Paul R. Evans

Plasmonic nanorod metamaterials for biosensing.

Label-free plasmonic biosensors rely either on surface plasmon polaritons or on localized surface plasmons on continuous or nanostructured noble-metal surfaces to detect molecular-binding events. Despite undisputed advantages, including spectral tunability, strong enhancement of the local electric field and much better adaptability to modern nanobiotechnology architectures, localized plasmons demonstrate orders of magnitude lower sensitivity compared with their guided counterparts. Here, we demonstrate an improvement in biosensing technology using a plasmonic metamaterial that is capable of supporting a guided mode in a porous nanorod layer. Benefiting from a substantial overlap between the probing field and the active biological substance incorporated between the nanorods and a strong plasmon-mediated energy confinement inside the layer, this metamaterial provides an enhanced sensitivity to refractive-index variations of the medium between the rods (more than 30,000 nm per refractive-index unit). We demonstrate the feasibility of our approach using a standard streptavidin-biotin affinity model and record considerable improvement in the detection limit of small analytes compared with conventional label-free plasmonic devices.

Growth and properties of gold and nickel nanorods in thin film alumina

Arrays of nickel and gold nanorods have been grown on glass and silicon substrates using porous alumina templates of less than 500 nm thickness. A method is demonstrated for varying the diameter of the nanorods whilst keeping the spacing constant. Optical extinction spectra for the gold nanorods show two distinct maxima associated with the transverse and longitudinal axes of the rods. Adding small quantities of oxygen to the aluminium before anodization is found to improve the sharpness of the extinction peaks. The spectral position of the longitudinal peak is shown to be sensitive to the nanorod diameter for constant length and spacing. For the nickel nanorods it is shown that the magnetic properties are governed by both interactions between the wires and shape anisotropy.

Guided plasmonic modes in nanorod assemblies: strong electromagnetic coupling regime

We demonstrate that the coupling between plasmonic modes of oriented metallic nanorods results in the formation of an extended (guided) plasmonic mode of the nanorod array. The electromagnetic field distribution associated to this mode is found to be concentrated between the nanorods within the assembly and propagates normally to the nanorod long axes, similar to a photonic mode waveguided by an anisotropic slab. This collective plasmonic mode determines the optical properties of nanorod assemblies and can be tuned in a wide spectral range by changing the nanorod array geometry. This geometry represents a unique opportunity for light guiding applications and manipulation at the nanoscale as well as sensing applications and development of molecular plasmonic devices.

Fabrication and optical properties of gold nanotube arrays

Arrays of gold nanotubes with polypyrrole cores were grown on glass substrates by electrodeposition into thin film porous alumina templates. Measurements of optical transmission revealed strong extinction peaks related to plasmonic resonances, which were sensitive to the polarization state and angle of incidence. On prolonging the electrodeposition of gold, the polypyrrole core became fully encapsulated and this had a dramatic effect on the optical properties of the arrays, which was rationalized by finite element simulation of the local field intensities resulting from plasmon excitation.

Polarization conversion through collective surface plasmons in metallic nanorod arrays

For two-dimensional (2D) arrays of metallic nanorods arranged perpendicular to a substrate several methods have been proposed to determine the electromagnetic near-field distribution and the surface plasmon resonances, but an analytical approach to explain all optical features on the nanometer length scale has been missing to date. To fill this gap, we demonstrate here that the field distribution in such arrays can be understood on the basis of surface plasmon polaritons (SPPs) that propagate along the nanorods and form standing waves. Notably, SPPs couple laterally through their optical near fields, giving rise to collective surface plasmon (CSP) effects. Using the dispersion relation of such CSPs, we deduce the condition of standing-wave formation, which enables us to successfully predict several features, such as eigenmodes and resonances. As one such property and potential application, we show both theoretically and in an experiment that CSP propagation allows for polarization conversion and optical filtering in 2D nanorod arrays. Hence, these arrays are promising candidates for manipulating the light polarization on the nanometer length scale.

Perovskite lead zirconium titanate nanorings : Towards nanoscale ferroelectric solenoids ?

