Dynamics of Templated Assembly of Nanoparticle Filaments within Nanochannels

Nanoparticles (NPs) can self‐assemble into complex, organized superstructures on patterned surfaces through fluid‐mediated interactions. However, the detailed mechanisms for such NP assemblies are largely unknown. Here, using in situ transmission electron microscopy, the stepwise self‐assembly dynamics of hydrophobic gold NPs into long filaments formed on the surfaces of water‐filled patterned nanochannel templates is observed. First, the formation of a meniscus between the nanochannel walls, during the slow drying of water, causes accumulation of the NPs in the middle of the nanochannels. Second, owing to the strong van der Waals attraction between the NP ligands, the NPs condense into filaments along the centers of the nanochannels. Filaments with highly fluctuating longitudinal NP densities are also observed to fragment into separated structures. Understanding the intermediate stages of fluid‐mediated NP self‐assembly on patterned surfaces will have important implications for the controlled formation of templated NP assemblies with numerous applications.