K. Wandelt

Core and valence level photoemission studies of iron oxide surfaces and the oxidation of iron

The core and valence level XPS spectra of FexO (x ~ 0.90–0.95); Fe2O3 (α and γ); Fe3O4; and FeOOH have been studied under a variety of sample surface conditions. The oxides may be characterized by a combination of valence level differences and core-level effects (chemical shifts, multiplet splittings, and shake-up structure). FeII and FeIII states are distinguishable, but octahedral and tetrahedral sites are not. The O 1 s BE cannot be used to distinghuish between the oxides since it has a nearly constant value. Fe 3d valence level structure spreads some 10 eV below EF, much broader than suggested by previous UPS and photoelectron-spin-polarization (ESP) measurements for FexO and Fe3O4. Fe surfaces (films, foils, (100) face) yield predominantly FeIII species when exposed to high exposures of oxygen or air, though there is evidence for some FeII also. At low exposures the FeII/FeIII ratio increases.

Photoemission studies of adsorbed oxygen and oxide layers

Abstract 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.

The electro-oxidation of formic acid on Pt–Pd single crystal bimetallic surfaces

The interrelationship between the macroscopic kinetic rate of HCOOH oxidation in 0.1 M HClO4 solution and the morphology/composition of the electrode is studied on Pt(111) modified by Pd (denoted hereafter as the Pt(111)–PdxML system, 0 < x < 1) and on Pt–Pd bulk single crystal alloy surfaces (denoted hereafter as the PtPdxat%(111) system, x = 6 and x = 25). The Pd surface composition of the Pt(111)–PdxML and PtPdxat%(111) electrodes was established previously ex-situ by low energy ion scattering (LEIS) measurements. The nature of adsorbed intermediates (COad) and the electrocatalytic properties (the onset of CO2 formation) at the Pt(111)–PdxML and the PtPdxat%(111) interface were studied by FTIR spectroscopy. The results show that Pd atoms either on the surface or in the surface have an unique catalytic activity for HCOOH oxidation, with Pd atoms being three (bulk alloys) or five times (Pd films) more active than Pt atoms at 0.4 V. FTIR spectra reveal that on Pt atoms adsorbed CO is produced from dehydration of HCOOH, whereas no CO adsorbed on Pd can be detected although a high production rate of CO2 is observed at low potentials, indicating that the reaction can proceed on Pd at low potentials without the Pt typical “poison” formation.

Adsorbate line shapes and multiple lines in XPS; comparison of theory and experiment

Abstract It is shown that XPS core lines from adsorbates can be asymmetric, and/ or split, even when only one adsorbate state is present on the surface. In accord with recent theoretical developments, both these effects can be attributed to screening of the core hole by the metal electrons.

A new and sophisticated electrochemical scanning tunneling microscope design for the investigation of potentiodynamic processes

One of the main topics in electrochemistry is the investigation of the potential controlled solid/liquid interface. As a local probe technique electrochemical scanning tunneling microscopy becomes more and more important for the analysis of atomic structures and local structuring effects. The described microscope is optimized for potentiodynamic imaging, i.e., the sample potential can be varied in a wide range during the scan of an image. In combination with cyclic voltammetry potential induced phase transitions on the surface can be imaged and directly correlated to distinctive profiles in the simultaneously recorded voltammogram. The new design grew out of the parallel development of the tunneling unit and the electrochemical periphery. This guarantees the best adaptation of tunneling microscopy to electrochemistry and vice versa. Low drift, high resolution, flexibility, reliability, and ease of handling are the characteristics of the new instrument.

Surface characterization by photoemission of adsorbed xenon (PAX)

The photoemission derived electron binding energies (with respect to the Fermi level) of xenon atoms adsorbed on nonuniform metal surfaces are found to be sensitive to the local work function of the respective adsorption site. As a consequence separated photoemission lines can be resolved corresponding to xenon atoms coexisting on differing surface patches. This effect makes photoemission of adsorbed xenon (PAX) a powerful tool to characterize heterogeneous surfaces on an atomic scale. Various examples are discussed to demonstrate the capability as well as the limits of this technique, such as the ‘‘titration’’ of surface defects and the determination of the surface topography of coldly deposited Ag films.

