Laser-induced breakdown spectroscopy (LIBS) technology is an appealing technique compared with many other types of elemental analysis because of the fast response, high sensitivity, real-time, and noncontact features. One of the challenging targets of LIBS is the enhancement of the detection limit. In this study, the detection limit of gas-phase LIBS analysis has been improved by controlling the pressure and laser pulse width. In order to verify this method, low-pressure gas plasma was induced using nanosecond and picosecond lasers. The method was applied to the detection of Hg. The emission intensity ratio of the Hg atom to NO (I<sub>Hg</sub>/I<sub>NO</sub>) was analyzed to evaluate the LIBS detection limit because the NO emission (interference signal) was formed during the plasma generation and cooling process of N<sub>2</sub> and O<sub>2</sub> in the air. It was demonstrated that the enhancement of <i>I</i><sub>Hg</sub>/<i>I</i><sub>NO</sub> arose by decreasing the pressure to a few kilopascals, and the <i>I</i><sub>Hg</sub>/<i>I</i><sub>NO</sub> of the picosecond breakdown was always much higher than that of the nanosecond breakdown at low buffer gas pressure. Enhancement of <i>I</i><sub>Hg</sub>/<i>I</i><sub>NO</sub> increased more than 10 times at 700 Pa using picosecond laser with 35 ps pulse width. The detection limit was enhanced to 0.03 ppm (parts per million). We also saw that the spectra from the center and edge parts of plasma showed different features. Comparing the central spectra with the edge spectra, <i>I</i><sub>Hg</sub>/<i>I</i><sub>NO</sub> of the edge spectra was higher than that of the central spectra using the picosecond laser breakdown process.
Zhen Zhen Wang, Yoshihiro Deguchi, Masakazu Kuwahara, Jun Jie Yan, and Ji Ping Liu, "Enhancement of Laser-Induced Breakdown Spectroscopy (LIBS) Detection Limit Using a Low-Pressure and Short-Pulse Laser-Induced Plasma Process," Appl. Spectrosc. 67, 1242-1251 (2013)