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<p>Scanning transmission x-ray microscopes (STXM) focus monochromatic x-rays into an intense sub-30 nm diameter spot. Samples are then positioned at the focal plane and raster scanned through the spot while the transmitted x-rays are acquired to build up images at x-ray photon energies. In addition, x-ray absorption spectroscopy (XAS) can be performed by recording image sequences over a photon energy range of interest. STXMs excel at characterizing thin sections of inhomogeneous soft matter with their combination of high spatial (<30 nm) and photon energy (<0.1 eV) resolution. However, the overarching theme of this thesis is to apply the intense, tightly focused spot of x-rays to induce spatially resolved chemical and physical changes, and directly pattern materials, primarily thin polymer films. The irradiated areas are then investigated using several types of microscopy (scanning transmission x-ray, atomic force, scanning electron) and XAS. The experiments cover three broad areas: i) Nanofabrication; realization of the smallest possible feature sizes, and fabrication schemes unique to focused x-rays with applications including nanofluidics. ii) Radiation chemistry and physics; investigating the mechanisms of radiation-induced processes such as bond formation/loss, morphological change, carbon contamination, and temperature increase. iii) X-ray optics; the spatial distribution of x-rays at a focal plane can be recorded in a thin polymer film and later read out using an atomic force microscope. Applications include feedback for optics fabrication and enhanced image processing, the ultimate goal being increased spatial resolution.</p> / Doctor of Philosophy (PhD)

The study of nanomaterials is a developing science with potentially large benefits in the development of catalysts, optical and chemical sensors, and solid state memory devices. As several of these devices require large arrays of nanoparticles, one of the greatest obstacles in material characterization and device development is the reliable manufacture of nanopatterns over a large surface area. In addition, various applications require different nanoparticle size and density. High density arrays with small nanoparticle sizes are difficult to achieve over a large surface area using current manufacturing processes. Herein, Nanoimprint Lithography (NIL) and Dynamic Templating are combined to create a new manufacturing process capable of developing high density arrays with small nanoparticle sizes. The NIL process involves the stamping of a polymer coated substrate by a silicon stamp with patterned nanofeatures. The stamp is then removed, leaving the pattern in the polymer, which is first etched and then coated with a thin layer of metal, filling the recessed regions of the pattern. The excess polymer is dissolved, leaving a pattern of nanoparticles on the substrate matching the pattern on the stamp. When Dynamic Templating is applied, a very thin layer of metal can be coated, which forms small nanoparticle sizes when dewetted. A custom NIL system has been developed to combine these two processes together, which has now proven to yield consistent large-area, dense arrays with a small nanoparticle size. An array spacing of 700 nm has been achieved, along with a nanoparticle size of 90 nm. Arrays have been created in gold and palladium, where there is now the potential to combine them with other solution-based syntheses which should lead to complex nanoparticle geometries suitable for sensor applications. / Mechanical Engineering

Incorporation of silver nanoparticles (AgNPs) into an increasing number of consumer products has led to concern over the potential ecological impacts of their unintended release to the environment. Dissolution is an important environmental transformation that affects the form and concentration of AgNPs in natural waters; however, studies on AgNP dissolution kinetics are complicated by nanoparticle aggregation. Herein, nanosphere lithography (NSL) was used to fabricate uniform arrays of AgNPs immobilized on glass substrates. Nanoparticle immobilization enabled controlled evaluation of AgNP dissolution in an air-saturated phosphate buffer (pH 7, 25 °C) under variable NaCl concentrations in the absence of aggregation. Atomic force microscopy (AFM) was used to monitor changes in particle morphology and dissolution. Over the first day of exposure to ≥10 mM NaCl, the in-plane AgNP shape changed from triangular to circular, the sidewalls steepened, and the height increased by 6-12 nm. Subsequently, particle height and in-plane radius decreased at a constant rate over a 2-week period. Dissolution rates varied linearly from 0.4 to 2.2 nm/d over the 10-550 mM NaCl concentration range tested. NaCl-catalyzed dissolution of AgNPs may play an important role in AgNP fate in saline waters and biological media. This study demonstrates the utility of NSL and AFM for the direct investigation of un-aggregated AgNP dissolution. / Master of Science

Multiple laser beam interference allows to produce periodic light patterns in the order of the wavelength of light. A simulation program helps to identify different patterns and to investigate the influence of changing parameters such as e.g. the angle of incidence or the polarization. A positive photoresist (Shipley S1805) is used to create two-dimensional metallic photonic crystals by UV interference lithography.