The local work function: Concept and implications

Abstract The term ‘local work function’ is now widely applied. The present work discusses the common physical basis of ‘photoemission of adsorbed xenon (PAX)’ and ‘two-photon photonemissionspectroscopy of image potential states’ as local work function probes. New examples with bimetallic and defective surfaces are presented which demonstrate the capability of PAX measurements for the characterization of heterogeneous surfaces on an atomic scale. Finally, implications of the existence of short-range variations of the surface potential at surface steps are addressed. In particular, dynamical work function change measurements are a sensitive probe for the step-density at surfaces and, as such, a powerful in-situ method to monitor film growth.

Electron spectroscopic studies of clean and oxidized iron

X-ray photoelectron spectroscopy (XPS) and soft X-ray appearance potential spectroscopy (APS) together with Auger electron spectroscopy (AES) were used to study the electronic properties of clean and oxidized (Fe3O4) iron surfaces. The features arising from excitations of electrons from Fe 2p core levels are discussed consistently within the common one-electron picture (i.e. neglecting final state effects). For pure Fe the shape of the APS L3 peak is evaluated taking into consideration the theoretical density of states above the Fermi level and is found to agree well with that observed. As a consequence it is shown that in this case the appearance potential is about 1 eV larger than the threshold energy for the excitation of a core electron to the Fermi level. Thus for 2p32 electrons this quantity results to be 704.8 eV from both XPS and APS techniques. Successive oxidation at 500°C leads to an increase of the appearance potentials of the Fe 2p levels by only 0.5 eV, whereas the positions of the corresponding XPS peaks are shifted by as much as 3.5 eV. However this apparent disagreement can be eliminated by taking into account the above mentioned effect concerning the appearance potentials from pure Fe and the fact that the threshold energies (which determine the appearance potentials) of the XPS signals are shifted only by 1.7 eV. This example demonstrates that considerable care has to be taken in discussing “binding energies” or “chemical shifts” as derived from different electron spectroscopic techniques. The observed splitting of the MVV Auger transition of Fe at 47 eV upon oxidation is interpreted in terms of the qualitative features of the valence band structure of Fe3O4 and ascribed to the participation of a cross-transition between O 2p and Fe 3p states.

Oxygen adsorption and oxide formation on Ni3Al (111)

The interaction of oxygen with the ordered Ni3Al (111) surface has been investigated in the temperature range from 300 to 1000 K using high-resolution electron-energy-loss spectroscopy (HREELS) and low-energy electron diffraction (LEED). The “2×2” LEED pattern of the clean Ni3Al (111) surface indicates a bulklike termination. After oxygen adsorption at 300 K the LEED pattern is diffuse suggesting the formation of an amorphous overlayer. The HREELS spectra show evidence for oxygen interaction with both aluminum and nickel atoms. At 600 K adsorption temperature the fcc surface order is restored, however, the observed (1×1) LEED pattern indicates the loss of chemical order. Again HREELS spectra suggest interaction of oxygen with both aluminum and nickel. For an adsorption temperature of 800 K LEED shows an unrotated oxygen induced superstructure with a lattice spacing of 2.93 A in addition to the (1×1) substrate spots. The HREELS spectra exhibit an intense loss at 81.9 meV, which is also known from oxygen in...

An X-ray photoelectron spectroscopy study of the chemical changes in oxide and hydroxide surfaces induced by Ar+ ion bombardment☆

In the course of X-ray photoemission studies on the oxidation of metals and alloys and on bulk oxides, we found that in addition to physical sputtering Ar+ ion bombardment can in many cases reduce an oxide to a mixture of the original oxide, lower oxides and metal. The effect is even more pronounced in systems containing hydroxyl groups which are readily destroyed by the ion beam. Specific examples for oxidized cobalt, nickel and iron surfaces and their bulk oxides and hydroxides are given. The relative reduction rates of CoII and FeIII in CoFe2O4 are also examined. From these observations, it is clear that any depth compositional profiling using ion sputtering in conjunction with Auger or X-ray photoelectron spectroscopy should be treated with extreme caution. The mechanism for the chemical changes induced by ion bombardment is briefly discussed.