Characterisation of a micrometer-scale active plasmonic element by means of complementary computational and experimental methods.

In this article, we investigate an active plasmonic element which will act as the key building block for future photonic devices. This element operates by modulating optical constants in a localised fashion, thereby providing an external control over the strength of the electromagnetic near field above the element as well as its far-field response. A dual experimental approach is employed in tandem with computational methods to characterise the response of this system. First, an enhanced surface plasmon resonance experiment in a classical Kretschmann configuration is used to measure the changes in the reflectivity induced by an alternating electric current. A lock-in amplifier is used to extract the dynamic changes in the far-field reflectivity resulting from Joule heating. A clear modulation of the materials' optical constants can be inferred from the changed reflectivity, which is highly sensitive and dependent on the input current. The changed electrical permittivity of the active element is due to Joule heating. Second, the resulting expansion of the metallic element is measured using scanning Joule expansion microscopy. The localised temperature distribution, and hence information about the localisation of the modulation of the optical constants of the system, can be extracted using this technique. Both optical and thermal data are used to inform detailed finite element method simulations for verification and to predict system responses allowing for enhanced design choices to maximise modulation depth and localisation.

Propagating Surface Plasmon Polaritons on Systems with Variable Periodicity and Variable Gap-Depth.

Here we report on both simulations and experimental results on propagation and transmission of Surface Plasmon Polaritons (SPPs) through tunable gaps which were initially motivated by excitation of SPPs on a periodic arrangement of nanowires with mechanically tuneable periodicity. The general ability to vary the two-dimensional lattice constant results in an additional degree of freedom, permitting excitation of SPP's for any combination of wavelength and angle of incidence within the tuning range of the system. Fabrication of the tunable system includes a transition from a continuously metal coated surface to small metal ribbons which can be separated from each other as a result of mechanical strain applied to the flexible PDMS substrate. This also results in the creation of tuneable gaps between the metal ribbons and variations in the thickness of the metal coatings. In order to explain the propagation of SPPs through such gaps we have employed Finite Difference Time Domain (FDTD) simulations of SPPs through model systems which contain gaps with varying depths and metal fillings.

Comparison of two field-induced ErIII single ion magnets.

We present the synthesis, magnetic and photophysical properties of four mononuclear LnIII complexes in two isostructural lattices containing GdIII and ErIII. A heptadentate Schiff base ligand and acetate versus trifluoroacetate were used to synthesise complexes 1-4, among which the two ErIII complexes 2 and 4 exhibit field-induced SIM behaviour with almost similar Ueff values (31.6 K for 2 and 32.7 K for 4). Ab initio calculations show the structure of the low-lying energy states and highlight that there is already significant tunnelling in the ground doublet state, but the application of a weak magnetic field of 0.05 T is sufficient for ac magnetic measurements to suppress tunnelling in the ground state. The calculated main magnetic axes (gZ) of the ground Kramers doublets show small differences between the two ErIII compounds 2 and 4 due to their different ligand fields.

Linear self-assembly and grafting of gold nanorods into arrayed micrometer-long nanowires on a silicon wafer via a combined top-down/bottom-up approach.

Macroscopically long wire-like arrangements of gold nanoparticles were obtained by controlled evaporation and partial coalescence of an aqueous colloidal solution of capped CTAB-Au nanorods onto a functionalised 3-mercaptopropyl trimethoxysilane (MPTMS) silicon substrate, using a removable, silicon wafer with a hydrophobic surface that serves as a "handrail" for the initial nanorods' linear self-assembly. The wire-like structures display a quasi-continuous pattern by thermal annealing of the gold nanorods when the solvent (i.e. water) is evaporated at temperatures rising from 20°C to 140°C. Formation of both single and self-replicating parallel 1D-superstructures consisting of two or even three wires is observed and explained under such conditions.

Quantifying nanoscale biochemical heterogeneity in human epithelial cancer cells using combined AFM and PTIR absorption nanoimaging.

Subcellular chemical heterogeneity plays a key role in cell organization and function. However the biomechanics underlying the structure-function relationship is governed by cell substructures which are poorly resolved using conventional chemical imaging methods. To date, advances in sub-diffraction limited infrared (IR) nanoscopy have permitted intracellular chemical mapping. In this work we report how image analysis applied to a combination of IR absorption nanoimaging and topographic data permits quantification of chemical complexity at the nanoscale, enabling the analysis of biochemical heterogeneity in mammalian cancer cells on the scale of subcellular features.

