Tanya Hutter

Metal Oxide Nanoparticle Mediated Enhanced Raman Scattering and Its Use in Direct Monitoring of Interfacial Chemical Reactions

Metal oxide nanoparticles (MONPs) have widespread usage across many disciplines, but monitoring molecular processes at their surfaces in situ has not been possible. Here we demonstrate that MONPs give highly enhanced (×10(4)) Raman scattering signals from molecules at the interface permitting direct monitoring of their reactions, when placed on top of flat metallic surfaces. Experiments with different metal oxide materials and molecules indicate that the enhancement is generic and operates at the single nanoparticle level. Simulations confirm that the amplification is principally electromagnetic and is a result of optical modulation of the underlying plasmonic metallic surface by MONPs, which act as scattering antennae and couple light into the confined region sandwiched by the underlying surface. Because of additional functionalities of metal oxides as magnetic, photoelectrochemical and catalytic materials, enhanced Raman scattering mediated by MONPs opens up significant opportunities in fundamental science, allowing direct tracking and understanding of application-specific transformations at such interfaces. We show a first example by monitoring the MONP-assisted photocatalytic decomposition reaction of an organic dye by individual nanoparticles.

Study of thioflavin-T immobilized in porous silicon and the effect of different organic vapors on the fluorescence lifetime.

Steady-state and time-resolved emission techniques have been employed to study the fluorescence properties of thioflavin-T (ThT) adsorbed on oxidized porous silicon (PSi) surfaces, with an average pore size of ∼10 nm. We found that the average fluorescence decay time of ThT, when it is adsorbed on the PSi surface, is rather long, τ(av) = 1.3 ns. We attribute this relatively long emission lifetime to the effect of the immobilization of ThT on the PSi surface, which inhibit the rotation of the aniline with respect to the benzothiazole moieties of ThT. We also measured the fluorescence properties of ThT in PSi samples in equilibrium with vapors of several liquids, such as methanol, acetonitrile, and water. We found that the fluorescence intensity drops by a factor of 10, and the average decay time, measured by a time-correlated single-photon counting technique, decreases by a factor of 3. We explain these results in terms of liquid condensation of the vapors in the PSi pores, which leads to partial dissolution of the ThT molecules in the liquid pools.

Optimized Vertical Carbon Nanotube Forests for Multiplex Surface-Enhanced Raman Scattering Detection

The highly sensitive and molecule-specific technique of surface-enhanced Raman spectroscopy (SERS) generates high signal enhancements via localized optical fields on nanoscale metallic materials, which can be tuned by manipulation of the surface roughness and architecture on the submicrometer level. We investigate gold-functionalized vertically aligned carbon nanotube forests (VACNTs) as low-cost straightforward SERS nanoplatforms. We find that their SERS enhancements depend on their diameter and density, which are systematically optimized for their performance. Modeling of the VACNT-based SERS substrates confirms consistent dependence on structural parameters as observed experimentally. The created nanostructures span over large substrate areas, are readily configurable, and yield uniform and reproducible SERS enhancement factors. Further fabricated micropatterned VACNTs platforms are shown to deliver multiplexed SERS detection. The unique properties of CNTs, which can be synergistically utilized in VACNT-based substrates and patterned arrays, can thus provide new generation platforms for SERS detection.

Single Nanoparticle-Based Heteronanojunction as a Plasmon Ruler for Measuring Dielectric Thin Films

Nondestructive, noninvasive and accurate measurement of thin film thicknesses on dielectric substrates is challenging. In this work a ruler for measuring thin film thicknesses utilizes the heteronanojunction construct formed between a plasmonic nanoparticle and a high refractive index nonplasmonic substrate. The high near-field sensitivity in the nanojunction renders it suitable for measuring the thickness of intervening dielectric thin films. We demonstrate this by controlling the thickness of dielectric spacer layers created by overgrowing SiO2 thin films on commercially available silicon substrates. While Rayleigh (using dark-field) scattering measurements show that the spectral response is well correlated to the thickness of SiO2 spacer layers the distance-dependence is much steeper with surface-enhanced Raman scattering (SERS). Good agreement between 3D simulations and experimental results confirm the plasmon ruler constructs sensitivity to the dielectric thin film spacing. Thus, we postulate that this single nanoparticle based heteronanojunction configuration can serve as a convenient and simple ruler in metrology of thin films as well as a platform for SERS-based detection even in cases where plasmonically active films are not a suitable substrate.

Diffractive optical elements with porous silicon layers

We investigate the basic chromatic properties of dispersive surface relief diffractive optical elements with porous silicon (PSi) layers. Rigorous and scalar wavelength-dependent diffraction efficiencies are juxtaposed and compared to reflection coefficients of uniform silicon and PSi layers. The application of the device as an enhanced sensor is discussed. A spectral covariance criterion for efficient evaluation of the spectral changes induced by analyte filling the pores is presented. Experimental results for the device reveal an increased spectral selectivity of the diffractively structured PSi layers compared to uniform PSi layers.

