<p> We have developed a high density lipoprotein (HDL)-based platform for transport and delivery of hydrophobic gold nanoparticles (AuNP). The ability of apolipoprotein E3 (apoE3) to act as a ligand for the low-density lipoprotein receptor (LDLr) was exploited to gain entry of HDL with AuNP into glioblastoma cells. AuNP of 3, 10 and 17 nm diameter, the latter two synthesized by phase transfer process, were solubilized by integration into reconstituted HDL (rHDL). Absorption spectroscopy indicated the presence of stable particles with signature surface plasmon bands, while electron microscopy revealed AuNP embedded in rHDL core. The rHDL-AuNP complexes displayed robust binding to the LDLr, were internalized by the glioblastoma cells, and appeared as aggregated AuNP in the endosomal-lysosomal compartments. The rHDL-AuNP generated little cytotoxicity and were able to cross the blood brain barrier. The findings bear significance since they offer an effective means of delivering AuNP across tumor cell membrane.</p><p>

<p> Carbon nanotubes (CNTs) are materials with significant potential applications due to their desirable mechanical and electronic properties, which can both vary based on their structure. Electronic applications for CNTs are still few and not widely available, mainly due to the difficulty in the control of fabrication. Carbon nanotubes are grown in batches, but despite many years of research from their first discovery in 1991, there are still many unanswered questions regarding how to control the structure of CNTs. This work attempts to bridge some of the gap between question and answer by focusing on the catalyst particle used in common CNT growth procedures. Ostwald ripening studies on iron nanoparticles are performed in an attempt to link catalyst morphology during growth and CNT chirality (the structure aspect of a nanotube that determines its electrical properties). These results suggest that inert gas dynamics play a critical role on the catalyst morphology during CNT growth. A novel method for CNT catalyst activation by substrate manipulation is presented. Results of this study build upon prior knowledge of the role of the chemistry of the substrate supporting CNT catalysts. By bombarding sapphire, a substrate known to not support CNT growth, with an argon ion beam, the substrate is transformed into an active CNT growth support by modifying both the structure and chemistry of the sapphire surface. Finally, catalyst formation is studied with transmission electron microscopy by depositing an iron gradient film in order to identify a potential critical catalyst size and morphology for CNT growth. A relationship between catalyst size and morphology has been identified that adds evidence to the hypothesis that a catalysts activity is determined by its size and ability to properly reduce.</p>

<p> The research presented herein exploits the terminal phosphate group on single stranded DNA molecules for direct immobilization to surfaces utilized in semiconductor device fabrication with the end goal of transistor based DNA sensors. As a demonstration of the feasibility of this immobilization strategy DNA immobilization to a variety of surfaces was evaluated for usefulness in biosensor applications. It was determined that DNA can be directly immobilized to a variety of semiconductor surfaces through the terminal phosphate group. Further, this immobilization allows for the hybridization of the immobilized DNA to complementary target in solution. The immobilization of DNA to hafnium dioxide was particularly of interest due to its use in modern nanoelectronics manufacturing. The interactions between DNA and various forms of hafnium dioxide were thoroughly studied in order to understand and optimize the immobilization of DNA to hafnium dioxide for field effect transistor (FET) based DNA sensors. A secondary immobilization route of DNA to a subset of hafnium dioxide surfaces was identified and we have shown that this mechanism is through the nitrogenous bases of the probe molecule. Finally, a novel FET sensor was designed and developed which incorporated III-V materials and hafnium dioxide. The development of the sensor was carried out with the long term goal of determining if FET DNA sensors would have increased sensitivity if fabricated with: 1) the direct immobilization of probe DNA; 2) hafnium dioxide gate dielectric; and/or 3) III-V FET structure. Here, we demonstrate a proof-of-concept device that incorporates these three features and is capable of detecting DNA in solution, DNA immobilized to the surface, and DNA hybridization events.</p>

