Control of the plasmonic near-field in metallic nanohelices.

The optical response of metallic nanohelices is mainly governed by a longitudinal localised surface plasmon resonance (LSPR) which arises due to the helical anisotropy of the system. Up to now, experimental studies have predominantly addressed the far-field response, despite the fact that the LSPR being of broad interest for converting incoming light into strongly enhanced (chiral) optical near-fields. Here, we demonstrate the control and spatial reproducibility of the plasmon-induced electromagnetic near-field around metallic nanohelices via surface-enhanced Raman scattering. We discuss how the near-field intensity of these nanostructures can be custom-tailored through both the nanoscaled helical structure and the electronic properties of the constituting metals. Our experiments, which employ graphene as an accurate probing material, are in quantitative agreement with corresponding numerical simulations. The findings demonstrate metallic nanohelices as reference nanostructured surfaces able to provide and fine-tune optical fields for fundamental studies as well as sensing or (chiro-optical) imaging applications.

Hot-Volumes as Uniform and Reproducible SERS-Detection Enhancers in Weakly-Coupled Metallic Nanohelices.

Reproducible and enhanced optical detection of molecules in low concentrations demands simultaneously intense and homogeneous electric fields acting as robust signal amplifiers. To generate such sophisticated optical near-fields, different plasmonic nanostructures were investigated in recent years. These, however, exhibit either high enhancement factor (EF) or spatial homogeneity but not both. Small interparticle gaps or sharp nanostructures show enormous EFs but no near-field homogeneity. Meanwhile, approaches using rounded and separated monomers create uniform near-fields with moderate EFs. Here, guided by numerical simulations, we show how arrays of weakly-coupled Ag nanohelices achieve both homogeneous and strong near-field enhancements, reaching even the limit forreproducible detection of individual molecules. The unique near-field distribution of a single nanohelix consists of broad hot-spots, merging with those from neighbouring nanohelices in specific array configurations and generating a wide and uniform detection zone ("hot-volume"). We experimentally assessed these nanostructures via surface-enhanced Raman spectroscopy, obtaining a corresponding EF of ~107 and a relative standard deviation <10%. These values demonstrate arrays of nanohelices as state-of-the-art substrates for reproducible optical detection as well as compelling nanostructures for related fields such as near-field imaging.

Vertical Single-Crystalline Organic Nanowires on Graphene: Solution-Phase Epitaxy and Optical Microcavities.

Vertically aligned nanowires (NWs) of single crystal semiconductors have attracted a great deal of interest in the past few years. They have strong potential to be used in device structures with high density and with intriguing optoelectronic properties. However, fabricating such nanowire structures using organic semiconducting materials remains technically challenging. Here we report a simple procedure for the synthesis of crystalline 9,10-bis(phenylethynyl) anthracene (BPEA) NWs on a graphene surface utilizing a solution-phase van der Waals (vdW) epitaxial strategy. The wires are found to grow preferentially in a vertical direction on the surface of graphene. Structural characterization and first-principles ab initio simulations were performed to investigate the epitaxial growth and the molecular orientation of the BPEA molecules on graphene was studied, revealing the role of interactions at the graphene-BPEA interface in determining the molecular orientation. These free-standing NWs showed not only efficient optical waveguiding with low loss along the NW but also confinement of light between the two end facets of the NW forming a microcavity Fabry-Pérot resonator. From an analysis of the optical dispersion within such NW microcavities, we observed strong slowing of the waveguided light with a group velocity reduced to one-tenth the speed of light. Applications of the vertical single-crystalline organic NWs grown on graphene will benefit from a combination of the unique electronic properties and flexibility of graphene and the tunable optical and electronic properties of organic NWs. Therefore, these vertical organic NW arrays on graphene offer the potential for realizing future on-chip light sources.

On-surface derivatisation of aromatic molecules on graphene: the importance of packing density.

An efficient, high-throughput method for the formation of densely packed molecular films on graphene is reported. The films exhibit high stability and remain intact during a subsequent derivatisation reaction, offering a versatile route for the non-covalent functionalisation of graphene.

Understanding and optimising the packing density of perylene bisimide layers on CVD-grown graphene.

The non-covalent functionalisation of graphene is an attractive strategy to alter the surface chemistry of graphene without damaging its superior electrical and mechanical properties. Using the facile method of aqueous-phase functionalisation on large-scale CVD-grown graphene, we investigated the formation of different packing densities in self-assembled monolayers (SAMs) of perylene bisimide derivatives and related this to the amount of substrate contamination. We were able to directly observe wet-chemically deposited SAMs in scanning tunnelling microscopy (STM) on transferred CVD graphene and revealed that the densely packed perylene ad-layers adsorb with the conjugated π-system of the core perpendicular to the graphene substrate. This elucidation of the non-covalent functionalisation of graphene has major implications on controlling its surface chemistry and opens new pathways for adaptable functionalisation in ambient conditions and on the large scale.

Direct Observation of Degenerate Two-Photon Absorption and Its Saturation in WS2 and MoS2 Monolayer and Few-Layer Films.

The optical nonlinearity of WS2 and MoS2 monolayer and few-layer films was investigated using the Z-scan technique with femtosecond pulses from the visible to the near-infrared range. The nonlinear absorption of few- and multilayer WS2 and MoS2 films and their dependences on excitation wavelength were studied. WS2 films with 1-3 layers exhibited a giant two-photon absorption (TPA) coefficient as high as (1.0 ± 0.8) × 10(4) cm/GW. TPA saturation was observed for the WS2 film with 1-3 layers and for the MoS2 film with 25-27 layers. The giant nonlinearity of WS2 and MoS2 films is attributed to a two-dimensional confinement, a giant exciton effect, and the band edge resonance of TPA.

Noncovalently functionalized monolayer graphene for sensitivity enhancement of surface plasmon resonance immunosensors.

A highly efficient surface plasmon resonance (SPR) immunosensor is described using a functionalized single graphene layer on a thin gold film. The aim of this approach was two-fold: first, to amplify the SPR signal by growing graphene through chemical vapor deposition and, second, to control the immobilization of biotinylated cholera toxin antigen on copper coordinated nitrilotriacetic acid (NTA) using graphene as an ultrathin layer. The NTA groups were attached to graphene via pyrene derivatives implying π-π interactions. With this setup, an immunosensor for the specific antibody anticholera toxin with a detection limit of 4 pg mL(-1) was obtained. In parallel, NTA polypyrrole films of different thicknesses were electrogenerated on the gold sensing platform where the optimal electropolymerization conditions were determined. For this optimized polypyrrole-NTA setup, the simple presence of a graphene layer between the gold and polymer film led to a significant increase of the SPR signal.