Improvements in discrimination of bulk and trace elements in long-wavelength double pulse LIBS

•Enhancement by improved coupling & excitation efficiency, not increased ablated mass•S/N enhancements of 14 and 7 times for bulk and trace elements, respectively•S/B enhancements of 15 and 4 times for bulk and trace elements, respectively•Max enhancement observed for smaller quantities of ablated sample•Significant conclusions for delicate, mass-limited samples

In this work we study the effectiveness of long-wavelength heating in double pulse (DP) LIBS, quantitatively comparing figures of merit with those from traditional single pulse (SP) LIBS. The first laser pulse serves as the source of sample ablation, creating an aerosol-like plume that is subsequently reheated by the second laser pulse. At power densities used, the long-wavelength CO2 laser pulse does not ablate any of the solid sample in the atmospheric conditions investigated, meaning plasma emission and enhanced signal can be entirely attributed to the reheated plume rather than increased sample ablation. The signal discrimination was improved significantly using long-wavelength DP-LIBS. For bulk elemental analysis, DP-LIBS provided maximum enhancements of about 14 and 15 times for S/N and S/B, respectively, compared to SP-LIBS using the same quantity of ablated sample. For trace elemental analysis, maximum enhancements of about 7 and 4 times for S/N and S/B, respectively, were observed. These improvements are attributed to effective coupling between the second heating pulse and expanding plume and more efficient excitation of plume species than from the single pulse alone. Most significant improvements were observed in the case of low prepulse energy and minimal sample ablation. While bulk elemental analysis observed improvements for all prepulse energies studied, trace element discrimination only significantly improved for the lowest prepulse energy studied.