<p> Recently, there has been growing interest in using transition metals (TM) for catalytic and electromagnetic applications, due to the ability of TMs to form stable compounds in multiple oxidation states. In this research, the focus has been on the synthesis and characterization of carbon-supported TM nanoparticles (NPs), specifically palladium (Pd) and gold (Au) NPs, for catalytic applications, and transition metal oxides (TMO) NPs, specifically Fe₃O₄ NPs for electromagnetic applications. Carbon supports have several advantages, such as enabling even distribution of particles, offering large specific surface area with excellent electron conductivity, and relative chemical inertness. </p><p> In this dissertation, for catalytic applications, emphasis was on removal of trichloroethylene (TCE) from groundwater. For this application, carbon-supported Pd/Au NP catalysts were developed. Pd was chosen because it is more active, stable and selective for desired end-products, and Au has shown to be a good promotor of Pd&rsquo;s catalytic activity. Often, commercially available Pd-based catalysts are made using harsh chemicals, which can be harmful to the environment. Here, an environmentally friendly process with aspects of green chemistry was developed to produce carbon-supported Pd/Au NP catalysts. This process uses a combination of sonochemistry and solvothermal syntheses. The carefully designed carbon-supported Pd/Au NP catalyst material was systematically characterized, tested against TCE, and optimized for increased rate of removal of TCE. Electron microscopy and spectroscopy techniques were used to study the material including structure, configuration and oxidative state. The Pd/Au NPs were found mainly to form clusters with an aggregate-Pd_ShellAu_Core structure. Using state-of-the-art direct detection with electron energy loss spectroscopy, the Pd NPs were found to have an oxidative state of zero (0). The formation of the catalyst material was studied in detail by varying several synthesis parameters including type of solvent, sonication time, synthesis temperature etc. The most optimized catalyst was found remove TCE at double the rate of corresponding commercial Pd-based catalysts in a hydrogen headspace. This material was found to catalyze the removal of TCE via traditional hydrodehalogenation and shows promise for the removal of other contaminants such as trichloropropane (TCP), carbon tetrachloride (CT). </p><p> This green approach to make and optimize TM materials for specific applications was extended to TMOs, specifically magnetite (Fe₃O₄) and further developed for the application of electromagnetism. As catalysts, Fe₃O₄ is used for removal of <i>p</i>-nitrophenol from water. However, since the carbon-supported Pd/Au material system was developed and optimized for catalysis, here, carbon-supported Fe₃O₄ NPs were developed for electromagnetic applications. There has been growing interest in tuning the magnetic properties of materials at room temperature with the use of external electric fields, for long-term applications in data storage and spintronic devices. While a complete reversible change of material properties has not yet been achieved, some success in partial switching has been achieved using multiferroic spinel structures such as Fe₃O₄. These materials experience a change in magnetic moment at room temperature when exposed to the electric fields generated by electrochemical cells such as lithium ion batteries (LIBs) and supercapacitors (SC). In the past, a 1% reversible change was observed in Fe₃O₄ using LIBs. Here, building on the developments from previous material system, Fe₃O₄ NPs were directly hybridized onto the graphene support in order to increase the observable change in magnetic moment. The material was systematically designed and tested for this application, including a study of the material formation. A simple, environmentally friendly synthesis using the solvothermal process was implemented to make the graphene-supported Fe₃O₄ NPs. This new material was found to produce a reversible change of up to 18% in a LIB. In order to overcome some of the difficulties of testing with a LIB, a corresponding hybrid SC was designed, built and calibrated. The graphene-supported Fe₃O₄ NPs were found to produce a net 2% reversibility in the SC, which has not been reported before. The results from both the LIB and SC were analyzed to better understand the mechanism of switching in a spinel ferrite such as Fe₃O₄, which can help optimize the material for future applications. </p><p> The focus of this dissertation was on the development of a methodology for carbon-supported TM and TMO NPs for specific applications. It is envisioned that this approach and strategy will contribute towards the future optimization of similar material systems for a multitude of applications.</p><p>

<p> III-V optoelectronic device integration in a CMOS post-process compatible manner is important for the intimate integration of silicon-based electronic and photonic integrated circuits. The low temperature, self-catalyzed growth of high crystalline quality Wurtzite-phase InP nanopillars directly on silicon presents a viable approach to integrate high performance nano-optoelectronic devices. </p><p> For the optical transmitter side of the photonic link, InGaAs quantum wells have been grown in a core-shell manner within InP nanopillars. Position-controlled growth with varying pitch is used to systematically control emission wavelength across the same growth substrate. These nanopillars have been fabricated into electrically-injected quantum well in nanopillar LEDs operating within the silicon transparent 1400&ndash;1550 nm spectral window and efficiently emitting micro-watts of power. A high quality factor (Q ~ 1000) undercut cavity quantum well nanolaser is demonstrated, operating in the silicon-transparent wavelength range up to room temperature under optical excitation. </p><p> We also demonstrate an InP nanopillar phototransistor as a sensitive, low-capacitance photoreceiver for the energy-efficient operation of a complete optical link. Efficient absorption in a compact single nanopillar InP photo-BJT leads to a simultaneously high responsivity of 9.5 A/W and high 3dB-bandwidth of 7 GHz. </p><p> For photovoltaic energy harvesting, a sparsely packed InP nanopillar array can absorb ~90% of the incident light because of the large absorption cross section of these near-wavelength nanopillars. Experimental data based on wavelength and angle resolved integrating sphere measurements will be presented to discuss the nearly omnidirectional absorption properties of these nanopillar arrays.</p><p>

