X-ray excited

A typical x-ray photoelectron spectmm consists of a plot of the iatensity of photoelectrons as a function of electron E or Ej A sample is shown ia Figure 8 for Ag (21). In this spectmm, discrete photoelectron responses from the cote and valence electron energy levels of the Ag atoms ate observed. These electrons ate superimposed on a significant background from the Bremsstrahlung radiation inherent ia n onm on ochrom a tic x-ray sources (see below) which produces an increa sing number of photoelectrons as decreases. Also observed ia the spectmm ate lines due to x-ray excited Auger electrons. 

Several instmmental methods are available for quantitative estimation of from moderate to trace amounts of cerium in other materials. X-ray fluorescence is widely available, versatile, and suitable for deterrninations of Ce, and any other Ln, at percent levels and lower in minerals and purer materials. The uv-excited visible luminescence of cerium is characteristic and can be used to estimate Ce content, at ppm levels, in a nonluminescing host. X-ray excited optical luminescence (15), a technique especially appropriate for Ln elements including cerium, rehes on emissions in the visible, and also measures ppm values. Atomic emission spectrometry is appHcable to most lanthanides, including Ce (16). The precise lines used for quantitative measurement must be chosen with care, but once set-up the technique is suitable for routine analyses. 

Section 2.1.3 shows that in an XPS spectrum. X-ray excited Auger peaks are often as prominent as the photoelectron peaks themselves. For many elements, the chemical shifts in Auger peaks are actually greater than the shifts in photoelectron peaks. The two shifts can be combined in a very useful quantity called the Auger parameter a, first used by Wagner [2.30] and defined in its modified form [2.31] as... 

Detection limits for various elements by TXRF on Si wafers are shown in Fig. 4.13. Synchrotron radiation (SR) enables bright and horizontally polarized X-ray excitation of narrow collimation that reduces the Compton scatter of silicon. Recent developments in the field of SR-TXRF and extreme ultra violet (EUV) lithography nurture our hope for improved sensitivity down to the range of less than 10 atoms cm ... 

The setup in Figure 1-7 becomes an effective generator of nearly monochromatic x-rays when various elements inserted in the sample position are irradiated by x-rays of energy sufficient to excite the characteristic spectra that is, when by x-ray excitation the characteristic... 

Fig. 1-15. The molybdenum spectrum excited by 35-kv electrons and by the polychromatic beam from a 35-kv x-ray tube. With x-ray excitation, most of the energy appears in the characteristic lines. With electron excitation, most of it is wasted in the continuous spectrum.

Figure 1-15 illustrates an outstanding difference between electron and x-ray excitation of characteristic spectra. The former method more conveniently yields spectra of high intensity, but (as might have been expected from Figure 1-3) it unfortunately leads to a much higher background, the continuous spectrum, than is obtained with x-ray excitation. 

Each line iri an x-ray series thus has a common initial state and a different final state. (Note contrast with other spectra.) The initial state is characterized by a hole in an energy level. To create this hole, an electron is expelled by collision with a high-velocity electron in electron excitation, and by the absorption of a photon in x-ray excitation. The Einstein equivalence law must be satisfied in either of these elementary processes. 

Usually, high intensity is desirable in a continuous spectrum to be used for x-ray excitation. The efficiency of x-ray production,... 

This section contains an illustrative, highly approxirmite calculation of the intensity of cobalt Ka lines produced by x-ray excitation. 

The alternating component of the applied voltage causes a continuous variation in the efficiency of the x-ray excitation (Step II) during each cycle of operation. A polychromatic x-ray beam has a different total absorption coefficient and a different ratio of photoelectric to scattering absorption coefficient for each wavelength (Step V). It is very difficult to take account of these factors exactly. Fortunately, reasonable estimates will suffice in the making of the calculations for Table 4-4 and Figure 4-15. The efficiency has been taken as that for the root-mean-... 

Before turning to Method II, we shall discuss the variation with film thickness in the intensity of a characteristic line produced in a film by x-ray excitation. The discussion that follows is significant also for x-ray emission spectrography, and the ideas are explicit or implicit in the work of Glocker and Schreiber.11... 

The first extensive1 study of x-ray excitation (1.17) as a method of producing x-ray spectra for analytical purposes was carried out by Glocker and Schreiber,17 who not only treated absorption effects very thoroughly and introduced the concept of critical thickness, but who... 

In most ordinary cases, the disadvantages of x-ray excitation are more than compensated by the absence of the disadvantages peculiar to electron excitation, by the great convenience of Coolidge tubes (1.3), and by the absence of the large background count to which the continuous x-ray spectrum excited by electrons gives rise (1.5). 

The differences between x-ray and electron excitation must obviously stem from differences in the interaction of x-rays (1.11) and of electrons (1.4) with matter. Electrons are retarded rather quickly when they strike a sample, and they lose much of their energy in classical collision processes (4.1). Because electrons transfer their energy so rapidly, the critical thickness (Equation 6-8) for electron excitation is very much less than we saw it to be for x-ray excitation a.calculation based on experiments on a variety of materials53 gives 1CT3 cm (105 A) as a good value for the depth to which 50-kv electrons penetrate aluminum, and bears out the previous statement. Because the energy of every electron decreases as it penetrates, the x-ray excited by any electron will be of... 

Laby21 demonstrated in 1930, with a photographic plate as detector, that copper or iron in zinc could be detected in concentrations approaching 1 part per million by weight. To be sure, he used electron excitation so that absorption effects were minimized (7.10). By contrast, attempts made in the authors laboratory to estimate alkaline-earth metals in brines were unsuccessful, primarily because of the high absorption effects that accompanied x-ray excitation. The use of dilution with a relatively transparent solvent can sometimes reduce or eliminate absorption effects (7.8), but this procedure will fail if the element to be determined is present at too low a concentration in the presence of another substance (the salt in brine in the example cited) primarily responsible for the absorption effect. A case in which dilution is helpful in connection with the absorption effect of the. element sought is that of tetraethyllead fluid in gasoline (7.13). 

The second feature, the use of a secondary radiator, entails a loss of intensity because it introduces a second x-ray excitation process, but this loss is, offset to a large extent by the increased absorption of the characteristic lines from the radiator. The third feature also merits further comment. As Figure 11-7 shows, the proportional counter... 

Characteristic x-ray emission spectra, from x-ray excitation, 27, 28 of platinum, measurement by Bragg, 25, 26, 35 origin, 30-34... 

The Preparation and X-ray-excited Intrinsic Scintillation Luminescence Properties of Ba3BP30i2, BaBPOs and Ba3BP07 [14, 15]... 

Fig. 21.4 The X-ray-excited luminescence spectrum of Ba3BP30i2 host. The dotted lines are the Gaussian decomposition.

Therefore, there could exist rich defects in Ba3BP30i2, BaBPOs and Ba3BP07 powders. From the point of energy-band theory, these defects will create defect energy levels in the band gap. It can be suggested that the electrons and holes introduced by X-ray excitation in the host might be mobile and lead to transitions within the conduction band, acceptor levels, donor levels and valence band. Consequently, some X-ray-excited luminescence bands may come into being. 

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