Ligand-dependent nano-mechanical properties of CdSe nanoplatelets: calibrating nanobalances for ligands affinity monitoring

Abstract

The influence of ligands on the low frequency vibration of different thicknesses cadmium selenide colloidal nanoplatelets is investigated using resonant low frequency Raman scattering. The strong vibration frequency shifts induced by ligand modifications as well as the sharp spectral linewidths make low frequency Raman scattering a tool of choice to follow ligand exchange as well as the nano-mechanical properties of the NPLs, as evidenced by a carboxylate to thiolate exchange study. Apart from their molecular weight, the nature of the ligands, such as the sulfur to metal bond of thiols, induces a modification of the NPLs as a whole, increasing the thickness by one monolayer. Moreover, as the weight of the ligands increases, the discrepancy between the massload model and the experimental measurements increase. These effects are all the more important when the number of layers is small and can only be explained by a modification of the longitudinal sound velocity. This modification takes its origin in a change of lattice structure of the NPLs, that reflects on its elastic properties. These nanobalances are finally used to characterize ligands affinity with the surface using binary thiols mixtures, illustrating the potential of low frequency Raman scattering to finely characterize nanocrystals surfaces.