<p> Nanofabrication through multiphoton absorption has generated considerable interest because of its unique ability to generate 2D and 3D structures in a single laser-direct-write step as well as its ability to generate feature sizes well below the diffraction limited laser spot size. The majority of multiphoton fabrication has been used to create 3D structures of photopolymers which have applications in a wide variety of fields, but require additional post-processing steps to fabricate conductive structures. It has been shown that metal ions can also undergo multiphoton absorption, which reduces the metal ions to stable atoms/nanoparticles which are formed at the laser focal point. When the focus is located at the substrate surface, the reduced metal is deposited on the surface, which allows arbitrary 2D patterning as well as building up 3D structures from this first layer. Samples containing the metal ions can be prepared either in a liquid solution, or in a polymer film. The polymer film approach has the benefit of added support for the 3D metallic structures; however it is difficult to remove the polymer after fabrication to leave a free standing metallic structure. With the ion solution method, free standing metallic structures can be fabricated but need to be able to withstand surface tension forces when the remaining unexposed solution is washed away.</p><p> So far, silver nanowires with resistivity on the order of bulk silver have been fabricated, as well as a few small 3D structures. This research focuses on the surfactant assisted multiphoton reduction of silver ions in a liquid solution. The experimental setup consists of a Coherent Micra 10 Ultrafast laser with 30fs pulse length, 80MHz repetition rate, and a wavelength centered at 800nm. This beam is focused into the sample using a 100x objective with a N.A. of 1.49. Silver structures such as nanowires and grid patterns have been produced with minimum linewidth of 180nm. Silver nanowires with resistivity down to 6x bulk silver have been fabricated. Three-dimensional structures have also been fabricated with up to a 10&micro;m height at a thickness of 500nm. This method can fabricate structures with the possible applications in plasmonic metamaterials, photonic crystals, MEMS/NEMS and micro/nanocircuitry. </p><p>

<p> We present a versatile biosensing strategy that uses nucleic acids programmed to undergo an isothermal toehold mediated strand displacement in the presence of analyte. This rearrangement results in a double biotinylated duplex formation that induces the rapid aggregation of streptavidin decorated quantum dots (QDs). As biosensor reporters, QDs are advantageous to organic fluorophores and fluorescent proteins due to their enhanced spectral and fluorescence properties. Moreover, the nanoscale regime aids in an enhanced surface area that increase the number of binding of macromolecules, thus making cross-linking possible. The biosensing transduction response, in the current approach, is dictated by the analysis of the natural single particle phenomenon known as fluorescence intermittency, or blinking is the stochastic switching of fluorescence intensity ON (bright) and OFF (dark) states observed in single QD or other fluorophores. In contrast to binary blinking that is typical for single QDs, aggregated QDs exhibit quasi-continuous emission. This change is used as an output for the novel biosensing techniques developed by us. Analysis of blinking traces that can be measured by laser scanning confocal microscopy revealed improved detection of analytes in the picomolar ranges. Additionally, this unique biosensing approach does not require the analyte to cause any fluorescence intensity or color changes. Lastly, this biosensing method can be coupled with therapeutics, such as RNA interference inducers, that can be conditionally released and thus used as a theranostic probes.</p><p>

