Sputtering ionization

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. 

For a good understanding of SIMS spectra it is important to have at least a qualitative understanding of phenomena such as sputtering, ionization and neutralization, ion-induced electron and light emission, and the energy distribution of sputtered particles. 

The formation of secondary ions is the most difficult feature in SIMS. Where sputtering is relatively well understood, the process of sputter ionization is not, and a theory that describes the process of secondary ion formation satisfactorily does not yet exist. A number of trends can be rationalized, though. 

The important features of the sputter ionization process can be summarized as follows. First, the point at which the secondary particles escape from the surface is not the point of the initial impact by the primary ion. Instead, there is a surface damage zone that includes the points of primary particle impact and secondary particle escape. Second, the cascade collision results in generation of secondary ions with much lower energy than that of primary ions. Third, there is significant variation in secondary ion yield with chemical elements and chemical states of the surface, which makes quantitative analysis difficult. 

DIFFERENCES IN SPUTTERING/IONIZATION MECHANISMS BETWEEN SIMS AND GD-MS... 

The approach has been to amalgamate theory and experiment throughout this book. Both classical and quantum models are used as they are both important in understanding the sputtering, ionization, neutralization, quantification, dissociation, implantation, chemical reactions, and cluster formation that are encountered in the sputtering process. 

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 Dynamic Secondary Ion Ma s Spectrometry (SIMS), a focused ion beam is used to sputter material from a specific location on a solid surface in the form of neutral and ionized atoms and molecules. The ions are then accelerated into a mass spectrometer and separated according to their mass-to-charge ratios. Several kinds of mass spectrometers and instrument configurations are used, depending upon the type of materials analyzed and the desired results. 

In Surface Analysis by Laser Ionization (SAU) ionized and neutral atoms are sputtered from the sample surface, typically using an ion beam (like SIMS) or a... 

The detection limit of each element depends upon the electron affinity or ionization potential of the element itself, the chemical nature of the sample in which it is contained, and the type and intensity of the primary ion beam used in the sputtering process. 

Because SIMS can measure only ions created in the sputtering process and not neutral atoms or clusters, the detection limit of a particular element is affected by how efficiently it ionizes. The ionization efficiency of an element is referred to as its ion yield. The ion yield of a particular element A is simply the ratio of the number of A ions to the total number of A atoms sputtered from the mixing zone. For example, if element A has a 1 100 probability of being ionized in the sputtering process—that is, if 1 ion is formed from every 100 atoms of A sputtered from the sample—the ion yield of A would be 1/100. The higher the ion yield for a given element, the lower (better) the detection limit. 

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. 

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