A numerical study of expected accuracy and precision in Calibration-Free Laser-Induced Breakdown Spectroscopy in the assumption of ideal analytical plasma

Year: 2007

Authors: Tognoni E., Cristoforetti G., Legnaioli S., Palleschi V., Salvetti A., Mueller M., Panne U., Gornushkin I.

Autors Affiliation: Institute for Chemical-Physical Processes of the National Research Council Via Moruzzi 1, 56124 Pisa, Italy
Department of Analytical Chemistry, Reference Materials, Federal Institute for Materials Research and Testing (Bam), Richard-Willstaetter-Str.11, 12489 Berlin, Germany;
Department of Chemistry, University of Florida, Gainesville, FL 32611, United States

Abstract: Calibration-Free Laser-Induced Breakdown Spectroscopy (CF-LIBS) has been proposed several years ago as ail approach for quantitative analysis of Laser-Induced Breakdown Spectroscopy spectra. Recently developed refinement of the spectral processing method is described in the present work. Accurate quantitative results have been demonstrated for several metallic alloys. However, the degree of accuracy that can be achieved with Calibration-Free Laser-Induced Breakdown Spectroscopy analysis of generic samples still needs to be thoroughly investigated. The authors have undertaken a systematic Study of errors and biasing factors affecting the calculation in the Calibration-Free Laser-Induced Breakdown Spectroscopy spectra processing. These factors may be classified in three main groups: 1) experimental aberrations (intensity fluctuations and inaccuracy in the correction for spectral efficiency of a detection system), 2) inaccuracy in theoretical parameters used for calculations (Stark broadening coefficients and partition functions) and 3) plasma non-ideality (departure from thermal equilibrium, spatial and temporal inhomogeneities, optical thickness, etc.). In this study, the effects of experimental aberrations and accuracy of spectral data were investigated, assuming, that the analytical plasma is ideal. Departure of the plasma conditions from ideality will be the object of future work. The current study was based on numerical simulation. Two kinds of metallic alloys, iron-based and aluminum-based, were studied. The relative weight of the error contributions was found to depend on the sample composition. For the here-investigated samples, the experimental aberrations contribute to the overall uncertainty on the quantitative results more than theoretical parameters. The described simulation method can be applied to the Calibration-Free Laser-Induced Breakdown Spectroscopy analysis of any other kind of sample. (C) 2007 Elsevier B.V. All rights reserved.


Volume: 62 (12)      Pages from: 1287  to: 1302

KeyWords: Accuracy; LIBS; Precision; Quantitative analysis; Standard-less analysis
DOI: 10.1016/j.sab.2007.10.005

Citations: 183
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