Laser microprobe for mass analysis

Figure 6.3. Laser microprobe for mass analysis (LaMMA) configuration.

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-... 

Laser microprobe MS (LMMS) can be used for direct analysis of normal-phase HPTLC plates [802,837]. Kubis et al. [802] used polyamide TLC plates polyamide does not interfere with compound identification by the mass spectrum, owing to its low-mass fragment-ions (m/z < 150). LMMS is essentially a surface analysis technique, in which the sample is ablated using a Nd-YAG laser. The UV irradiation desorbs and ionises a microvolume of the sample the positive and negative ions can be analysed by using a ToF mass spectrometer. The main characteristics of TLC-LMMS are indicated in Table 7.84 [838],... 

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. 

Infrared and ultraviolet probes for surface analysis are then considered.The applications of IR spectroscopy and Raman microscopy are discussed, and a brief account is also given of laser-microprobe mass spectrometry (LAMMA). 

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,... 

Optical examination of etched polished surfaces or small particles can often identify compounds or different minerals hy shape, color, optical properties, and the response to various etching attempts. A semi-quantitative elemental analysis can he used for elements with atomic number greater than four by SEM equipped with X-ray fluorescence and various electron detectors. The electron probe microanalyzer and Auer microprobe also provide elemental analysis of small areas. The secondary ion mass spectroscope, laser microprobe mass analyzer, and Raman microprobe analyzer can identify elements, compounds, and molecules. Electron diffraction patterns can be obtained with the TEM to determine which crystalline compounds are present. Ferrography is used for the identification of wear particles in lubricating oils. 

Laser microprobe mass analysis was used for the structural characterization of Af-oxide metabolites of metrenperone (sinomedol 5, R = Me), seganserine 6, and ramastine 9 (88M16). An assay of rimazolium 1 was developed by using an ion-selective electrode by direct titration with... 

Asbestos can be determined by several analytical techniques, including optical microscopy, electron microscopy, X-ray diffraction (XRD), light scattering, laser microprobe mass analysis, and thermal analysis. It can also be characterized by chemical analysis of metals by atomic absorption, X-ray fluorescence, or neutron activation techniques. Electron microscopy methods are, however, commonly applied for the analysis of asbestos in environmental matrices. 

Laser microprobe mass analyzers permit mass spectrometric analysis of very small volumes (0.01-1 pm3) of thin Sections. The method is based on laser induced ion production from a microvolume and analysis of the evaporated ions in a time-of-flight mass-spectrometer. The technique allows detection of all elements and isotopes with a sensitivity approaching the ppm range and an extremely low limit of detection 10 15 to 10-20 g. Transmission type instruments such as the LAMMA 500 are designed for the analysis of particles of 3 pm in diam. The lateral resolution is about 0.5-1 pm. Because the area to be analyzed is selected by an optical microscope, distribution of chemical constituents can be precisely correlated with morphologic structures (Hillenkamp et al., 1982 39), Simons, 198440), Kaufmann, 1984)41 >. 

Characterization thus involves analytical electron microscopy, ordinary microprobe analysis or other techniques for localizing elements or chemical compounds (Scanning Auger Spectroscopy, Raman Microprobe, Laser Microprobe Mass Spectrometry). It also requires, in most cases, some physical separation of the catalyst for separate analysis (e.g., near surface parts and center of pellets, by peeling or progressive abrasion pellets present at various heights in the catalyst bed, etc.). 

The technique based on laser-induced breakdown coupled to mass detection, which should thus be designated LIB-MS, is better known as laser plasma ionization mass spectrometry (LI-MS). The earliest uses of the laser-mass spectrometry couple were reported in the late 1960s. Early work included the vaporization of graphite and coal for classifying coals, elemental analyses in metals, isotope ratio measurements and pyrolysis [192]. Later work extended these methods to biological samples, the development of the laser microprobe mass spectrometer, the formation of molecular ions from non-voIatile organic salts and the many multi-photon techniques designed for (mainly) molecular analysis [192]. 

For example, microprobe analysis of complex samples (laser microprobe mass analysis LAMMA) was performed by using a setup with no expansion chamber and by focusing the laser beam on a small area on the surface of the sample. Although coal and shale samples were successfully analyzed using LAMMA [52], the nature of the bonding in these types of materials cannot be evaluated because it is not clear if a certain compound is the result of desorption or of pyrolysis. More successfully analyzed were the inorganic components of such composite materials where the thermal decomposition was not a concern. 

