Solar cells have extrinsic losses from a variety of sources which can be minimized by optimization of the design and fabrication processes. Reflection from the front surface is one such loss mechanism and has been managed in the past with the usage of planar antireflection coatings. While effective, these coatings are each limited to a single wavelength of light and do not account for varying incident angles of the incoming light source. Three-dimensional nanostructures have shown the ability to inhibit reflection for differing wavelengths and angles of incidence. Nanocones were modeled and show a broadband, multi-angled reflectance decrease due to an effective grading of the index. Finite element models were created to simulate incident light on a zinc oxide nanocone textured silicon substrate. Zinc oxide is advantageous for its ease of production, benign nature, and refractive index matching to the air source region and silicon substrate. Reflectance plots were computed as functions of incident angle and wavelength of light and compared with planar and quintic refractive index profile models. The quintic profile model exhibits nearly optimum reflection minimization and is thus used as a benchmark. Physical quantities, including height, width, density, and orientation were varied in order to minimize the reflectance. A quasi-random nanocone unit cell was modeled to better mimic laboratory results. The model was comprised of 10 nanocones with differing structure and simulated a larger substrate by usage of periodic boundary conditions. The simulated reflectance shows approximately a 50 percent decrease when compared with a planar model. When a seed layer is added, simulating a layer of non-textured zinc oxide, on which the nanocones are grown, the reflectance shows a fourfold decrease when compared with planar models. At angles of incidence higher than 75 degrees, the nanocone model outperformed the quintic model.

CMOS SRAM area scaling is slowing down due to several challenges faced by transistors at nanoscale such as increased leakage. This calls for new concepts and technologies to overcome CMOS scaling limitations. In this thesis, we propose a multi-state memory to store multiple bits in a single cell, enabled by graphene and graphene nanoribbon crossbar devices (xGNR). This could provide a new dimension for scaling. We present a new multi-state volatile memory fabric called Graphene Nanoribbon Tunneling Random Access Memory (GNTRAM) featuring a heterogeneous integration between graphene and CMOS. A latch based on the xGNR devices is used as the memory element which exhibits 3 stable states. We propose binary and ternary GNTRAM and compare them with respect to 16nm CMOS SRAM and 3T DRAM. Ternary GNTRAM (1.58 bits/cell) shows up to 1.77x density-per-bit benefit over CMOS SRAMs and 1.42x benefit over 3T DRAM in 16nm technology node. Ternary GNTRAM is also up to 1196x more power-efficient per bit against high-performance CMOS SRAMs during stand-by. To enable further scaling, we explore two approaches to increase the number of bits per cell. We propose quaternary GNTRAM (2 bits/cell) using these approaches and extensively benchmark these designs. The first uses additional xGNR devices in the latch to achieve 4 stable states and the quaternary memory shows up to 2.27x density benefit vs. 16nm CMOS SRAMs and 1.8x vs. 3T DRAM. It has comparable read performance in addition to being power-efficient, up to 1.32x during active period and 818x during stand-by against high performance SRAMs. However, the need for relatively high-voltage operation may ultimately limit this scaling approach. An alternative approach is also explored by increasing the stub length in the xGNR devices, which allows for storing 2 bits per cell without requiring an increased operating voltage. This approach for quaternary GNTRAM shows higher benefits in terms of power, specifically up to 4.67x in terms of active power and 3498x during stand-by against high-performance SRAMs. Multi-bit GNTRAM has the potential to realize high-density low-power nanoscale memories. Further improvements may be possible by using graphene more extensively, as graphene transistors become available in future.

Manufactured oxide nanoparticles (NPs) have large production and widespread applications, which will inevitably enter the environment. NPs can interact with proteins in living beings due to the fact that NPs can transport into blood or across cell membranes into cells. Conformational change of protein molecules after sorption on oxide NPs has been reported. Therefore, it is important to understand the adsorption mechanism of protein onto oxide NPs surfaces. Although few works have reported protein adsorption behaviors, a general systematic comparison of the effects of particle size and surface groups on protein adsorption by widely studied NPs still needs to be made. Moreover, the relationship between adsorption maxima, which are related to protein conformational change and particle toxicity, and protein conformational change has not yet been studied. Therefore, in this work, the adsorption behavior of bovine serum albumin (BSA) protein on three types of nano oxide particles (viz., TiO2, SiO2, and Al2O3) was investigated in order to explore their interaction mechanisms, compared with that on regular bulk particles (BPs). The BSA adsorption maxima on oxide particles were regulated by the surface area of oxide particles. BSA adsorption was primarily induced by electrostatic attraction and ligand exchange between BSA and oxide surfaces. Surface hydrophilicity, surface charge and aggregation of oxide particles also affected their adsorption of BSA. Calculations suggested that a multilayer of BSA covered α-Al2O3, and single layer covered the other oxide particle surfaces. Primary structures of BSA molecules were adsorbed and changed on surfaces of oxide particles.

