Molecular fluorophores and semiconductor quantum dots (QDs) have been used as cellular imaging agents for biomedical research, but each class has challenges associated with their use, including poor photostability or toxicity. Silicon is a semiconductor material that is inexpensive and relatively environmental benign in comparison to heavy metal-containing quantum dots. Thus, red-emitting silicon nanoparticles (Si NPs) are desirable to prepare for cellular imaging application to be used in place of more toxic QDs. However, Si NPs currently suffer poorly understood photoinstability, and furthermore, the origin of the PL remains under debate. This dissertation first describes the use of diatomaceous earth as a new precursor for the synthesis of photoluminescent Si NPs. Second, the stabilization of red PL from Si NPs in aqueous solution via micellar encapsulation is reported. Thirdly, red to blue PL conversion of decane-terminated Si NPs in alcohol dispersions is described and the origins (i.e., color centers) of the emission events were studied with a comprehensive characterization suite including FT-IR, UV-vis, photoluminescence excitation, and time-resolved photoluminescence spectroscopies in order to determine size or chemical changes underlying the PL color change. In this study, the red and blue PL was determined to result from intrinsic and surface states, respectively. Lastly, we determined that the blue emission band assigned to a surface state can be introduced by base addition in originally red-emitting silicon nanoparticles, and that red PL can be restored by subsequent acid addition. This experimentally demonstrates blue PL is surface state related and can overcome the intrinsic state related excitonic recombination pathway in red PL event. Based on all the data collected and analyzed, we present a simple energy level diagram detailing the multiple origins of Si NP PL, which are related to both size and surface chemistry.

Ruthenium oxide (RuO2) nanorods are an emergent technology in nanostructure devices. As the physical size of electronics approaches a critical lower limit, alternative solutions to further device miniaturization are currently under investigation. Thin-film nanorod growth is an interesting technology, being investigated for use in wireless communications, sensor systems, and alternative energy applications. In this investigation, self-assembled RuO2 nanorods are grown on a variety of substrates via a high density plasma, reactive sputtering process. Nanorods have been found to grow on substrates that form native oxide layers when exposed to air, namely silicon, aluminum, and titanium. Samples were analyzed with Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) techniques. Conductive Atomic Force Microscopy (C-AFM) measurements were performed on single nanorods to characterize structure and electrical conductivity. The C-AFM probe tip is placed on a single nanorod and I-V characteristics are measured, potentially exhibiting rectifying capabilities. An analysis of these results using fundamental semiconductor physics principles is presented. Experimental data for silicon substrates was most closely approximated by the Simmons model for direct electron tunneling, whereas that of aluminum substrates was well approximated by Fowler-Nordheim tunneling. The native oxide of titanium is regarded as a semiconductor rather than an insulator and its ability to function as a rectifier is not strong. An electronic model for these nanorods is described herein.

Modification of nanostructures via laser processing is of great interest for a wide range of applications such as aerospace and the storage of nuclear waste. The primary goal of this dissertation is to improve the understanding of nanostructures through two primary routes: the modification of aerogels and pulsed laser ablation in ethanol. A new class of materials, patterned aerogels, was fabricated by photopolymerizing selected regions of homogeneous aerogel monoliths using visible light. The characterization and fabrication of functionally graded, cellular and compositionally anisotropic aerogels and ceramics is discussed. Visible light was utilized due to it’s minimal absorption and scattering by organic molecules and oxide nanoparticles within wet gels. This allowed for the fabrication of deeply penetrating, well resolved patterns. Similarly, nanoporous monoliths with a typical aerogel core and a mechanically robust exterior ceramic layer were synthesized from silica aerogels cross-linked with polyacrylonitrile. Simple variations of the exposure geometry allowed fabrication of a wide variety of anisotropic materials without requiring layering or bonding. Nanoparticle solutions were prepared by laser ablation of metal foils (Fe and Mo) in ethanol. Ablation of Fe generated Fe3O4 and Fe3C nanoparticles which were superparamagnetic with a saturation magnetization Ms = 124 emu/g. Zero field cooled (ZFC) measurements collected at an applied field of 50 Oe displayed a maximum magnetic susceptibility at 120 K with a broad distribution. Field cooled (FC) measurements showed a thermal hysteresis indicative of temperature dependent magnetic viscosity. Pulsed laser ablation of a Mo foil in ethanol generated inhomogeneous nanoparticles where Mo and MoC coexisted within the same aggregate. Formation of these unique nanoparticles is likely due to phase separation that occurs when a high temperature carbide phase cools after the laser pulse terminates. Similarly, magnetic nanoparticle suspensions were generated by pulsed laser ablation of Fe and Mo in ethanol. The formation of several carbide phases with no discernable alloy formation was seen. A decrease in magnetization with a decrease in Fe concentration was seen which was reconciled with the decreased Fe content in the system. However, at Fe concentrations below ~ 40%, an increase in Ms and Hc was observed which was reconciled with the disappearance of the ε–Fe3C. TEM analysis showed the formation of core-shell nanoparticles and Energy Filtered TEM showed the distribution of Fe-based nanoparticles in the suspensions.

