform method we have presented previously (including certain convenient modifications) and by dynamical calculations. Results from the analysis of the I-V spectra by the convolution-transform method indicate that the outermost Ir(111) layer spacing is either unrelaxed or contracts by 4% of its bulk value depending upon whether the θ=7° data or the θ = 25° data are used. In agreement with this, the dynamical calculations show that the outermost Ir(111) layer spacing contracts by 2.5± 5% and, in addition, that the registry of the first layer of the crystal surface is not shifted, maintaining the fcc structure.     

Unoccupied electron states in low-energy electron total-current and transmission spectroscopy of molybdenum disulfide

A theoretical interpretation of the fine structure in the low-energy electron total-current spectra and low-energy electron transmission spectra measured along the normal to the (0001)MoS₂ single-crystal surface is proposed. The calculations took into account the energy dependence of band level broadening and the electronic structure of the high final unoccupied states (above the vacuum level E_vac), which become occupied by electrons entering a solid. A comparison with the available experimental and theoretical data is performed. The effects of the bulk band structure are shown to play a dominant role in the formation of the spectra (the extrema in the spectra identify the energy position of critical points, such as the band edges or the points of extremal curvature of the dispersion branches). The proposed method makes it possible to separate the bulk effects in spectra from surface effects, this approach can be used to advantage in monitoring the state of a surface in the course of its treatment.     

A study of the nitridation of silicon surfaces by low-energy electron diffraction and auger electron spectroscopy

Low-energy electron diffraction (LEED) and Auger electron spectroscopy (AES) have been used to study the initial stages of the nitridation of silicon. Most of the experiments involved pressures of 10^?5?10^?7 torr of ammonia and silicon temperatures in the range 800–1100°C. An earlier study of the nitridation of the Si (111) surface, has been extended to allow comparison between the (111), (311) and (100) faces of silicon. These surfaces provide a series of unit meshes with different shapes and symmetries while retaining some common geometrical features. Of particular interest for epitaxial theory is the growth of an impurity induced nitride structure, which is common to both Si(111) and Si (311). This may be explained if the nucleation and orientation of the niti ide are determined by the geometry of localised sites, common to both substrates. Subsequent growth of the nitride layer is then dominated by intra-layer bonding, so that the difference in substrate symmetries has little effect.     

Correlation of electron self-energy with geometric structure in low-energy electron diffraction

In low-energy electron diffraction (LEED) studies of surface geometries where the energy dependence of the intensities is analyzed, the in-plane lattice parameter of the surface is usually set to a value determined by x-ray diffraction for the bulk crystal. In cases where it is not known, for instance in films that are incommensurate with the substrate, it is desirable to fit the in-plane lattice parameters in the same analysis as the perpendicular interlayer spacings. We show that this is not possible in a conventional LEED I(E) analysis because the inner potential, which is typically treated as an adjustable parameter, is correlated with the geometrical structure. Therefore, without having prior knowledge of the inner potential, it is not possible to determine the complete surface structure simply from LEED I(E) spectra, and the in-plane lattice parameter must be determined independently before the I(E) analysis is performed. This can be accomplished by establishing a more precise experimental geometry. Further, it is shown that the convention of omitting the energy dependency of the real part of the inner potential means geometrical LEED results cannot be trusted beyond a precision of approximately 0.01 ?.     

On the electron band structure of liquid metals

The electronic structure and the density of states of simple liquid metals is discussed on the basis of a nonlocal and energy-dependent pseudopotential of the Phillips-Kleinman type. As an example we treat lithium. To calculate this pseudopotential we need to know the states and the eigenvalues of the liquid metal ion cores. For these quantities we use: first, the core data of the free atom; second, of the free ion; third, the data we have determined from the measured phonon dispersion curves. The deviations between the band structures, the density of states as calculated with these pseudopotentials and those of free electrons are considerable.     

Study of iron implanted MgO crystals by low-energy electron induced X-ray spectroscopy

Magnesium oxide crystals implanted with Fe⁺ ions have been studied by means of Low-Energy-Electron-Induced X-ray Spectroscopy. All the implantations were carried out with 100 or 150 keV ion energy, at doses in the range from 10¹⁵ to 10¹⁷ ions cm^?2. The structure of the Fe L_II, L_III X-ray emission bands provides information about the iron chemical state. Fe L_II/L_III band intensity ratio measurements have been performed with a 3 keV electron excitation in order to investigate the whole implanted layer. In addition, by using a filtered Fourier transform technique on observed spectra, some modifications in the oxygen K emission band can be observed in implanted MgO crystals after thermal annealings in air. The oxygen spectrum fine structure suggests that the MgO matrix, partially destroyed by iron implantation, is restored after high temperature treatments. All the implantation, is restored after high temperature treatments. All the results are discussed on the basis of previous Mössbauer Spectroscopy studies and ion channeling investigations.     

Photoelectron spectroscopy studies of the band structure of silver halides

X-ray photoelectron spectroscopy has been used to probe the valence bands of the silver halides. Previous ultraviolet photoemission and optical absorption experiments together with the theoretical band structure calculations form the basis for interpretation of the spectra. Density of states maxima from the halogen p levels are clearly resolved from those of the silver 4d states. Additional splittings due to k space symmetry are observable and in the case of AgCl and AgBr, give excellent conformation of existing band structure calculations. The role of spin-orbit coupling is shown to be unimportant in determining the primary shape of the photoelectron spectrum. The spectrum of AgF shows the inversion of silver 4d and halogen 2p levels suggested by the optical absorption spectra and predicted by several recent band calculations. A new interpretation is proposed for the AgF optical spectrum in which the observed excitons are due to the forbidden Γ₁₂→ Γ₁ and Γ_25′ → Γ₁ tr the high temperature body centered cubic structure. These spectra clearly show the broadening of the I 5p levels which causes the band gap to decrease above the transition temperature.     