Two batches of CdSe QDs with different sizes were synthesized for immobilizing in polyisoprene (PI), polymethylmethacrylate (PMMA), and low-density polyethylene (LDPE). The combinations of QDs and polymer substrates were evaluated for their analytical fit-for-use in applicable immunoassays. Hydrogen peroxide standards were injected into the flow injection analyzer (FIA) constructed to simulate enzyme-generated hydrogen peroxide reacting with bis-(2,4,6-trichlorophenyl) oxalate. Linear correlations between hydrogen peroxide and chemilumenscent intensities yielded regression values greater than 0.9750 for hydrogen peroxide concentrations between 1.0 x 10-4 M and 1.0 x 10-1 M. The developed technique’s LOD was approximately 10 ppm. Variability of the prepared QD-polymer products was as low as 3.2% throughout all preparations.Stability of the preparations was tested during a 30-day period that displayed up to a four-fold increase in the first 10 days. The preparations were decently robust to the FIA system demonstrating up to a 15.20% intensity loss after twenty repetitive injections.

Quantum dots are semiconductive particles whose properties are highly influenced by the presence of at least one electron. Cadmium selenide quantum dots were synthesized via colloidal synthesis. Contrary to previous preparations, more focus was placed on the temperature rather than the duration of time at which they form. A series of colored solutions were obtained because the excited quantum dots of various sizes emitted specific wavelengths of light. The emission spectra showed that the temperature-dependent quantum dots were successfully synthesized. The quantum dots were also immobilized on various surfaces, and the luminescence properties were examined. The quantum dots that were immobilized in sol-gels through chemiluminescence (CL) analyses were found to be stable and were able to maintain their luminescence properties with extensive uses and long-term storage. Linear calibration curves were obtained for concentrations of hydrogen peroxide from 1.75 x 10-4 M to 1.75 x 10-2 M in TCPO-CL.

ABSTRACT The Characterization and Analysis of In-vitro and Elevated Temperature Repassivation of Ti-6Al-4V via AFM Techniques Aaron J Guerrero Research in the corrosion of orthopaedic implants is a growing research field where implants have been known to show adverse effects in patients who have encountered the unfortunate dissolution of their implants due to corrosion. Once corrosion begins within the body, many adverse biological reactions can occur such as late on-set infections resulting in severe health complications. The focus of this research is specifically related to the problem of late on-set infections caused by localized corrosion of orthopaedic implants. In medical implants today the most common form of corrosion protection is the implant materials’ ability to impede corrosion through the formation of an oxide layer. This ability to passivate and quickly repassivate a uniform and stable oxide layer dictates how well an orthopaedic implant will survive in-vivo. To better understand the repassivation of orthopaedic implant materials, research was conducted at the nanoscale via atomic force microscopy (AFM) on anodized Ti-6Al-4V. Using an Asylum Research MFP-3DTM AFM and AFM lithography techniques, nano scratch test methods were created simulating in-vitro surface repassivation conditions. These nano-scratches were created and characterized in Hank’s balanced saline solution (HBSS) with the AFM in contact mode at 1 and 3 Hz scan rates. HBSS was used as it best simulates the pH, ionic compounds, and constituents that are commonly found in blood. It was discovered that the AFM was successful in creating in-vitro repassivation conditions. However, the ability of the AFM to successfully observe repassivation was limited by the speed of the AFM scanner. Using the same AFM scratch methods, experiments were performed in air and in-vitro and characterized with AFM conductance measurements at 20, 37, & 45 °C. The conductance measurements were taken using an AFM conductance module and allowed for observations of decreasing current measurements over time. The current data was then used to calculate current density, resistivity, conductance, and electron mobility and compared to similar experiments This study highlights the ability of the AFM to create and characterize repassivation and shows promise in developing further capability to use the AFM for characterization of repassivation on the nanoscale. Keywords: Orthopaedics, late on-set infections, repassivation, AFM, lithography, conductive measurements.

