Quantum electrodynamics at room temperature coupling a single vibrating molecule with a plasmonic nanocavity.

Interactions between a single emitter and cavity provide the archetypical system for fundamental quantum electrodynamics. Here we show that a single molecule of Atto647 aligned using DNA origami interacts coherently with a sub-wavelength plasmonic nanocavity, approaching the cooperative regime even at room temperature. Power-dependent pulsed excitation reveals Rabi oscillations, arising from the coupling of the oscillating electric field between the ground and excited states. The observed single-molecule fluorescent emission is split into two modes resulting from anti-crossing with the plasmonic mode, indicating the molecule is strongly coupled to the cavity. The second-order correlation function of the photon emission statistics is found to be pump wavelength dependent, varying from g(2)(0) = 0.4 to 1.45, highlighting the influence of vibrational relaxation on the Jaynes-Cummings ladder. Our results show that cavity quantum electrodynamic effects can be observed in molecular systems at ambient conditions, opening significant potential for device applications.

Revealing Nanostructures through Plasmon Polarimetry.

Polarized optical dark-field spectroscopy is shown to be a versatile noninvasive probe of plasmonic structures that trap light to the nanoscale. Clear spectral polarization splittings are found to be directly related to the asymmetric morphology of nanocavities formed between faceted gold nanoparticles and an underlying gold substrate. Both experiment and simulation show the influence of geometry on the coupled system, with spectral shifts Δλ = 3 nm from single atoms. Analytical models allow us to identify the split resonances as transverse cavity modes, tightly confined to the nanogap. The direct correlation of resonance splitting with atomistic morphology allows mapping of subnanometre structures, which is crucial for progress in extreme nano-optics involving chemistry, nanophotonics, and quantum devices.

Tuneable 2D self-assembly of plasmonic nanoparticles at liquid|liquid interfaces.

Understanding the structure and assembly of nanoparticles at liquid|liquid interfaces is paramount to their integration into devices for sensing, catalysis, electronics and optics. However, many difficulties arise when attempting to resolve the structure of such interfacial assemblies. In this article we use a combination of X-ray diffraction and optical reflectance to determine the structural arrangement and plasmon coupling between 12.8 nm diameter gold nanoparticles assembled at a water|1,2-dichloroethane interface. The liquid|liquid interface provides a molecularly flat and defect-correcting platform for nanoparticles to self-assemble. The amount of nanoparticles assembling at the interface can be controlled via the concentration of electrolyte within either the aqueous or organic phase. At higher electrolyte concentration more nanoparticles can settle at the liquid|liquid interface resulting in a decrease in nanoparticle spacing as observed from X-ray diffraction experiments. The plasmonic coupling between the nanoparticles as they come closer together is observed by a red-shift in the optical reflectance spectra. The optical reflectance and the X-ray diffraction data are combined to introduce a new 'plasmon ruler'. This allows extraction of structural information from simple optical spectroscopy techniques, with important implications for understanding the structure of self-assembled nanoparticle films at liquid interfaces.

Polymer-assisted self-assembly of gold nanoparticle monolayers and their dynamical switching.

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.

Rapid ultrasensitive single particle surface-enhanced Raman spectroscopy using metallic nanopores.

Nanopore sensors embedded within thin dielectric membranes have been gaining significant interest due to their single molecule sensitivity and compatibility of detecting a large range of analytes, from DNA and proteins, to small molecules and particles. Building on this concept we utilize a metallic Au solid-state membrane to translocate and rapidly detect single Au nanoparticles (NPs) functionalized with 589 dye molecules using surface-enhanced resonance Raman spectroscopy (SERRS). We show that, due to the plasmonic coupling between the Au metallic nanopore surface and the NP, signal intensities are enhanced when probing analyte molecules bound to the NP surface. Although not single molecule, this nanopore sensing scheme benefits from the ability of SERRS to provide rich vibrational information on the analyte, improving on current nanopore-based electrical and optical detection techniques. We show that the full vibrational spectrum of the analyte can be detected with ultrahigh spectral sensitivity and a rapid temporal resolution of 880 µs.

