Gold nanoparticles were deposited onto a silicon substrate using electroless deposition. The process was optimized by adjusting the deposition time, the temperature of the plating solution, the amount of time that the silicon was exposed to hydrofluoric acid, and the concentration of the plating solution. The nanoparticles deposited on the silicon were characterized using scanning electron microscopy. The optimized electroless deposition process was then used to modify the surface of silicon solar cells with gold nanoparticles for enhanced power generation. Spectral response and I-V curve tests were performed on the modified solar cells to quantify the enhancements. The modified surfaces of the silicon solar cells were characterized by scanning electron microscopy and reflectance measurements. The electroless deposition process was also used to generate nanostructures for surface-enhanced Raman scattering (SERS). A template-nanohole array was fabricated on silicon by focused ion beam milling. Gold nanoparticles were deposited in the holes of the template, resulting in interesting gold-nanodoughnut structures. The gold nanodoughnuts were examined by scanning electron microscopy, and their potential as SERS substrates were tested using Rhodamine 6G as a molecular probe under 633 nm laser excitation. / Graduate / 0494 / 0485 / mmillard@uvic.ca

The clinical evaluation of people with possible myocardial infarction (MI) is often limited by atypical symptoms and inconclusive initial electrocardiograms. A recent consensus from the American College of Cardiology has redefined acute MI to include cardiac markers as central to diagnosis. To address this clinical need, a sensitive microfluidic surface-enhanced Raman spectroscopy (SERS) nanochannel-based optical device is being developed for ultimate use as a point-of-care device for the simultaneous measurement of MI blood biomarkers. The device can provide enhancements of the Raman signal of the analyte measured of up to 1013 using a mechanical aggregation technique at the interface of nanofluidic structures enabling repeatable SERS measurements. Specifically in this research iterations of a sensitive, low volume SERS platform technology were designed that provided quantitative information across a specific range. With the SERS platforms studied, not only were SERS enhancements of up to 1013 achieved but also imprecision values of less than 10% across the 10-50 pM range using a ratiometric approach and qualitative detection down to 100 aM was achieved. Beyond assessment of SERS substrates, assay designs were investigated and characterized including, label-free techniques and competitive immunoassay formats. Lastly, detecting the SERS signal of multiplexed reporter molecules was investigated. By identifying the analyte and assay constraints the design and optimization of future assays will be aided using this SERS platform technology.

Biological/biochemistry analyses traditionally require bulky instruments and a great amount of volume of biological/chemical agents, and many procedures have to be performed in certain locations such as medical centers or research institutions. These limitations usually include time delay in testing. The delays may be critical for some aspects such as disease prevention or patient treatment. One solution to this issue is the realization of point-of-care (POC) testings for patients, a domain in public health, meaning that health cares are provided near the sites of patients using well-designed and portable medical devices. Transportation of samples between local and central institutions can therefore be reduced, facilitating early and fast diagnosis. A closely related topic in engineering, lab-on-a-chip (LOC), has been discussed and practiced in recent years. LOC emphasizes integrating several functions of laboratory processes in a small portable device and performing analysis using only a very small amount of sample volume, to achieve low-cost and rapid analysis. From an engineer's point of view, LOC is the strategy to practice the idea of POC testing. This dissertation aimed at exploring the POC potentials of porous membrane-base LOC devices, which can be used to simplify traditional and standard laboratory procedures. In this study, three LOC prototypes are shown and discussed. First the protein sensor incorporating with silica nanofiber membrane, which has shown 32 times more improvement of sensitivity than a conventional technique and a much shorter detection time; secondly the bacteria filter chip that uses a sandwiched aluminum oxide membrane to stabilize the bacteria and monitor the efficacy of antibiotics, which has reduced the test time from 1 day of the traditional methods to 1 hour; the third is the sensor combining microfluidics and silica nanofiber membrane to realize Surface Enhanced Raman Spectroscopy on bio-molecules, which has enhancement factor 10^9 and detection limit down to nanomolar, but simple manufacturing procedures and reduced fabrication cost. These results show the porous-base membrane LOC devices may have potentials in improving and replacing traditional detection methods and eventually be used in POC applications.

Thesis (Ph. D.)--University of Texas at Austin, 1998. / Vita. Includes bibliographical references (leaves 274-296). Available also in a digital version from Dissertation Abstracts.

Thesis (Ph.D.)--Victoria University of Wellington, 2010. / Includes bibliographical references.

