Escape depths

Owing to the limited escape depth of photoelectrons, the surface sensitivity of XPS can be enlianced by placing the analyser at an angle to the surface nonnal (the so-called take-off angle of the photoelectrons). This can be used to detemiine the thickness of homogeneous overlayers on a substrate. 

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. 

X-Ray Fluorescence analysis (XRF) is a well-established instrumental technique for quantitative analysis of the composition of solids. It is basically a bulk evaluation method, its analytical depth being determined by the penetration depth of the impinging X-ray radiation and the escape depth of the characteristic fluorescence quanta. Sensitivities in the ppma range are obtained, and the analysis of the emitted radiation is mosdy performed using crystal spectrometers, i.e., by wavelength-dispersive spectroscopy. XRF is applied to a wide range of materials, among them metals, alloys, minerals, and ceramics. 

The availability of high-intensity, tunable X-rays produced by synchrotron radiation has resulted in the development of new techniques to study both bulk and surface materials properties. XAS methods have been applied both in situ and ex situ to determine electronic and structural characteristics of electrodes and electrode materials [58, 59], XAS combined with electron-yield techniques can be used to distinguish between surface and bulk properties, In the latter procedure X-rays are used to produce high energy Auger electrons [60] which, because of their limited escape depth ( 150-200 A), can provide information regarding near surface composition. 

Before any attempt to establish a correlation between the surface structure of the oxidized alloys and their CO conversion activity one must stress that the surface composition of the samples under reaction conditions may not necessarily be Identical to that determined from ESCA data. Moreover, surface nickel content estimates from ESCA relative Intensity measurements are at best seml-quantlta-tlve. This can be readily rationalized If one takes Into consideration ESCA finite escape depth, the dependence of ESCA Intensity ratio... 

Conversion electron Mossbauer spectroscopy (CEMS) measurements with back scattering geometry have the merit that spectra can be obtained from a sample with much less isotope content compared with transmission measurements. Another merit is that a sample, deposited on a thick substrate, could be measured, and that because of the limited escape depth of the conversion electrons, depth-selective surface studies are possible. The CEMS technique was found to be best applicable to specimens of 10-100 pg Au cm, i.e., about two orders of magnitudes thinner than required for measurements in transmission mode [443]. This way (1) very thin films of gold alloys, as well as laser- and in beam-modified surfaces in the submicrometers range of depth [443], and (2) metallic gold precipitates in implanted MgO crystals [444] were investigated. 

Local surface structure and coordination numbers of neighbouring atoms can be extracted from the analysis of extended X-ray absorption fine structures (EXAFS). The essential feature of the method22 is the excitation of a core-hole by monoenergetic photons modulation of the absorption cross-section with energy above the excitation threshold provides information on the distances between neighbouring atoms. A more surface-sensitive version (SEXAFS) monitors the photoemitted or Auger electrons, where the electron escape depth is small ( 1 nm) and discriminates in favour of surface atoms over those within the bulk solid. Model compounds, where bond distances and atomic environments are known, are required as standards. 

When the electron beam enters the sample, it penetrates a small volume, typically about one cubic micron (10-18m3 ). X-rays are emitted from most of this volume, but Auger signals arise from much smaller volumes, down to about 3 x 10 25m3. The Auger analytical volume depends on the beam diameter and on the escape depth of the Auger electrons. The mean free paths of the electrons depend on their energies and on the sample material, with values up to 25 nm under practical analytical conditions. 

Figure 4. Kinematics of the solid-state EMS spectrometer [11]. (a) The polar angles made by kf and k, with respect to the incident (z) direction are Of = 14° and 6% = 76°. In (b) is shown a typical sample membrane relative to the electron trajectories. The surface sensitivity is largely determined by the escape depth of the 1.2 keV electrons ( 2 nm) and is indicated by the shaded area. 

Fig. 5. Electron escape depth as a function of electron energy. The energies of several photon sources are shown.

UHV techniques are usually classified in terms of the electron/photon method, as is shown in Table 2.3 which lists the common electron bombardment and emission techniques that have been employed in electrochemical studies. A detailed description of UHV surface analysis techniques is beyond the scope of this book there are many excellent reference texts that can be consulted for this purpose (see further reading list). It is sufficient to note that methods involving electron bombardment or emission are inherently surface-sensitive as a result of the low pathlength, or escape depth, of electrons in condensed media. In addition, Table 2.3 briefly describes the type of information each method provides. 

As with XRF, electron microscope-based microanalysis is relatively-insensitive to light elements (below Na in the periodic table), although this can be improved upon with developments in thin-window or windowless detectors which allow analysis down to C. It is better than XRF because of the high vacuum used ( 10-8 torr), but a fundamental limitation is the low fluorescent yield of the light elements. As with XRF analysis it is surface sensitive, since the maximum depth of information obtained is limited not by the penetration of the electron beam but by the escape depth of the fluorescent X-rays, which is only a few microns for light elements. In quantitative analysis concentrations may not add up to 100% because, if the surface is not smooth, some X-rays from the sample may be deflected away from the detector. It may be possible in such cases to normalize the concentration data to 100% if the analyst is certain that all significant elements have been measured, but it is probably better to repeat the analysis on a reprepared sample. 

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