Ordered binary and ternary photonic crystals, composed of different sized polymer-composite spheres with diameter ratios up to 120%, are generated using bending induced oscillatory shearing (BIOS). This viscoelastic system creates polydisperse equilibrium structures, producing mixed opaline colored films with greatly reduced requirements for particle monodispersity, and very different sphere size ratios, compared to other methods of nano-assembly.

Despite the availability of elaborate varieties of nanoparticles, their assembly into regular superstructures and photonic materials remains challenging. Here we show how flexible films of stacked polymer nanoparticles can be directly assembled in a roll-to-roll process using a bending-induced oscillatory shear technique. For sub-micron spherical nanoparticles, this gives elastomeric photonic crystals termed polymer opals showing extremely strong tunable structural colour. With oscillatory strain amplitudes of 300%, crystallization initiates at the wall and develops quickly across the bulk within only five oscillations. The resulting structure of random hexagonal close-packed layers is improved by shearing bidirectionally, alternating between two in-plane directions. Our theoretical framework indicates how the reduction in shear viscosity with increasing order of each layer accounts for these results, even when diffusion is totally absent. This general principle of shear ordering in viscoelastic media opens the way to manufacturable photonic materials, and forms a generic tool for ordering nanoparticles.

Dynamic switching of plasmonic monolayers built of gold nanoparticles (AuNPs) is achieved using nano-coatings of poly(isopropyl acrylamide) (PNIPAM). The distance between AuNPs can be dynamically tuned through the repeatable expansion and contraction of the PNIPAM shells at different temperatures, which results in rapid switching of the optical properties of the AuNP monolayer.

In recent years, single-molecule sensitivity achievable by surface-enhanced Raman spectroscopy (SERS) has been widely reported. We use this to investigate supramolecular host-guest chemistry with the macrocyclic host cucurbit[7]uril, on a few-to-single-molecule level. A nanogap geometry, comprising individual gold nanoparticles on a planar gold surface spaced by a single layer of molecules, gives intense SERS signals. Plasmonic coupling between the particle and the surface leads to strongly enhanced optical fields in the gap between them, with single-molecule sensitivity established using a modification of the well-known bianalyte method. Changes in the Raman modes of the host molecule are observed when single guests included inside its cavity internally stretch it. Anisotropic intermolecular interactions with the guest are found which show additional distinct features in the Raman modes of the host molecule.

We fabricate heterocomponent dimers built from a single 40 nm gold and a single 40 nm silver nanoparticle separated by sub-5 nm gaps. Successful assembly mediated by a specialized DNA origami platform is verified by scanning electron microscopy and energy-dispersive X-ray characterization. Dark-field optical scattering on individual dimers is consistent with computational simulations. Direct plasmonic coupling between each nanoparticle is observed in both experiment and theory only for these small gap sizes, as it requires the silver dipolar mode energy to drop below the energy of the gold interband transitions. A new interparticle-spacing-dependent coupling model for heterodimers is thus required. Such Janus-like nanoparticle constructs available from DNA-mediated assembly provide an effective tool for controlling symmetry breaking in collective plasmon modes.

Longitudinal antenna and transverse cavity modes can be excited when bringing a faceted plasmonic nanoparticle close to a metallic substrate. Their interaction leads to a rich optical response, understandable in terms of the modal symmetry.

Resumen del trabajo presentado al 5th International Topical meeting on Nanophotonics and Metamaterials, celebrado en Seefeld (Austria) del 5 al 8 de enero de 2015.

The optical response of plasmonic cavities formed by metallic nanoparticles deposited on a metallic substrate separated by self-assembled monolayers of conductive organic molecules can be precisely controlled by the exact chemical composition of the monolayers.

Plasmonic nanostructures show great promise in enhancing the solar water splitting efficiency due to their ability to confine light to extremely small volumes inside semiconductors. While size plays a critical role in the plasmonic performance of Au nanoparticles (AuNPs), its influence on plasmonassisted water splitting is still not fully understood. This holds especially true for low band gap semiconductors, for which interband excitations occur in wavelength regions that overlap with plasmonic resonances. Here, BiVO4 films are modified with AuNPs of diameters varying from 10 to 80 nm to study the size dependence of the plasmonic effect. Plasmon resonance energy transfer (PRET) is found to be the dominant effect in enhancing the water splitting efficiency of BiVO4. "Hot electron" injection effect is weak in the case of BiVO4/AuNP. This is attributed to the interband excitation of BiVO4, which is unfavourable for the hot electrons accumulation in BiVO4 conduction band. The resonant scattering effect also contributes to the enhanced water splitting efficiency for the larger diameter AuNPs. It is also for the first time found that higher PRET effect can be achieved at larger off-normal irradiation angle.

