Surface sensitivity free path

Such ideal low mean free paths are the basis of FEED, the teclmique that has been used most for detennining surface structures on the atomic scale. This is also the case of photoelectron diffraction (PD) here, the mean free path of the emitted electrons restricts sensitivity to a similar depdi (actually double the depth of FEED, since the incident x-rays in PD are only weakly adenuated on this scale). 

As we have seen, the electron is the easiest probe to make surface sensitive. For that reason, a number of hybrid teclmiques have been designed that combine the virtues of electrons and of other probes. In particular, electrons and photons (x-rays) have been used together in teclmiques like PD [10] and SEXAFS (or EXAFS, which is the high-energy limit of XAES) [2, Hj. Both of these rely on diffraction by electrons, which have been excited by photons. In the case of PD, the electrons themselves are detected after emission out of the surface, limiting the depth of sampling to that given by the electron mean free path. 

Because a set of binding energies is characteristic for an element, XPS can analyse chemical composition. Almost all photoelectrons used in laboratory XPS have kinetic energies in the range of 0.2 to 1.5 keV, and probe the outer layers of tire sample. The mean free path of electrons in elemental solids depends on the kinetic energy. Optimum surface sensitivity is achieved with electrons at kinetic energies of 50-250 eV, where about 50% of the electrons come from the outennost layer. 

The strong point of AES is that it provides a quick measurement of elements in the surface region of conducting samples. For elements having Auger electrons with energies hr the range of 100-300 eV where the mean free path of the electrons is close to its minimum, AES is considerably more surface sensitive than XPS. 

Xps is a surface sensitive technique as opposed to a bulk technique because electrons caimot travel very far in soHds without undergoing energy loss. Thus, even though the incident x-rays penetrate the sample up to relatively large depths, the depth from which the electron information is obtained is limited by the "escape depth" of the photoemitted electrons. This surface sensitivity of xps is quantitatively defined by the inelastic mean free path parameter which is given the symbol X. This parameter is defined to be the distance an electron travels before engaging in an interaction in which it experiences an energy loss. 

Surface sensitivity in LEED is provided by the limited mean free path for inelastic scattering of slow electrons. This mean fi-ee path is the distance traveled by an electron in the solid before it collides inelastically, loses energy, and thus becomes... 

Figure 4.7. The mean free path of an electron depends on its kinetic energy and determines how much surface information it carries. Optimum surface sensitivity is obtained with...

Characterization techniques become surface sensitive if the particles or radiation to be detected come from the outer layers of the sample. Low energy electrons, ions and neutrals can only travel over distances between one and ten interatomic spacings in the solid state, implying that such particles coming off a catalyst reveal surface-specific information. The inherent disadvantage of the small mean free path is that measurements need to be carried out in vacuum, which conflicts with the wish to investigate catalysts under reaction conditions. 

A technique becomes surface sensitive if the radiation or particles to be detected travel no more than a few atomic distances through the solid. Figure 3.1 shows that the mean free path, A, of electrons in elemental solids depends on the kinetic energy, but is limited to less than 1-2 nm for kinetic energies in the range 15-1000 eV [16]. 

Although valence band spectra probe those electrons that are involved in chemical bond formation, they are rarely used in studying catalysts. One reason is that all elements have valence electrons, which makes valence band spectra of multi-component systems difficult to sort out. A second reason is that the mean free path of photoelectrons from the valence band is at its maximum, implying that the chemical effects of for example chemisorption, which are limited to the outer surface layer, can hardly be distinguished from the dominating substrate signal. In this respect UPS, discussed later in this chapter, is much more surface sensitive and therefore better suited for adsorption studies. 

Depending on the energy tico of the incident photons, valence band states and even core level electrons can be excited. UPS is a surface-sensitive technique since electrons have a very short inelastic mean free path, Xi, which depends on the kinetic energy Ek, and has a minimum value of 0.5 nm for T k 100 eV. The leading edge of the valence band is taken as the VBM or HOMO maximum and has to be referred to which has to be determined from a clean inorganic metal surface. Those electrons with k > 0 are removed from the sample and transmitted to the detector. The fundamental equation of the photoemission process is (Einstein, 1905) ... 

Diffraction, by X-rays or neutrons, has been the standard method for determining the structures of crystals. The mean free path of X-rays and neutrons is very long, and thus is not sensitive to surfaces. To probe the structures of surfaces, the probing particles must have a very short mean free path in solids. Two methods are extensively used for determining surface structures low-energy electron diffraction (LEED) and atomic-beam diffraction. A helium... 

The category of electron spectroscopy includes those instruments that measure intensity of ejected secondary electrons as a function of their energy. These electrons have a very short, mean free path in solids and therefore are inherently sensitive to the first few atomic layers on the surface. 

This process is an evaporation that is conducted at such low pressures that the distance between the hot and condensing surfaces is less than the mean free path of the molecules. Each unit is a single stage, but several units in series are commonly employed. Molecular distillation is applied to thermally sensitive high molecular weight materials in the range of 250-1200 molecular... 

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