Electrospinning is a process by which polymer fibers can be produced using an electrostatically driven fluid jet. Electrospun fibers can be produced at the micro- or nano-scale and are, therefore, very promising for air filtration applications. However, because electrospun fibers are electrically charged, it is difficult to control the morphology of filtration media. Fiber size, alignment and uniformity are very important factors that affect filter performance. The focus of this project is to understand the relationship between filter morphology and performance and to develop new methods to create filtration media with optimum morphology. This study is divided into three focus areas: unimodal and bimodal microscale fibrous media with aligned, orthogonal and random fiber orientations; unimodal and bimodal nanoscale fibers in random orientations; bimodal micrometer and nanometer fiber media with orthogonally aligned orientations. The results indicate that the most efficient filters, which are those with the highest ratio of particle collection efficiency divided by pressure drop, can be obtained through fabricating filters in orthogonal layers of aligned fibers with two different fiber diameters. Moreover, our results show that increasing the number of layers increases the performance of orthogonally layered fibers. Also, controlling fiber spacing in orthogonally layered micrometer fiber media can be an alternative way to study the filtration performance. Finally, such coatings presented throughout this research study can be designed and placed up-stream, down-stream, and/or in between conventional filters.

Recent progress and a coordinated national research program have brought considerable effort to bear on the synthesis and application of carbon nanostructures for field emission. at the College of William and Mary, we have developed field emission arrays of vertically oriented graphene (carbon nanosheets, CNS) that have demonstrated promising cathode performance, delivering emission current densities up to 2 mA/mm2 and cathode lifetime >800 hours. The work function (&phis;) of CNS and other carbonaceous cathode materials has been reported to be &phis;∼4.5-5.1 eV. The application of low work function thin films can achieve several orders of magnitude enhancement of field emission.;Initially, the intrinsic CNS field emission was studied. The mean height of the CNS was observed to decrease as a function of operating time at a rate of ∼0.05 nm/h (I 1∼40 muA/mm2). The erosion mechanism was studied using a unique UHV diode design which allowed line-of-site assessment from the field emission region in the diode to the ion source of a mass spectrometer. The erosion of CNS was found to occur by impingement of hyperthermal H and O neutrals and ions generated at the surface oxide complex of the Cu anode by electron stimulated desorption. Techniques for minimizing this erosion are presented.;The Mo2C (&phis;∼3.7 eV) beading on CNS at previously reported carbide formation temperatures of ∼800??C was circumvented by physical vapor deposition of Mo and vacuum annealing at ∼300??C which resulted in a conformal Mo2C coating and stable field emission of 1∼50 muA/mm2. For a given applied field, the emission current was >102 greater than uncoated CNS.;ThO2 thin film coatings were presumed to be even more promising because of a reported work function of &phis; ∼2.6 eV. The fundamental behavior of the initial oxidation of polycrystalline Th was studied in UHV (p<1x10-11 Torr), followed by studies of thin film coatings on Ir and thermionic emission characteristics. Although a work function of 3.3 eV was determined by a RichardDushman plot, activation of the thin film was not achieved at T<1700??C. Rather, the deposited ThO2 film decomposed, surface diffused and aggregated into stable ThO2(111) crystallites.;Thin film ThO2 coatings deposited on CNS initially demonstrated excellent field emission (up to ∼2 muA/mm2) and apparently activated spontaneously without significant thermal energy. Fowler-Nordheim plots suggested a work function of &phis; ∼2.6 eV. Undesired beading and ThO2 surface diffusion away from active emission sites resulted in rapidly deteriorating performance at higher field emission currents. Techniques that should provide a more stable ThO2/CNS conformal coating are presented.;The impact of thin films of Mo2C and ThO2on the magnitude of field emission from carbon nanosheets (CNS) was substantial. For a given field emission current density, J ∼2 muA/mm 2, the necessary applied field for uncoated CNS was ∼12 V/mum, but only ∼8 V/mum when coated with Mo2C (&phis;∼3.7 eV) and ∼5 V/mum when coated with ThO2 (&phis;∼2,6 eV). The mechanism for enhanced emission and the stability of the coatings are discussed, with special focus on the activation of ThO2 thin films. The major limitation observed in these studies has been the difference in surface energy of the graphene and the coatings which resulted in a tendency for the films to bead and separate from active emission sites at elevated currents. Suggested techniques to prevent this unwanted surface diffusion are presented.

