Non-linear optics for an online probing of the specific surface area of nanoparticles in the aerosol phase

In the present study the generation of non-linear optical (NLO) effects, such as second harmonic generation (SHG), by black carbon particles, also named soot, and by other types of nanoparticles in aerosol phase is quantified and analysed. Its potential for measuring the specific surface area of an aerosol is put forward. SHG is a Non Linear Optical phenomenon that is typically used in biosciences and fundamental physics and has shown to have large potential for the investigation of surface sensitive phenomena. It exists in two forms, coherent SHG and incoherent SHG, also named Hyper Rayleigh Scattering (HRS). While applications on particles in solution or organic molecules located on the surface of droplets exist, the SHG naturally induced by solid nanoparticles in aerosol phase without any SHG enhancing additive has neither been detected nor quantified yet. The present work aims at narrowing this gap by exposing a jet of well-characterized nanoaerosols to a femtosecond laser featuring high peak pulse energies allowing to induce NLO phenomena. The experiments are carried out in an innovative optical setup allowing to analyse the NLO response resolved in time, wavelength and angle, thus having the capability to isolate SHG from other phenomena, such as laser filamentation. The optical setup was calibrated in order to quantify the generated signal power and optimized in order to have a high sensitivity and in order to avoid NLO generation from its own optical elements. The results confirm that soot particles, as well as DEHS droplets and arc generated carbon nanoparticles, feature SHG at intensities that are more than 7 orders of magnitude smaller than that of static light scattering. SHG depends in particular on aggregate and/or monomer size. On the other hand, SHG induced by soot does not seem to depend on the organic or elementary carbon content. The experiments also show that the detected NLO signal increases linearly with particle surface area, independently of the particle shape or composition. Finally, the angular response of NLO signal is fundamentally different from that of linear scattering. Due to the isotropic nature of the angular response, the observed SHG signal is probably non-coherent and thus related to Hyper Raleigh Scattering. These findings show the potential of non-linear optics, in particular to quantify in situ the specific surface of an aerosol. Giving access to this information which is crucial in the evaluation of toxicity of aerosols, the present work can thus give way to a new class of laser based diagnostics for aerosols.