Nineteenth-century nanotechnology: The plasmonic properties of daguerreotypes.

Plasmons, the collective oscillations of mobile electrons in metallic nanostructures, interact strongly with light and produce vivid colors, thus offering a new route to develop color printing technologies with improved durability and material simplicity compared with conventional pigments. Over the last decades, researchers in plasmonics have been devoted to manipulating the characteristics of metallic nanostructures to achieve unique and controlled optical effects. However, before plasmonic nanostructures became a science, they were an art. The invention of the daguerreotype was publicly announced in 1839 and is recognized as the earliest photographic technology that successfully captured an image from a camera, with resolution and clarity that remain impressive even by today's standards. Here, using a unique combination of daguerreotype artistry and expertise, experimental nanoscale surface analysis, and electromagnetic simulations, we perform a comprehensive analysis of the plasmonic properties of these early photographs, which can be recognized as an example of plasmonic color printing. Despite the large variability in size, morphology, and material composition of the nanostructures on the surface of a daguerreotype, we are able to identify and characterize the general mechanisms that give rise to the optical response of daguerreotypes. Therefore, our results provide valuable knowledge to develop preservation protocols and color printing technologies inspired by past ones.

Hot Hole Photoelectrochemistry on Au@SiO2@Au Nanoparticles.

There is currently a worldwide need to develop efficient photocatalytic materials that can reduce the high-energy cost of common industrial chemical processes. One possible solution focuses on metallic nanoparticles (NPs) that can act as efficient absorbers of light due to their surface plasmon resonance. Recent work indicates that small NPs, when photoexcited, may allow for efficient electron or hole transfer necessary for photocatalysis. Here we investigate the mechanisms behind hot hole carrier dynamics by studying the photodriven oxidation of citrate ions on Au@SiO2@Au core-shell NPs. We find that charge transfer to adsorbed molecules is most efficient at higher photon energies but still present with lower plasmon energy. On the basis of these experimental results, we develop a simple theoretical model for the probability of hot carrier-adsorbate interactions across the NP surface. These results provide a foundation for understanding charge transfer in plasmonic photocatalytic materials, which could allow for further design and optimization of photocatalytic processes.

Al-Pd Nanodisk Heterodimers as Antenna-Reactor Photocatalysts.

Photocatalysis uses light energy to drive chemical reactions. Conventional industrial catalysts are made of transition metal nanoparticles that interact only weakly with light, while metals such as Au, Ag, and Al that support surface plasmons interact strongly with light but are poor catalysts. By combining plasmonic and catalytic metal nanoparticles, the plasmonic "antenna" can couple light into the catalytic "reactor". This interaction induces an optical polarization in the reactor nanoparticle, forcing a plasmonic response. When this "forced plasmon" decays it can generate hot carriers, converting the catalyst into a photocatalyst. Here we show that precisely oriented, strongly coupled Al-Pd nanodisk heterodimers fabricated using nanoscale lithography can function as directional antenna-reactor photocatalyst complexes. The light-induced hydrogen dissociation rate on these structures is strongly dependent upon the polarization angle of the incident light with respect to the orientation of the antenna-reactor pair. Their high degree of structural precision allows us to microscopically quantify the photocatalytic activity per heterostructure, providing precise photocatalytic quantum efficiencies. This is the first example of precisely designed heterometallic nanostructure complexes for plasmon-enabled photocatalysis and paves the way for high-efficiency plasmonic photocatalysts by modular design.

High Chromaticity Aluminum Plasmonic Pixels for Active Liquid Crystal Displays.

