Photoacoustic identification of laser-induced microbubbles as light scattering centers for optical limiting in a liquid suspension of graphene nanosheets

Liquid suspensions of carbon nanotubes, graphene and transition metal dichalcogenides have exhibited excellent performance in optical limiting. However, the underlying mechanism has remained elusive and is generally ascribed to their superior nonlinear optical properties such as nonlinear absorption or nonlinear scattering. Using graphene as an example, we show that photo-thermal microbubbles are responsible for optical limiting as strong light scattering centers: graphene sheets absorb incident light and become heated up above the boiling point of water, resulting in vapor and microbubble generation. This conclusion is based on the direct observation of bubbles above the laser beam as well as a strong correlation between laser-induced ultrasound and optical limiting. In situ Raman scattering of graphene further confirms that the temperature of graphene under laser pulses rises above the boiling point of water but still remains too low to vaporize graphene and create graphene plasma bubbles. Photo-thermal bubble scattering is not a nonlinear optical process and requires very low laser intensity. This understanding helps us to design more efficient optical limiting materials and understand the intrinsic nonlinear optical properties of nanomaterials.