Purification–chemical structure–electrical property relationship in gold nanoparticle liquids

Macroscopic assemblies of nanoparticles with fluid like characteristics, i.e. nanoparticle liquids (NPLs), are a new class of materials that exhibit unique properties compared with dispersions of nanoparticles in a molecularly distinct matrix phase. By focusing on reaction ratios, techniques to maximize concentration of reactants and quantification of chemical content during washing steps, a high degree of control over the purity of NPLs was maintained while allowing for easy scalability in batch sizes and synthesis throughput. A range of tertiary amines and quaternary ammoniums were used to successfully synthesize Au NPLs from a range of Au nanoparticles with nominal diameters from 6 to 20 nm and initially stabilized with either citrate or dodecanethiol. Stable Au NPLs after purification exhibited a sub-equivalence ratio of canopy to ligand molecules within the corona. This small canopy density most likely arose from the incommensurate areal density of anionic charge within the ligand shell relative to the larger size of the cationic canopy molecule, resulting in a population of cation–anion pairs too weakly bound to be retained in the initial assembly of the canopy post-purification. Finally, increasing either the volume fraction or molecular weight of the canopy was found to increase exponentially the electrical resistance of the bulk NPLs. Removal of excess canopy molecules created a conductive Au NPL that improved hot-current switching durability by at least two orders of magnitude beyond prior reports. Published in 2010 by John Wiley & Sons, Ltd.