Spatiotemporal tracking of gold nanorods after intranasal administration for brain targeting.

Intranasal administration is becoming increasingly more attractive as a fast delivery route to the brain for therapeutics circumventing the blood-brain barrier (BBB). Gold nanorods (AuNRs) demonstrate unique optical and biological properties compared to other gold nanostructures due to their high aspect ratio. In this study, we investigated for the first time the brain region-specific distribution of AuNRs and their potential as a drug delivery platform for central nervous system (CNS) therapy following intranasal administration to mice using a battery of analytical and imaging techniques.

Rational design of bimetallic photocatalysts based on plasmonically-derived hot carriers.

Hot carriers generated by plasmonic excitations have recently opened up new avenues in photocatalysis. The transfer of these energetic carriers to adjacent molecules can promote chemical transformations that are important for hydrogen generation by water splitting, CO reduction and degradation of organic pollutants. Here, we have developed and optimised a plasmonic hot-carrier catalytic system based on silica nanoparticles decorated with plasmonic gold nanoparticles as a source of hot carriers, equipped with platinum nanoclusters as co-catalyst for the enhancement of hot-carrier extraction.

Optoelectronic Synapses Based on Hot-Electron-Induced Chemical Processes.

Highly efficient information processing in the brain is based on processing and memory components called synapses, whose output is dependent on the history of the signals passed through them. Here, we have developed an artificial synapse with both electrical and optical memory effects using chemical transformations in plasmonic tunnel junctions. In an electronic implementation, the electrons tunneled into plasmonic nanorods under a low bias voltage are harvested to write information into the tunnel junctions via hot-electron-mediated chemical reactions with the environment.

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.

Optimizing hot carrier effects in Pt-decorated plasmonic heterostructures.

Hot carrier generation by light in various semiconductors and metallic nanostructures is important for many photocatalytic and photochemical processes, including water and hydrogen splitting. Here, we report on investigations of hot electron generation and extraction from Pt decorated SiO2-Au nanoparticles using the degradation of methylene blue dye as a test-bed. Enhanced catalytic activity was found with an increase of Pt loading on the surface of the heterostructures.

Nanocone-based plasmonic metamaterials.

Metamaterials and metasurfaces provide unprecedented opportunities for designing light-matter interactions. Optical properties of hyperbolic metamaterials with meta-atoms based on plasmonic nanorods, important in nonlinear optics, sensing and spontaneous emission control, can be tuned by varying geometrical sizes and arrangement of the meta-atoms. At the same time the role of the shape of the meta-atoms forming the array has not been studied.

Reactive tunnel junctions in electrically driven plasmonic nanorod metamaterials.

Non-equilibrium hot carriers formed near the interfaces of semiconductors or metals play a crucial role in chemical catalysis and optoelectronic processes. In addition to optical illumination, an efficient way to generate hot carriers is by excitation with tunnelling electrons. Here, we show that the generation of hot electrons makes the nanoscale tunnel junctions highly reactive and facilitates strongly confined chemical reactions that can, in turn, modulate the tunnelling processes.

Universal switching of plasmonic signals using optical resonator modes.

We propose and investigate, both experimentally and theoretically, a novel mechanism for switching and modulating plasmonic signals based on a Fano interference process, which arises from the coupling between a narrow-band optical Fabry-Pérot cavity and a surface plasmon polariton (SPP) source. The SPP wave emitted from the cavity is actively modulated in the vicinity of the cavity resonances by altering the cavity Q-factor and/or resonant frequencies. We experimentally demonstrate dynamic SPP modulation both by mechanical control of the cavity length and all-optically by harnessing the ultrafast nonlinearity of the Au mirrors that form the cavity.

Integrated plasmonic circuitry on a vertical-cavity surface-emitting semiconductor laser platform.

Integrated plasmonic sources and detectors are imperative in the practical development of plasmonic circuitry for bio- and chemical sensing, nanoscale optical information processing, as well as transducers for high-density optical data storage. Here we show that vertical-cavity surface-emitting lasers (VCSELs) can be employed as an on-chip, electrically pumped source or detector of plasmonic signals, when operated in forward or reverse bias, respectively. To this end, we experimentally demonstrate surface plasmon polariton excitation, waveguiding, frequency conversion and detection on a VCSEL-based plasmonic platform.

Bulk plasmon-polaritons in hyperbolic nanorod metamaterial waveguides.

Hyperbolic metamaterials comprised of an array of plasmonic nanorods provide a unique platform for designing optical sensors and integrating nonlinear and active nanophotonic functionalities. In this work, the waveguiding properties and mode structure of planar anisotropic metamaterial waveguides are characterized experimentally and theoretically. While ordinary modes are the typical guided modes of the highly anisotropic waveguides, extraordinary modes, below the effective plasma frequency, exist in a hyperbolic metamaterial slab in the form of bulk plasmon-polaritons, in analogy to planar-cavity exciton-polaritons in semiconductors.

Hyperbolic polaritonic crystals based on nanostructured nanorod metamaterials.

Surface plasmon polaritons usually exist on a few suitable plasmonic materials; however, nanostructured plasmonic metamaterials allow a much broader range of optical properties to be designed. Here, bottom-up and top-down nanostructuring are combined, creating hyperbolic metamaterial-based photonic crystals termed hyperbolic polaritonic crystals, allowing free-space access to the high spatial frequency modes supported by these metamaterials.