Research to increase the efficiency of conventional solar cells is constantly underway. The goal of this work is to increase the efficiency of conventional solar cells by incorporating quantum dot (QD) nanoparticles in the absorption mechanism. The strategy is to have the QDs absorb UV and fluoresce photons in the visible region that are more readily absorbed by the cells. The outcome is that the cells have more visible photons to absorb and have increased power output. The QDs, having a CdSe core and a ZnS shell, were applied to the solar cells as follows. First, the QDs were synthesized in an octadecene solution, then they were removed from the solution and finally they were dried and deposited into polydimethylsiloxane (PDMS) and the PDMS/QD composite is allowed to cure. The cured sample is applied to a silicon solar panel. The panel with the PDMS/QD application outputs 2.5% more power than the one without, under identical illumination by a tungsten halogen lamp, using QDs that fluoresce in the orange region. This work demonstrates the feasibility of incorporating QDs to increase the efficiency of conventional solar cells. Because the solar cells absorb better in the red region, future effort will be to use QDs that fluoresce in that region to further boost cell output.

This work focuses on understanding the buckling deformation mechanisms of bending, wrinkling, and folding that occur on the surfaces and interfaces of polymer systems. We gained fundamental insight into the formation mechanism of these buckled structures for thin glassy films placed on an elastomeric substrate. By taking advantage of geometric confinement, we demonstrated new strategies in controlling wrinkling morphologies. We were able to achieve surfaces with controlled patterned structures which will have a broad impact in optical, adhesive, microelectronics, and microfluidics applications. Wrinkles and strain localized features, such as delaminations and folds, are observed in many natural systems and are useful for a wide range of patterning applications. However, the transition from sinusoidal wrinkles to more complex strain localized structures is not well understood. We investigated the onset of wrinkling and strain localizations under uniaxial strain. We show that careful measurement of feature amplitude allowed not only the determination of wrinkle, fold, or delamination onset, but also allowed clear distinction between each feature. The folds observed in this experiment have an outward morphology from the surface in contrast to folds that form into the plane, as observed in a film floating on a liquid substrate. A critical strain map was constructed, where the critical strain was measured experimentally for wrinkling, folding, and delamination with varying film thickness and modulus. Wrinkle morphologies, i.e. amplitude and wavelength of wrinkles, affect properties such as electron transport in stretchable electronics and adhesion properties of smart surfaces. To gain an understanding of how the wrinkle morphology can be controlled, we introduced a geometrical confinement in the form of rigid boundaries. Upon straining, we found that wrinkles started near the rigid boundaries where maximum local strain occurred and propagated towards the middle as more global strain was applied. In contrast to homogeneous wrinkling with constant amplitude that is observed for an unconfined system, the wrinkling observed here had varying amplitude as a function of distance from the rigid boundaries. We demonstrated that the number of wrinkles can be tuned by controlling the distance between the rigid boundaries. Location of wrinkles was also controlled by introducing local stress distributions via patterning the elastomeric substrate. Two distinct wrinkled regions were achieved on a surface where the film is free-standing over a circular hole pattern and where the film is supported by the substrate. The hoe diameter and applied strain affected the wavelength and amplitude of the free-standing membrane. Using discontinuous dewetting, a one-step fabrication method was developed to selectively deposit a small volume of liquid in patterned microwells and encapsulate it with a polymeric film. The pull-out velocity, a velocity at which the sample is removed from a bath of liquid, was controlled to observe how encapsulation process is affected. The polymeric film was observed to wrinkle at low pull-out velocity due to no encapsulation of liquid; whereas the film bent at medium pull-out velocity due to capillary effect as the liquid evaporated through the film. To quantify the amount of liquid encapsulated, we mixed salt in water and measured the size of the deposited salt crystals. The salt crystal size, and hence the amount of liquid encapsulated, was controlled by varying either the encapsulation velocity or the size of the patterned microwells. In addition, we showed that the deposited salt crystals are protected by the laminated film until the film is removed, providing advantageous control for delivery and release. Yeast cells were also captured in the microwells to show the versatility. This encapsulation method is useful for wide range of applications, such as trapping single cells for biological studies, growing microcrystals for optical and magnetic applications, and single-use sensor technologies.

