Plasmonic Metamaterials for Nanochemistry and Sensing.

Plasmonic nanostructures were initially developed for sensing and nanophotonic applications but, recently, have shown great promise in chemistry, optoelectronics, and nonlinear optics. While smooth plasmonic films, supporting surface plasmon polaritons, and individual nanostructures, featuring localized surface plasmons, are easy to fabricate and use, the assemblies of nanostructures in optical antennas and metamaterials provide many additional advantages related to the engineering of the mode structure (and thus, optical resonances in the given spectral range), field enhancement, and local density of optical states required to control electronic and photonic interactions. Focusing on two of the many applications of plasmonic metamaterials, in this Account, we review our work on the sensing and nanochemistry applications of metamaterials based on the assemblies of plasmonic nanorods under optical, as well as electronic interrogation. Sensors are widely employed in modern technology for the detection of events or changes in their local environment. Compared to their electronic counterparts, optical sensors offer a combination of high sensitivity, fast response, immunity to electromagnetic interference, and provide additional options for signal retrieval, such as optical intensity, spectrum, phase, and polarization. Owing to the ability to confine and enhance electromagnetic fields on subwavelength scales, plasmonics has been attracting increasing attention for the development of optical sensors with advantages including both nanometer-scale spatial resolution and single-molecule sensitivity. Inherent hot-electron generation in plasmonic nanostructures under illumination or during electron tunneling in the electrically biased nanostructures provides further opportunities for sensing and stimulation of chemical reactions, which would otherwise not be energetically possible. We first provide a brief introduction to a metamaterial sensing platform based on arrays of strongly coupled plasmonic nanorods. Several prototypical sensing examples based on this versatile metamaterial platform are presented. Record-high refractive index sensitivity of gold nanorod arrays in biosensing based on the functionalization of the nanorod surface for selective absorption arises because of the modification of the electromagnetic coupling between the nanorods in the array. The capabilities of nanorod metamaterials for ultrasound and hydrogen sensing were demonstrated by precision coating of the nanorods with functional materials to create core-shell nanostructures. The extension of this metamaterial platform to nanotube and nanocavity arrays, and metaparticles provides additional flexibility and removes restrictions on the illumination configurations for the optical interrogation. We then discuss a nanochemical platform based on the electrically driven metamaterials to stimulate and detect chemical reactions in the tunnel junctions constructed with the nanorods by exploiting elastic tunneling for the activation of chemical reactions via generated hot-electrons and inelastic tunneling for the excitation of plasmons facilitating optical monitoring of the process. This represents a new paradigm merging electronics, plasmonics, photonics and chemistry at the nanoscale, and creates opportunities for a variety of practical applications, such as hot-electron-driven nanoreactors and high-sensitivity sensors, as well as nanoscale light sources and modulators. With a combination of merits, such as the ability to simultaneously support both localized and propagating modes, nanoporous texture, rapid and facile functionalization, and low cost and scalability, plasmonic nanorod metamaterials provide an attractive and versatile platform for the development of optical sensors and nanochemical platforms using hot-electrons with high performance for applications in fundamental research and chemical and pharmaceutical industries.