Abstract
We synthesized micrometer-sized three-dimensional superlattices consisting of gold (Au) nanocrystals modified with three types of water-soluble thiolates in different dimensions: mercaptosuccinic acid (MSA), N-(2-mercaptopropionyl)-glysine (MPG), and glutathione in its reduced form (GTR). The nanoparticles were assembled at an air/water interface by decreasing the repulsive interactions between the surface modifiers. This was accomplished by adjusting acid concentration. Using x ray and transmission electron diffractometry, MSA- and MPG-modified Au nanoparticle superlattices were identified as hcp single-crystal structures, while the GTR-modified nanoparticle superlattices were determined to be a fcc single-crystal structure. Optical absorption studies show that the surface plasmon peaks redshifted as the nanoparticle density of the assemblages increased and the peak widths decreased when the nanoparticles formed lattice arrangements. In contrast, optical absorption studies of randomly assembled nanoparticles demonstrated increased peak widths as nanoparticle density increased. To explain these observed characteristic features in the surface plasmons, we introduced a qualitative model for the electronic polarizability of these superlattices.
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