Surfaces functionalized with bio-molecular targeting agents are conventionally used for highly-specific protein and cell adhesion. This thesis explores an alternative approach: Small non-biological adhesive elements are placed on a surface randomly, with the rest of the surface rendered repulsive towards biomolecules and cells. While the adhesive elements themselves, for instance in solution, typically exhibit no selectivity for various compounds within an analyte suspension, selective adhesion of targeted objects or molecules results from their placement on the repulsive surface. The mechanism of selectivity relies on recognition of length scales of the surface distribution of adhesive elements relative to species in the analyte solution, along with the competition between attractions and repulsions between various species in the suspension and different parts of the collecting surface. The resulting binding selectivity can be exquisitely sharp; however, complex mixtures generally require the use of multiple surfaces to isolate the various species: Different components will be adhered, sharply, with changes in collector composition. The key feature of these surface designs is their lack of reliance on biomolecular fragments for specificity, focusing entirely on physicochemical principles at the lengthscales from 1 – 100 nm. This, along with a lack of formal patterning, provides the advantages of simplicity and cost effectiveness. This PhD thesis demonstrates these principles using a system in which cationic poly-L-lysine (PLL) patches (10 nm) are deposited randomly on a silica substrate and the remaining surface is passivated with a bio-compatible PEG brush. TIRF microscopy revealed that the patches were randomly arranged, not clustered. By precisely controlling the number of patches per unit area, the interfaces provide sharp selectivity for adhesion of proteins and bacterial cells. For instance, it was found that a critical density of patches (on the order of 1000/m2) was required for fibrinogen adsorption while a greater density comprised the adhesion threshold for albumin. Surface compositions between these two thresholds discriminated binding of the two proteins. The binding behavior of the two proteins from a mixture was well anticipated by the single- protein binding behaviors of the individual proteins. The mechanism for protein capture was shown to be multivalent: protein adhesion always occurred for averages spacings of the adhesive patches smaller than the dimensions of the protein of interest. For some backfill brush architectures, the spacing between the patches at the threshold for protein capture clearly corresponded to the major dimension of the target protein. For more dense PEG brush backfills however, larger adhesion thresholds were observed, corresponding to greater numbers of patches involved with the adhesion of each protein molecule. . The thesis demonstrates the tuning of the position of the adhesion thresholds, using fibrinogen as a model protein, using variations in brush properties and ionic strength. The directions of the trends indicate that the brushes do indeed exert steric repulsions toward the proteins while the attractions are electrostatic in nature. The surfaces also demonstrated sharp adhesion thresholds for S. Aureus bacteria, at smaller concentrations of adhesive surfaces elements than those needed for the protein capture. The results suggest that bacteria may be captured while proteins are rejected from these surfaces, and there may be potential to discriminate different bacterial types. Such discrimination from protein-containing bacterial suspensions was investigated briefly in this thesis using S. Aureus and fibrinogen as a model mixture. However, due to binding of fibrinogen to the bacterial surface, the separation did not succeed. It is still expected, however, that these surfaces could be used to selectively capture bacteria in the presence of non-interacting proteins. The interaction of these brushes with two different cationic species PLL and lysozyme were studied. The thesis documents rapid and complete brush displacement by PLL, highlighting a major limitation of using such brushes in some applications. Also unanticipated, lysozyme, a small cationic protein, was found to adhere to the brushes in increasing amounts with the PEG content of the brush. This finding contradicts current understanding of protein-brush interactions that suggests increases in interfacial PEG content increase biocompatibility.

<p>This work detailed in this thesis has developed two new technologies for modifying polymer surfaces with variable chemistry and topography: 1. Surfadditive (surface-active-additive) approach for polymer surface chemistry modification during molding. This concept was demonstrated by the synthesis and application of two types of surfadditives. The first type of surfadditive is a block copolymer having the “head-neck-body” structure. The “head” and “neck” of the chain molecule provides functionality and enables the surfadditive to migrate to the surface, while the “body” of the molecule provides rooting to the bulk material. The second type of surfadditive is a magnetic nanoparticle having an iron core and PMMA/POSS block copolymer shell. Both surfadditives were successfully applied in the molding processes of PMMA samples for surface chemistry modification. Various factors affecting the migration processes were investigated; 2. A one step “cutting-edge” based on controlled chattering for surface topography construction (patterning). This technology was developed by using an oscillating diamond knife in ultramicrotomy and was operated at high cutting speed with controlled oscillation. One dimensional wavy patterns on PMMA and epoxy sample surfaces were successfully fabricated by this one-step method. The sizes of patterns were tunable form 30 nm to 3 µm through adjusting cutting speed and oscillation frequency. Besides, this technology was also able to fabricate nanowires structures with high aspect ratios (10,000) and adjustable sizes from a variety of materials.</p> / Doctor of Philosophy (PhD)