Microprobe

Boyd G T, Shen Y R and Hansch T W 1986 Continuous-wave second-harmonic generation as a surface microprobe Opt. Lett. 11 97-9... 

The basis of the nuclear microprobe (NMP) is a source of energetic ions from a particle accelerator. These... 

Table 7.8 contains values of p,/p for the common target elements employed in X-ray work. A more extensive set of mass absorption coefficients for K, L, and M emission lines within the wavelength range from 0.7 to 12 A is contained in Heinrich s paper in T. D. McKinley, K. F. J. Heinrich, and D. B. Wittry (eds.). The Electron Microprobe, Wiley, New York, 1966, pp. 351-377. This article should be consulted to ascertain the probable accuracy of the values and for a compilation of coefficients and exponents employed in the computations. 

Edx is based on the emission of x-rays with energies characteristic of the atom from which they originate in Heu of secondary electron emission. Thus, this technique can be used to provide elemental information about the sample. In the sem, this process is stimulated by the incident primary beam of electrons. As will be discussed below, this process is also the basis of essentially the same technique but performed in an electron spectrometer. When carried out this way, the technique is known as electron microprobe analysis (ema). 

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. 

Elemental chemical analysis provides information regarding the formulation and coloring oxides of glazes and glasses. Energy-dispersive x-ray fluorescence spectrometry is very convenient. However, using this technique the analysis for elements of low atomic numbers is quite difficult, even when vacuum or helium paths are used. The electron-beam microprobe has proven to be an extremely useful tool for this purpose (106). Emission spectroscopy and activation analysis have also been appHed successfully in these studies (101). 

Raman Microspectroscopy. Raman spectra of small soflds or small regions of soflds can be obtained at a spatial resolution of about 1 p.m usiag a Raman microprobe. A widespread appHcation is ia the characterization of materials. For example, the Raman microprobe is used to measure lattice strain ia semiconductors (30) and polymers (31,32), and to identify graphitic regions ia diamond films (33). The microprobe has long been employed to identify fluid iaclusions ia minerals (34), and is iacreasiagly popular for identification of iaclusions ia glass (qv) (35). 

Fig. 6. Schematic diagram of a Raman microprobe where BS = beam splitter, L = lens, and MI = mirror, (a) The illumination pathway (b) the collection...

A principal advantage of the Raman microprobe is that the optics are those of a conventional light microscope a wide variety of special-purpose objectives developed for materials and biological microscopy are available. The Raman microprobe also offers the advantage of fluorescence reduction owing to the high spatial resolution of the microscope if a region of low fluorescence can be chosen for observation. 

The spatial resolution of the Raman microprobe is about an order of magnitude better than that obtainable using an infrared microscope. Measurement times, typically of a few seconds, are the same as for other Raman spectrographs. To avoid burning samples, low (5—50-mW) power lasers are employed. 

Raman spectroscopy of graphite can be an experimental challenge, because the material is a strong blackbody absorber. Generally, low (1—10-mW) laser power is used to minimise heating, which causes the band positions to change. In addition, the expansion of the graphite causes the material to go out of the focus of the optical system, an effect which can be more pronounced in microprobe work. 

Fig. 7. Raman microprobe spectra of (a) polystyrene [9003-33-6], (b) low density polyethylene, and (c) polycarbonate [24936-68-3].

Laser Raman Microprobe. A more sophisticated microscope is the Laser Raman Microprobe, sometimes referred to as MOLE (the molecular orbital laser examiner). This instmment is designed around a light microscope to yield a Raman spectmm (45) on selected areas or particles, often <1 ia volume. The data are related, at least distantly, to iafrared absorption, siace the difference between the frequency of the exciting laser and the observed Raman frequency is the frequency of one of the IR absorption peaks. Both, however, result from rotational and vibrational states. Unfortunately, strong IR absorption bands are weak Raman scatterers and vice versa hence there is no exact correspondence between the two. 

Sample preparation is straightforward for a scattering process such as Raman spectroscopy. Sample containers can be of glass or quartz, which are weak Raman scatterers, and aqueous solutions pose no problems. Raman microprobes have a spatial resolution of - 1 //m, much better than the diffraction limit imposed on ir microscopes (213). Eiber-optic probes can be used in process monitoring (214). 

K. L. WiUiams, A.n Introduction to X-Ray Spectromety X-Ray F/uorescence and Electron Microprobe Mnalysis AHen Unwin, Boston, Mass., 1987. 

Polymer—Cp—MCl complexes have been formed with the Cp-group covalendy bound to a polystyrene bead. The metal complex is uniformly distributed throughout the bead, as shown by electron microprobe x-ray fluorescence. Olefin hydrogenation catalysts were then prepared by reduction with butyl hthium (262). 

Not only is topographical information produced in the SEM, but information concerning the composition near surface regions of the material is provided as well. There are also a number of important instruments closely related to the SEM, notably the electron microprobe (EMP) and the scanning Auger microprobe (SAM). Both of these instruments, as well as the TEM, are described in detail elsewhere in this volume. 

Electron Probe Microanalysis, EPMA, as performed in an electron microprobe combines EDS and WDX to give quantitative compositional analysis in the reflection mode from solid surfaces together with the morphological imaging of SEM. The spatial resolution is restricted by the interaction volume below the surface, varying from about 0.2 pm to 5 pm. Flat samples are needed for the best quantitative accuracy. Compositional mapping over a 100 x 100 micron area can be done in 15 minutes for major components Z> 11), several hours for minor components, and about 10 hours for trace elements. 

Quantitative Electron-Probe Microanalysis. (V. D. Scott and G. Love, eds.) John Wiley Sons, New York, 1983. Taken from a short course on the electron microprobe for scientists working in the field. A thorough discussion of EDS and WDS is given, including experimental conditions and specimen requirements. The ZAF correction factors are treated extensively, and statistics, computer programs and Monte Carlo methods are explained in detail. Generally, a very useftd book. 

Infrared microscopes can focus the beam down to a 20-pm spot size for microprobing in either the transmission or reflection mode. Trace analysis, microparticle analysis, and spatial profiling can be performed routinely. 

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