Photoelectron spectroscopy in the energy region 30 to 800 eV using synchrotron radiation

With the advent of synchrotron radiation, the photoemission techniques were extended to a continuous range of excitation energies in the far ultraviolet and soft x-ray regions, adding tremendously to the usefulness of photoemission as a probe of the electronic structure of materials. In this paper, we discuss the application of photoelectron spectroscopy using synchrotron radiation to the studies of oxygen chemisorption/oxidation of Si surfaces, metal overlayers on III-V semiconductor surfaces, chemisorption on transition metal surfaces, and the surface electronic structure of CuNi alloys.     

Bonds and Fermi surfaces studied by photoelectron spectroscopy

Photoelectron spectroscopy with synchrotron radiation employing high energy and angular resolutions is a very efficient tool for experimental investigations of the electronic structure of solids and their surfaces. In addition to standard band-mapping applications, photoemission intensity and line-shape analyses provide valuable information about wave functions, bonds and interactions of a many-electron system. In this report we choose covalent semiconductor surfaces as well as metallic clean and nanostructured surfaces of layered materials to serve as model systems for assessing the spatial origin of photoelectrons and the three-dimensional shape of Fermi surfaces. Received: 11 July 2001 / Accepted: 23 July 2001 / Published online: 3 April 2002     

Hard X-ray photoemission spectroscopy: Variable depth analysis of bulk,surface and interface electronic properties

The electronic properties of surfaces and buried interfaces can vary considerably in comparison to the bulk. In turn, analyzing bulk properties, without including those of the surface, is understandably challenging. Hard X-ray photoelectron spectroscopy (HAXPES) allows the well known ability of photoemission to interrogate the electronic structure of material systems with bulk volume sensitivity. This is achieved by tuning the kinetic energy range of the analyzed photoelectrons in the multi-keV regime. This unique ability to probe truly bulk properties strongly compliments normal photoemission, which generally probes surface electronic structure that is different than the bulk selected examples of HAXPES and possible implications towards the study of complex oxide-based interfaces and highly correlated systems are discussed.     

Elementary processes at semiconductor/electrolyte interfaces: perspectives and limits of electron spectroscopy

Semiconductor device properties based on electrolyte contacts or modified by electrochemical reactions are dominated by the electronic structure of the interface. Electron spectroscopy as e.g. photoemission is the most appropriate surface science techniques to investigate elementary processes at semiconductor/electrolyte interfaces. For such investigations a specific experimental set-up (SoLiAS) has been built-up which allows performing model experiments as well as surface analysis after emersion under different experimental conditions. The experimental approach is presented by a number of experiments performed during the last years with GaAs as substrate material. Model experiments by adsorption and coadsorption of electrolyte species give information on fundamental aspects of semiconductor/electrolyte interactions. Emersion experiments give information on a final composition and the related electronic structure of electrodes after electrochemical reactions. The use of frozen electrolytes will help to bridge the gap between these two approaches. With the combination of the experimental procedures one may expect a detailed analysis of electrolyte (modified) interfaces covering chemical composition, electronic structure of surfaces/interfaces as well as surface/interface potentials.     

Momentum-resolved inverse photoemission

Inverse photoemission including isochromat spectroscopy is shown to be a versatile technique to probe empty electronic states in solids and at clean and adsorbate covered surfaces. The complete set of quantum numbers of an electronic state can be determined and examples will be discussed for bulk and surface electronic states. For sufficiently low kinetic energy of the primary electrons, inverse photoemission is shown to be applicable to adsorbates also. This allows one to assess directly the unoccupied electronic states of the adsorbate which play an important role in the formation of the surface chemical bond. Examples are discussed for atomic and molecular chemisorption as well as adsorption on alkali promoted surfaces.     

Tuning dimensionality by nanowire adsorption on layered materials

The dimensionality of electronic states determines a number of physical phenomena such as phase transitions, transport, or superconductivity. Employing scanning tunneling microscopy combined with angle-resolved photoemission spectroscopy we demonstrate how the dimensionality of electronic states can be continuously tuned from three to two dimensions. This is achieved by adsorption of nanowires on surfaces of layered crystals without changing the chemical composition of the material. Exemplary results for Rb nanowires on TiTe2 are discussed with the help of electronic structure calculations.     