Self-assembly and applications of ultraconcentrated nanoparticle solutions.

We demonstrate a highly efficient method for concentrating, purifying and separating gold nanoparticles. The method relies on localized density gradients that can be formed at an aqueous | organic phase interface. We show that this method is able to concentrate aqueous gold nanoparticles to the point where confinement leads to variable interparticle separations. Furthermore, the physical properties of the resulting solution are drastically altered when compared to water. For example, densities higher than 4.5 g/cm(3) could be generated without nanoparticle aggregation. As far as we are aware, this is one of the highest reported densities of an aqueous solution at room temperature. Finally, the compositions of the solutions generated are highly dependent on parameters such as particle size and background analyte making this technique highly advantageous for the separation of multimodal NP populations and chemical purification, with 99.5% and >99.9% efficiency, respectively.

Superhydrophobic surfaces as an on-chip microfluidic toolkit for total droplet control.

We propose and outline a novel technique designed to utilize the unique surface repulsion present between aqueous droplets and customizable superhydrophobic surfaces for the on-chip spatial and temporal manipulation of droplets within microfluidic architectures. Through the integration of carefully designed and prepatterned superhydrophobic surfaces into polymer microfluidic chipsets, it is possible to take advantage of this enhanced surface repulsion to passively manipulate droplets on the microscale for a wide range of droplet operations, including but not limited to acceleration, deceleration, merging, and path control. This work aims to help fulfill and stimulate development based around current requirements for additional passive analytical manipulation and detection techniques in order to enable a reduction in experimental design complexity with the goal of facilitating and improving portability for Lab-on-a-chip devices.

Self-assembled nanoparticle arrays for multiphase trace analyte detection.

Nanoplasmonic structures designed for trace analyte detection using surface-enhanced Raman spectroscopy typically require sophisticated nanofabrication techniques. An alternative to fabricating such substrates is to rely on self-assembly of nanoparticles into close-packed arrays at liquid/liquid or liquid/air interfaces. The density of the arrays can be controlled by modifying the nanoparticle functionality, pH of the solution and salt concentration. Importantly, these arrays are robust, self-healing, reproducible and extremely easy to handle. Here, we report on the use of such platforms formed by Au nanoparticles for the detection of multi-analytes from the aqueous, organic or air phases. The interfacial area of the Au array in our system is ≈25 mm(2) and can be made smaller, making this platform ideal for small-volume samples, low concentrations and trace analytes. Importantly, the ease of assembly and rapid detection make this platform ideal for in-the-field sample testing of toxins, explosives, narcotics or other hazardous chemicals.

Plasmonic ruler at the liquid-liquid interface.

We report on a simple, fast, and inexpensive method to study adsorption and desorption of metallic nanoparticles at a liquid/liquid interface. These interfaces provide an ideal platform for the formation of two-dimensional monolayers of nanoparticles, as they form spontaneously and are defect-correcting, acting as 2D "nanoparticle traps". Such two-dimensional, self-assembled nanoparticle arrays have a vast range of potential applications in displays, catalysis, plasmonic rulers, optoelectronics, sensors, and detectors. Here, we show that 16 nm diameter gold nanoparticles can be controllably adsorbed to a water/1,2-dichloroethane interface, and that we can control the average interparticle spacing at the interface over the range 6-35 nm. The particle density and average interparticle spacing are experimentally assessed by measuring the optical plasmonic response of the nanoparticles in the bulk and at the interface and by comparing the experimental data with existing theoretical results.

Microfluidic evaporator for on-chip sample concentration.

We present a simple technique for the concentration of liquid samples in microfluidic devices applicable for single or multiple-phase configurations. The strategy consists of capturing the sample of interest within microfluidic traps and breaking its continuity by the introduction of a gas phase, which is also used to evaporate it.