GaSe valence band structure from angle-resolved photoemission spectroscopy

Energy-wavevector dispersion curves for the GaSe valence bands obtained from angle-resolved photoemission spectra are compared with pseudopotential band calculations. It is found that the third density-of-states feature below the top of the valence bands (peak C) is related to the Ga-Se bond rather than the Ga-Ga bond. A peak not appearing in the angle-integrated spectra appears as the most intense feature at normal emission, and helps to identify completely the nature of the valence bands down to 7–8 eV below the Fermi energy.     

有耗色散光子晶体带隙结构的本征值分析新方法

为计算有耗色散光子晶体的带隙结构,提出了新的本征值分析方法.该方法借助于量子输运问题中的思想,在本征值方程的推导过程中进行了巧妙的变换,将复杂的非线性本征值问题转化为线性本征值问题:并利用频域有限差分(FDFD)方法直接求解线性本征值方程,最终得到有耗色散光子晶体结构的相关物理参数.与其他方法相比,该方法的最大特点为概念清晰、计算简便,最终节省了计算时间及所需内存量.利用该方法,对介质光子晶体结构进行模拟,结果与传统FDFD方法符合较好,从而验证了方法的有效性.此外,利用所提方法计算了有耗色散光子晶体结构的色散曲线,得到了表面等离子波激发的区域,进一步讨论了损耗对其色散曲线及本征模场的影响.相关结果对色散有耗光子晶体的研究具有一定的理论指导意义.     

Influence of electron band structure on dipole-nuclear acoustic resonance

For an arbitrary Fermi surface a quantum theoretical treatment of dipole-nuclear acoustic resonance in cubic metals is presented for the first time. In contrast to current theories the validity of our results is not restricted to certain temperature regions.     

Photo field-emission spectroscopy of optical transitions in the band structure of tungsten

Photo field-emission currents of clean and barium-covered tungsten tips in a sligthly modified FEM-configuration have been measured under UHV-conditions by modulating monochromatic mercury arc radiation and phase-sensitive detection. From Fowler-Nordheim plots of the field-emission currents field strength and work function were determined as usual. The photo field-emission current—voltage characteristics show various slopes and shoulders which are dependent on excitation energy, work function, and applied field. The shoulders are interpreted to indicate optical transitions, whose final and initial energies are evaluated from the excitation energy and the Schottky lowering of the barrier maximum. A comparison with the band structure of tungsten as calculated by Mattheiss or Christensen and Feuerbacher demonstrates that apart from single nondirect transitions from or to band extrema direct (k-conserving) transitions are prevailing. Some properties of this new method for the investigation of band structure details are given.     

Observation of unfilled electron states in alkali graphite intercalation compounds by secondary electron spectroscopy

The energy position of distinct σ-electron energy bands above the Fermi level has been measured in pure graphite, in a variety of stage 1 alkali intercalation compounds and in several stages of C_xK. Changes of the σ-band gap between occupied and unoccupied states near the Λ-point by a nonuniform shift of the valence- and conduction-bands are small for the heavy alkali graphite intercalation compounds, whereas a change of 1 eV is observed for C₆Li.     

Investigation of the band structure of germanium chalcogenides by means of photoelectron spectroscopy

The valence band photoelectron spectra of amorphous GeS, GeSe and GeTe have been measured. The ultraviolet and X-ray excited spectra show three bands associated with bonding p-states, anti-bonding and bonding s-states, respectively. In the ultraviolet photoemission spectra the p-band shows a pronounced fine structure. Features of the valence band density of states estimated on the basis of a tightbinding model are in reasonable agreement with experiment. Some problems connected with the extension of the ionicity concept of Phillips and van Vechten to the IV–VI compounds are discussed.     

Na and K on Al(100) studied by low-energy electron diffraction and high-resolution core-level spectroscopy

The temperature effects on sub-monolayers of V deposited at the TiO₂(001) surface have been studied by ultraviolet and X-ray photoelectron spectroscopies, UPS and XPS, from 300 up to 623 K.

V coverages, Θ_v, between 0.2 and 0.7 monolayers (ML) were deposited by an e-beam evaporator at 300 K. The V 2p_3/2 core line region exhibits two well-defined components whose relative intensity depends on Θ_v. These two components, assigned to different oxidation states of V, are correlated with two features, with a dominant V 3d character, detected within the TiO₂(001) band gap of the UPS valence band spectra.

UPS and XPS measurements performed after in-situ thermal treatments show unambiguous and reproducible changes of these spectral components. After annealing at 623 K only the higher binding energy component is present in the V 2p_3/2 spectra; the Ti 2_p core lines recover the typical symmetry of the clean and stoichiometric TiO₂(001) surface and the higher binding energy feature only is detected in the TiO₂ band gap. These data suggest that, within the volume probed by XPS and UPS, Ti ions have a mainly d⁰ configuration, while V has a single and stable open-shell configuration, as revealed by the significant intensity detected within the TiO₂ band gap. These annealing-induced changes are due, as suggested by the O 1s/Ti 2p core line intensity trend, to an oxygen diffusion from the TiO₂ bulk to the surface. Finally, a detailed analysis of the data indicates that different V/TiO₂(001) interfaces exhibit different behaviours after annealing treatments, depending on Θ_v. For Θ_v = 0.7 ML, V interdiffuses into the TiO₂ sub-surface layers, whereas for Θ_v = 0.2 ML it remains at the surface. This finding is consistent with a rearrangement of V atoms. which under annealing occupy first the energetically most favorable surface sites (Θ_v = 0.2 ML) before interdiffusing into the TiO₂ lattice (Θ_v = 0.7 ML).