Abstract
A resonance/non-resonance, doublet-based, self-absorption-free, laser-induced breakdown spectroscopy (SAF-LIBS) technique is proposed for greatly expanding the measurement range of quantitative elemental analysis by using a quasi-optically thin line. The quasi-optically thin spectral line is obtained by matching the measured doublet atomic lines' intensity ratios with the theoretical one, and the applicable measurement range is expanded by utilizing the resonance and non-resonance lines. The specific calibration process consists of two parts: the nonlinear LIBS calibration and the linear SAF-LIBS calibration. For quantitative measurements, the approximate content of the unknown sample is determined first by using the LIBS calibration curve, and then the SAF-LIBS spectra and the resonance or non-resonance calibration curve that corresponds to the predetermined content are used for further implementing the quantitative analysis. Univariate quantitative analysis results of Cu show that this resonance/non-resonance doublet-based SAF-LIBS technique not only captures the quasi-optically thin spectral line in a wide range of elemental content, but also possesses high correlation coefficients of calibration curves, small relative errors of measurement and low limits of detection. The applicability and limitations of this technique are also discussed, and the evolution as well as the related major determinants of self-absorption are analyzed by taking advantage of the spatial-temporal evolution images of plasma emissivity.
Highlights
Laser-induced breakdown spectroscopy (LIBS) is a spectrochemical analysis technique based on emission spectroscopy
We recently proposed a self-absorption-free LIBS (SAF-LIBS) technique [18,19] to directly capture quasi-optically thin spectral line by matching the measured doublet atomic lines intensity ratios with the theoretical one
In this work, resonance and non-resonance doublets were introduced into SAF-LIBS to expand its applicable elemental content range and enhance the quantitative performance
Summary
Laser-induced breakdown spectroscopy (LIBS) is a spectrochemical analysis technique based on emission spectroscopy. Sun et al [15] employed an internal reference to make correction of the self-absorption effect in CF-LIBS, and found that the linearity of all points on the Boltzmann plot was enhanced and the accuracy of the quantitative analysis results was improved. All these methods tend to be complex and time consuming, and require some fulfilled conditions and additional plasma parameters. How to greatly expand the applicable measurement range of SAFLIBS becomes an urgent challenge
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