Plasmonic enhancement of dye sensitized solar cells via a tailored size-distribution of chemically functionalized gold nanoparticles.

A substantial and stable increase of the current density Jsc of ruthenium (Ru) dye sensitized solar cells (DSC) of up to 16.18% and of the power efficiency of up to 25.5% is demonstrated in this article via plasmonic enhancement. The key aspect of this work is the use of a tailored bimodal size distribution of functionalized gold nanoparticles (AuNPs) that have been chemically immobilized onto the mesoporous titanium dioxide (TiO2) layer via short, stable dithiodibutyric acid linkers. The size distribution of the AuNPs is a result of theoretical calculations that aimed at the perfection of the absorption characteristics of the complete solar cell system over a wide range of wavelengths. The functionalization of the AuNPs serves to bind them at a close but defined distance to TiO2-particles and additionally to chemically protect them against potential corrosion by the electrolyte. Simulations of near field (enhanced absorption) and far field (scattering) contributions have been used to tailor a complex AuNPs bimodal size distribution that had subsequently demonstrated experimentally a close to optimum improvement of the absorbance over a wide wavelength range (500-675 nm) and therefore an impressive DSC efficiency enhancement. Finally, the modified DSCs are exhibiting pronounced longevity and stable performance as confirmed via long time measurements. In summary, the presented systems show increased performance compared to non plasmonic enhanced cells with otherwise identical composition, and are demonstrating a previously unpublished longevity for iodide electrolyte/AuNPs combinations.

Highly efficient broadband ultrafast plasmonics.

To date, considerable experimental and theoretical focus has been placed on the spatial control of Surface Plasmon Polaritons (SPPs) using nanostructured surfaces; however, research aimed toward accessing the ultrafast dynamics of SPPs remains vastly unexplored. Despite this, SPPs have the potential to exhibit some of the fastest possible optical processes, while maintaining the advantage of nanoscale spatial manipulation. Here, we present an experimental and computational investigation of a system that provides access to the efficient excitation of broadband, propagating SPP modes. To achieve this, a surface array of tailor designed, reduced symmetry nanostructures has been fabricated to enable the required control of the plasmon dispersion map to match sub 20 fs pulses in the near infra-red. Using a combination of optical spectroscopy and frequency resolved optical gating techniques, complimented by finite element computational analysis, the efficient excitation of propagating broadband plasmonic modes is demonstrated.

Optimisation of ruthenium dye sensitised solar cells efficiency via Sn diffusion into the TiO2 mesoporous layer.

Dye sensitised solar cells (DSCs) typically include a mesoporous titanium dioxide (TiO2) scaffold, sensitised with an adsorbed dye, as the main active element responsible for the photon absorption and charge separation functionalities. The sintering process employed in the TiO2 active layer fabrication plays a crucial role in the formation of the nanoparticle (NP) scaffold and hence in the performance of a dye sensitised solar cell, as it allows the particles to form efficient inter-crystalline electric contacts providing high electron conductivity. Furthermore, the DSC design requires a conductive transparent top electrode which is typically made of fluorinated stannic oxide. Here we report on a highly spatially resolved scanning electron microscopy study in conjunction with focussed ion beam milling and energy dispersive X-ray (EDX) mapping of the distribution of all relevant elements within a DSC subsequent to a classical sintering process in the range of 350°C-550°C. Additionally, the article provides quantitative results regarding the found Sn diffusion and its effect on efficiency confirmed via J-V measurements. The effective spatial resolution of the EDX studies was calculated by Monte Carlo simulations of the electron trajectories and X-ray emission region. This permits to construct a model for the migration of Sn from the transparent conductive oxide into the TiO2 scaffold, resulting in alterations in the composition of the complex system which has a direct effect on the DSC performance. J-V measurements conclude that sintering temperature of 500°C is close to the optimum regarding Sn diffusion enhancement of DSCs. Sintering temperatures above 500°C were causing a drop in the DSC efficiency and are therefore not recommended. In order to optimize the DSC efficiency, the results are summarized by a model that explains how the efficiency varies with the Sn diffusion process.

Highly ordered Fe-Au heterostructured nanorod arrays and their exceptional near-infrared plasmonic signature.

