How to determine the morphology of plasmonic nanocrystals without transmission electron microscopy?

This paper reports the complete ellipsometric characterization of gold nanoparticles (NPs) embedded in a photoresist films. The effective dielectric function of nanocomposite films as well as the shape distribution and the volume fraction of NPs are extracted from ellipsometric measurements by introducing an effective medium theory which takes into account the NP shape distribution and the intrinsic confinement effect. This theory remains valid as long as the nanoparticle interaction is negligible. We show that the magnitude of the confinement depends on the nanoparticle shape and the environment through chemical damping. This suggests that the NP shape distribution can be directly estimated by ellipsometry, while the determination of absolute radius distribution requires transmission electron microscopy measurements. The imaginary part of the effective dielectric function exhibits a strong asymmetric surface plasmon band, while a large variation of the real part occurs close to the resonance. The redshift and the broadening of the plasmon band as the gold volume fraction increases are correlated to the evolution of NP shape distribution. This evolution is attributed to a competition between the nucleation and the coalescence of NPs. This unambiguously demonstrates that ellipsometry combined with a shape-distributed effective medium theory is a powerful alternative tool to transmission electron microscopy for the NP shape analysis.