Ray and UV Photoelectron Spectroscopy

When a photon of energy hv impinges on a solid, the ejected photoelectrons have a kinetic energy distribution made up of a series of discrete bands reflecting the sample s electronic structure. The experimental determination of the kinetic energy of the photoelectrons enables, through the relationship 

The combined UPS and XPS facilities available in the Vacuum Generators ESCA-3 Spectrometer (the name by which the prototype became known) provided a powerful means (5, 3a) of exploring solids, their surfaces, and in turn the reasons for their inherent chemical reactivities. We shall see that XPS and UPS enable both qualitative and quantitative characterization of the solid surface at the atomic level, the chemical environment of a particular 

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A variety of model catalysts have been employed we start with the simplest. Single-crystal surfaces of noble metals (platinum, rhodium, palladium, etc.) or oxides are structurally the best defined and the most homogeneous substrates, and the structural definition is beneficial both to experimentalists and theorists. Low-energy electron diffraction (LEED) facilitated the discovery of the relaxation and reconstruction of clean surfaces and the formation of ordered overlayers of adsorbed molecules (3,28-32). The combined application of LEED, Auger electron spectroscopy (AES), temperature-programmed desorption (TPD), field emission microscopy (FEM), X-ray and UV-photoelectron spectroscopy (XPS, UPS), IR reflection... 

Modem investigations of the Fischer-Tropsch synthesis by X-ray and UV photoelectron spectroscopy have shown the presence of surface carbides and oxygen atoms in the adsorption of CO on various metals. 

Photoelectron Spectroscopy. As a subdivision of electron spectroscopy, photoelectron or photoemission spectroscopy (PES) includes those instruments that use a photon source to eject electrons from surface atoms. The techniques of x-ray photoelectron spectroscopy (XPS) and uv photoelectron spectroscopy (UPS) are the principles in this group. Auger electrons are emitted also because of x-ray bombardment, but this combination is used infrequent-... 

The electronic structure of in situ PEDOTfTos has been investigated by Inganas, Salaneck, and their group.ii They used x-ray photoelectron spectroscopy (XPS) and UV photoelectron spectroscopy (UPS) and compared the data to quantum chemical calculations (AMI, MNDO, and VEH methods). In Figure 8.7, the UPS spectrum of in situ PEDOTfTos compared to the VEH (valence effective Hamiltonian) DOVS (density of valence electronic states) curve is shown. ... 

A number of surface-sensitive spectroscopies rely only in part on photons. On the one hand, there are teclmiques where the sample is excited by electromagnetic radiation but where other particles ejected from the sample are used for the characterization of the surface (photons in electrons, ions or neutral atoms or moieties out). These include photoelectron spectroscopies (both x-ray- and UV-based) [89, 9Q and 91], photon stimulated desorption [92], and others. At the other end, a number of methods are based on a particles-in/photons-out set-up. These include inverse photoemission and ion- and electron-stimulated fluorescence [93, M]- All tirese teclmiques are discussed elsewhere in tliis encyclopaedia. 

Further structural information is available from physical methods of surface analysis such as scanning electron microscopy (SEM), X-ray photoelectron or Auger electron spectroscopy (XPS), or secondary-ion mass spectrometry (SIMS), and transmission or reflectance IR and UV/VIS spectroscopy. The application of both electroanalytical and surface spectroscopic methods has been thoroughly reviewed and appropriate methods are given in most of the references of this chapter. 

The nature of the final state depends upon the energy, hv, of the exciting photons. In X-ray photoelectron spectroscopy (XPS) the exciting photons are provided by sources such as A1 Ka (1,486 eV) or Mg Ka (1,253 eV) and excitation of the core electrons of the molecules is observed. In UV photoelectron spectroscopy (UPS), Hel (21.2eV) or Hell (40.8 eV) radiation is used and excitation from the valence region of the neutral molecule is observed. XPS and UPS are surface-sensitive techniques, which are capable of providing extremely useful information on the chemical nature of a surface or interface and, in the case of the XPS, the conformational state of the molecules at the surface [64]. 

UV-photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS) are powerful analytical tools the energy of the photons required to eject the electron is characteristic of an element and of its oxidation state. 

The experiments were performed in stainless steel UHV chambers which were equipped with the instrumentation necessary to perform Auger Electron Spectroscopy (AES), X-ray Photoelectron Spectroscopy (XPS), UV Photoelectron Spectroscopy (UPS), Low Energy Electron Diffraction (LEED), work function measurements (A( )), High Resolution Electron Energy Loss Spectroscopy (HREELS), and Temperature Programmed Desorption (TPD). The Au(lll) crystal was heated resist vely and cooled by direct contact of the crystal mounting block with a liquid nitrogen reservoir. The temperature of the Au(lll) crystal was monitored directly by means of a... 

ESCA involves the measurement of binding energies of electrons ejected by interactions of a molecule with a monoenergetic beam of soft X-rays. For a variety of reasons the most commonly employed X-ray sources are Al and MgKol>2 with corresponding photon energies of 1486.6 eV and 1253.7 eV respectively. In principle all electrons, from the core to the valence levels can be studied and in this respect the technique differs from UV photoelectron spectroscopy (UPS) in which only the lower energy valence levels can be studied. The basic processes involved in ESCA are shown in Fig. 1. 

Figure 1. Electronic processes in (a) Auger electron spectroscopy (AES), (b) x-ray photoelectron spectroscopy (XPS), and (c) uv photoelectron spectroscopy...

There has been substantial progress in experimental and theoretical surface analytical methods over the last years. Methods based on X-rays and UV light for diffraction, absorption, or photoelectron spectroscopies benefit from new generation synchrotron light sources. To name a few, surface experimental methods include XPS, AES and SIMS for investigating the surface chemistry A

adsorption energetics and kinetics as well as XPD, RAIRS, HREELS, LEED and STM for molecular and surface structure... 

In situ methods permit the examination of the surface in its electrolytic environment with application of the electrode potential of choice. Usually they are favored for the study of surface layers. Spectroscopic methods working in the ultra high vacuum (UHV) are a valuable alternative. Their detailed information about the chemical composition of surface films makes them an almost inevitable tool for electrochemical research and corrosion studies. Methods like X-ray Photoelectron Spectroscopy (XPS), UV Photoelectron Spectroscopy (UPS), Auger Electron Spectroscopy (AES) and the Ion Spectroscopies as Ion Scattering Spectroscopy (ISS) and Rutherford Backscattering (RBS) have been applied to metal surfaces to study corrosion and passivity. 

Experimental data can be obtained by ultra-violet absorption spectroscopy, electron energy loss spectroscopy and photoelectron spectroscopy. UV absorption and EELs have been described briefly in Chapter 3. The former provides information only about the band-gap, while EELs gives more general information about the conduction bands. Both X-rays and UV photons can be used to generate photoelectrons these two methods are given the acronyms XPS and UPS. The energy spectrum of the emitted electrons provides information about the density of electron states in the valence bands. In principle the size of the band gap can be obtained, but care must be taken as the absolute energy... 

X-Ray photoelectron spectroscopy (or ESCA) and UPS are one-electron excitation methods using X rays and UV photons as sources, respectively. 

UV photoelectron spectroscopy (UPS), x-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED) are most commonly applied in this context. In the first method (UPS) electrons are excited by UV light (sources He I = 21.22 eV He II = 40.82 eV) and information on the electronic structure of the valence band region is obtained. The second method (XPS) provides information about the... 

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