Molecular SIMS sputtering

It is a remarkable feature of secondary ion mass spectrometry (SIMS) that considerable chemical information is accessible through the procedurally simple physical technique of sputtering. SIMS--espec ia 11 y under low primary ion flux conditions ("static SIMS," a 1 s o known as "molecular SIMS" when applied to compounds)—provides information on molecular weight and molecular structure and allows isotopic analysis. The surface sensitivity of SIMS permits its use in imaging, in monitoring of surface... 

The most common application of dynamic SIMS is depth profiling elemental dopants and contaminants in materials at trace levels in areas as small as 10 pm in diameter. SIMS provides little or no chemical or molecular information because of the violent sputtering process. SIMS provides a measurement of the elemental impurity as a function of depth with detection limits in the ppm—ppt range. Quantification requires the use of standards and is complicated by changes in the chemistry of the sample in surface and interface regions (matrix efiects). Therefore, SIMS is almost never used to quantitadvely analyze materials for which standards have not been carefiilly prepared. The depth resoludon of SIMS is typically between 20 A and 300 A, and depends upon the analytical conditions and the sample type. SIMS is also used to measure bulk impurities (no depth resoludon) in a variety of materials with detection limits in the ppb-ppt range. 

The limitations of SIMS - some inherent in secondary ion formation, some because of the physics of ion beams, and some because of the nature of sputtering - have been mentioned in Sect. 3.1. Sputtering produces predominantly neutral atoms for most of the elements in the periodic table the typical secondary ion yield is between 10 and 10 . This leads to a serious sensitivity limitation when extremely small volumes must be probed, or when high lateral and depth resolution analyses are needed. Another problem arises because the secondary ion yield can vary by many orders of magnitude as a function of surface contamination and matrix composition this hampers quantification. Quantification can also be hampered by interferences from molecules, molecular fragments, and isotopes of other elements with the same mass as the analyte. Very high mass-resolution can reject such interferences but only at the expense of detection sensitivity. 

TOF-SIMS can be applied to identify a variety of molecular fragments, originating from various molecular surface contaminations. It also can be used to determine metal trace concentrations at the surface. The use of an additional high current sputter ion source allows the fast erosion of the sample. By continuously probing the surface composition at the actual crater bottom by the analytical primary ion beam, multi element depth profiles in well defined surface areas can be determined. TOF-SIMS has become an indispensable analytical technique in modem microelectronics, in particular for elemental and molecular surface mapping and for multielement shallow depth profiling. 

The impact of an ion beam on the electrode surface can result in the transfer of the kinetic energy of the ions to the surface atoms and their release into the vacuum as a wide range of species—atoms, molecules, ions, atomic aggregates (clusters), and molecular fragments. This is the effect of ion sputtering. The SIMS secondary ion mass spectrometry) method deals with the mass spectrometry of sputtered ions. The SIMS method has high analytical sensitivity and, in contrast to other methods of surface analysis, permits a study of isotopes. In materials science, the SIMS method is the third most often used method of surface analysis (after AES and XPS) it has so far been used only rarely in electrochemistry. 

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]. 

Figure 2.8. Schematic of a sputtering event in secondary ion mass spectrometry (SIMS). Mainly neutral species are ejected, but also some positively charged and negatively charged ions. For samples containing analyte with relatively low masses, intact molecular ions can be desorbed. The greater portion of ejected compounds is, however, fragments.

SIMS ions ions ZZ sputtered ions > 1 nm 50 nm + + + > ngg 1 high depth resolution good imaging huge variation of RSCs, intense molecular ions... 

Molecular cluster ions are very useful because they reveal which elements are in contact in the sample. Of course, this presupposes that such clusters are emitted intact and are not the result of recombination processes above the surface. Oechs-ner [13] collected evidence that direct cluster emission processes predominate in the case when relatively strong bonds exist between neighbor atoms. Direct emission becomes even more likely if the two atoms differ significantly in mass, and when the heavier atom receives momentum from the sputter cascade in the solid. Thus, there is little doubt that clusters of the type ZrO+, FeCl3-, MoS+, CH3+, PdCO+, or Rh2NO+ (which we will encounter in the applications later) stem from direct emission processes and reflect bonds present in the sample [2, 4], Some evidence exists, however, that atomic recombination may play a role in the SIMS of metals, and in alloys where the two constituents have comparable mass... 

---