The InsulPatch is a novel integrated patch-pump device used to deliver drugs, especially macromolecular drugs that are difficult to deliver through an oral pathway and that require transdermal delivery. The patch-pump is a promising replacement for conventional syringes and battery-powered pumps because it is slim, powerless, painless, and relatively inexpensive. The majority of this thesis focuses on the fabrication and testing of microfluidic devices for the delivery of insulin, which is a model drug that is widely used and needs to be delivered transdermally. In this thesis, we demonstrate the fabrication of the patch-pump, which includes an insect-mimetic microfluidic pump fabricated using photolithography and replica molding, and a microneedle array fabricated using 3D printing. The microfluidic pump is used to drive the fluid flow powered by pressurized air or the user’s pulse, and the microneedle array is used to inject the fluid through the skin painlessly. Using pressurized air-driven flow testing, we have tested the flow rate across microfluidic pumps of various flow channel widths over a range of physiologically relevant actuation frequencies and pressures. We have found that for the specific channel design we have been using, the flow rate generally positively correlates with the actuation pressure. For devices with wider flow channels, the flow rate generally negatively correlates with the actuation frequency, whereas the flow rate increases and then decreases with increasing actuation frequency for devices with narrower flow channels. This property of these devices is beneficial in insulin delivery because the demand for insulin is generally reduced in vigorous exercise (with elevated heart rate/actuation frequency) and increased in hypertension patients (with elevated blood/actuation pressure). A major future direction of the study is to test a wide range of device designs in a sample of human subjects by attaching the device onto the wrist and measuring the pulse-driven flow across the device. We can further change the channel design parameters of the device so that it will be ideal for insulin delivery. Using the ex vivo flow testing and human subject data, we can further tailor the device design to specific patients using a genetic algorithm-guided optimization based on the heart rate and blood pressure of the patient and the desired flow rate. We will also perform computational modeling using COMSOL Multiphysics to predict the flow across devices of different designs as well as to understand the physics behind the pulse-driven flow. Finally, a 3D-printed insulin reservoir will be incorporated into our patch-pump system for the storage of U-500 insulin. / M.S. / The InsulPatch is a slim, powerless device (“patch-pump”) that can be used to deliver drugs through the skin, especially designed for drugs that are difficult to deliver orally. The patch technology is a promising replacement for conventional injection using syringes and bulky battery-powered pumps. At this stage, the primary drug that our device aims to deliver is insulin, which generally needs to be delivered through the skin. In this thesis, we demonstrate how our patch-pump is made and how its performance is tested. The patch-pump has two parts: the microfluidic pump and the microneedle array. The microfluidic pump is fabricated using a technique called photolithography, in which a photosensitive polymer is selectively cured by UV light, and replica molding, in which the precursor of another polymer is poured on a mold and cured. The microneedle array is made using 3D printing and designed in such a way so that it can be readily connected to the microfluidic pump. The microfluidic pump is used to drive the fluid flow powered by the user’s pulse, and the microneedle array is used to inject the fluid through the skin painlessly. Through testing the flow across the microfluidic pump prototypes using pressurized air, we characterized the correlation between the flow rate of fluid across the device and parameters including the actuation pressure and frequency of the pressurized air as well as the width of the flow channel. Future directions of the study include testing the devices in human subjects to characterize pulse-driven flow across the devices, computational modeling of the devices, and further changes of the device design to optimize the performance of the device. We will also optimize the device design computationally to tailor the device design to specific diabetic patients. Finally, we will incorporate a 3D-printed insulin reservoir into our system for the storage of insulin solution. / Withhold all access to the ETD for 1 year / patent / I hereby certify that, if appropriate, I have obtained and submitted with my ETD a written permission statement from the ower(s) of each third part copyrighted matter to be included in my thesis or dissertation, allowing distribution as specified above. I certify that the version I submitted is the same as that approved by my advisory committee.