Photoemission studies of adsorbed oxygen and oxide layers

A comprehensive review is given about the enormous versatility of photoelectron spectroscopy to study the especially complex interaction of oxygen with metal surfaces and the nature of the reaction products. The great variety of well definable parameters of a photoemission experiment, e.g. energy, direction of incidence and polarization of the primary photon beam as well as the detection direction of the photocurrent, yields - through the distributions of energy, momentum and spin polarization of the photoelectrons - detailed insight in the kinetic, thermodynamic, electronic and structural aspects of oxygen adsorption on metal surfaces and incipient oxidation. Characteristic electron binding energies, multiplet and satellite structures of both the oxygen and substrate emission allow a distinction between possible states of adsorbed oxygen, i.e. condensed, molecularly and atomically adsorbed, and incorporated oxygen. Even a distinction between octahedral and tetrahedral oxygen coordination of oxide cations may be possible. Analysis of peak intensities (as a measure of coverages and concentrations) as a function of time and temperature provides information about the kinetics and thermodynamics of adsorbed layer and oxide formation. Angular resolved photoemission studies have led to the determination of absolute adsorption site geometries, individual ad-orbital symmetries and two-dimensional band structure formation within the oxygen overlayer. Measurement of the photoelectron spin-polarization offers a method to study surface magnetism, e.g. of ferromagnetic oxides. The determination of local work functions through the photoemission behavior of co-adsorbed rare gas atoms establishes a uniquely important tool to characterize heterogenous surfaces, e.g. oxygenated surfaces with coexisting oxygen states. Numerous different oxygen/metal systems are chosen to demonstrate the state of the art. Results from other surface spectroscopies and theoretical model calculations are, of course, considered and still open problems are named, e.g. the ionicity of the oxygen chemisorption bond. Problems inherent in sputter profiling through surface oxides as observed with photoemission are briefly addressed. This work is rounded by a list of about 600 references in alphabetic order of the reacting metals.     

Density functional theory of transition metal phthalocyanines,I: electronic structure of NiPc and CoPc—self-interaction effects

We present a two-part systematic density functional theory study of the electronic structure of selected transition metal phthalocyanines. We use a semi-local generalized gradient approximation (GGA) functional, as well as several hybrid exchange-correlation functionals, and compare the results to experimental photoemission data. Here, we study the low-spin systems NiPc and CoPc. We show that hybrid functionals provide computed photoemission spectra in excellent agreement with experimental data, whereas the GGA functional fails qualitatively. This failure is primarily because of under-binding of localized orbitals due to self-interaction errors.     

Angle-resolved photoemission and LEED from rare-earth metals

Angle-resolved photoemission and LEED studies of single-crystal surfaces of the rare-earth metals are still relatively few in number. The reasons for this are outlined and comparisons are made between the procedures used to obtain clean and well-ordered surfaces suitable for study. Valence-band photoemission spectra are compared with surface electronic structure and photocurrent calculations in order to identify surface and bulk features. Core-level spectroscopy indicates that the 5p levels of the lanthanides show intensity variations with emission angle that are not explicable in terms of a simple core-level shift. Although the 4p levels of Y have some band character, detailed comparison of the 4p photoemission lineshape with those produced by photocurrent calculations enables the surface core-level shift to be determined. Quantitative LEED studies of close-packed (0001) surfaces show essentially a bulk-terminated structure for Sc, a structural reconstruction of the divalent surface of Sm and a magnetic reconstruction of ferromagnetic Gd. The more open (11 0) and (10 0) surfaces of all the rare-earth metals studied undergo extensive reconstructions into a close-packed structure almost identical to that of a (0001) surface. Angle-resolved photoemission and LEED have yet to distinguish between these structures, indicating a reconstruction depth of at least five atomic layers.     