Chromatic devices such as flat panel displays could, in principle, be substantially improved by incorporating aluminum plasmonic nanostructures instead of conventional chromophores that are susceptible to photobleaching. In nanostructure form, aluminum is capable of producing colors that span the visible region of the spectrum while contributing exceptional robustness, low cost, and streamlined manufacturability compatible with semiconductor manufacturing technology. However, individual aluminum nanostructures alone lack the vivid chromaticity of currently available chromophores because of the strong damping of the aluminum plasmon resonance in the visible region of the spectrum. In recent work, we showed that pixels formed by periodic arrays of Al nanostructures yield far more vivid coloration than the individual nanostructures. This progress was achieved by exploiting far-field diffractive coupling, which significantly suppresses the scattering response on the long-wavelength side of plasmonic pixel resonances. In the present work, we show that by utilizing another collective coupling effect, Fano interference, it is possible to substantially narrow the short-wavelength side of the pixel spectral response. Together, these two complementary effects provide unprecedented control of plasmonic pixel spectral line shape, resulting in aluminum pixels with far more vivid, monochromatic coloration across the entire RGB color gamut than previously attainable. We further demonstrate that pixels designed in this manner can be used directly as switchable elements in liquid crystal displays and determine the minimum and optimal numbers of nanorods required in an array to achieve good color quality and intensity.

Molecular Plasmonics.

Graphene supports surface plasmons that have been observed to be both electrically and geometrically tunable in the mid- to far-infrared spectral regions. In particular, it has been demonstrated that graphene plasmons can be tuned across a wide spectral range spanning from the mid-infrared to the terahertz. The identification of a general class of plasmonic excitations in systems containing only a few dozen atoms permits us to extend this versatility into the visible and ultraviolet. As appealing as this extension might be for active nanoscale manipulation of visible light, its realization constitutes a formidable technical challenge. We experimentally demonstrate the existence of molecular plasmon resonances in the visible for ionized polycyclic aromatic hydrocarbons (PAHs), which we reversibly switch by adding, then removing, a single electron from the molecule. The charged PAHs display intense absorption in the visible regime with electrical and geometrical tunability analogous to the plasmonic resonances of much larger nanographene systems. Finally, we also use the switchable molecular plasmon in anthracene to demonstrate a proof-of-concept low-voltage electrochromic device.

Aluminum nanocrystals.

We demonstrate the facile synthesis of high purity aluminum nanocrystals over a range of controlled sizes from 70 to 220 nm diameter with size control achieved through a simple modification of solvent ratios in the reaction solution. The monodisperse, icosahedral, and trigonal bipyramidal nanocrystals are air-stable for weeks, due to the formation of a 2-4 nm thick passivating oxide layer on their surfaces. We show that the nanocrystals support size-dependent ultraviolet and visible plasmon modes, providing a far more sustainable alternative to gold and silver nanoparticles currently in widespread use.

Active tunable absorption enhancement with graphene nanodisk arrays.

If not for its inherently weak optical absorption at visible and infrared wavelengths, graphene would show exceptional promise for optoelectronic applications. Here we show that by nanopatterning a graphene layer into an array of closely packed graphene nanodisks, its absorption efficiency can be increased from less than 3% to 30% in the infrared region of the spectrum. We examine the dependence of the enhanced absorption on nanodisk size and interparticle spacing. By incorporating graphene nanodisk arrays into an active device, we demonstrate that this enhanced absorption efficiency is voltage-tunable, indicating strong potential for nanopatterned graphene as an active medium for infrared electro-optic devices.

Near-field mediated plexcitonic coupling and giant Rabi splitting in individual metallic dimers.

Strong coupling between resonantly matched localized surface plasmons and molecular excitons results in the formation of new hybridized energy states called plexcitons. Understanding the nature and tunability of these hybrid nanostructures is important for both fundamental studies and the development of new applications. We investigate the interactions between J-aggregate excitons and single plasmonic dimers and report for the first time a unique strong coupling regime in individual plexcitonic nanostructures. Dark-field scattering measurements and finite-difference time-domain simulations of the hybrid nanostructures show strong plexcitonic coupling mediated by the near-field inside each dimer gap, which can be actively controlled by rotating the polarization of the optical excitation. The plexciton dispersion curves, obtained from coupled harmonic oscillator models, show anticrossing behavior at the exciton transition energy and giant Rabi splitting ranging between 230 and 400 meV. These energies are, to the best of our knowledge, the largest obtained on individual hybrid nanostructures.