Secondary Ion Mass Spectrometry SIMS

SIMS can be performed in two modes dynamic SIMS, which uses a high primary ion beam intensity and static SIMS, which uses a very low primary ion beam intensity. 

SIMS is by far the most sensitive surface technique, but also the most difficult one to quantify. SIMS is very popular in materials research for making concentration depth profiles and chemical maps of the surface. The principle of SIMS is conceptually simple A primary ion beam (Ar+, 0.5-5 keV) is used to sputter atoms, ions and molecular fragments from the surface which are consequently analyzed with a mass spectrometer. It is as if one scratches some material from the surface and puts it in a mass spectrometer to see what elements are present. However, the theory behind SIMS is far from simple. In particular the formation of ions upon sputtering in or near the surface is hardly understood. The interested reader will find a wealth of information on SIMS in the books by Benninghoven et al. [2J and Vickerman el al. [4], while many applications have been described by Briggs et al. [5]. 

When a surface is exposed to a beam of ions, energy is deposited in the surface region of the sample by a collision cascade. Some of the energy will return to the 

The advantages of SIMS are its high sensitivity (detection limit of parts per millions for certain elements) and its ability to detect hydrogen and the emission of molecular fragments, which often bear tractable relationships with the parent structure on the surface. Disadvantages are that secondary ion formation is a poorly understood phenomenon and that quantitation is often difficult. A major drawback is the matrix effect secondary ion yields of one element can vary tremendously with its chemical environment. This matrix effect and the elemental sensitivity variation of five orders of magnitude across the periodic table make quantitative interpretation of SIMS spectra of technical catalysts extremely difficult. 

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 signal intensity of an elemental positive or negative secondary ion is given by / =/pF/ esurlT (4-1) 

When a surface is exposed to a beam of ions, energy is deposited in the surface region of the sample by a collision cascade. Some of the energy will return to the surface and stimulate the ejection of atoms, ions, and multi atomic clusters (Fig. 4.1). In SIMS, secondary ions (positive or negative) are detected directly with a 

SIMS was also used to study naphtha reforming catalysts It was found that the carbon profile along the pellet had wide irregularities. Two different regions could be distinguished, areas quite free of coke where the carbon signal was very low, and areas where the peak signal was close to the maximum. The size of these areas varied between 20 and 100 pm. 

SIMS is the most sensitive of all the commonly employed surfaee analytical techniques and there are several variations, all requiring UHV. All these teehnicques are capable of examining specimens up to 50 mm.  

Source Reprinted with permission from Fitzer E, Rozploch F, Laser Raman spectroscopy for the determination of the C—C bonding length in carbon, Carbon, 24(5), 594-595,1988. Copyright 1988, Elsevier. 

The SIMS spectrometer is simply a source of mono-energetic and collimated ions that are targeted at a surface that is contained in a vacuum. The ejected ions are then carefully collected and their molar mass analysed. The ability to differentiate between different species will depend on knowledge of the fragmentation pattern or the ability to identify a unique ion that can be associated with a particular structure. 

Other fragments that have been identified are  

Cullity, Elements of X-ray Diffraction, Addison Wesley, Reading, MA, 1978. 

Balta-Celleja and C. G. Vonk, X-ray Scattering of Synthetic Polymers, Elsevier, Amsterdam, 1989. 

Nguyen, in New Characterization Techniques for Thin Polymer Films, ed. H. M. Tong and L. T. Nguyen, WUey, New York, 1990, p. 57. 

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Ions are also used to initiate secondary ion mass spectrometry (SIMS) [ ], as described in section BI.25.3. In SIMS, the ions sputtered from the surface are measured with a mass spectrometer. SIMS provides an accurate measure of the surface composition with extremely good sensitivity. SIMS can be collected in the static mode in which the surface is only minimally disrupted, or in the dynamic mode in which material is removed so that the composition can be detemiined as a fiinction of depth below the surface. SIMS has also been used along with a shadow and blocking cone analysis as a probe of surface structure [70]. 

Secondary ion mass spectrometry (SIMS) is by far the most sensitive surface teclmique, but also the most difficult one to quantify. SIMS is very popular in materials research for making concentration depth profiles and chemical maps of the surface. For a more extensive treatment of SIMS the reader is referred to [3] and [14. 15 and 16]. The principle of SIMS is conceptually simple When a surface is exposed to a beam of ions... 

Confusingly, FAB is sometimes called secondary ion mass spectrometry (SIMS), the secondary referring to the nature of the process (primary bombardment, secondary emission), but see next item. 

Spectrometric Analysis. Remarkable developments ia mass spectrometry (ms) and nuclear magnetic resonance methods (nmr), eg, secondary ion mass spectrometry (sims), plasma desorption (pd), thermospray (tsp), two or three dimensional nmr, high resolution nmr of soHds, give useful stmcture analysis information (131). Because nmr analysis of or N-labeled amino acids enables determiaation of amino acids without isolation from organic samples, and without destroyiag the sample, amino acid metaboHsm can be dynamically analy2ed (132). Proteia metaboHsm and biosynthesis of many important metaboUtes have been studied by this method. Preparative methods for labeled compounds have been reviewed (133). 

Environment. Detection of environmental degradation products of nerve agents directly from the surface of plant leaves using static secondary ion mass spectrometry (sims) has been demonstrated (97). Pinacolylmethylphosphonic acid (PMPA), isopropylmethylphosphonic acid (IMPA), and ethylmethylphosphonic acid (EMPA) were spiked from aqueous samples onto philodendron leaves prior to analysis by static sims. The minimum detection limits on philodendron leaves were estimated to be between 40 and 0.4 ng/mm for PMPA and IMPA and between 40 and 4 ng/mm for EMPA. Sims analyses of IMPA adsorbed on 10 different crop leaves were also performed in order to investigate general apphcabiflty of static sims for... 