Surface-Enhanced Raman Scattering (SERS) has the potential to be a rapid disease diagnostic platform. SERS is a well-known ultrasensitive, label-free method for the detection and identification of molecules at low concentrations. The Raman cross-sections are primarily enhanced by plasmonic effects for molecules close to (< 5 nm) the surface of nanostructured metal substrates. Due to the unique Raman vibration features that provide molecular signatures, we have shown that SERS can provide a rapid (< one hour), label-free, sensitive and specific diagnosis for a number of diseases. This work demonstrates the capability of SERS to be an effective optical diagnostic approach, in particular, for bacterial infectious diseases such as urinary tract infections (UTI) and sexually transmitted diseases (STD), and cancer cell identification. More specifically, this work demonstrates the ability of SERS to distinguish different vegetative bacterial cells with species and strain specificity based on their intrinsic SERS molecular signatures. With the exception of C. trachomatis - the causative agent of chlamydia - whose SERS molecular signatures are found to be aggregated proteins on the cell membrane, all bacterial SERS molecular signatures are due to purine molecules resulting from nucleic acid metabolism as part of the rapid onset of the starvation response of these pathogens. The differences in relative contribution of different purine metabolites for each bacterium gives rise to the SERS strain and species specificity. The ability of SERS to distinguish cancer and normal cells grown in vitro based on changes of SERS spectral feature as a function of time after sample processing is also demonstrated. Furthermore, the difference of spectral features on the gold and silver SERS substrate of the same bacteria can be used as additional attribute for identification. This work demonstrate the potential of SERS platform to provide antibiotic-specific diagnostics in clinical settings within one hour when combined with a portable Raman microscopy instrument, an effective enrichment procedure, multivariate data analysis and an expendable SERS reference library with drug-susceptibility profile for each bacterial strain determined a priori, as well as the ability of SERS platform as a powerful bioanalytical probe for learning about near cell membrane biochemical processes.

Plasmonic nanocrystals have a unique ability to support localized surface plasmon resonances and exhibit rich and intriguing optical properties. Engineering plasmonic nanocrystals can maximize their potentials for specific applications. In this dissertation, we developed three unprecedented Au nanorod-based plasmonic nanocrystals through rational design of the crystal shape and/or composition, and successfully demonstrated their applications in light condensation, photothermal conversion, and surface-enhanced Raman spectroscopy (SERS). The “Au nanorod-Au nanosphere dimer” nanocrystal was synthesized via the ligand-induced asymmetric growth of a Au nanosphere on a Au nanorod. This dimeric nanostructure features an extraordinary broadband optical absorption in the range of 400‒1400nm, and it proved to be an ideal black-body material for light condensation and an efficient solar-light harvester for photothermal conversion. The “Au nanorod (core) @ AuAg alloy (shell)” nanocrystal was built through the epitaxial growth of homogeneously alloyed AuAg shells on Au nanorods by precisely controlled synthesis. The resulting core-shell structured, bimetallic nanorods integrate the merits of the AuAg alloy with the advantages of anisotropic nanorods, exhibiting strong, stable and tunable surface plasmon resonances that are essential for SERS applications in a corrosive environment. The “high-index faceted Au nanorod (core) @ AuPd alloy (shell)” nanocrystal was produced via site-specific epitaxial growth of AuPd alloyed horns at the ends of Au nanorods. The AuPd alloyed horns are bound with high-index side facets, while the Au nanorod concentrates an intensive electric field at each end. This unique configuration unites highly active catalytic sites with strong SERS sites into a single entity and was demonstrated to be ideal for in situ monitoring of Pd-catalyzed reactions by SERS. The synthetic strategies developed here are promising towards the fabrication of novel plasmonic nanocrystals with fascinating properties for nanoplasmonics and nanophotonics.

No description available.

