Controlling Oriented Attachment of Gold Nanoparticles by Size and Shape

The concept of nanoparticles (NPs) as building blocks offers new possibilities to produce complex and tailored structures from the nano- to the mesoscale. In order to control a polymerization of particles, knowledge of the mechanism and kinetics of the reaction are necessary. We show that controlled assembly of cetylpyridinium chloride-stabilized gold NPs utilizing induced dipole-dipole interactions can lead to the formation of defined one-dimensional structures in solution. Three different shaped NPs (cubes, octahedra, and truncated cuboctahedra) were investigated individually. The assembly process is analogous to a step growth polymerization and is quantitatively describable with kinetics of a polyesterification. In situ kinetic studies reveal that there is an ideal particle size and shape for the induced dipole-driven assembly. Even small changes in size have remarkable effects on the assembly behavior. We further demonstrate that the transition from oriented assembly to oriented attachment requires a critical particle size (critical interface area) resulting from a size-dependent energy barrier for the crystallographic fusion. A combination of ideal size, shape, and degree of destabilization enables controlled oriented attachment of gold NPs in solution to chainlike structures under ambient conditions.

Automated summary

The concept of utilizing nanoparticles as building blocks presents new opportunities for creating complex structures from nano- to mesoscale. By controlling the assembly of gold nanoparticles using induced dipole-dipole interactions, one-dimensional structures can be formed in solution. Different shaped nanoparticles were analyzed individually, with an ideal size and shape identified for induced dipole-driven assembly.