The adsorption of Xenon on both low and high work-function metals

The structure of unoccupied electronic states in Xe condensed on differently prepared metal surfaces has been observed by inverse photoemission spectroscopy. The Xe/metal interface is interpreted in the framework of Schottky barrier theory. On low workfunction surfaces a wetting to non-wetting phase transition is inferred from dramatic changes in the unoccupied level structure. Existing data in the literature indicate non-wetting behaviour of Xe on low work-function materials to be a quite general phenomenon.     

Photoemission study of the carrier bands in Bi(111)

We present high-resolution photoemission data from the Bi(111)-surface. The electronic structure of the semimetal close to the Fermi level has been found to change dramatically with respect to the well established bulk band structure. The Fermi surfaces observed for the electron and hole bands resemble those of the next group-V element, antimony, probably as a consequence of surface relaxation. This results in a relatively high surface charge density. The observed temperature dependence of the electron Fermi energy confirms this result. Received 8 June 2000     

Density functional theory of transition metal phthalocyanines,II: electronic structure of MnPc and FePc—symmetry and symmetry breaking

We present a two-part systematic density functional theory (DFT) study of the electronic structure of selected transition metal phthalocyanines. We use a semi-local generalized gradient approximation (GGA) functional, as well as several hybrid exchange-correlation functionals, and compare the results to experimental photoemission data. Here, we study the intermediate spin systems MnPc and FePc. We show that DFT calculations of these systems are extremely sensitive to the choice of functional and basis set with respect to the obtained electronic configuration and to symmetry breaking. Interestingly, all simulated spectra are in good agreement with experiment despite the differences in the underlying electronic configurations.     

角分辨光电子能谱技术及其应用进展

角分辨光电子能谱（ARPES）是研究晶体表面电子结构,如能带,费米面,以及多体相互作用的重要工具。本文概述了光电子激发的一般过程和单粒子近似下的理论模型。详细讨论了角分辨光电子能谱的能带勾画（Energy Band Mapping）和费米面成像（Fermi Surface Mapping）技术,以及高分辨下的角分辨光电子能谱在强相关体系研究中的应用。文章最后简单介绍了当前角分辨光电子能谱研究的新进展,如研究宽禁带半导体材料的表面电子结构,有机功能材料与金属的界面,金属超薄膜中的量子阱态,以及高温超导机理研究等。     

Controlling geometric and electronic properties of highly ordered CuPc thin films

Geometric and electronic properties of ordered copper phthalocyanine (CuPc) thin films grown on hydrogen- and antimony-passivated Si(1 1 1) surfaces have been studied using near edge X-ray absorption fine structure (NEXAFS) and photoemission spectroscopy. The H- and Sb-passivations of vicinal Si surfaces resulted in different molecular orientations in thick films, namely upright and near lying molecules, respectively. In the absence of the vicinality, the molecules on the Sb-passivated surface changed towards upright orientation. The work function of the films was monitored during the growth and correlated with the molecular orientation.     

Electron structure and electron dynamics at InSb(111)2×2 semiconductor surface

The conduction band electronic structure and the electron dynamics of the clean InSb(111)2×2 surface have been studied by laser based pump-and-probe photoemission. The results are compared to earlier studies of the InSb(110) surface. It is found that both the energy location and the time dependence of the photoexcited structures are very similar for the two surfaces. This indicates that the dominant part of the photoemission signal in the conduction band region is due to excitations of electrons in the bulk region and that the surface electronic states play a minor role. The fast decay of the excited state, τ∼12 ps, indicates that diffusion of hot electrons into the bulk is an important mechanism. Received: 9 May 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +46-0824/913-1, E-mail: gm@matphys.kth.se     

Degradation of La0.8Ca0.2MnO3 single crystal surface: Electron spectroscopy studies

The electronic structure of degraded (as grown and chemically polished) and ion-sputtered La_0.8Ca_0.2MnO₃ single crystal surfaces has been studied by X-ray photoemission and Auger electron spectroscopy techniques. XPS spectra of deep core levels (Mn2p, O1s, La3d, La4d) were taken from as grown, chemically polished and cleaned in UHV by Ar⁺ ion-bombardment surfaces. XPS data show different oxidation state of Mn and La ions on the degraded and ion-sputtered surfaces of the manganite crystal. Mn2p_3/2 line width and energy position suggest mixed valence state of the manganese ions at the degraded and ion-sputtered crystal surfaces.     

