Primary Electron Sources

Two kinds of electron sources may be employed in local analysis. The first is a thermionic source which produces electrons when heated, and the second is 

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A few methanogens can also use some non-methanol alcohols as a primary electron source for C02-methanogenesis (Table 2 [25-28,212]) by expressing an alcohol... 

When photosynthesis first evolved, it was most likely to have been carried out by organisms that used compounds other than water as the primary electron source. Cyanobacteria were the first organisms to use water as the source of electrons, giving rise to the present oxygen-containing atmosphere. 

The electron sources used in most sems are thermionic sources in which electrons are emitted from very hot filaments made of either tungsten (W) or lanthanum boride (LaB ). W sources are typically heated to ca 2500—3000 K in order to achieve an adequate electron brightness. LaB sources require lower temperatures to achieve the same brightness, although they need a better vacuum than W sources. Once created, these primary electrons are accelerated to some desired energy with an energy spread (which ultimately determines lateral resolution) on the order of ca 1.5 eV. 

One important sem source that is not based on thermionic emission is the field emission (fe) source. Fe-sem systems typically give images of much higher resolution than conventional sems due to the much narrower energy distribution (on the order of 0.25 eV) of the primary electron beam. A fe source is a pointed W tip from which electrons tunnel under the influence of a large electric field. This different mechanism of electron generation also results in a brightness comparable to a conventional thermionic source with much less current. 

Once the primary electron beam is created, it must be demagnified with condenser lenses and then focused onto the sample with objective lenses. These electron lenses are electromagnetic in nature and use electric and magnetic fields to steer the electrons. Such lenses are subject to severe spherical and chromatic aberrations. Therefore, a point primary beam source is blurred into a primary beam disk to an extent dependent on the energy and energy spread of the primary electrons. In addition, these lenses are also subject to astigmatism. AH three of these effects ultimately limit the primary beam spot size and hence, the lateral resolution achievable with sem. 

Instmmentation for tern is somewhat similar to that for sem however, because of the need to keep the sample surface as clean as possible throughout the analysis to avoid imaging surface contamination as opposed to the sample surface itself, ultrahigh vacuum conditions (ca 10 -10 Pa) are needed in the sample area of the microscope. Electron sources in tern are similar to those used in sem, although primary electron beam energies needed for effective tern are higher, typically on the order of ca 100 keV. 

Scanning Auger Electron Spectroscopy (SAM) and SIMS (in microprobe or microscope modes). SAM is the most widespread technique, but generally is considered to be of lesser sensitivity than SIMS, at least for spatial resolutions (defined by primary beam diameter d) of approximately 0.1 im. However, with a field emission electron source, SAM can achieve sensitivities tanging from 0.3% at. to 3% at. for Pranging from 1000 A to 300 A, respectively, which is competitive with the best ion microprobes. Even with competitive sensitivity, though, SAM can be very problematic for insulators and electron-sensitive materials. 

The acetoxy dienone (218) gives phenol (220). Here, an alternative primary photoreaction competes effectively with the dienone 1,5-bonding expulsion of the lOjS-acetoxy substituent and hydrogen uptake from the solvent (dioxane). In the case of the hydroxy analog (219) the two paths are balanced and products from both processes, phenol (220) and diketone (222), are isolated. In the formation of the spiro compound (222) rupture of the 1,10-bond in the dipolar intermediate (221) predominates over the normal electron transmission in aprotic solvents from the enolate moiety via the three-membered ring to the electron-deficient carbon. While in protic solvents and in 10-methyl compounds this process is inhibited by the protonation of the enolate system in the dipolar intermediate [cf. (202), (203)], proton elimination from the tertiary hydroxy group in (221) could reverse the efficiencies of the two oxygens as electron sources. 

The electron itself is frequently used as a primary source of radiation, various kinds of accelerators being available for that purpose. Particularly important are pulsed electron sources, such as the nanosecond and picosecond pulse radiolysis machines, which allow very fast radiation-induced reactions to be studied (Tabata et al, 1991). Note that secondary electron radiation always constitutes a significant part of energy transferred by heavy charged particles. For these reasons, the electron occupies a central role in radiation chemistry. 

Figure 5.6 Interaction of a beam of primary electrons with a thin solid sample, showing the various processes which can take place (Pollard and Heron 1996 51). Various types of electron can be scattered or ejected back towards the source, or transmitted through the sample. Characteristic X-rays and bremsstrahlung can be produced, and also cathodoluminescence. These products form the basis of analytical and imaging electron microscopy, and of a range of other techniques. (After Woldseth 1973 Fig. 4.1 - reproduced by permission of the Royal Society of Chemistry.)...

Ionization in Cl is the result of one or several competing chemical reactions. Therefore, the sensitivity in Cl strongly depends on the conditions of the experiment. In addition to primary electron energy and electron current, the reagent gas, the reagent gas pressure, and the ion source temperature have to be stated with the sensitivity data to make a comparison. Modem magnetic sector instmments are specified to have a sensitivity of about 4 x 10" C pg for the [Mh-H] quasi-molecular ion of methylstearate, m/z 299, at / = 1000 in positive-ion Cl mode. This is approximately one order of magnitude less than for El. 

The sulphonyl chloride 23 is proposed as a protecting group for the Gabriel synthesis of secondary amines from primary amines. At the deprotecting stage, carbon-sulphur bond cleavage is achieved using zinc and acid as the electron source [109]. 

Electron ionization (El) was the primary ionization source for mass analysis until the 1980s, limiting the chemist to the analysis of small molecules well below the mass range of common bioorganic compounds. This limitation motivated the development of the techniques commonly known as ESI, 1 MALDI, 2 and fast atom bombardment (FAB) 3,4 (Table 1). These ion sources allow for rapid and easy peptide analyses that previously required laborious sample preparation or were not possible with electron ionization. The mechanism of ionization these ion sources employ, which is somewhat responsible for their ability to generate stable molecular ions, is protonation and/or deprotonation. 

In SIMSLAB from VG Scientific, both surface analytical techniques - SIMS and SNMS - have been applied (see Figure 5.34). In this mass spectrometer different types of primary ion sources are available. Ar+, Cs+, Ga+ or O) primary ions are accelerated in the secondary ion source on the solid sample surface. Similar to the CAMECA IMS-7f, with this experimental arrangement, besides depth profiling, a microlocal analysis can also be performed. The sputtered secondary ions (for SIMS) or the post-ionized sputtered neutrals (for SNMS) - the post-ionization is carried out by an electron beam in an ionizer box (right-hand schematic in Figure 5.34) - are separated... 

Equations 5.10 and 5.11 are representative of efficient mechanisms whereby each primary electron from the radioactive source can result in the formation of as many as 101 organic ions. Equation 5.12 emphasizes strongly the necessity of controlling all sources of contamination in the system. 

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