Abstract
In this review, we report and critically discuss the application of LIBS for the determination of plasma-emission fundamental parameters, such as transition probabilities, oscillator strengths, Stark broadening and shifts, of the emission lines in the spectrum. The knowledge of these parameters is of paramount importance for plasma diagnostics or for quantitative analysis using calibration-free LIBS methods. In the first part, the theoretical basis of the analysis is laid down; in the second part, the main experimental and analytical approaches for the determination by LIBS of the spectral line spectroscopic parameters are presented. In the conclusion, the future perspectives of this kind of analysis are discussed.
Highlights
We focus our attention on the main models of plasma radiation and on the different experimental strategies that may be used for the determination of the fundamental spectral parameters using Laser-induced breakdown spectroscopy (LIBS)
The excitation–deexcitation equilibrium is described by Equation (3), which links the number of photons emitted per second in a given transition between two levels of energy Ek and Ei, respectively (central wavelength λ0 = hc/(Ek − Ei )) to the number density of the corresponding species na, at the same temperature T: (
To link the measured intensities to the Aki spectral parameters, the optically thin full-width at half-maximum (FWHM) of the lines (∆λ0 ) must be known. This link shows that in optically thick plasmas, the knowledge of the Stark coefficient of the emission lines of interest is essential for the determination of the Aki, using either Equation (20) or the Boltzmann plot methods, unless the SA parameter can be evaluated with other independent methods
Summary
Laser-induced breakdown spectroscopy (LIBS) [1] is a spectroanalytical technique that is attracting a wide interest for its applications to in situ industrial processes [2,3,4,5], environmental analysis [6,7,8], the study of geological materials [9,10,11] and cultural heritage objects [12,13,14] and planetary exploration [15,16,17], to mention a few. The advantages with respect to other more assessed microanalytical techniques were mainly exploited especially in geological [21,22,23], cultural heritage [24,25,26] and biomedical applications [27,28,29] Another important field where LIBS analysis has been applied, sometimes neglected with respect to the large variety of practical applications, is the study of the complex processes occurring in the plasma during its formation and evolution [30].
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