Optical trapping enables the non-contact manipulation of micro and nanoparticles with extremely high precision. Recent research on integrated optical trapping using the evanescent fields of photonic devices has opened up new opportunities for the manipulation of nano- and microparticles in lab-on-a-chip devices. Considerable interest has emerged for the use of optical microcavities as “sensors-on-a-chip”, due to the possibility for the label-free detection of nanoparticles and molecules with high sensitivity. This dissertation focuses on the demonstration of an on-chip optical manipulation system with multiple functionalities, including trapping, buffering, sorting, and sensing. We demonstrate the optically trapping of polystyrene particles with diameters from 110 nm to 5.6 \(\mu m\) using silicon microrings and photonic crystal cavities. By integrating multiple microrings with different resonant wavelengths, we show that tuning the laser wavelength to the resonance wavelengths of different rings enables trapped particles to be transferred back and forth between the rings in a controllable manner. We term this functionality “buffering”. We furthermore demonstrate an integrated microparticle passive sorting system based on the near-field optical forces exerted by a 3-dB optical power splitter that consists of a slot waveguide and a conventional channel waveguide. In related work, we demonstrate an ultra-compact polarization splitter design leveraging the giant birefringence of silicon-on-insulator slot waveguides to achieve a high extinction ratio over the entire C band. We demonstrate trapping-assisted particle sensing, using the shift in the microcavity resonance induced by the trapped particle. We show that this permits the sensing of proteins via a binding assay approach, in which the presence of green fluorescent protein causes the particles to bind. By detecting the size distribution of particles clusters using the microcavity, we quantitatively detect the GFP concentration. In a complementary approach, we demonstrate a reusable and reconfigurable surface-enhanced Raman scattering (SERS) sensing platform. We use a photonic crystal cavity to trap silver nanoparticles in a controllable manner, and measure SERS from molecules on their surfaces. We anticipate that the on-chip sensing approaches we introduce could lead to various applications in nanotechnology and the environmental and life sciences. / Engineering and Applied Sciences

This thesis explores the use of Raman Spectroscopy to study the battery cathode material LiFePO4. Surface Enhanced Raman Spectroscopy (SERS) was incorporated into the study due to fluorescence that traditionally plagues Raman. By imaging LiFePO4 nanoparticles, an understanding can be gained of the complex chemistry taking place when the material is lithiated and delithiated at the nanoscale level and the phase changes of the material that occur during this process. The use of bimetallic (Au/Ag) SERS substrates allowed for more stable substrates with longer shelf life compared single metal Ag substrates. Further tuning of these substrates can be applied to the ever evolving science of energy storage material technology as a way to track phase changes in the material. / text

A novel lithographic fabrication method is used to fabricate nanopillars arrays of anisotropic Ag and TCO electrodes. Optical and electrical properties of the electrodes including bandgap, free carrier concentration, resistivity and surface plasmon frequency of different electrodes can be tuned by adjusting the dimensions and geometry of the pillars. Given the ability to tune the nonlocal responses of the plasmonic field enhancements, we attempt to determine the nature of the effective refractive index profile within the visible wavelength region for multi-layer hybrid nanostructures. Knowledge of the effective optical constants of the obtained structure is critical for various applications. nanopillars of TCO\Ag core shell structures have been successfully fabricated. The Maxwell-Garnett mixing law has been used to determine the optical constants of the nanostructure based on spectroscopic ellipsometry measurements. Simulated reflection spectra indicate a down shift in the Brewster angle of the pillars resulting from the reduction in the effective refractive index of the nanostructure. Two plasmonic resonances were observed, with one in the visible region and the other in the IR region. Plasmon hybridization model is used to describe the behavior of metal and metal oxide core shell nanostructured electrodes. Different charge density distributions around the pillars determine the plasma frequency which depends on the core and surrounding media dielectric constants. Finite Difference Time Domain (FDTD) simulation of different structures agree well with experiment and help us to understand electric field behavior at different structures with different geometries and dielectric constants. Plasmonic Ag nanopillar arrays are effective substrates for surface enhanced Raman spectroscopy (SERS). An enhancement factor up to 6 orders of magnitude is obtained. Monolayers of C60 is deposited on the Ag nanopillars and the interface of C60/Ag is studied which is important in optoelectronic devices. Electron delocalization between C60 and Ag is confirmed.

