Hierarchy in Au nanocrystal ordering in supracrystals: a potential approach to detect new physical properties

Here we describe the morphologies of Au nanocrystals self-assembled in fcc 3D superlattices called supracrystals. The average size of the nanocrystals is either 5 or 7 nm with a very small size distribution (<7%). The coating agents used to stabilize the nanocrystals are dodecanethiol (C12H25-SH), tetradecanethiol (C14H29-SH), and hexadecanethiol (C16H33-SH). The influences of the evaporation time, the volume of the chamber used to evaporate the toluene solvent, and the substrate temperature are studied. For nanocrystals characterized by the same size and coating agent, the supracrystal morphologies markedly change on increasing the evaporation time from 8 to 9 to 25 h whereas a slight change takes place on increasing the chamber volume. The nanocrystals' ability to self-order in supracrystals decreases upon increasing the chain length of the coating agent from dodecanethiol (C12) to tetradecanethiol (C14) to hexadecanethiol (C16). Decreasing the evaporation rate (25 h) and/or increasing the substrate temperature (50 °C) improves the nanocrystal ordering in fcc supracrystals. A hierarchy in nanocrystal ordering has the following sequence disordered assemblies, supracrystal film sitting on a disordered nanocrystal film, supracrystal films grown layer-by-layer, and finally supracrystals grown in solution with various well-defined shapes.