The precise structural details of metallic nanogaps within optical antennae are found to dramatically modify the plasmonic response, producing a complex pattern of electromagnetic modes that can be directly observed in scattering experiments. We analyze this situation theoretically in the nanoparticle-on-mirror construct, which forms a plasmonic nanogap sensitive to even atomic-scale restructuring of nanoparticle morphology. We focus on the effect of nanoparticle faceting, which allows the formation of ultrathin cavities between the particle and the underlying metallic film in the nanoparticle-on-mirror geometry. Two different sets of modes are identified: longitudinal antenna modes, which are strongly radiative and excited for all facet width ranges, and transverse cavity modes produced at large facets and exhibiting extreme confinement. The interaction and hybridization of antenna and cavity modes is determined by their symmetry and the precise morphology of the nanogap edges. Understanding such complex optics from nanoparticle-on-mirror structures is important to elucidate a wide variety of emerging photochemical and optoelectronic processes.

Plasmonic sensors are extremely promising candidates for label-free single molecule analysis but require exquisite control over the physical arrangement of metallic nanostructures. We employ self-assembly based on the DNA origami technique for accurate positioning of individual 40 nm gold nanoparticles with gaps of 3.3 +/- 1 nm. This is probed through far field scattering measurements on individual dimers. This plasmonic coupling allows us to use surface enhanced Raman scattering (SERS) to detect a small number of dye molecules as well as short single-stranded DNA oligonucleotides in the vicinity of the dimers. This demonstrates that DNA origami is a powerful tool with great potential for a wide variety of biosensing and single-molecule applications.

Plasmonic coupling of gold nanoparticles to a gold surface creates intense plasmonic hot spots with large electromagnetic field-enhancements within the cavity formed by the two metallic surfaces. The localised field in such structures is extremely sensitive to morphological fluctuations and subtle changes in the dielectric properties of the cavity contents. Here, we present an optical method that pins down the properties of the gap contents with high sensitivity, termed normalising plasmon resonance (NPR) spectroscopy. We use this on a variety of ultrathin molecular spacers such as filled and empty cucurbiturils, and graphene. Clear differences in the spectral positions and intensities of plasmonic modes observed in the scattering spectrum resolve thickness differences of 0.1 nm, and refractive index changes from molecular filling.

Raman spectroscopy is a powerful tool to unambiguously identify chemical compounds by their unique vibrational “finger-print”. The Raman cross-section of a single molecule, however, is extremely small and intense laser sources, long integration times and high concentrations of analytes are typical prerequisites for Raman spectroscopy. A common route to alleviate these drawbacks is the use of surface plasmon polaritons (SPP) to guide and concentrate light in constrained geometries such as nanometer-sized gaps. The resulting local electric field and chemical enhancements are sufficient to perform surface-enhanced Raman spectroscopy (SERS) down to the single-molecule level. Here, we demonstrate advances in nanolithography which enable reproducible fabrication of optical antennas for the visible range with sub-5 nm features on large and wavy substrates. A material-independent process route is described that employs cutting-edge electron-beam lithography (EBL) operated in ultra-silent laboratories to enable undisturbed lithography. Through the use of a reactive ion etching step, free-standing antennas with pillar heights of up to 250 nm have been fabricated. These antennas show a three-fold increase in luminescence intensity and spatial confinement in comparison to antennas in direct contact with the substrate. This underlines their great potential for optical direct-sensing experiments targeting few to single molecules in the feed-gap region through SERS.

Nanometer-sized gaps between plasmonically coupled adjacent metal nanoparticles enclose extremely localized optical fields, which are strongly enhanced. This enables the dynamic investigation of nanoscopic amounts of material in the gap using optical interrogation. Here we use impinging light to directly tune the optical resonances inside the plasmonic nanocavity formed between single gold nanoparticles and a gold surface, filled with only yoctograms of semiconductor. The gold faces are separated by either monolayers of molybdenum disulfide (MoS2) or two-unit-cell thick cadmium selenide (CdSe) nanoplatelets. This extreme confinement produces modes with 100-fold compressed wavelength, which are exquisitely sensitive to morphology. Infrared scattering spectroscopy reveals how such nanoparticle-on-mirror modes directly trace atomic-scale changes in real time. Instabilities observed in the facets are crucial for applications such as heat-assisted magnetic recording that demand long-lifetime nanoscale plasmonic structures, but the spectral sensitivity also allows directly tracking photochemical reactions in these 2-dimensional solids.