Eliminating material constraints for nonlinearity with plasmonic metamaterials.

Nonlinear optical materials comprise the foundation of modern photonics, offering functionalities ranging from ultrafast lasers to optical switching, harmonic and soliton generation. Optical nonlinearities are typically strong near the electronic resonances of a material and thus provide limited tuneability for practical use. Here we show that in plasmonic nanorod metamaterials, the Kerr-type nonlinearity is not limited by the nonlinear properties of the constituents.

Near-field hyperspectral optical imaging.

This Minireview presents an overview of near-field hyperspectral imaging and discusses its applications. Based on a fibre-tip probe, the hyperspectral near-field optical microscope allows the simultaneous acquisition of near-field images over a broad spectral range (400 to 1000 nm), enabling the recovery of local spectroscopic information, which is essential for understanding the resonant interaction of light with nanostructured objects because the far-field and near-field spectral responses can differ significantly, as is the case for plasmonic nanostructures. The optical information is collected through local interactions with the evanescent fields at the surface of the sample; therefore, the approach provides spectroscopic information with nanoscale spatial resolution.

Hydrogen detected by the naked eye: optical hydrogen gas sensors based on core/shell plasmonic nanorod metamaterials.

Gold-core/palladium-shell metamaterials for hydrogen detection are presented. The more than 30% change in both the reflection and transmission from the metamaterial layer that is observed when the layer is exposed to 2% hydrogen mixture is clearly noticeable to the naked eye as a change in the brightness of light transmitted by the metamaterial. This sensor should make a contribution to the safety of processes involving hydrogen.

Low-temperature plasmonics of metallic nanostructures.

The requirements for spatial and temporal manipulation of electromagnetic fields on the nanoscale have recently resulted in an ever-increasing use of plasmonics for achieving various functionalities with superior performance to those available from conventional photonics. For these applications, ohmic losses resulting from free-electron scattering in the metal is one major limitation for the performance of plasmonic structures. In the low-frequency regime, ohmic losses can be reduced at low temperatures.

Hybrid FIB milling strategy for the fabrication of plasmonic nanostructures on semiconductor substrates.

The optical properties of plasmonic semiconductor devices fabricated by focused ion beam (FIB) milling deteriorate because of the amorphisation of the semiconductor substrate. This study explores the effects of combining traditional 30 kV FIB milling with 5 kV FIB patterning to minimise the semiconductor damage and at the same time maintain high spatial resolution. The use of reduced acceleration voltages is shown to reduce the damage from higher energy ions on the example of fabrication of plasmonic crystals on semiconductor substrates leading to 7-fold increase in transmission.

All-plasmonic modulation via stimulated emission of copropagating surface plasmon polaritons on a substrate with gain.

We experimentally demonstrate suppressed absorption and stimulated emission of surface plasmon polaritons (SPP) leading to all-plasmonic modulation of an SPP signal propagating at the interface between a metal and a gain medium; these observations are supported by the developed theory. The use of copropagating signal and control waves can provide more than 10 times more efficient SPP stimulated emission compared to out-of-plane pumping and opens up the possibility to realize integratable plasmonic components for active nanophotonic circuitry.

Low-loss multilayered metamaterial exhibiting a negative index of refraction at visible wavelengths.

We experimentally demonstrate a low-loss multilayered metamaterial exhibiting a double-negative refractive index in the visible spectral range. To this end, we exploit a second-order magnetic resonance of the so-called fishnet structure. The low-loss nature of the employed magnetic resonance, together with the effect of the interacting adjacent layers, results in a figure of merit as high as 3.

Electronically controlled surface plasmon dispersion and optical transmission through metallic hole arrays using liquid crystal.

The enhanced optical properties of metal films periodically perforated with an array of sub-wavelength size holes have recently been widely studied in the field of surface plasmon optics. The ability to design the optical transmission of such nanostructures, which act as plasmonic crystals, by varying their geometrical parameters gives them great flexibility for numerous applications in photonics, opto-electronics, and sensing. Transforming these passive optical elements into devices that may be actively controlled has presented a new challenge.

Molecular plasmonics with tunable exciton-plasmon coupling strength in J-aggregate hybridized Au nanorod assemblies.

Controlling coherent electromagnetic interactions in molecular systems is a problem of both fundamental interest and important applicative potential in the development of photonic and opto-electronic devices. The strength of these interactions determines both the absorption and emission properties of molecules coupled to nanostructures, effectively governing the optical properties of such a composite metamaterial. Here we report on the observation of strong coupling between a plasmon supported by an assembly of oriented gold nanorods (ANR) and a molecular exciton.

Near-field magneto-optical analysis in reflection mode SNOM.

Observation of magnetic domains with in-plane magnetisations is demonstrated by scanning near-field optical microscopy (SNOM) in reflection mode. The longitudinal and transverse magneto-optical Kerr effects are employed as the contrast mechanisms; these are observed as either a change in the polarisation of the reflected light or reflectance, depending on magnetisation direction. SNOM images of Co and Ni thin films show magneto-optical contrast depending on polarisation of the incident and detected light.