Porous metal oxide materials, particularly those comprised of silica or titania, find use in many applications such as low-k dielectric materials for microelectronics as well as chemical sensors, micro/nanofluidic devices, and catalyst substrates. For this dissertation, the focus will be on the processing of porous metal oxide materials covering two subjects: hierarchical porosity exhibited over two discrete length scales and incorporation of functional nanomaterials. To generate the porous silica materials, the technique of supercritical carbon dioxide infusion (scCO2) processing was heavily relied upon. Briefly, the scCO2 infusion processing utilizes phase selective chemistries within a pre-organized amphiphilic block copolymer template using scCO2 as the reaction medium to selectively hydrolyze and condense silica precursors to yield mesoporous materials. To further develop the scCO 2 infusion processing technique, hierarchically porous silica materials were generated on unique substrates. Hierarchically structured silica nanochannels were created using a combination of scCO2 infusion processing and nanoimprint lithography (NIL) patterned sacrificial polymer templates to yield mesopores and airgap structures respectively. Hierarchically porous silica materials were also generated on alternative substrates, in the form of cellulose filter paper, which were used to host the amphiphilic block copolymer template to yield tri-modal porosity silica materials. To extend the applicability of mesoporous silica generated from scCO 2 infusion processing, functional nanomaterials, in the form of pre-synthesized gold nanoparticles, fullerene derivatives, and polyhedral oligomeric silsequioxanes (POSS) were embedded within the mesoporous silica to produce unique composite materials. The functional nanomaterials were able to impart specific properties, typically only affored to the functional nanomaterials, upon the mesoporous silica thin film with an example being enhanced thermal and hydrothermal properties of mesoporous silica doped with POSS molecules. To continue research with functional nanomaterials, nanoparticle composite materials, comprised of crystalline metal oxide nanoparticles and binder/filler materials, either organic or inorganic, were also evaluated as novel NIL resist materials. Patterning of the nanoparticle composite materials, specifically, but not limited to, titanium dioxide based materials, into two dimensional, arbitrarily shaped, sub-micron features was readily achieved on either rigid or flexible substrates. True three-dimensional structures, based on nanoparticle composite materials, were fabricated by utilizing release layers and pre-patterned substrates.

Nanoparticles are regarded as exciting new building blocks for functional materials due to their fascinating physical properties because of the nano-confinement. Organizing nanoparticles into ordered hierarchical structures are highly desired for constructing novel optical and electrical artificial materials that are different from their isolated state or thermodynamics random ensembles. My research integrates the surface chemistry of nanoparticles, interfacial assembly and lithography techniques to construct nanoparticle based functional structures. We designed and synthesized tailor-made ligands for gold, semiconductor and magnetic nanoparticle, to modulate the assembly process and collective properties of the assembled structures, by controlling the key parameters such as particle-interface interaction, dielectric environments and inter-particle coupling etc. Top-down technologies such as micro contact printing, photolithography and nanoimprint lithography are used to guide the assembly into arbitrarily predesigned structures for potential device applications.

<p> Optical rectennas, which are micro-antennas to convert optical-frequency radiation to alternating current combined with ultrahigh-speed diodes to rectify the current, can in principle provide high conversion efficiency solar cells and sensitive detectors. Currently investigated optical rectennas using metal/insulator/metal (MIM) diodes are limited in their RC response time and poor impedance matching between diodes and antennas. A new rectifier, the geometric diode, can overcome these limitations. The thesis work has been to develop geometric diode rectennas, along with improving fabrication processes for MIM diode rectennas. The geometric diode consists of a conducting thin-film, currently graphene, patterned into a geometry that leads to diode behavior. In contrast with MIM diodes that have parallel plate electrodes, the planar structure of the geometric diode provides a low RC time constant, on the order of 10^-15 s, which permits operation at optical frequencies. Fabricated geometric diodes exhibit asymmetric DC current-voltage characteristics that match well with Monte Carlo simulations based on the Drude model. The measured diode responsivity at DC and zero drain-source bias is 0.012 A/W. Since changing the gate voltage changes the graphene charge carrier concentration and can switch the majority charge type, the rectification polarity of the diode can be reversed. Furthermore, the optical rectification at 28 THz has been measured from rectennas formed by coupling geometric diodes with graphene and metal bowtie antennas. The performance of the rectenna IR detector is among the best reported uncooled IR detectors. The noise equivalent power (NEP) of the rectenna detector using geometric diode was measured to be 2.3 nW Hz^-1/2. Further improvement in the diode and antenna design is expected to increase the detector performance by at least a factor of two. Applications for geometric diodes and graphene bowtie antennas include detection of terahertz and optical waves, ultra-high speed electronics, and optical power conversion.</p>