Laser-induced breakdown spectroscopy signal enhancement effect for argon caused by the presence of gold nanoparticles

The effect of the presence of nanoparticles (NPs) on the laser induced breakdown spectroscopy (LIBS) signal of argon gas was studied experimentally. 10–20 nm diameter gold NPs, produced by a spark discharge nanoparticle generator, were suspended in argon gas. The effect of particle size, number concentration and mass concentration, as well as laser pulse energy on the LIBS argon signal was systematically investigated. It was found that the breakdown threshold of the gas decreases considerably, facilitating the detection of Ar emission at such laser fluences, which do not allow plasma formation without the presence of the NPs. Our observations persist even at aerosol mass concentrations that are too low to allow the direct detection of nanoparticles. The effect, which is attributed to electron thermo- and field emission induced by the high intensity laser pulse, shows an asymptotically increasing magnitude with the aerosol mass concentration. The signal enhancement was found to be 102–104 and the effect is suggested to be useful in trace gas analysis or for the indirect detection of NPs. The achievable indirect aerosol mass concentration detection limit was estimated to be in the parts per trillion regime (as low as 50 ng·m−3), which is comparable to the best literature values reported for direct analysis.