Gold nanoparticles are separated above a planar gold film by 1.1 nm thick self-assembled molecular monolayers of different conductivities. Incremental replacement of the nonconductive molecules with a chemically equivalent conductive version differing by only one atom produces a strong 50 nm blue-shift of the coupled plasmon. With modeling this gives a conductance of 0.17G(0) per biphenyl-4,4'-dithiol molecule and a total conductance across the plasmonic junction of 30G(0). Our approach provides a reliable tool quantifying the number of molecules in each plasmonic hotspot, here <200.

Plasmonic sensors are extremely promising candidates for label-free single-molecule analysis but require exquisite control over the physical arrangement of metallic nanostructures. Here we employ self-assembly based on the DNA origami technique for accurate positioning of individual gold nanoparticles. Our innovative design leads to strong plasmonic coupling between two 40 nm gold nanoparticles reproducibly held with gaps of 3.3 ± 1 nm. This is confirmed through far field scattering measurements on individual dimers which reveal a significant red shift in the plasmonic resonance peaks, consistent with the high dielectric environment due to the surrounding DNA. We use surface-enhanced Raman scattering (SERS) to demonstrate local field enhancements of several orders of magnitude through detection of a small number of dye molecules as well as short single-stranded DNA oligonucleotides. This demonstrates that DNA origami is a powerful tool for the high-yield creation of SERS-active nanoparticle assemblies with reliable sub-5 nm gap sizes.

Recently, plasmonics has attracted extensive attention for its ability to enhance evanescent electric fields at nanometer spatial scales. Much research has become dedicated to the use of sharp metal tips as nanoscale optical antennae, exploiting surface plasmon resonances. Unlike planar metallic surfaces, tips support localized surface plasmons (LSPs) and benefit from strong field localization at the tip apex. This gives rise to a high spatial resolution when applied to existing plasmonic applications such as surface-enhanced Raman spectroscopy (SERS), leading to tip-enhanced Raman spectroscopy (TERS), which allows for high-resolution chemical mapping of surfaces.

Within the framework of a method-of-moments algorithm, the natural frequencies and natural modes of a scatterer/antenna can be found by looking for the complex frequencies where the determinant of the impedance matrix becomes zero. However, for nanotopologies, the value of this determinant can easily go beyond the resolution or representation limits available on present-day computers. In this work, we propose a substitute for the matrix determinant that avoids this problem altogether: the characteristic term. A robust numerical procedure for locating natural frequencies using this new target function is outlined. Then, the natural frequencies of three different nanostructures, namely, a gold and nickel nanopatch and a gold nanodimer, are calculated and validated by numerically and experimentally obtained scattering/extinction spectra.

Nanomaterials find increasing application in communications, renewable energies, electronics and sensing. Because of its unsurpassed speed and highly tuneable interaction with matter, using light to guide the self-assembly of nanomaterials can open up novel technological frontiers. However, large-scale light-induced assembly remains challenging. Here we demonstrate an efficient route to nano-assembly through plasmon-induced laser threading of gold nanoparticle strings, producing conducting threads 12±2 nm wide. This precision is achieved because the nanoparticles are first chemically assembled into chains with rigidly controlled separations of 0.9 nm primed for re-sculpting. Laser-induced threading occurs on a large scale in water, tracked via a new optical resonance in the near-infrared corresponding to a hybrid chain/rod-like charge transfer plasmon. The nano-thread width depends on the chain mode resonances, the nanoparticle size, the chain length and the peak laser power, enabling nanometre-scale tuning of the optical and conducting properties of such nanomaterials.

Deep-ultraviolet surface-enhanced Raman scattering (UV-SERS) is a promising technique for bioimaging and detection because many biological molecules possess UV absorption lines leading to strongly resonant Raman scattering. Here, Al nanovoid substrates are developed by combining nanoimprint lithography of etched polymer/silica opal films with electron beam evaporation, to give a high-performance sensing platform for UV-SERS. Enhancement by more than 3 orders of magnitude in the UV-SERS performance was obtained from the DNA base adenine, matching well the UV plasmonic optical signatures and simulations, demonstrating its suitability for biodetection.