Electronic structure of the organic semiconductor copper tetraphenylporphyrin (CuTPP)

The electronic structure of thin films of the organic semiconductor copper tetraphenylporphyrin (CuTPP) has been studied using synchrotron radiation-excited resonant soft X-ray emission spectroscopy (RSXE), near edge X-ray absorption fine structure (NEXAFS) spectroscopy, and X-ray photoemission spectroscopy (XPS). The C and N partial density of states for both the valence and conduction band electronic structure has been determined, while XPS was used to provide information on the chemical composition and the oxidation states of the copper. Good agreement was found between the experimental measurements of the valence and conduction bands and the results of density functional theory calculations.     

Direct observation of the mass renormalization in SrVO3 by angle resolved photoemission spectroscopy

Band dispersions and Fermi surfaces of the three-dimensional Mott-Hubbard system SrVO3 are directly observed by angle-resolved photoemission spectroscopy. An observed spectral weight distribution near the Fermi level (E(F)) shows cylindrical Fermi surfaces as predicted by band-structure calculations. By comparing the experimental results with calculated surface electronic structures, we conclude that the obtained band dispersion reflects the bulk electronic structure. The enhanced effective electron mass obtained from the energy band near E(F) is consistent with the bulk thermodynamic properties and hence with the normal Fermi-liquid behavior of SrVO3.     

One-dimensional metal structures at decorated steps

It is shown how wire structures a few nanometers wide can be fabricated by decorating step edges at vicinal surfaces. Their growth modes and electronic states are studied using Scanning Tunneling Microscopy (STM) and inverse photoemission. The observed growth modes are two-dimensional analogs of Stranski-Krastanov growth and layer-by-layer growth in three dimensions, e.g., for Cu on stepped Mo(1 1 0) and W(1 1 0), respectively. Contrast between different metals is achieved in STM pictures by resonant tunneling via surface states and image states, with the latter providing a map of the work function. The limit of single atomic rows decorating step edges is studied by inverse photoemission, and an energy shift of 0.4 eV is found for electronic states of step atoms. We expect stripe structures to become useful for the study of two- vs one-dimensional magnetism, for magnetoresistive films, and in the design of anisotropic materials.     

Spin- and angle-resolved photoelectron spectroscopy from solid surfaces with circularly polarized light

Spin-polarized photoemission with circularly polarized light represents a relatively new technique in surface science. It became feasible with the increased availability of circularly polarized light in the vacuum ultraviolet and soft X-ray regime, generated in dedicated synchrotron radiation facilities. Another important ingredient was the development of efficient electron spin polarization detectors. Supported by group theoretical considerations, this technique was first employed to study the process of optical spin orientation in single crystalline non-magnetic materials. In these samples, spin-dependent effects arise solely from spin-orbit coupling. The experiments revealed the strong influence of spin-orbit coupling on the details of the electronic band structure, such as the symmetry character of the electronic wave functions, hybridization phenomena, and the behavior of degeneracies. The results opened the way to a detailed understanding of the electronic structure and permit a rigorous test of both state-of-the-art bulk band theories and fully relativistic photoemission calculations. Since 1990, spin-polarized photoemission with circularly polarized light is also used to investigate ferromagnetic systems. These experiments led to the discovery of the counterpart of optical spin orientation in ferromagnets, namely, the magnetic dichroisms. Magnetic dichroism means that the spin-dependent photoexcitation from a ferromagnetically ordered system manifests itself already in the photoelectron intensity distributions. Because of this particular property, techniques based on magnetic dichroisms are currently receiving wide interest in the spectroscopic investigation of magnetic systems and phenomena.

The following article reviews the current status of the field of spin- and angle-resolved photoemission from solids using circularly polarized radiation. We survey the development of this technique over the last 10 years, covering its applications to both non-magnetic and ferromagnetic systems.