The process of forcibly dewetting a solid substrate from a bulk liquid so as to leave a thin residual layer on the surface is referred to as forced dewetting. This novel experimental approach helps to investigate interfacial species by minimizing the interference of the bulk liquid when coupled with spectroscopy. In this work, the scope of liquids investigating using this approach has been expanded from simple fluids to one type of complex fluid, a nematic liquid crystal, 4-n-pentyl-4'-cyanobiphenyl (5CB).In order to better understand the interfacial behavior of the simple fluids, water, chloroform, and n-pentane vapors were adsorbed onto omega-terminated SAM-modifed Ag (11-mercaptoundecanoic acid, 11-mercaptoundenanol, and undecanethiol) surfaces under vapor-saturated conditions. The kinetics of solvent adsorption on each of these surfaces were investigated and the thicknesses of the adsorbed layer were compared to predictions from Lifshitz theory of long-range van der Waals interactions. Although the predicted thicknesses do not match the experimental values for adsorbed films, the predicted thicknesses do match those observed experimentally using forced dewetting. The correlation between these predicted and observed thicknesses implies that residual film formation under the conditions of forced dewetting used in this laboratory is dictated by interfacial forces alone.The surface adsorption behavior of 5CB was investigated using surface-enhanced Raman spectroscopy with the aid of localized surface plasmon resonances-surface plasmon polaritron coupling. The results clearly indicate that 5CB is adsorbed to smooth Ag surface in a facial orientation with pi-d orbital interaction suggested.Finally, forced dewetting studies of bare, -NH2-temintaed SAM, and -CH3-temintaed SAM modified-SiO2 substrates from 5CB were undertaken. Residual layer thicknesses were monitored as a function of substrate velocity. The transition from the regime in which interfacial forces dictate residual layer thickness to the regime in which fluid dynamic forces dictate thickness was observed for the first time and was evaluated in terms of the average 5CB director orientation. Unlike simple fluids, 5CB has strong interfacial interactions from surface anchoring depending on the chemical nature of the substrate, which makes the residual layer thicknesses at least 100 times larger than observed in simple fluids.

Two experiments explore the application of plasmonic nanoparticles to cellular pathology. The first devised a platform by which gold-silver nanoparticles act as differentiable labels for cell surface receptors under dark field imaging. By conjugating particles of various constitutions with receptor-targeting antibodies, particles scatter characteristically according to their plasmon peak. The second experiment programmed receptor placement via the patterning of two substrates and used the binding of SERS nanoparticles to explore the quantification of such targets at high-density. On one substrate, anchor pairs established receptors at specified distances in order to define the relationship between scattering intensity and the distance between SERS particles. On the second, anchor regions are filled with increasing densities of receptors and the particle-saturated substrates are probed to relate scattering intensity to particle density. This should discover the density-threshold between linear and non-linear scattering and inform the quantification of particles in the exponential density regime.

Two experiments explore the application of plasmonic nanoparticles to cellular pathology. The first devised a platform by which gold-silver nanoparticles act as differentiable labels for cell surface receptors under dark field imaging. By conjugating particles of various constitutions with receptor-targeting antibodies, particles scatter characteristically according to their plasmon peak. The second experiment programmed receptor placement via the patterning of two substrates and used the binding of SERS nanoparticles to explore the quantification of such targets at high-density. On one substrate, anchor pairs established receptors at specified distances in order to define the relationship between scattering intensity and the distance between SERS particles. On the second, anchor regions are filled with increasing densities of receptors and the particle-saturated substrates are probed to relate scattering intensity to particle density. This should discover the density-threshold between linear and non-linear scattering and inform the quantification of particles in the exponential density regime.