These samples were measured non-destructively by energy-dispersive XRF with synclirotron radiation excitation (SYXRS), by g-XRF, by wavelength-dispersive XRF (WDXRS), and by Rutherford back scattering (RBS), by X-ray reflectometry (XRR) and by destructive secondary ion mass spectrometry (SIMS) as well (both last methods were used for independant comparison). 

In Secondary Ion Mass Spectrometry (SIMS), a solid specimen, placed in a vacuum, is bombarded with a narrow beam of ions, called primary ions, that are suffi-ciendy energedc to cause ejection (sputtering) of atoms and small clusters of atoms from the bombarded region. Some of the atoms and atomic clusters are ejected as ions, called secondary ions. The secondary ions are subsequently accelerated into a mass spectrometer, where they are separated according to their mass-to-charge ratio and counted. The relative quantities of the measured secondary ions are converted to concentrations, by comparison with standards, to reveal the composition and trace impurity content of the specimen as a function of sputtering dme (depth). 

Static Secondary Ion Mass Spectrometry (SIMS) involves the bombardment of a sample with an energetic (typically 1-10 keV) beam of particles, which may be either ions or neutrals. As a result of the interaction of these primary particles with the sample, species are ejected that have become ionized. These ejected species, known as secondary ions, are the analytical signal in SIMS. 

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. 

With today s technology, the definition of the surface as it effects a material s performance in many cases means the outer one or two monolayers. It is the specific chemistry of these immediate surface molecules that determines many of the chemical and physical properties. Therefore, it is important to have available a tool that is able to characterize the chemistry of these layers. One such method that has met with considerable success is Static Secondary Ion Mass Spectrometry (SIMS). 

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. 

W. Reuter, in Secondary Ion Mass Spectrometry SIMS V, Springer-Verlag,... 

Secondary Ion Mass Spectrometry Dynamic Secondary Ion Mass Spectrometry Static Secondary Ion Mass Spectrometry SIMS using a Quadruple Mass Spectrometer SIMS usii a Magnetic Sector Mass Spectrometer See Magnetic SIMS... 

Surface analysis has made enormous contributions to the field of adhesion science. It enabled investigators to probe fundamental aspects of adhesion such as the composition of anodic oxides on metals, the surface composition of polymers that have been pretreated by etching, the nature of reactions occurring at the interface between a primer and a substrate or between a primer and an adhesive, and the orientation of molecules adsorbed onto substrates. Surface analysis has also enabled adhesion scientists to determine the mechanisms responsible for failure of adhesive bonds, especially after exposure to aggressive environments. The objective of this chapter is to review the principals of surface analysis techniques including attenuated total reflection (ATR) and reflection-absorption (RAIR) infrared spectroscopy. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and secondary ion mass spectrometry (SIMS) and to present examples of the application of each technique to important problems in adhesion science. 

In secondary ion mass spectrometry (SIMS), a beam of energetic primary ions is focused onto the surface of a solid. Some of the ions are reflected but most of the energy of the primary ions is dissipated in the surface by binary collisions that cause neutrals, excited neutrals, and ions (positive and negative) to be ejected or sputtered from the surface. The secondary ions can be analyzed by a mass spectrometer to provide information about the surface composition of the solid. 

Briggs, D., Brown, A. and Vickerman, J.C., Handbook of Static Secondary Ion Mass Spectrometry (SIMS). John Wiley and Sons, Chichester, 1989. 

Further structural information is available from physical methods of surface analysis such as scanning electron microscopy (SEM), X-ray photoelectron or Auger electron spectroscopy (XPS), or secondary-ion mass spectrometry (SIMS), and transmission or reflectance IR and UV/VIS spectroscopy. The application of both electroanalytical and surface spectroscopic methods has been thoroughly reviewed and appropriate methods are given in most of the references of this chapter. 

It is worth noting, prior to citing actual metal atom studies, the recent secondary ion mass spectrometry (SIMS) on an argon matrix-isolated propene sample, demonstrating the applicability of SIMS analysis to the characterization of matrix-isolated species. The same group h s reported the first C NMR spectra of organic molecules trapped in an argon matrix. ... 

Elementary steps in which a bond is broken form a particularly important class of reactions in catalysis. The essence of catalytic action is often that the catalyst activates a strong bond that cannot be broken in a direct reaction, but which is effectively weakened in the interaction with the surface, as we explained in Chapter 6. To monitor a dissociation reaction we need special techniques. Temperature-programmed desorption is an excellent tool for monitoring reactions in which products desorb. However, when the reaction products remain on the surface, one needs to employ different methods such as infrared spectroscopy or secondary-ion mass spectrometry (SIMS). 

Raman experiments are confirmed by XPS and secondary ion mass spectrometry (SIMS) measurements performed by Thiine et al. [38] on a surface... 

There are two principal sources of reliable partitioning data for any trace element glassy volcanic rocks and high temperature experiments. For the reasons outlined above, both sources rely on analytical techniques with high spatial resolution. Typically these are microbeam techniques, such as electron-microprobe (EMPA), laser ablation ICP-MS, ion-microprobe secondary ion mass spectrometry (SIMS) or proton-induced X-ray emission (PIXE). 

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