Post-ionization, SNMS

Sputtered Neutral Mass Spectrometry (SNMS) is the mass spectrometric analysis of sputtered atoms ejected from a solid surface by energetic ion bombardment. The sputtered atoms are ionized for mass spectrometric analysis by a mechanism separate from the sputtering atomization. As such, SNMS is complementary to Secondary Ion Mass Spectrometry (SIMS), which is the mass spectrometric analysis of sputtered ions, as distinct from sputtered atoms. The forte of SNMS analysis, compared to SIMS, is the accurate measurement of concentration depth profiles through chemically complex thin-film structures, including interfaces, with excellent depth resolution and to trace concentration levels. Genetically both SALI and GDMS are specific examples of SNMS. In this article we concentrate on post ionization only by electron impact. 

In other articles in this section, a method of analysis is described called Secondary Ion Mass Spectrometry (SIMS), in which material is sputtered from a surface using an ion beam and the minor components that are ejected as positive or negative ions are analyzed by a mass spectrometer. Over the past few years, methods that post-ion-ize the major neutral components ejected from surfaces under ion-beam or laser bombardment have been introduced because of the improved quantitative aspects obtainable by analyzing the major ejected channel. These techniques include SALI, Sputter-Initiated Resonance Ionization Spectroscopy (SIRIS), and Sputtered Neutral Mass Spectrometry (SNMS) or electron-gas post-ionization. Post-ionization techniques for surface analysis have received widespread interest because of their increased sensitivity, compared to more traditional surface analysis techniques, such as X-Ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES), and their more reliable quantitation, compared to SIMS. 

SNMS sensitivity depends on the efficiency of the ionization process. SNs are post-ionized (to SN" ) either hy electron impact (El) with electrons from a hroad electron (e-)heam or a high-frequency (HF-) plasma (i.e. an e-gas), or, most efficiently, hy photons from a laser. In particular, the photoionization process enables adjustment of the fragmentation rate of sputtered molecules by varying the laser intensity, pulse width, and/or wavelength. 

The basic principle of e-beam SNMS as introduced by Lipinsky et al. in 1985 [3.60] is simple (Fig. 3.30) - as in SIMS, the sample is sputtered with a focused keV ion beam. SN post-ionization is accomplished by use of an e-beam accelerated between a filament and an anode. The applied electron energy Fe a 50 20 eV is higher than the range of first ionization potentials (IP) of the elements (4—24 eV, see Fig. 3.31). Typical probabilities of ionization are in the 0.01% range. SD and residual gas suppression is achieved with electrostatic lenses before SN post-ionization and energy filtering, respectively. 

Fig. 3.36. Experimental, Fe-related HF- calculated according to [3.74] from plasma SNMS sensitivity factors S(pe)x Ref [3.71] (salts) [3.72] alloys, [3.73] with elements X ordered according to round robins (r.r.). their post-ionization probabilities...

Surface analysis by non-resonant (NR-) laser-SNMS [3.102-3.106] has been used to improve ionization efficiency while retaining the advantages of probing the neutral component. In NR-laser-SNMS, an intense laser beam is used to ionize, non-selec-tively, all atoms and molecules within the volume intersected by the laser beam (Eig. 3.40b). With sufficient laser power density it is possible to saturate the ionization process. Eor NR-laser-SNMS adequate power densities are typically achieved in a small volume only at the focus of the laser beam. This limits sensitivity and leads to problems with quantification, because of the differences between the effective ionization volumes of different elements. The non-resonant post-ionization technique provides rapid, multi-element, and molecular survey measurements with significantly improved ionization efficiency over SIMS, although it still suffers from isoba-ric interferences. 

In SNMS, sputtered neutrals are post-ionized before they enter the mass spectrometer. In contrast to SIMS, SNMS does not suffer from the matrix effects associated with the ionization probability of sputtered particles. Here, the sensitivity for a cer-... 

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... 

