Double-pulse laser ablation coupled to laser-induced breakdown spectroscopy

•Double-pulse laser ablation was coupled to laser-induced breakdown spectroscopy.•Nonmatrix-matched calibration of manganese in various alloys was performed.•Improved sensitivities and precisions compared to single-pulse LA were demonstrated.•Remaining matrix effects and internal standardization are discussed.

Laser ablation coupled to laser-induced breakdown spectroscopy (LA-LIBS) is an analytical method, which minimizes sample matrix effects typically found in quantitative LIBS-based direct solid analyses. This paper reports the application of double-pulse laser ablation (DP-LA) to improve the analyte response and the achievable precisions of LA-LIBS. Two coaxial laser beams were applied at the ablation site and the analytical signals were then collected from a second free-standing LIBS plasma downstream of the ablation site. Signal improvements of up to one order of magnitude were observed compared to single-pulse LA-LIBS. The effect of the interpulse delay on the observed signal-to-noise ratios was studied and the quantification capabilities of the optimized DP-LA-LIBS setup were investigated for manganese and iron in a broad range of different alloy types. A linear response was observed for manganese across the different matrices, allowing for nonmatrix-matched calibrations. Matrix effects were observed when analyzing aluminum samples, which, however, could be compensated for by applying iron as internal standard. Size distributions of the ablated material and electron density measurements provide additional insight into the double-pulse process, with additional future work suggested.