Ionization cross section measurement

In the following sections of this article, we describe the principles of ionization cross-section measurements, including a brief description of the fast-beam apparatus and the high-resolution double-focusing mass spectrometer employed in the present studies. A comprehensive review of semiempirical calculations of total ionization cross sections is given. Comparisons between these calculated cross sections and the experimental results are presented. The decomposition of the various molecules in a low-temperature plasma is discussed on the basis of the measured ionization-cross-section data, and comparisons are made with the results of in situ plasma diagnostics studies using mass spectrometric techniques. 

We review the general concept of ionization-cross-section measurements and describe briefly the two experimental techniques employed in the particular ionization-cross-section measurements discussed in this article. A comprehensive review of electron impact ionization is given in the book by Mark and Dunn (1985). 

In both the fast-beam apparatus and the double-focusing mass spectrometer, absolute cross sections can be determined with uncertainties of 15% for the parent ionization cross sections and 18% for the dissociative ionization cross sections. These error margins include statistical and all known systematic uncertainties and are typical for ionization-cross-section measurements carried out with this apparatus (Tamovsky and Becker, 1992 Tamovsky and Becker, 1993). 

Electron impact ionization of the parent molecule is only one of several important ion formation processes in nonthermal plasmas. Secondary processes such as electron impact ionization of neutral fragments produced by dissociation of the parent molecule and ion-molecule reactions are other mechanisms contributing to the formation of plasma ions. It is interesting to compare ion abundances in a realistic plasma with the ion abundances predicted from electron impact ionization cross sections measured under single-collision conditions. Although mass spectrometry of plasma ions is a known and well-developed diagnostic method (Osher, 1965 Drawln, 1968 Schmidt et al., 1999), its application to plasmas for thin-film deposition is not very common. The main reasons are deleterious effects of insulating deposits on the ion collection orifice (which connects the mass spectrometer to the plasma) and on the ion transfer optics, which render it... 

As mentioned in the previous chapter, for inner-shell ionization of heavy target atoms, the effects of the projectile Coulomb trajectory and of binding or antibinding should be enhanced as compared with the manifestations of polarization and saddle-point ionization.The possibility for an investigation of the former effects through a comparison of inner-shell ionization cross sections measured with proton and antiproton impact was realized by Andersen et al. [3.52]. Although preliminary data for impact on Ti, Cu, Se, and Nb exist (see Morenzoni [4.22]), no final results from this investigation have yet been published. 

If the single-ionization cross sections measured for impact of protons and equivelodty positrons, or for antiprotons and equivelodty electrons, are compared, the effect of the large mass difference between the two kinds of particles can be studied. Sudi a comparison is shown in fig. 4.18 for a He target. For the largest projectile velodties, there is no difference between measured with light and heavy projectiles. This is in accordance with the prediction of the first Bom approximation eq (4.3) which (at high velodty) does not depend on the projectile mass. 

Ionization cross-section. A measure of the probability that a given ionization process will occur when an atom or molecule interacts with an electron or a photon. 

A tabulation of the ECPSSR cross sections for proton and helium-ion ionization of Kand L levels in atoms can be used for calculations related to PIXE measurements. Some representative X-ray production cross sections, which are the product of the ionization cross sections and the fluorescence yields, are displayed in Figure 1. Although these A shell cross sections have been found to agree with available experimental values within 10%, which is adequate for standardless PKE, the accuracy of the i-shell cross sections is limited mainly by the uncertainties in the various Zrshell fluorescence yields. Knowledge of these yields is necessary to conven X-ray ionization cross sections to production cross sections. Of course, these same uncertainties apply to the EMPA, EDS, and XRF techniques. The Af-shell situation is even more complicated. 

Of course, it is possible to contemplate experiments that examine photoionization of oriented chiral molecules. An expression has been given for the angle integrated (total) ionization cross-section in such circumstances [48] and CDAD-type measurements have been reported on adsorbed chiral molecules [49, 50], but the interplay of natural and geometric chirality in angle-resolved dichroism measurements remains very much a topic for future investigation. 

Quantum mechanical and selected semiclassical and semiempirical methods for the calculation of electron impact ionization cross sections are described and their successes and limitations noted. Experimental methods for the measurement of absolute and relative ionization cross sections are also described in some detail. Four theoretical methods, one quantum mechanical and three semiclassical, have been used to calculate cross sections for the total ionization of the inert gases and small molecules and the results compared with experimental measurements reported in the literature. Two of the theoretical methods, one quantum mechanical and one semiclassical, have been applied to the calculation of orientation-dependent electron impact ionization cross sections and the results compared with recent experiments. 

In this chapter we focus attention on the efficiency of ionization, the ionization cross section, and consider some recent experimental measurements and theoretical studies of the ionization process. A sketch of electron impact ionization curves, the variation of the ionization cross section as a function of the electron energy, using CO as an example, are shown in Figure 1. The mass spectrum, collected at the electron energy corresponding to the maximum in the ionization cross section, is also shown, although there will be no further discussion of fragmentation in this... 

Theoretical models of the electron impact ionization process have focused on the calculation of the ionization cross section and its energy dependence they are divided into quantum, semiclassical and semiempirical. Methods for the calculation of the ionization cross section and experimental techniques developed for the measurement of absolute ionization cross sections will be described in more detail below. Cross sections calculated using the semiempirical additivity method developed by Deutsch and Mark (DM) and their coworkers,12-14 the binary-encounter-Bethe (BEB) method of Kim and Rudd,15 16 and the electrostatic model (EM) developed by Vallance, Harland, and Maclagan17,18 are compared to each other and to experimental data. 

This expression reproduces the experimentally measured ionization efficiency curves surprisingly well, considering the simplicity of the model on which it is based. There is a discontinuity in the function at the maximum (when X = Xmax) but this affects only a small region of the ionization efficiency curve, and satisfactory values of the cross section are still obtained over this region. A great advantage of this method is that it is very simple to apply, depending on only three parameters the molecular polarizability volume, the ionization potential, and the maximum electron impact ionization cross section. These can be measured or calculated values (from the ab initio EM method described above, for example). 

The experimental determination of a total electron impact ionization cross section requires the measurement of four quantities19 ... 

In order to measure cross sections, a beam of electrons of known energy is directed through a gas sample of known pressure and the resulting ion and electron currents measured.63 If mass selective ion detection is used, then partial ionization cross sections oz may be determined. These cross sections correspond to the production of z electrons and an ion or ions having total charge +ze. Some instruments allow the counting cross section oc, also known as the ion production cross section, to be determined ... 

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