Laser-Induced Breakdown Spectroscopy (LIBS) is a widely used technique for elemental analysis. The analysis of the obtained LIBS spectra generally assumes plasma homogeneity. However, using focused laser beams for interrogation, LIBS probes materials on the microscale and is, thus, prone to artefacts from sample heterogeneities on the micrometre scale. An ablation at a material boundary of two matrices may result in a significant inhomogeneity in the plasma plume, which can severely impact the accuracy of quantitative analysis. Since this propagation of the surface morphology into the plasma plume is driven by the plasma expansion, its final impact is strongly pressure dependent. This study examines the influence of varying ambient pressures (7-1000 mbar) on plasma morphology, spectral characteristics, and key plasma properties such as electron number density at a well-defined Cu-Sn boundary, in comparison with the results obtained using homogeneous alloys. Several approaches of plasma imaging with bandpass filters, spectroscopy, and Radon transform-based 3D reconstruction were employed to analyse elemental distribution, signal-to-noise (SNR) and signal-to-background (SBR) ratios, as well as electron number densities. The 3D reconstructions revealed a pronounced plasma asymmetry for the ablation at the material boundary, in contrast to the near-axial symmetry observed for the ablation of homogeneous alloys. At lower pressures, this distinct elemental separation in plasma persisted, while higher pressures led to an increased collisional mixing and homogenization. SNR and SBR were consistently lower for ablation at the boundary compared to homogeneous samples. These findings highlight how boundary ablation contributes to plasma inhomogeneities in LIBS analysis of heterogeneous materials and emphasize the need to account for these effects when using LIBS for elemental mapping of fine heterogeneous structures.

ActivAir Brno Czech Republic

Bundesanstalt für Materialforschung und prüfung Berlin Germany

Central European Institute of Technology Brno University of Technology Purkyňova 656 123 CZ 61200 Brno Czech Republic

Central European Institute of Technology Brno University of Technology Purkyňova 656 123 CZ 61200 Brno Czech Republic; Faculty of Mechanical Engineering Brno University of Technology Technická 2896 2 Brno Czech Republic

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