Due to deteriorating water quality and the world’s increasing demand for clean water, the need for cheap, easy and portable techniques to characterize and quantify pollutants in waters is urgent. Hence, surface-enhanced Raman spectroscopy (SERS) have gained considerable attention in this field. Atrazine and bentazon are two of the most occurring pesticides causing pollution in Sweden, and where therefore examined in this study, along with 4-mercaptopyridine (mpy) as a reference molecule. In this project, silver and gold nanoparticles where synthesised and used as SERS substrates for detection of contaminants in water by using a handheld Raman device provided by Serstech AB. Sodium chloride (NaCl) and magnesium sulfate (MgSO4) where used as aggregation agents allowing the nanoparticles to form hot spots. Mpy was detected to 0.5 nM and an enhancement factor of 108 using silver nanoparticles aggregated with NaCl was obtained. No Raman signal was obtained from atrazine nor bentazon using the handheld Raman device with silver nanoparticles aggregated with NaCl. Therefore the Raman cross-section of the probe molecules where investigated using the handheld Raman device and a conventional Raman device. Bentazon was not detectable using the handheld Raman device but detectable using a conventional Raman device. Atrazine was detectable at high concentrations i.e. atrazine powder using the handheld Raman device and detectable at 100 nM using a conventional Raman device. Since bentazon was not detectable with the handheld Raman device, more focus was put on getting a detectable signal from atrazine using the handheld Raman device. Investigation of the adsorption of atrazine and bentazon to the silver nanoparticle surface was performed. Due to the weaker adsorption to the nanoparticle surface, MgSO4 was used aggregation agent instead of NaCl with mpy, atrazine and bentazon. Mpy was detectable using MgSO4 as aggregation agent, atrazine and bentazon was not. Measurements of mpy, atrazine and bentazon without any salt was performed. For these measurements, no detectable signal from neither molecule was obtained, indicating that the formation of hot spots is necessary to obtained a detectable Raman signal. Measurements of mpy and atrazine with gold nanostars where performed. Enhancement factor using the gold nanostars was calculated to 107, and a detectrable signal from mpy was obtained, not from atrazine. Measurements of atrazine and mpy simultaneously was performed, where mpy peaks was observed but no atrazine peaks. The affinity of the probe molecule and the nanoparticle is crucial to obtain a detectable signal. This study inducates that both the chemical enhancement and electromagnetic enhancement are needed to obtain a detectable signal. For that, strongly binding species is necessary. Considering the simplicity of this method and the limited optimization efforts, there is plenty of room for improvements, including different probe molecules and different SERS substrates. With the right conditions, the evaluated technique reveals a promising and accessible method using a commercially available handheld Raman spectrometer for detection and quantification of contaminants in water.

Blood is considered one of the most important types of forensic evidence found at a crime scene. The use of surface-enhanced Raman spectroscopy (SERS) provides a potentially non-destructive and highly sensitive technique for the confirmation of blood and this method can be applied using a portable Raman device with quick sample preparation and processing. Crime scenes are inherently complex and the impact of SERS analysis provides easy use and practical application for in-field sample analysis. SERS is one of the few confirmatory techniques employed for the identification of blood at a crime scene or in the forensic laboratory. This method is able to distinguish between blood and other body fluids by collecting a SERS spectrum from a sample placed on a surface that has been embedded with gold nanoparticles (AuNPs). The AuNPs create an electric field surface enhancement that produces an intense molecular vibrational signal, leading to a SERS enhancement. The SERS enhancement allowed for sensitive blood detection at dilutions greater than 1:10,000. A stain transfer method to the SERS substrate was optimized by extracting dried bloodstains with water, saline, and various acid solutions. Fifty percent aqueous acetic acid solutions was found to be the most efficient in retaining the blood components and releasing the hemoglobin component of blood for detection. The SERS spectrum of blood is a robust signature of hemoglobin that does not significantly change between donors nor over time. Characteristic peaks for the identification of blood are 754, 1513, and 1543 wavenumbers (cm-1), attributed to a pyrrole ring breathing mode (15) and two Cβ-Cβ stretches (11, 38), respectively. These key SERS peaks, high sensitivity, and signal enhancement are favorable when compared to normal Raman spectroscopy. A quick and easy-to-use procedure for on-site sample analysis for the detection of blood on different substrates was developed and applied on a portable Raman device. Various nonporous and porous substrates including glass, ceramic tile, cotton, denim, fleece, nylon, acetate, wool, polyester, wood, and coated wood yielded strong results for identification of bloodstains. In addition, different commercial and in-house SERS substrates were tested to determine effectiveness for the detection and identification of blood. SERS identification of blood for forensic work is a potentially non-destructive and portable tool that can be applied for quick and easy examination of evidence at a crime scene. The high sensitivity and selectivity of SERS provides a robust spectroscopic signature that aids in the confirmation of blood, even when it is not visible to the naked eye. It is a more favorable method when compared to current presumptive and confirmatory tests for blood and can be applied to stains on different SERS substrates and a variety sample surfaces for universal testing.