Microanalysis microprobe

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. 

Laser ionization mass spectrometry or laser microprobing (LIMS) is a microanalyt-ical technique used to rapidly characterize the elemental and, sometimes, molecular composition of materials. It is based on the ability of short high-power laser pulses (-10 ns) to produce ions from solids. The ions formed in these brief pulses are analyzed using a time-of-flight mass spectrometer. The quasi-simultaneous collection of all ion masses allows the survey analysis of unknown materials. The main applications of LIMS are in failure analysis, where chemical differences between a contaminated sample and a control need to be rapidly assessed. The ability to focus the laser beam to a diameter of approximately 1 mm permits the application of this technique to the characterization of small features, for example, in integrated circuits. The LIMS detection limits for many elements are close to 10 at/cm, which makes this technique considerably more sensitive than other survey microan-alytical techniques, such as Auger Electron Spectroscopy (AES) or Electron Probe Microanalysis (EPMA). Additionally, LIMS can be used to analyze insulating sam-... 

Duncumb, P. (2000) Proceedings of Symposium Fifty Years of Electron Microprobe Analysis . August 1999, Microscopy and Microanalysis. 

The technique is referred to by several acronyms including LAMMA (Laser Microprobe Mass Analysis), LIMA (Laser Ionisation Mass Analysis), and LIMS (Laser Ionisation Mass Spectrometry). It provides a sensitive elemental and/or molecular detection capability which can be used for materials such as semiconductor devices, integrated optical components, alloys, ceramic composites as well as biological materials. The unique microanalytical capabilities that the technique provides in comparison with SIMS, AES and EPMA are that it provides a rapid, sensitive, elemental survey microanalysis, that it is able to analyse electrically insulating materials and that it has the potential for providing molecular or chemical bonding information from the analytical volume. 

The primary methods of analyzing for lead in environmental samples are AAS, GFAAS, ASV, ICP/AES, and XRFS (Lima et al. 1995). Less commonly employed techniques include ICP/MS, gas chromato-graphy/photoionization detector (GC/PID), IDMS, DPASV, electron probe X-ray microanalysis (EPXMA), and laser microprobe mass analysis (LAMMA). The use of ICP/MS will become more routine in the future because of the sensitivity and specificity of the technique. ICP/MS is generally 3 orders of magnitude more sensitive than ICP/AES (Al-Rashdan et al. 1991). Chromatography (GC,... 

Stoichiometric variations in compositions of a material and of surface layers can be revealed by AEM. Because a relatively small amount of scattering occurs through a thin HRTEM specimen, X-rays are generated from a volume that is considerably less than in the case of electron microprobe analysis (EPMA). For quantitative microanalysis, a ratio method for thin crystals (57) is used, given by the equation ... 

There are now several different types of machines that are all capable of microanalysis. All have advantages and disadvantages, but the choice of which to use is often governed by expense and availability to a particular institution. Electron probe microanalysis is by far the most popular, but here particle-induced X-ray emission (PIXE), the laser microprobe mass analyzer (LAMMA), electron energy loss spectroscopy (EELS), and secondary ion mass spectrometry (SIMS) are also considered. 

Of all of the machines used for microanalysis LAMMA seems to be the most problematic. A laser beam is used to disintegrate a spot in the sample, and the material emitted is then analyzed in a mass spectrometer. It has similar lateral resolution to PIXE, and like SIMS can be used to distinguish between isotopes of the same element. It has, however, proved very difficult to quantify, and is destructive to the specimen. One recent investigation (13) ofthe distribution of stable isotopes of calcium, magnesium, and potassium in Norway spruce used three microprobes EDAX at 0.3 pm lateral resolution isotope specific point analysis, using LAMMA at 1.5 pm lateral resolution and isotope specific imaging using SIMS at 1-3 pm lateral resolution. 

As indicated in Fig. 7.2, X-rays are among the by-products in an electron microscope. Already at the beginning of this century, people knew that matter emits X-rays when it is bombarded with electrons. The explanation of the phenomenon came with the development of quantum mechanics. Nowadays, it is the basis for determining composition on the submicron scale and, with still increasing spatial resolution, is used in the technique referred to as Electron Microprobe Analysis (EMA), Electron Probe Microanalysis (EPMA) or Energy Dispersive Analysis of X-rays (EDAX, EDX) [21]. 

C.-U. Ro and R. W. Linton, New directions in microprobe mass spectrometry molecular microanalysis using neural networks. Microbeam Anal., 1(2), 1992, 75-87. 

The ion microprobe mass analyzer s unique features permit three dimensional microanalysis of all elements in the periodic table and in... 

The Laser Raman microprobe constitutes a physical method of microanalysis based on the vibration spectra characteristic of polyatomic structures. A focused laser beam excites the sample. The light diffused by the Raman effect is used for identification and localisation of the molecular constituents present in the sample. An optical microscope allows a survey of the interesting structures and the placing of the laser beam. The spectra obtained from fossil organic particles generally match well the corresponding IR-spectra, but the features in particular yield additional information, which will be discussed below with the given examples (Fig. 23, p. 36). 

Raman microscopy was developed in the 1970s. Delhaye (34) in 1975 made the first micro Raman measurement. Simultaneously, Rosasco (35, 36) designed a Raman microprobe instrument at the National Bureau of Standards (now the NIST). This early work established the utility of Raman spectroscopy for microanalysis. The technique provides the capability of obtaining analytical-quality Raman spectra with 1 pm spatial resolution using samples in the picogram range. Commercial instruments are available. 

Electron microprobes permit chemical microanalysis as well as SEM and BSE detection, often referred to as analytical electron microscopy (AEM), or electron probe microanalysis (EPMA)56 57. This is because another product of the surface interaction with an incident electron beam is X-ray photons which have wavelengths and energies dependent on element identity and on the electron shell causing the emission. Analysis of these photons can give a local chemical analysis of the surface. Resolution of 1 pm is attainable. Two types of X-ray spectrometer can be employed ... 

Quantitative chemical analysis using the characteristic x-rays emitted by the specimen in the electron microscope is considered in Chapter 7. Since the basic principles are the same as for the electron microprobe (which will be familiar to most geologists and mineralogists), emphasis is placed on those aspects of the technique that are related to the use of thin foil specimens. The intensities of the characteristic x-ray peaks depend on the crystallographic orientation of the specimen with respect to the electron beam this effect is the basis of the relatively new technique ALCHEMl (atom location by channeling enhanced microanalysis), which under certain conditions can be used to determine the location of minor element atoms in a crystal structure. This technique is potentially very useful for mineralogical studies and is therefore discussed in some detail. 

It was in 1949, at the first European conference on electron microscopy in DelO. that R. Castaing described the electron probe microanalyser he had designed under the guidance of A. Guinier. In his thesis (1951), Castaing also described the basic physical principles that were subsequently to make the microprobe a tool for quantitative microanalysis. Current electron microprobe analysers differ little in their basic principle from that originally described by Castaing. Of course, improvements have been made over the years, notably the enhancement of detection systems and the automation of the equipment. 

The essential elements of an electron microprobe are the electron column and the wavelength dispersive spectrometers (Fig. 8.5). The electron column is very similar to that of a scanning electron microscope. Certain elements are added to it (such as a beam controller, viewfinder, etc.) to make it an instrument dedicated to elemental microanalysis. 

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