Antony Murphy

High-performance biosensing using arrays of plasmonic nanotubes

We show that aligned gold nanotube arrays capable of supporting plasmonic resonances can be used as high performance refractive index sensors in biomolecular binding reactions. A methodology to examine the sensing ability of the inside and outside walls of the nanotube structures is presented. The sensitivity of the plasmonic nanotubes is found to increase as the nanotube walls are exposed, and the sensing characteristic of the inside and outside walls is shown to be different. Finite element simulations showed good qualitative agreement with the observed behavior. Free standing gold nanotubes displayed bulk sensitivities in the region of 250 nm per refractive index unit and a signal-to-noise ratio better than 1000 upon protein binding which is highly competitive with state-of-the-art label-free sensors.

Manipulating polarization of light with ultrathin epsilon-near-zero metamaterials

One of the basic functionalities of photonic devices is the ability to manipulate the polarization state of light. Polarization components are usually implemented using the retardation effect in natural birefringent crystals and, thus, have a bulky design. Here, we have demonstrated the polarization manipulation of light by employing a thin subwavelength slab of metamaterial with an extremely anisotropic effective permittivity tensor. Polarization properties of light incident on the metamaterial in the regime of hyperbolic, epsilon-near-zero, and conventional elliptic dispersions were compared. We have shown that both reflection from and transmission through λ/20 thick slab of the metamaterial may provide nearly complete linear-to-circular polarization conversion or 90° linear polarization rotation, not achievable with natural materials. Using ellipsometric measurements, we experimentally studied the polarization conversion properties of the metamaterial slab made of the plasmonic nanorod arrays in different dispersion regimes. We have also suggested all-optical ultrafast control of reflected or transmitted light polarization by employing metal nonlinearities.

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.

Ultrasensitive Non‐Resonant Detection of Ultrasound with Plasmonic Metamaterials

Ultrasound and photoacoustic imaging have recently been developed for clinical diagnostics and biomedical research. Optical sensors for ultrasound detection provide very high sensitivity and bandwidth, advancing the horizon for the biomedical application of acoustic waves. Here we take advantage of the high sensitivity of plasmonic nanorod metamaterials to variations in the refractive index of their surroundings to demonstrate the ultrasensitive detection of acoustic waves. The measured detection limit is approximately 500 Pa as determined by the signal to noise ratio. The theoretical detection limit of the metamaterial sensor has been shown to exceed that of surface plasmon resonance based sensors in resonant conditions, predicting an ultimate sensitivity of a few tens of Pa. The non-resonant nature, signal linearity, high-bandwidth and sub-nanosecond response time of metamaterial-based sensors make them very promising for state-of-the-art health and biomedical applications. Photoacoustic and ultrasound imaging is widely used in clinical diagnostics and bio-medical research. [ 1 , 2 ] Specialized and emerging ultrasound-based technologies include tissue characterization and image segmentation, microscanning and intravascular scanning, elasticity imaging, refl ex transmission imaging, computed tomography, Doppler tomography and thermo-acoustics, to name a few. [ 3 , 4 ] Most of the recent achievements in ultrasound imaging have been enabled by advances in ultrasound detection technology, [ 2 ] and some signifi cant recent progress has been made employing “acoustic” metamaterials as specially fabricated acoustic lenses that allow much higher, sub-wavelength spatial resolution imaging to be achieved. [ 5 , 6 ] It is widely recognized that both the detection sensitivity and bandwidth are important in order to attain highquality, high-resolution imaging [ 7 , 8 ] and the ultrasound detector

Fabrication and optical properties of large-scale arrays of gold nanocavities based on rod-in-a-tube coaxials

Centimeter sized arrays of gold coaxial rod-in-a tube cavities have been fabricated using anodized aluminum oxide as a template. The etching process used to create the cavities enables the production of extremely small gaps between tube and rod, on the order of 5 nm, smaller than those created by standard fabrication techniques. Normal incidence spectroscopy reveals two extinction peaks in the visible and near infrared wavelength range associated with resonant plasmonic modes excited in the structure. Numerical simulations show that the modes are associated with in-phase and out-of-phase hybridization of transverse dipolar excitations in the nanorod and in the tube.

Application of AAO Matrix in Aligned Gold Nanorod Array Substrates for Surface-Enhanced Fluorescence and Raman Scattering

In this paper, we probed surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) from probe molecule Rhodamine 6G (R6G) on self-standing Au nanorod array substrates made using a combination of anodization and potentiostatic electrodeposition. The initial substrates were embedded within a porous alumina template (AAO). By controlling the thickness of the AAO matrix, SEF and SERS were observed exhibiting an inverse relationship. SERS and SEF showed a non-linear response to the removal of AAO matrix due to an inhomogeneous plasmon activity across the nanorod which was supported by FDTD calculations. We showed that by optimizing the level of AAO thickness, we could obtain either maximized SERS, SEF or simultaneously observe both SERS and SEF together.

The controlled fabrication and geometry tunable optics of gold nanotube arrays

Arrays of vertically aligned gold nanotubes are fabricated over several square centimetres which display a geometry tunable plasmonic extinction peak at visible wavelengths and at normal incidence. The fabrication method gives control over nanotube dimensions with inner core diameters of 15-30 nm, wall thicknesses of 5-15 nm and nanotube lengths of up to 300 nm. It is possible to tune the position of the extinction peak through the wavelength range 600-900 nm by varying the inner core diameter and wall thickness. The experimental data are in agreement with numerical modelling of the optical properties which further reveal highly localized and enhanced electric fields around the nanotubes. The tunable nature of the optical response exhibited by such structures could be important for various label-free sensing applications based on both refractive index sensing and surface-enhanced Raman scattering.

Plasmon enhanced fluorescence studies from aligned gold nanorod arrays modified with SiO2 spacer layers

Here, we demonstrate that quasi self-standing Au nanorod arrays prepared with plasma polymerisation deposited SiO2 dielectric spacers support surface enhanced fluorescence (SEF) while maintaining high signal reproducibility. We show that it is possible to find a balance between enhanced radiative and non-radiative decay rates at which the fluorescent intensity is maximized. The SEF signal optimised with a 30 nm spacer layer thickness showed a 3.5-fold enhancement with a signal variance of <15% thereby keeping the integrity of the nanorod array. We also demonstrate the decreased importance of obtaining resonance conditions when localized surface plasmon resonance is positioned within the spectral region of Au interband transitions. Procedures for further increasing the SEF enhancement factor are also discussed.

Strong coupling in molecular exciton-plasmon Au nanorod array systems

We demonstrate here a strong coupling between localized surface plasmon modes in self-standing nanorods with excitons in a molecular J-aggregate layer through angular tuning. The enhanced exciton-plasmon coupling creates a Fano like line shape in the differential reflection spectra associated with the formation of hybrid states, leading to anti-crossing of the upper and lower polaritons with a Rabi frequency of 125 meV. The recreation of a Fano like line shape was found in photoluminescence demonstrating changes in the emission spectral profile under strong coupling.

Hyperbolic Polaritonic Crystals Based on Nanostructured Nanorod Metamaterials

Surface plasmon polaritons usually exist on a few suitable plasmonic materials; however, nanostructured plasmonic metamaterials allow a much broader range of optical properties to be designed. Here, bottom-up and top-down nanostructuring are combined, creating hyperbolic metamaterial-based photonic crystals termed hyperbolic polaritonic crystals, allowing free-space access to the high spatial frequency modes supported by these metamaterials.