Metal-based nanoparticles (MNPs) are becoming increasingly common in commercial products. Release of these materials into the environment raises concerns about the potential risks they pose to aquatic life. Predicting these risks requires an understanding of MNPs' chemical transformations. In this study, arrays of immobilized MNPs fabricated by nanosphere lithography (NSL) were used to investigate environmental transformations of MNPs. Specifically, sulfidation of silver nanoparticles (Ag NPs) and dissolution of copper-based nanoparticles (Cu NPs) were investigated. Atomic force microscopy (AFM) and transmission electron microscopy were the primary analytical techniques for these investigations. Because the MNPs were immobilized on a solid surface, the samples were field deployable, environmentally relevant metal concentrations were maintained, and the confounding influence of MNP aggregation was eliminated. Ag NP samples were deployed in a full-scale wastewater treatment plant. Sulfidation occurred almost exclusively in anaerobic zones of the WWTP, where the initial sulfidation rate was 11-14 nm of Ag converted to Ag2S per day. Conversion to Ag2S was complete within 7-10 d. Dissolution rates of Cu-based NPs were measured in situ over a range of pH by flow-cell AFM. Based on the measured rates, CuO/Cu(OH)2 NPs dissolve completely within a matter of hours at any pH, metallic Cu NPs persist for a few hours to days, and CuxS NPs do not dissolve significantly over the time scales studied. Field deployment of samples in a freshwater stream confirmed these conclusions for a natural aquatic system. This research demonstrates that environmental transformations of MNPs will be a key factor in determining the ultimate form and concentration of NPs that aquatic organisms will be exposed to. / Ph. D.

Scanning Electrochemical Microscopy (SECM) is most commonly used to spatially resolve reaction rates, image surface topography and surface reactivity. In this research, SECM is applied to various chemical systems in order to resolve local reaction chemistry and to produce patterns with dimensions of tens of microns in n-alkanethiol passivated gold substrates. Upon completing construction of the instrumentation, SECM was applied to capillary electrophoresis to accurately and reproducibly place the electrode directly above a very small capillary opening. Feedback SECM was then used to image and pattern surfaces, effectively distinguishing between insulating and conductive domains. Finally, the size of desorbed features patterned on a passivated gold substrate were studied as a function of both applied potential and ionic strength. Electrochemical detection in capillary electrophoresis requires decoupling the voltage applied to the working electrode from the separation voltage applied across the capillary. End-capillary electrochemical detection achieves this by placing the electrode just outside the ground end of the separation capillary. Obtaining adequate signal-to-noise in this arrangement requires using small inner diameter capillaries. Decreasing the inner diameter of the separation capillary, however, increases the difficulty of aligning the microelectrode with the open end of the capillary. Using SECM, the position of the capillary opening is determined while electroactive material is continuously emerging from the end of the capillary. The SECM instrument is then used to place the electrode at the position of maximum current for subsequent separations. Subsequent measurements found that the best signal-to-noise is obtained when the detection electrode is placed directly opposite the capillary opening and just outside of the capillary opening. When the electrode is further above the opening (but still opposite the capillary opening), the signal-to-noise does not dramatically decrease until the electrode is more than 30 μm above the 10 μm inner-diameter capillary. Limits of detection for 2,3-dihydroxybenzoic acid were found to be 8.2 fmol when aligned manually, and 3.8 fmol when the SECM is used to automatically align the microelectrode. SECM was then used to image a series of multi-disk electrode arrays in order to demonstrate the ability of the instrument to discriminate between conductive and insulating domains. Upon demonstrating the capacity of the SECM to image very small domains of conductor on an insulating substrate, n-alkanethiol passivated gold surfaces were patterned using site-selective desorption. A number patterns, potentially useful for enzyme deposition, were subsequently produced in the passivated gold substrate. The feature size of the desorbed domains was monitored as a function of applied potential and the ionic strength of the solution used for desorption. Results showed that applying a more negative potential or increasing the ionic strength of the solution increased the magnitude of the electric field at the surface of the passivated gold substrate and resulted in a more complete, larger desorption. Both ionic strength and applied desorption potential prove to be parameters useful for controlling the size of patterned features in site selective desorption. / Master of Science