Ellipsometry of Colloidal Solutions: New Experimental Setup and Application to Metallic Colloids

An ellipsometric cell is developed to simultaneously determine the shape distribution, the volume fraction, and the complex refractive index of gold and silver colloids. Simulation reveals that this cell drastically improves the detection limit of ellipsometry. Indeed, Ag and Au nanoparticles (NPs) are detected at the ppmv level. We demonstrate that the NPs shape distribution can be estimated from ellipsometric measurements by analyzing them with a shape distributed effective medium theory (SDEMT). The obtained distributions from ellipsometry are in agreement with those deduced from transmission electron microcopy (TEM). Contrary to TEM, ellipsometry probes a large number of NPs estimated at about 10¹¹ NPs. Finally, we show that the complex refractive index of colloids as determined from ellipsometry is sensitive to the optical properties of the solvent and the plasmonic properties of NPs.