While silicon has long been utilized for its electronic properties, its use as an optical material has largely been limited due to the poor efficiency of interband transitions. However, discovery of visible photoluminescence (PL) from nanocrystalline silicon in 1990 triggered many ensuing research efforts to optimize PL from nanocrystalline silicon for optical applications. Currently, use of photoluminescent silicon nanoparticles (Si NPs) is commercially limited by: 1) the instability of the energy and intensity of the PL, and 2) the low quantum yield of interband PL from Si NPs. Herein, red-emitting, hydrogen-passivated silicon nanoparticles (H-Si NPs) were synthesized by thermally-induced disproportionation of a HSiCl3-derived (HSiO1.5)n polymer. The H-Si NPs produced by this method were then subjected to various chemical and physical environments to assess the long-term stability of the optical properties as a function of changing surface composition. This dissertation is intended to elucidate correlations between the reported PL instability and the observed changes in the Si NP surface chemistry over time and as a function of environment. First, the stability of the H-Si NP surface at slightly elevated temperatures towards reactivity with a simple alkane was probed. The H-Si NPs were observed by FT-IR spectroscopy to undergo partial hydrosilylation upon heating in refluxing hexane, in addition to varying degrees of surface oxidation. The unexpected reactivity of the Si surface in n-hexane supports the unstable nature of the H-Si NP surface, and furthermore implicates the presence of highly-reactive Si radicals on the surfaces of the Si NPs. We propose that reaction of alkene impurities with the Si surface radicals is largely responsible for the observed surface alkylation. However, we also present an alternate mechanism by which Si surface radicals could react with alkanes to result in alkylation of the surface. Next, the energy and intensity stability of the interband PL from H-Si NPs in the presence of a radical trap was probed. Upon addition of (2,2,6,6,-tetramethyl-piperidin-1-yl)oxyl (TEMPO), the energy and intensity of the interband transition was observed to change over time, dependent on the reaction conditions. First, when the reaction occurred at 4ºC with minimal light exposure, the interband transition exhibited a gradual hypsochromic shift to between 595 nm and 655 nm, versus the λmax of the original low energy emission peak at 700 nm, depending on the amount of TEMPO in the sample. Second, when the reaction proceeded at room temperature with frequent exposure to 360 nm irradiation, the original interband transition at 660 nm was quenched while a new peak at 575 nm developed. Based on all the data collected and analyzed, we assign the 595 -- 655 nm transition as due to interband exciton recombination from Si NPs with reduced diameters relative to the original Si NPs. We furthermore assign the 575 nm transition as due to an oxide-related defect state resulting from rapid oxidation of photo-excited Si NPs.

Photovoltaic (PV) devices based on PbS quantum dot (QD) solids demonstrate high photon-to-electron conversion yields. However, record power conversion efficiencies remain limited mainly due to bulk and interfacial defects in the light absorbing material (QD solids). Interfacial defects can be formed when a semiconductor, such as QD solid, is contacted by another material and may predetermine the semiconductor/metal or semiconductor/metal-oxide junction properties. The objective of the work described in this dissertation was set to explore whether electrochemical contacting using liquid electrolytes can provide sufficient means of contacting the QD solids to investigate their PV performance without introducing the unwanted interfacial defects. I have initially focused on optimizing processing conditions for efficient QD solids deposition and studied their photovoltaic properties in a standardized solid-state, depleted heterojunction solar cell configuration. Further, a liquid contacting method was developed to study the relationship between photovoltages of QD solids and the energetics (e.g. reduction potentials) of the liquid contacting media. This electrochemical contacting of PbS QD solids was achieved by using anhydrous liquid electrolytes containing fast, non-coordinating, outer-sphere redox couples. Depending on the energetics of a redox couple, both rectifying and non-rectifying (Ohmic) PbS QD solid/electrolyte junctions were successfully formed with both p- and n-type QD solids. Furthermore, application of the liquid solution contacting method in studies of the PbS QD solids has unprecedentedly demonstrated that an ideal behavior of the photovoltage changes with respect to the changes in the energetics of the contacting media can be achieved. This fact supports the initially proposed hypothesis that such liquid contacting method will not introduce surface defects to the studied QD materials, allowing for their intrinsic properties to be better understood. The applicability of this method to both p- and n- type QD solids was demonstrated. Finally, a better understanding of the relationships between the surface and ligand chemistries of both p- and n-type QD solids and their photovoltaic properties was possible via applications of such method in conjunction with XPS and UPS studies.