Other techniques utilize lasers for sample evaporation/pyrolysis and excitation such as laser induced desorption (LID) or laser microprobe mass analysis (LAMMA) (see e g. [1]). Some of the sample introduction procedures in Py-MS enhance the information obtained from Py-MS by the use of time-resolved, temperature-resolved, or modulated molecular beams techniques [10]. In time-resolved procedures, the signal of the MS is recorded in time, and the continuous formation of fragments can be recorded. Temperature-resolved Py-MS allows a separation and ionization of the sample from a platinum/rhodium filament inside the ionization chamber of the mass spectrometer based on a gradual temperature increase [11]. The technique can be used either for polymer or for additives analysis. Attempts to improve selectivity in Py-MS also were done by using a membrane interface between the pyrolyzer and MS [12]. 

Schmidt. P.F. (1984). Localization of trace elements with the laser microprobe mass analyzer (LAMMA), Trace Elements in Medicine, 1,13-20 Sherwood. R.A., Rocks, B.F., and Riley, C. (1984). The use of flow-injection analysis (FIA) with atomic absorption detection for the determination of clinically relevant elements. Paper presented at 2nd BNAAS Symposium, Leeds, July 1984 Triebig, G., and Schaller, K.H. (1984). Copper, in Alessio, L, Berlin, A., Boni, M., Roi, R., Biological indicators for the assessment of human exposure to industrial chemicals, p. 57-62, EUR 8903 EN, Commission of the European Communities Van der Vyner, F.L, Verbreuken, A.H., Van Grieken, R.E., and DeBroe, M.E. (1985) Laser microprobe mass analysis A tool for evaluating histochemical staining of trace elements, Clin. Chem., 31. 351... 

X-ray diffraction, light scattering, light mod-nlation, IR spectroscopy, and j6-ray absorption are some of the techniques for asbestos analysis. Indnstrially processed asbestos fibers may be characterized by laser microprobe mass analysis (LAMMA). Organic components adsorbed on the asbestos snrface at... 

M. Neuberger. 1986. Laser microprobe mass analysis for the identification of asbestos fibers in lung tissue and broncho-alveolar washing fluid. Microchim. Acta 5(3-4) 197-213. 

Shepherd Chenery (1995) pioneered the laser ablation ICP-MS (inductively coupled plasma-mass spectrometry) method of analyzing individual fluid inclusions. An UV laser ablation microprobe is used to drill a hole into a mineral, to reach an inclusion up to 60/zm below the sample surface. For the laser ablation procedure the sample is placed in a modified thermal vacuum cell. The elevated temperature in the ablation cell raises the internal vapor pressure of the inclusion, which causes instantaneous rupture and highly efficient fluid expulsion as the beam breaches the inclusion wall. The vacuum pulls the vaporized fluid into the ICP-MS, where it is analyzed for major and minor ion concentrations. The advantages of the ICP-MS method are the small spot size of the laser (<2 m), allows analysis of small inclusions (> 10/zm) in a variety of minerals (halite, calcite, quartz, and others). A wide range of ions can be analyzed simultaneously, including low concentrations of minor ions. With multicollector ICP-MS, it will be possible to analyze strontium isotopes and other stable isotopes (5 C, S 0, S S) in fluid inclusions. Laser ablation ICP-MS is not as precise as other methods ( 30%) and the results can only be reported as ionic ratios as the volume of an inclusion cannot be determined prior to analysis. However, if the concentration... 

Optical microscopy (OM), polarized light microscopy (PLM), phase contrast microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and scanning transmission electron microscopy (STEM) are the methods normally used for identification and quantification of the trace amounts of asbestos fibers that are encountered in the environment and lung tissue. Energy-dispersive X-ray spectrometry (EDXS) is used in both SEM and TEM for chemical analysis of individual particles, while selected-area electron diffraction (SAED) pattern analysis in TEM can provide details of the cell unit of individual particles of mass down to 10 g. It helps to differentiate between antigorite and chrysotile. Secondary ion mass spectrometry, laser microprobe mass spectrometry (EMMS), electron probe X-ray microanalysis (EPXMA), and X-ray photoelectron spectroscopy (XPS) are also analytical techniques used for asbestos chemical characterization. 

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