To truly realize and exploit the extremely powerful information given from surface-enhanced Raman scattering (SERS) spectroscopy, it is critical to develop an understanding of how to design highly sensitive and selective substrates, produce specific and label-free spectra of target analytes, and fabricate long-lasting and in-the-field ready platforms for trace detection applications. The study presented in this dissertation investigated the application of two- and three-dimensional substrates composed of highly-ordered metal nanostructures. These systems were designed to specifically detect target analytes that would enable the trace, label-free, and real-time detection of chemicals and biomolecules. Specifically, this work provides new insight into the required properties for maximizing electromagnetic and chemical Raman enhancement in three-dimensional porous alumina substrates by designing metal nanostructure shape, density, aggregated state, and most importantly aligning the substrate pore size with the excitation wavelength used for plasmonic enhancement leading to the ppb detection of vapor phase hazardous chemicals. A new micropatterned silver nanoparticle substrate fabricated via soft lithography with specific functionalization was developed, which allows the simultaneous analyte and background detection for trace concentrations of the target biomolecule, immunoglobulin G. Also, a novel functionalized SERS hot spot fabrication technique, which utilizes highly specific aptamers as both the mediator for electrostatic assembly of gold nanoframe dimers as well as the biorecognition element for the target, riboflavin, to properly locate the tethered biomolecule within the enhanced region for trace detection, was demonstrated. We suggest that the understanding of SERS phenomena that occur at the interface of nanostructures and target molecules combined with the active functionalization and organization of metal nanostructures and trace detection of analytes discussed in this study can provide important insight for addressing some of the challenges facing the field of SERS sensor design such as high sensitivity and selectivity, reliable and repeatable label-free identification of spectral peaks, and the well-controlled assembly of functional metal nanostructures. This research will have a direct impact on the future application of SERS sensors for the trace detection of target species in chemical, environmental, and biomedical fields through the development of specific design criteria and fabrication processes.

<p>There is an urgent need to develop practical and effective systems to detect diseases, such as cancer, infectious diseases and cardiovascular diseases.</p><p>Nanotechnology is a new, maturing field that employs specialized techniques to detect and diagnose infectious diseases. To this end, there have been a wealth of techniques that have shown promising results, with fluorescence and surface-enhanced Raman scattering being two important optical modalities that are utilized extensively. The progress in this specialized niche is staggering and many research groups in academia, as well as governmental and corporate organizations, are avidly pursuing leads which have demonstrated optimistic results.</p><p>Although much fundamental science is still in the pipeline under the guise of both ex-vivo and in-vivo testing, it is ultimately necessary to develop diagnostic devices that are able to impact the greatest number of people possible, in a given population. Such systems make state-of-the-art technology platforms accessible to a large population pool. The development of such technologies provide opportunities for better screening of at-risk patients, more efficient monitoring of disease treatment and tighter surveillance of recurrence. These technologies are also intrinsically low cost, facilitating the large scale screening for disease prevention.</p><p>Fluorescence has long been established as the optical transduction method of choice, because of its wealth of available dyes, simple optical system, and long heritage from pathology. The intrinsic limitations of this technique, however, have given rise to a complementary, and more recent, modality: surface-enhanced Raman scattering (SERS). There has been an explosive interest in this technique for the wealth of information it provides without compromising its narrow spectral width.</p><p>A number of novel studies and advances are successively presented throughout this study, which culminate to an advanced SERS-based platform in the last chapter.</p><p>The finite element method algorithm is critically evaluated against analytical solutions as a potential tool for the numerical modeling of complex, three-dimensional nanostructured geometries. When compared to both the multipole expansion for plane wave excitation, and the Mie-theory with dipole excitation, this algorithm proves to provide more spatially and spectrally accurate results than its alternative, the finite-difference time domain algorithm.</p><p>Extensive studies, both experimental and numerical, on the gold nanostar and Nanowave substrate for determining their potential as SERS substrates, constituted the second part of this thesis. The tuning of the gold nanostar geometry and plasmon band to optimize its SERS properties were demonstrated, and significant 3-D modeling was performed on this exotic shape to correlate its geometry to the solution's exhibited plasmon band peak position and large FWHM. The Nanowave substrate was experimentally revived and its periodic array of E-field hotspots, which was until recently only inferred, was finally demonstrated via complex modeling.</p><p>Novel gold- and silver- coated magnetic nanoparticles were synthesized after extensive tinkering of the experimental conditions. These plasmonics-active magnetic nanoparticles were small and displayed high stability, were easy to synthesize, exhibited a homogeneous distribution, and were easily functionalizable with Raman dye or thiolated molecules.</p><p>Finally, bowtie-shaped cobalt micromagnets were designed, modeled and fabricated to allow the controllable and reproducible concentrating of plasmonics-active magnetic nanoparticles. The external application of an oscillating magnetic field was accompanied by a cycling of the detected SERS signal as the nanoparticles were concentrated and re-dispersed in the laser focal spot. This constituted the first demonstration of magnetic-field modulated SERS; its simplicity of design, fabrication and operation opens doors for its integration into diagnostic devices, such as a digital microfluidic platform, which is another novel concept that is touched upon as the final section of this thesis.</p> / Dissertation