In contrast to SIMS, in SNMS - where the evaporation and ionization processes are decoupled -the matrix effects are significantly lower, because the composition of sputtered and post-ionized neutrals corresponds more closely to the composition in the solid sample (compared to the sputtered secondary ions in SIMS), which means the RSCs of elements vary by about one order of magnitude. Consequently, a semi-quantitative analysis by SNMS can also be carried out if no suitable matrix matched CRM is available. This is relevant for thin film analysis, especially for the determination of elemental concentration profiles in depth, for studying the stoichiometric composition of thin films and interdiffusion effects. 

SNMS ions neutrals ZZ sputtered neutrals (post ionized by e-beam or laser) > 3 nm 5 pm (+) > P gg-1 high depth resolution elemental information poor sensitivity... 

Resonant and non-resonant laser post-ionization of sputtered uranium atoms using SIRIS (sputtered initited resonance ionization spectroscopy) and SNMS (secondary neutral mass spectrometry) in one instrument for the characterization of sub-pm sized single microparticles was suggested by Erdmann et al.94 Resonant ionization mass spectrometry allows a selective and sensitive isotope analysis without isobaric interferences as demonstrated for the ultratrace analysis of plutonium from bulk samples.94 Unfortunately, no instrumental equipment combining both techniques is commercially available. 

The principles of ion sources which use a primary ion beam for sputtering of solid material on sample surface in a high vacuum ion source of a secondary ion mass spectrometer or a sputtered neutral mass spectrometer are shown in Figure 2.30a and Figure 2.30b, respectively. Whereas in SIMS the positive or negative secondary ions formed after primary ion bombardment are analyzed, in SNMS the secondary sputtered ions are suppressed by a repeUer voltage and the sputtered neutrals which are post-ionized either in an argon plasma ( plasma SNMS ), by electron impact ionization ( e-beam SNMS ) or laser post-ionization are nsed for the surface analysis (for details of the ionization mechanisms see references 122-124). 

Mass spectrometry of secondary ions (SIMS) [78, 79] or of post-ionized secondary neutral particles (SNMS) [80-82], which both are ejected from a surface which is bombarded with an ion beam, is a very sensitive but for chemical compounds also destructive analytical technique. It yields excellent qualitative information. Quantitative results are difficult to obtain. A review is given in [83]. 

An average sensitivity of up to 10 for all elements is achieved by using SNMS. Higher sensitivities are possible with the laser post-ionization schemes. 

Laser SNMS requires the operation with properly selected duty cycles that control the delay times between the primary ion pulse, a pulsed extraction voltage for separating the secondary ions from post-ionized neutrals, and the firing of the postionizing laser pulse. Such duty cycles have, in addition, to be synchronized with the stepwise motion of the pulsed primary ion beam across the sample surface in the microprobe mode of laser SNMS. The selection of appropriate duration and decay times of the ion and laser pulses, of the laser intensity, and beam shape is important to make the photoion yields independent on the sputtered particle velocities. The detection volume must be matched to the entrance ion optics of the TOP such that it becomes independent of the individual ionization process. Usually, laser intensities in the range from 10 to lO Wcm are applied. While the particle density in the detection volume is monitored at small laser intensities, the particle flux is measured at high photon densities. 

A high percentage of the sputtered secondary particles are neutral and must be post-ionized for mass spectroscopy analysis (SNMS) (62). Post-ionization can be achieved by electron impact in a plasma or by an electron beam. Alternatively, resonant and nonresonant laser ionization can be applied. Applications of SNMS for catalyst characterization have still not been reported. 

Sputtering by kilovolt ion beams produces far more neutral species than ions. When static methods are employed, one can assume that a large percentage of these sputtered neutrals will be intact molecules. Thus, there is the very real possibility for improving detection limits (sensitivity) if these neutrals can be observed by post-ionization in the gas phase. Such techniques are known as secondary neutral mass spectrometry (SNMS). ... 

SIMS is one of the most powerful surface and microanalytical techniques for materials characterization. It is primarily used in the analysis of semiconductors, as well as for metallurgical, and geological materials. The advent of a growing number of standards for SIMS has gready enhanced the quantitative accuracy and reliability of the technique in these areas. Future development is expected in the area of small spot analysis, implementation of post-sputtering ionization to SIMS (see the articles on SALI and SNMS), and newer areas of application, such as ceramics, polymers, and biological and pharmaceutical materials. 

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