Calibration-Free Laser-Induced Breakdown Spectroscopy: State of the art

The aim of this paper is offering a critical review of Calibration-Free Laser-Induced Breakdown Spectroscopy (CF-LIBS), the approach of multi-elemental quantitative analysis of LIBS spectra, based on the measurement of line intensities and plasma properties (plasma electron density and temperature) and on the assumption of a Boltzmann population of excited levels, which does not require the use of calibration curves or matrixmatched standards. The first part of this review focuses on the applications of the CF-LIBS method. Quantitative results reported in the literature, obtained in the analysis of various materials and in a wide range of experimental conditions, are summarized, with a special emphasis on the departure from nominal composition values. The second part is a discussion of the simplifying assumptions which lie at the basis of the CF-LIBS algorithm (stoichiometric ablation and complete atomization, thermal equilibrium, homogeneous plasma, thin radiation, detection of all elements). The inspection of the literature suggests that the CF-LIBS method is more accurate in analyzing metallic alloys rather than dielectrics. However, the full exploitation of the method seems to be still far to come, especially for the lack of a complete characterization of the effects of experimental constraints. However, some general directions can be suggested to help the analyst in designing LIBS measurements in a way which is more suited for CF-LIBS analysis.