The study of interfacial processes has long been of interest to scientists. The properties of a material are generally governed by the characteristics of its surface, thus the development of surface specific experimental methods are always of great importance to the scientific community. This thesis presents the results of the spectroelectrochemical characterization of a cysteine-Ag adsorbate-substrate system. The system was probed using two spectroelectrochemical methods. The chiral effect which cysteine has on the electronic structure of the Ag substrate was studied by performing in situ second harmonic generation optical rotatory dispersion (SHG-ORD) experiments. Rotation angles (phi) obtained indicated that the overlayers of adsorbed cysteine molecules imprinted the electronic structure of the Ag with their inherent optical activity. Results also indicate that there are one or more other processes which are contributing to the observed phi values. The second half of this thesis discusses the effect that pH and applied potential have on the adsorption geometry of L-cysteine on polycrystalline Ag as studied by surface enhanced Raman scattering (SERS). Results obtained under neutral and acidic conditions showed that the coadsorption of Cl- plays an important role in the adsorption geometry. At more positive potentials Cl- will be coadsorbed on the Ag surface with cysteine. The Cl- helps to stabilize the adsorbed cysteine via interactions with the protonated amino group. Consequently, as the potential is changed in the cathodic direction the Cl- becomes desorbed from the surface, resulting in changing intensities observed in the SERS spectra. Tracking of which peaks, and consequently vibrational modes, are changing and in which way allowed for a qualitative determination of the adsorption geometry as a function of both pH and potential.

<p>The advancement in nanotechnology creates a new perspective on future medicine. With more and more understanding on controlling the functional behavior of the nanoplatform, scientists nowadays are aiming to improve the health care system by offering personalized medicine through nanotechnology. Lots of emphasis have been placed on a promising field called theranostics, which integrate imaging and therapeutic functions into one, that not only offers monitoring and imaging of the biological process, but also provides diagnosis and drug delivery simultaneously. Plasmonic gold nanostars, because of its anisotropic geometry and unique plasmonic property, have become one of the most anticipated nanoplatform in the field of nanotheranostics, aiming to achieve superior plasmonic properties for biomedical applications. The work herein will provide an introduction to the related field on plasmonics, nanobiophotonics and nanotheranostics. A facile plasmon-tunable surfactant-free nanostars synthesis method is described followed by an extensive characterization both computationally and experimentally. Its superior plasmon behavior on two-photon photoluminescence imaging and surface-enhanced Raman scattering detection are demonstrated both in cells and in animals. Therapeutic function assessment is carried out both as drug carriers (photodynamic therapy) and as endogenous stimulus responsive agents (photothermal therapy). Finally, the nanostars' cellular uptake mechanism is investigated based on nanostars' endogenous contrast; an enhanced photothermal therapy is achieved using an ultralow irradiance that has ever published. With nanostars being a novel and powerful theranostic agent, the potentials implication lies in the study of their pharmacokinetics, targeted delivery, diagnostic imaging, and toxicity.</p> / Dissertation