An atomic force microscopy beam-like cantilever is combined with an electrical tuning fork to form a shear force probe that is capable of generating an acoustic response from the mesoscopic water layer under ambient conditions while simultaneously monitoring force applied in the normal direction and the electrical response of the tuning fork shear force probe. Two shear force probes were designed and fabricated. A gallium ion beam was used to deposit carbon as a probe material. The carbon probe material was characterized using energy dispersive x-ray spectroscopy and scanning transmission electron microscopy. The probes were experimentally validated by demonstrating the ability to generate and observe acoustic response of the mesoscopic water layer.

Palladium-catalyzed carbon-carbon cross-coupling reactions have emerged a broadly useful, selective and widely applicable method to synthesize pharmaceutical active ingredients. As currently practiced in the pharmaceutical industry, homogeneous Pd catalysts are typically used in cross-coupling reactions. The rational development of heterogeneous catalysts for cross-coupling reactions is critical for overcoming the major drawbacks of homogeneous catalysis including difficulties in the separation, purification, and quality control process in drug production. In order to apply heterogeneous catalysis to flow reactors that may overcome this limitation, the catalyst must be strongly bound to a support, highly stable with respect to leaching, and highly active. While the primary role of supports in catalysis has been to anchor metal particles to prevent sintering and leaching, supports can also activate catalytic processes. In this study, by using a xi combined theoretical and experimental method, we probed the effect of graphene as support in the complex reaction cycle of Suzuki reactions. The density functional theory study provides a fundamental understanding of how a graphene support strongly binds the Pd nanoparticles and act as both an efficient charge donor and acceptor in oxidation and reduction reaction steps. Theoretical investigations prove that the Pd-graphene interaction promotes electron flow between the metal cluster and the defected graphene to reduce reaction barrier. The ability for graphene to both accept and donate charge makes graphene an unusually suitable support for multi-step catalytic processes that involve both oxidation and reduction steps. The computer-aided catalyst design with the atomic precise accuracy demonstrates the Pd/graphene catalyst can be further optimized and the first-row transition metal nanoparticles have great potential to replace Pd to catalyze the Suzuki reaction. The corresponding experimental study shows that the method to immobilize the Pd nanoparticles on the graphene is crucial to increasing the reactivity and stability of the resulted catalyst. A comparison of the activation energy and turn over frequency for a series of supported and homogeneous catalysts indicates that exposing palladium-graphene to defect inducing microwave radiation results in dramatically lower activation energies and higher turnover frequencies. Furthermore, the heterogeneity tests demonstrate the Suzuki reactions are carried out on the surface of the immobilized Pd nanoparticle agreeing with the theoretical results. A method to engineer the 2-D graphene support to a 3-D structure to minimize the re-stacking and agglomeration of the graphene lattice will also be introduced in this study.

Respiratory Syncytial Virus (RSV) is a potentially life-threatening respiratory pathogen that infects approximately 64 million children and immunocompromised adults globally per year. Currently, there is a need for prophylactic and therapeutic approaches effective against primary and secondary RSV infections. This project focuses on the development of a simple, smart, and scalable anti-RSV nanotherapeutic that combines novel cellular antiviral defense mechanisms targeting the inhibition of viral fusion and replication. An ICAM-1 targeted liposomal nanocarrier will be synthesized and coated with a layer of chitosan containing the anti-fusion HR2-D peptide as an extracellular defense mechanism. Additionally, chitosan complexed to dual expressing short hairpin RNA (shRNA) recombinant plasmids will be encapsulated within the nanocarrier, and provide an intracellular defense mechanism that will interfere with the expression of the NS1 and P proteins. In combination, both defense mechanisms are expected to induce a synergistic anti-RSV effect that will surpass those of conventional therapeutics. Through this research, the NS1 and P containing plasmid (pSH-NS1-P) was cloned, and the nanotherapeutic was successfully synthesized. Based on the acquired results, pSH-NS1-P was shown to express anti-RSV effects, and it was also concluded that both inserts were producing active shRNA. Additionally, the anti-RSV efficiency of HR2-D was confirmed. Overall, this research will lead to development of a dual-mechanistic anti-viral nanotherapeutic.