Metasurfaces are ultrathin, two-dimensional arrays of subwavelength resonators that have been demonstrated to control the flow of light in ways that are otherwise unattainable with natural materials. These arrays are typically composed of metallic Ag or Au nanostructures shaped like split rings, nanowire pairs or nanorods (commonly referred to as meta-atoms) that are arranged to produce a collective optical response spanning an impressive range of properties, from the perfect absorption of incident light to superresolution imaging. However, metasurfaces pose major challenges in their fabrication over large areas, which can be prohibitively expensive and time consuming using conventional nanolithography techniques. Here we show that differently shaped colloidal nanocrystals can be organized into metasurface architectures using robust, scalable assembly methods. These metasurfaces exhibit extreme in-plane electromagnetic coupling that is strongly dependent on nanocrystal size, shape and spacing. Colloidal metasurfaces that display near-ideal electromagnetic absorbance can be tuned from the visible into the mid-infrared wavelengths.

This work demonstrates the use of single-layer graphene as a template for the formation of subnanometer plasmonic gaps using a scalable fabrication process called "nanoskiving." These gaps are formed between parallel gold nanowires in a process that first produces three-layer thin films with the architecture gold/single-layer graphene/gold, and then sections the composite films with an ultramicrotome. The structures produced can be treated as two gold nanowires separated along their entire lengths by an atomically thin graphene nanoribbon. Oxygen plasma etches the sandwiched graphene to a finite depth; this action produces a subnanometer gap near the top surface of the junction between the wires that is capable of supporting highly confined optical fields. The confinement of light is confirmed by surface-enhanced Raman spectroscopy measurements, which indicate that the enhancement of the electric field arises from the junction between the gold nanowires. These experiments demonstrate nanoskiving as a unique and easy-to-implement fabrication technique that is capable of forming subnanometer plasmonic gaps between parallel metallic nanostructures over long, macroscopic distances. These structures could be valuable for fundamental investigations as well as applications in plasmonics and molecular electronics.

The vast majority of modern microelectronic devices rely on carriers within semiconductors due to their integrability. Therefore, the performance of these devices is limited due to natural semiconductor properties such as band gap and electron velocity. Replacing the semiconductor channel in conventional microelectronic devices with a gas or vacuum channel may scale their speed, wavelength and power beyond what is available today. However, liberating electrons into gas/vacuum in a practical microelectronic device is quite challenging. It often requires heating, applying high voltages, or using lasers with short wavelengths or high powers. Here, we show that the interaction between an engineered resonant surface and a low-power infrared laser can cause enough photoemission via electron tunnelling to implement feasible microelectronic devices such as transistors, switches and modulators. The proposed photoemission-based devices benefit from the advantages of gas-plasma/vacuum electronic devices while preserving the integrability of semiconductor-based devices.

High Raman enhancement factors (EFs) have been observed for surface-enhanced Raman spectroscopy (SERS) substrates fabricated from colloidal metal nanoparticles. Electrodynamic models of single nanoparticles often do not accurately predict the Raman EFs measured experimentally for such colloidal substrates, which often consist of nanoparticles that exhibit heterogeneity in both size and shape. Here, we investigate the size and shape dispersity of colloidal Ag nanocube samples and their effect on Raman EF. We generate an analytical model that incorporates nanocube size dispersion and calculates the Raman EF associated with an ensemble of differently sized nanocubes. For nanocubes that are ∼70-80 nm in size, this model is sufficient to correct the inaccuracies for electrodynamic simulations of a single nanocube model. For nanocubes >90 nm, size dispersity alone fails to account for the high EFs observed when these substrates are excited off-resonance. We hypothesize that shape defects may play a significant role in optical response at these larger sizes and discuss how these factors can play a role in our analytical model.

Tip-enhanced Raman spectroscopy enables access to chemical information with nanoscale spatial resolution and single-molecule sensitivities by utilizing optical probes that are capable of confining light to subwavelength dimensions. Because the probes themselves possess nanoscale features, they are notoriously difficult to fabricate, and more critically, can result in poor reproducibility. Here, we demonstrate high-performance, predictable, and readily tunable nanospectroscopy probes that are fabricated by self-assembly. Shaped metal nanoparticles are organized into dense layers and deposited onto scanning probe tips. When coupled to a metal surface, these probes behave like nanoantenna by supporting a strong optical resonance, producing dramatic Raman field enhancements in the range of 10(8)-10(9) with sub-50 nm spatial resolution. In contrast to other nanospectroscopy probes, our colloidal probes can be fabricated in a scalable fashion with a batch-to-batch reproducibility of ∼80% and serve as an important demonstration of bottom-up engineering.