Tuning Hierarchical Order and Plasmonic Coupling of Large-Area, Polymer-Grafted Gold Nanorod Assemblies via Flow-Coating

Solution-based printing of anisotropic nanostructures is foundational to many emerging technologies, such as energy storage devices, photonic elements, and sensors. Methods to rapidly (>mm/s) manufacture large area assemblies (>> m(2)) with simultaneous control of thickness (<10 nm), nanoparticle spacing (<5 nm), surface roughness (<5 nm), and global and local orientational order are still lacking. Herein, we demonstrate such capability using flow-coating to fabricate robust, self-supporting mono- and bilayer films of polystyrene-grafted gold nanorods (PS-AuNRs) onto solid substrates. The relationship among solvent evaporation, deposition speed, substrate surface energy, concentration, and film thickness for solutions of such hairy hybrid nanoparticles spans the Landau-Levich and evaporative film formation regimes. In the Landau-Levich regime, solvent evaporation rapidly concentrates the PS-AuNRs, leading to the formation of thin films with distinct, randomized side-by-side domains. Alternatively, processing at slower velocities in the evaporative regime results in the global alignment of PS-AuNRs. Processing speed and substrate surface energy afford tuning of the film's optical extinction of a given PS-AuNR via fine control of inter-rod distance and subsequent plasmonic coupling between neighboring nanorods. Because the concept of the polymer-grafted nanorod can be expanded to a variety of different polymer canopies, shapes, and core materials, the processing-structure relationships established in this work will have important implications on the future development of anisotropic nanostructure-based applications.

Automated summary

The study demonstrates the ability to fabricate efficient, self-supporting monolayer and bilayer films of polystyrene-grafted gold nanorods using flow-coating technology. By adjusting processing speed and substrate surface energy, fine control over the optical properties of the films was achieved, holding important implications for the future development of applications based on anisotropic nanostructures.