The potential of highly ordered array nanostructures in sensing applications is well recognized, particularly with the ability to define the structural composition and arrangement of the individual nanorods accurately. The use of heterogeneous nanostructures generates an additional degree of freedom, which can be used to tailor the optical response of such arrays. In this article, we report on the fabrication and characterization of well-defined Fe-Au bisegmented nanorod arrays in a repeating hexagonal arrangement. Through an asymmetric etching method, free-standing Fe-Au nanorod arrays on a gold-coated substrate were produced with an inter-rod spacing of 26 nm. This separation distance renders the array capable of sustaining resonant electromagnetic wave coupling between individual rods. Owing to this coupling, the subwavelength arrangement, and the structural heterogeneity, the nanorod arrays exhibit unique plasmonic responses in the near-infrared (NIR) range. Enhanced sensitivity in this spectral region has not been identified for gold-only nanorods of equivalent dimensions. The NIR response offers confirmation of the potential of these highly ordered, high-density arrays for biomedical relevant applications, such as subcutaneous spectroscopy and biosensing.

Magnetic-plasmonic dual modulated FePt-Au ternary heterostructured nanorods as a promising nano-bioprobe.

Ternary FePt-Au nanorods are synthesized as magnetic-plasmonic 1D nanostructures. Besides their widely tunable magnetic properties, their unique plasmonic response to the illumination polarization provides a powerful tool to optically image these sub-wavelength single nanorods. These nanoparticles also show the potential as a novel nano-bioprobe based on the demonstration of simultaneous magnetic manipulation and optical imaging of single particles inside live cells.

Magnetic manipulation and optical imaging of an active plasmonic single-particle Fe-Au nanorod.

Superparamagnetic microbeads play an important role in a number of scientific and biotechnology applications including single-molecule force measurements, affinity separation, and in vivo and in vitro diagnostics. Magneto-optically active nanorods composed of single-crystalline Au and polycrystalline Fe segments were synthesized with diameters of 60 or 295 nm using templated electrodeposition. The Fe section was magnetically soft and had a saturation magnetization of approximately 200 emu/g, resulting in a 10-fold increase in magnetization relative to that iron oxide nanoparticles. The strong plasmonic response of the Au segment of the rod in both the longitudinal and transverse directions made it possible to detect the orientation of a single rod in a polarized light microscope with nanometer resolution. These nanorods provide significantly improved physical properties over iron oxide superparamagnetic beads, making it possible to simultaneously manipulate and monitor the orientation of biomolecules with well-defined forces at the nanometer scale.

A spatially resolved study on the Sn diffusion during the sintering process in the active layer of dye sensitised solar cells.

Dye sensitised solar cells (DSSCs) use a mesoporous TiO(2) scaffold, typically assisted by an adsorbed dye, as the main active element, responsible for the photon absorption, exciton generation and charge separation functionality. The sintering process employed in the TiO(2) active layer fabrication plays a crucial role in the formation of the nanoparticle scaffold and hence the performance of a dye sensitised solar cell, as it allows the particles to form efficient inter-crystalline electric contacts to provide high electron conductivity. The sintering temperature, with typical values in the range of 450-600 degrees C, is of particular importance for the formation as it reduces the amount of unwanted organics between the individual crystallites and determines the formation of interfaces between the nanoparticles. Furthermore, the cell design requires a conductive transparent top electrode which is typically made of fluorinated tin oxide or indium tin oxide. Here we report on a highly spatially resolved scanning electron microscopy study including focussed ion beam (FIB) milling and energy dispersive X-ray (EDX) mapping of the distribution of all relevant elements within a DSSC subsequent to a classical sintering process. We find that the above quoted temperatures cause the Sn of the transparent conductive oxide (TCO) to migrate into the TiO(2) scaffold, resulting in unwanted alterations in the composition of the complex scaffold which has a direct effect on the DSSC performance. One potential solution to this problem is the invention of novel concepts in the manufacturing of DSSCs using lower sintering temperatures.

Polarization selective near-field focusing on mesoscopic surface patterns with threefold symmetry measured with PEEM.

Optically active surfaces that can provide strong localization of electromagnetic fields at predefined points are desired for applications that require high spatial resolution and high sensitivity. Here, we examine the geometric influences on, and polarization dependencies of, electromagnetic near fields on the surface of an array of tailor designed, mesoscalic, silver-coated structures with threefold symmetry characteristics. For spatially resolved mapping of the electromagnetic near fields and examining the influence of polarization, we use a photoelectron emission microscope. We find that the investigated structures not only provide an increase of the near-field intensity at their boundaries, but also that the symmetry centers of the structures focus energy in a polarization dependent manner. Changing the polarization of the incident light enables the localization of near-field intensities without displacing the excitation. Hence we show that breaking of symmetry can provide controllable centers of "hot spots" for the basis of an improved design to gain more efficient surface structures.