Rings of perovskite lead zirconium titanate (PZT) with internal diameters down to ∼5nm and ring thicknesses of ∼5–10nm have been fabricated and structurally, crystallographically, and chemically characterized using an analytical transmission electron microscope. Ring fabrication involved conformal solution deposition of a thin layer of PZT on the inside of a thin film of anodized aluminum oxide nanopores, and subsequent sectioning of the coated pores perpendicular to their cylinder axes. Although the starting solution used for the solution deposition was made from morphotropic phase boundary PZT, the nanorings were found to be on the zirconium-rich side of the PZT phase diagram. Nevertheless, coatings were found to be of perovskite crystallography. The dimensions of these nanorings are such that they have the potential to demonstrate polarization vortices, as modeled by Naumov et al. [Nature (London) 432, 737 (2004)], and moreover represent the perfect morphology to allow vortex alignment and the creation of the ferroelectric “solenoid” as modeled by Gorbatsevich and Kopaev [Ferroelectrics 161, 321 (1994)].Rings of perovskite lead zirconium titanate (PZT) with internal diameters down to ∼5nm and ring thicknesses of ∼5–10nm have been fabricated and structurally, crystallographically, and chemically characterized using an analytical transmission electron microscope. Ring fabrication involved conformal solution deposition of a thin layer of PZT on the inside of a thin film of anodized aluminum oxide nanopores, and subsequent sectioning of the coated pores perpendicular to their cylinder axes. Although the starting solution used for the solution deposition was made from morphotropic phase boundary PZT, the nanorings were found to be on the zirconium-rich side of the PZT phase diagram. Nevertheless, coatings were found to be of perovskite crystallography. The dimensions of these nanorings are such that they have the potential to demonstrate polarization vortices, as modeled by Naumov et al. [Nature (London) 432, 737 (2004)], and moreover represent the perfect morphology to allow vortex alignment and the creation...

Investigating the effects of reduced size on the properties of ferroelectrics

A series of experiments has been undertaken to understand more about the fundamental origin of the thickness-induced permittivity collapse often observed in conventional thin film ferroelectric heterostructures. The various experiments are discussed, highlighting the eventual need to examine permittivity collapse in thin film single crystal material. It has been seen that dielectric collapse is not a direct consequence of reduced size, and neither is it a consequence of unavoidable physics associated with the ferroelectric-electrode boundary. Research on three-dimensional shape-constrained ferroelectrics, emphasizing self-assembled structures based on nanoporous alumina templates and on FIB-milled single crystals, is also presented, and appears to represent an exciting area for ongoing research

Metallic nanorod arrays: negative refraction and optical properties explained by retarded dipolar interactions

We show that the optical properties of arrays of parallel-aligned metallic nanorods can be understood by means of a retarded dipolar interaction model. Exemplarily, arrays of gold nanorods having various lengths and diameters are investigated experimentally. A strong diameter dependence of the long-axis surface plasmon resonance (LSPR) as well as a lower energy limit of this mode for varying length was found. The model also shows that, for small nanorod distances (d<λ/2), the optical properties are independent of the azimuthal angle of the incoming plane wave and of the detailed arrangement of the nanorods. Furthermore, the model was used to explain the dependence of the LSPR on the angle of incidence and to find the conditions for which negative and extraordinary positive refractions occur in these structures.

Optical transmission measurements of silver, silver–gold alloy and silver–gold segmented nanorods in thin film alumina

Silver nanorods have been grown by electrodeposition into thin film porous alumina. Transmission measurements show two peaks related to the transverse and longitudinal resonance of the nanorods. The behaviour of the longitudinal resonance peak is found to vary with nanorod length and the spectral position to depend on nanorod diameter. As the distance between the nanorods is decreased a small blue-shift of the longitudinal peak is observed. Depositing a small gold cap on top of the silver nanorods causes a red-shift of the longitudinal peak whilst, conversely, the longitudinal peak of gold nanorod arrays is comparatively insensitive to the deposition of a silver cap. Gold-silver alloy nanorods were also deposited from a mixed salt bath and a linear dependence of the transverse peak position on alloy composition was observed.

Towards nonlinear plasmonic devices based on metallic nanorods

The nonlinear optical properties of gold nanorod arrays have been studied with a two‐colour continuosly working (CW) pump‐probe spectroscopy. The hybridization of the nanorod arrays with a nonlinear polymer (poly‐3BCMU) has been investigated for the purposes of active photonic component design. The sensitivity of the plasmonic resonances of the hybrid nanostructured system to pump‐induced changes in the refractive index of the polymer surroundings has been used to control the optical extinction of the array. Both reversible and non‐reversible behaviour has been observed reflecting the combined effects from the third‐order nonlinear response of the hybrid metallo‐dielectric system and post‐photopolymerization triggered reactions in the polymer.