Depth atomic spectroscopy

FIGURE 40.18 Depth profiles by laser secondary neutral mass spectrometry (laser SNMS), secondary ion mass spectrometry (SIMS) with Ar and 02 primary ions, and Auger electron spectroscopy (AES) of implanted boron. Reprinted from Higashi, Y., Quantitative depth profiling by laser-ionization sputtered neutral mass spectrometry (1999) Spectrochimica Acta Part B Atomic Spectroscopy, 54(1), 109-122. Copyright (1999), with permission from Elsevier Science. 

Higashi, Y. (1999) Quantitative depth profiling by laser-ionization sputtered neutral mass spectrometry. Spectrochimica Acta Part B Atomic Spectroscopy, 54, 109-122. 

FIGURE 10-20 RF-GDOES depth profile of a microelectronic multilayer system. Note the thickness and composition of each layer shown above each peak or band and the elemental composition indicated by the curves. (From N. Jakubowski, A. Bogaerts, and V. Hoffmann, Atomic Spectroscopy in Elemental Ar alysis, M. Cullen, ed., p. 129, Boca Raton, FL CRC Press, 2004. With permission.)... 

AES Auger electron spectroscopy After the ejection of an electron by absorption of a photon, an atom stays behind as an unstable Ion, which relaxes by filling the hole with an electron from a higher shell. The energy released by this transition Is taken up by another electron, the Auger electron, which leaves the sample with an element-specific kinetic energy. Surface composition, depth profiles... 

SIMS Secondary Ion mass spectroscopy A beam of low-energy Ions Impinges on a surface, penetrates the sample and loses energy In a series of Inelastic collisions with the target atoms leading to emission of secondary Ions. Surface composition, reaction mechanism, depth profiles... 

Electron Microprobe A.na.Iysis, Electron microprobe analysis (ema) is a technique based on x-ray fluorescence from atoms in the near-surface region of a material stimulated by a focused beam of high energy electrons (7—9,30). Essentially, this method is based on electron-induced x-ray emission as opposed to x-ray-induced x-ray emission, which forms the basis of conventional x-ray fluorescence (xrf) spectroscopy (31). The microprobe form of this x-ray fluorescence spectroscopy was first developed by Castaing in 1951 (32), and today is a mature technique. Primary beam electrons with energies of 10—30 keV are used and sample the material to a depth on the order of 1 pm. X-rays from all elements with the exception of H, He, and Li can be detected. 

Several features of ISS quantitative analysis should be noted. First of all, the relative sensitivities for the elements increase monotonically with mass. Essentially none of the other surface spectroscopies exhibit this simplicity. Because of this simple relationship, it is possible to mathematically manipulate the entire ISS spectrum such that the signal intensity is a direct quantitative representation of the surface. This is illustrated in Figure 5, which shows a depth profile of clean electrical connector pins. Atomic concentration can be read roughly as atomic percent direcdy from the approximate scale at the left. 

X-ray scattering studies at a renewed pc-Ag/electrolyte interface366,823 provide evidence for assuming that fast relaxation and diffu-sional processes are probable at a renewed Sn + Pb alloy surface. Investigations by secondary-ion mass spectroscopy (SIMS) of the Pb concentration profile in a thin Sn + Pb alloy surface layer show that the concentration penetration depth in the solid phase is on the order of 0.2 pm, which leads to an estimate of a surface diffusion coefficient for Pb atoms in the Sn + Pb alloy surface layer on the order of 10"13 to lCT12 cm2 s i 820 ( p,emicai analysis by electron spectroscopy for chemical analysis (ESCA) and Auger ofjust-renewed Sn + Pb alloy surfaces in a vacuum confirms that enrichment with Pb of the surface layer is probable.810... 

Since ion beams (like electron beams) can be readily focussed and deflected on a sample so that chemical composition imaging is possible. The sputtered particles largely originate from the top one or two atom layers of a surface, so that SIMS is a surface specific technique and it provides information on a depth scale comparable with other surface spectroscopies. 

As already indicated above, what one may consider a surface depends on the property under consideration. Adhesion is very much an outer atomic layer issue, unless one is dealing with materials like fibreboard in which the polymer resin may also be involved in mechanical anchoring onto the wood particles. Gloss and other optical properties are related to the penetration depth of optical radiation. The latter depends on the optical properties of the material, but in general involves more than a few micrometer thickness and therewith much more than the outer atomic layers only. It is thus the penetration depth of the probing technique that needs to be suitably selected with respect to the surface problem under investigation. Examples selected for various depths (< 10 nm, 10 s of nm, 100 nm, micrometer scale) have been presented in Chapter 10 of the book by Garton on Infrared Spectroscopy of Polymer Blends, Composites and Surfaces... 

Fig. 2. Solid-phase arsenic in ppm versus depth in m from a continuous core. The core consists of clayey silt to depth of 28 m, and fine sand thereafter with a silt horizon at 34 m depth. As was measured by digestion with an HCI-HNO3-H2O aqua regia solution followed by inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectroscopy analysis.

The elemental composition, oxidation state, and coordination environment of species on surfaces can be determined by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) techniques. Both techniques have a penetration depth of 5-20 atomic layers. Especially XPS is commonly used in characterization of electrocatalysts. One common example is the identification and quantification of surface functional groups such as nitrogen species found on carbon-based catalysts.26-29 Secondary Ion Mass spectrometry (SIMS) and Ion Scattering Spectroscopy are alternatives which are more surface sensitive. They can provide information about the surface composition as well as the chemical bonding information from molecular clusters and have been used in characterization of cathode electrodes.30,31 They can also be used for depth profiling purposes. The quantification of the information, however, is rather difficult.32... 

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