Constructing a library of metal and metal–oxide nanoparticle heterodimers through colloidal assembly

Nanoparticle dimers composed of different metals or metal oxides, as well as different shapes and sizes, are of wide interest for applications ranging from nanoplasmonic sensing to nanooptics to biomedical engineering. Shaped nanoparticles, like triangles and nanorods, can be particularly useful in applications due to the strong localized plasmonic hot-spot that forms at the tips or corners. By placing catalytic, but traditionally weakly- or non-plasmonic nanoparticles, such as metal oxides and metals like palladium, in these hot-spots, an enhanced function for sensing, photocatalysis or optical use is predicted. Here, we present an electrostatic colloidal assembly strategy for nanoparticles, incorporating different sizes, shapes and metal or metal oxide compositions into heterodimers with smaller gaps than are achievable using nanofabrication techniques. This versatile method is demonstrated on 14 combinations, including a variety of shaped gold nanoparticles as well as palladium, iron oxide, and titanium oxide nanoparticles. These colloidal nanoparticles are stabilized with traditional surfactants, such as citrate, CTAB, PVP and oleic acid/oleylamines, indicating the wide applicability of our approach. Heterodimers of gold and palladium are further analyzed using cathodoluminescence to demonstrate the tunability of these "plasmonic molecules". Since systematically altering the absorption and emission of the plasmonic nanoparticles dimers is crucial to extending their functionality, and small gap sizes produce the strongest hot-spots, this method indicates that the electrostatic approach to heterodimer assembly can be useful in creating new nanoparticle dimers for many applications.