PCB-Integrated Optical Waveguide Sensors: An Ammonia Gas Sensor

This paper presents a novel platform for the formation of cost-effective PCB-integrated optical waveguide sensors. The sensor design relies on the use of multimode polymer waveguides that can be formed directly on standard PCBs and commercially-available chemical dyes, enabling the integration of all essential sensor components (electronic, photonic, chemical) on low-cost substrates. Moreover, it enables the detection of multiple analytes from a single device by employing waveguide arrays functionalised with different chemical dyes. The devices can be manufactured with conventional methods of the PCB industry, such as solder-reflow processes and pick-and-place assembly techniques. As a proof of principle, a PCB-integrated ammonia gas sensor is fabricated on a FR4 substrate. The sensor operation relies on the change of the optical transmission characteristics of chemically functionalised optical waveguides in the presence of ammonia molecules. The fabrication and assembly of the sensor unit, as well as fundamental simulation and characterisation studies, are presented. The device achieves a sensitivity of approximately 30 ppm and a linear response up to 600 ppm at room temperature. Finally, the potential to detect multiple analytes from a single device is demonstrated using principal-component analysis.

Development of an open technology sensor suite for assisted living: a student-led research project.

Many countries have a rapidly ageing population, placing strain on health services and creating a growing market for assistive technology for older people. We have, through a student-led, 12-week project for 10 students from a variety of science and engineering backgrounds, developed an integrated sensor system to enable older people, or those at risk, to live independently in their own homes for longer, while providing reassurance for their family and carers. We provide details on the design procedure and performance of our sensor system and the management and execution of a short-term, student-led research project. Detailed information on the design and use of our devices, including a door sensor, power monitor, fall detector, general in-house sensor unit and easy-to-use location-aware communications device, is given, with our open designs being contrasted with closed proprietary systems. A case study is presented for the use of our devices in a real-world context, along with a comparison with commercially available systems. We discuss how the system could lead to improvements in the quality of life of older users and increase the effectiveness of their associated care network. We reflect on how recent developments in open source technology and rapid prototyping increase the scope and potential for the development of powerful sensor systems and, finally, conclude with a student perspective on this team effort and highlight learning outcomes, arguing that open technologies will revolutionize the way in which technology will be deployed in academic research in the future.

Some Methods for Improving the Reliability of Optical Porous Silicon Sensors

The area of chemical sensors is one of the fastest growing both in research and in commercial fields. Most of the research work in this area is concentrated towards reducing the size of sensors and the identification and quantification of multiple species. Quick response, minimum hardware requirement, good reversibility, sensitivity, and selectivity are expected from an excellent sensor, and hence there is a need for further research. The applications of chemical sensors include quality and process control, biomedical analysis, medical diagnostics, environmental pollution control, continuous and long term monitoring of pollutants and hazardous substances. There are however several outstanding problems hindering applications of chemical sensors based on optical readout. It is widely accepted that in many instances the sensitivity is not the limitation of the sensor. Indeed many sensors display over-sensitivity at the expense of specificity and are vulnerable to noise. In real applications the environment in which sensors are located is not sterile: additional substances present will cause spurious readouts, and moreover, the substances may react over the sensors surface and readouts will be then cross-correlated.

Optical fibre-tip probes for SERS: numerical study for design considerations

Enhancement of sub-wavelength optical fields using sub-micron plasmonic probes has found many applications in chemical, material, biological and medical sciences. The enhancement is via localised surface-plasmon resonance (LSPR) which enables the highly sensitive vibrational-spectroscopy technique of surface-enhanced Raman scattering (SERS). Combining SERS with optical fibres can allow the monitoring of biochemical reactions in situ with high resolution. Here, we study the electromagnetic-field enhancement of a tapered optical fibre-tip coated with gold nanoparticles (AuNPs) using finite-element simulations. We investigate the electric-field enhancement associated with metallic NPs and study the effect of parameters such as tip-aperture radius, cone angle, nanoparticle size and gaps between them. Our study provides an understanding of the design and application of metal-nanoparticle-coated optical-fibre-tip probes for SERS. The approach of using fibre-coupled delivery adds flexibility and simplifies the system requirements in SERS, making it suitable for cellular imaging and mapping bio-interfaces.

Impedance-based sensor for potassium ions

A conductometric sensor for potassium ions in solution is presented. Interdigitated, planar gold electrodes were coated with a potassium-selective polymer membrane composed of a poly(vinyl chloride) matrix with about 65 wt% of plasticiser and 2-5 wt% of a potassium-selective ionophore. The impedance of the membrane was measured, using the electrodes as a transducer, and related to the concentration of potassium in a sample solution in contact with the membrane. Sensitivity was optimised by varying the sensor components, and selectivity for potassium over sodium was also shown. The resulting devices are compact, miniature, robust sensors which, by means of impedance measurements, eliminate the need for a reference electrode. The sensor was tested for potassium concentration changes of 2 mM across the clinically relevant range of 2.7-18.7 mM.