Bridging the Gap between Crosslinking Chemistry and Directed Assembly of Metasurfaces Using Electrohydrodynamic Flow

TL;DR

This paper combines electrohydrodynamic flow and chemical crosslinking to assemble dense, uniform gold nanosphere oligomers with subnanometer gaps, enhancing their optical properties for large-area plasmonic and metasurface applications.

Contribution

It introduces a novel method integrating EHD flow and chemical crosslinking to produce uniform nanoantenna arrays with controlled gap sizes and enhanced optical responses.

Findings

Field enhancement of 600 observed in simulations

Measured SERS enhancement of 1.4x10^9

Achieved 10% RSD in SERS signal over 1 mm^2 area

Abstract

Advances in understanding chemical and physical driving forces in self-assembly allow the fabrication of unique nanoarchitectures with subwavelength building blocks as the basis for plasmonic and metamaterial devices. Chemical crosslinking of colloidal nanospheres has produced among the smallest gap spacings, necessary to obtain regions of greatly enhanced electric field, hotspots, which are critical to tailor light-matter interactions. However, obtaining uniform electromagnetic response of dense nanoantennas over large area for use in devices remains challenging. In this work, electrohydrodynamic (EHD) flow and chemical crosslinking is combined to form dense, yet discrete, Au nanosphere clusters (oligomers) on a working electrode. EHD provides a long range driving force to bring nanospheres together and anhydride crosslinking yields 0.9 nm gap spacings. Using selective chemistry, nanospheres are simultaneously crosslinked onto a block copolymer template, producing oligomers with a narrower wavelength band width and higher hotspot intensity than monolayer structures produced without a template. We investigate nanoantenna response via full wave simulations, ultraviolet-visible spectroscopy, and surface enhanced Raman scattering (SERS). Nanoantennas exhibit uniform hotspot intensity and gap spacing. Simulations show field enhancements of 600, correlating well with measured average SERS enhancement of 1.4x10^9. Nanoantenna substrates produce a SERS signal with a relative standard deviation of 10% measured over a 1 mm2 area, crucial for nano-optical devices such as optical sensors, among other applications. Understanding long range (EHD flow) and short range (chemical crosslinking) driving forces provides the control for assembling colloidal nanoparticles in architectures for large area plasmonic and metasurface device fabrication.