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 (≫cm²) 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.