Post-ionization

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. 

Previous studies of the interaction of energetic particles with suri ces have made it clear that under nearly all conditions the majority of atoms or molecules removed from a surface are neutral, rather than charged. This means that the chained component can have large relative fluctuations (orders of magnitude) depending on the local chemical matrix. Calibration with standards for surfaces is difficult and for interfaces is nearly impossible. Therefore, for quantification ease, the majority neutral component of the departing flux must be sampled, and this requires some type of ionization above the sample, often referred to as post-ionization. SALI uses effi-... 

SALI applies two methods of post-ionization, MPI and SPI, each of which can be used in one of the three modes of analysis survey analysis, depth profiling, and mapping ... 

A comparison of the various post-ionization techniques electron-gas bombardment, resonant and nonresonant laser ionization, etc. While some of the numbers are outdated, the relative capabilities of these methods have remained the same. This is a well-written review article that reiterates the specific areas where post-ionization has advantages over SIMS. 

A discussion of the motivation behind doing sputtered neutral analysis versus SIMS, plus a description of the first prototype SALI instrument. A well written introduction for someone without previous surface analysis experience it also includes an historical overview of the various post-ionization techniques. 

Surface Analysis by Laser Ionization Post-Ionization Secondary Ion Mass Spectrometry Multi-Photon Nonresonant Post Ionization Multiphoton Resonant Post Ionization Resonant Post Ionization Multi-Photon Ionization Single-Photon Ionization... 

SIMS using Time-of-Flight Mass Spectrometer Post Ionization SIMS... 

Depending on the matrix and the post-ionization technique, SN" spectra can be dominated by atomic or molecular signals. In particular, compounds with high mass... 

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. 

After post-ionization in the 3 cm long cylindrical plasma space between sample surface and the opposite wall, SN" enter a 90° electrostatic ion energy analyzer (ion optics) suppressing ionized plasma gas particles to a degree of 10 -10 noise levels are correspondingly low (1 cps). The transmission of the electrostatic ion optics is in the range of a few per cent. 

In both electron post-ionization techniques mass analysis is performed by means of a quadrupole mass analyzer (Sect. 3.1.2.2), and pulse counting by means of a dynode multiplier. In contrast with a magnetic sector field, a quadrupole enables swift switching between mass settings, thus enabling continuous data acquisition for many elements even at high sputter rates within thin layers. 

The product netx(Px.o) fx is equal to the post-ionization probability a ... 

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. 

As illustrated in Fig. 3.41, several laser schemes can be used to ionize elements and molecules. Scheme (a) in this figure stands for non-resonant ionization. Because the ionization cross-section is very low, a very high laser intensity is required to saturate the ionization process. Scheme (b) shows a simple single-resonance scheme. This is the simplest but not necessarily the most desirable scheme for resonant post-ionization. Cross-... 

Post-ionization occurs with the probability a (Xf note a photoion) ... 

For post-ionized particles, it is possible to define a generalized transformation probability P (A Xf) ... 

For IBSCA analysis, standard HV or, better, UHV-equipment with turbomolecular pump and a residual gas pressure of less than 10 Pa is necessary. As is apparent from Fig. 4.46, the optical detection system, which consists of transfer optics, a spectrometer, and a lateral-sensitive detector, is often combined with a quadrupole mass spectrometer for analysis of secondary sputtered particles (ions or post-ionized neutrals). 

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-... 

Multiply charged ions of minor abundance are frequently observed in FI and FD mass spectra. Their increased abundance as compared to El spectra can be rationalized by either of the following two-step processes i) Post-ionization of gaseous M ions can occur due to the probability for an M ion to suffer a second or even third ionization while drifting away from the emitter surface. [69,70] Especially ions generated in locations not in line-of-sight to the counter electrode pass numerous whiskers on their first 10-100 pm of flight ... 

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