Ge1-xSnx alloys are among a small class of benign semiconductors with composition tunable bandgaps in the near-infrared spectrum. As the amount of Sn is increased the band energy decreases and a transition from indirect to direct band structure occurs. Hence, they are prime candidates for fabrication of Si-compatible electronic and photonic devices, field effect transistors, and novel charge storage device applications. Success has been achieved with the growth of Ge1-xSnx thin film alloys with Sn compositions up to 34%. However, the synthesis of nanocrystalline alloys has proven difficult due to larger discrepancies (~14%) in lattice constants. Moreover, little is known about the chemical factors that govern the growth of Ge1-xSnx nanoalloys and the effects of quantum confinement on structure and optical properties. A synthesis has been developed to produce phase pure Ge1-xSnx nanoalloys which provides control over both size and composition. Three sets of Ge1-xSnx nanocrystals have been studied, 15–23 nm, 3.4–4.6 nm and 1.5–2.5 nm with Sn compositions from x = 0.000–0.279. Synthetic parameters were explored to control the nucleation and growth as well as the factors that have led to the elimination of undesired metallic impurities. The structural analysis of all nanocrystals suggests the diamond cubic structure typically reported for Ge1-xSnx thin films and nanocrystalline alloys. As-synthesized Ge1-xSnx nanoalloys exhibit high thermal stability and moderate resistance against sintering up to 400–500 °C and are devoid of crystalline and amorphous elemental Sn impurities.

The idea of utilizing nanomaterials in bio-related applications has been extensively practiced during the recent decades. Magnetic nanoparticles (MPs), especially superparamagnetic iron oxide nanoparticles have been demonstrated as promising candidates for biomedicine. A protective coating process with biocompatible materials is commonly performed on MPs to further enhance their colloidal and chemical stability in the physiological environment. Mesoporous hollow silica is another class of important nanomaterials that are extensively studied in drug delivery area for their ability to carry significant amount of guest molecules and release in a controlled manner. In this study, different synthetic approaches that are able to produce hybrid nanomaterials, constituting both mesoporous hollow silica and magnetite nanoparticles, are described. In a two-step approach, pre-synthesized magnetite nanoparticles are either covalently conjugated to the surface of polystyrene beads and coated with silica or embedded/enclosed in the porous shell during a nanosized CaCO3 templated condensation of silica precursors, followed by acid dissolution to generate the hollow structure. It was demonstrated that the hollow interior is able to load large amount of hydrophobic drugs such as ibuprofen while the mesoporous shell is capable of prolonged drug. In order to simplify the fabrication procedure, a novel in-situ method is developed to coat silica surface with magnetite nanoparticles. By refluxing the iron precursor with mesoporous hollow silica nanospheres in polyamine/polyalcohol mixed media, one is able to directly form a high density layer of magnetite nanoparticles on silica surface during the synthesis, leaving reactive amine groups for further surface functionalization such as fluorescence conjugation. This approach provides a convenient synthesis for silica nanostructures with promising potential for drug delivery and multimodal imaging. In addition to nanoparticles, nanowires also benefit the research and development of instruments in clinical diagnosis. Semiconductive nanowires have demonstrated their advantage in the fabrication of lab-on-a-chip devices to detect many charge carrying molecules such as antibody and DNA. In our study, In2O3 and silicon nanowire based field effect transistors were fabricated through bottom-up and top-down approaches, respectively, for ultrasensitive bio- detection of toxins such as ricin. The specific binding and non-specific interaction of nanowires with antibodies were also investigated.

Electrocatalysis is key to both sensitive electrochemical sensing and efficient electrochemical energy conversion. Despite high catalytic activity, traditional metal catalysts have poor stability, low selectivity, and high cost. Metal-free, carbon-based materials are emerging as alternatives to metal-based catalysts because of their attractive features including natural abundance, environmental friendliness, high electrical conductivity, and large surface area. Altering surface functionalities and heteroatom doping are effective ways to promote catalytic performance of carbon-based catalysts. The first chapter of this dissertation focuses on developing electrode modification methods for electrochemical sensing of biomolecules. After electrochemical pretreatment, glassy carbon demonstrates impressive figures-of-merit in detecting small, redox-active biomolecules such as DNA bases and neurotransmitters. The results highlight a simplified surface modification procedure for producing efficient and highly selective electrocatalysts. The next four chapters focus on evaluating nitrogen-doped carbon nano-onions (𝑛-CNOs) as electrocatalysts for oxygen reduction and CO2 reduction. 𝑛-CNOs exhibit excellent electrocatalytic performance toward O2 to H2O reduction, which is a pivotal process in fuel cells. 𝑛-CNOs demonstrate excellent resistance against CO poisoning and long-term stability compared to state-of-the-art Pt/C catalysts. In CO2 electrochemical conversion, 𝑛-CNOs demonstrate significant improvement in catalytic performance toward reduction of CO2 to CO with a low overpotential and high selectivity. The outstanding catalytic performance of 𝑛-CNOs originates from the asymmetric charge distribution and creation of catalytic sites during incorporation of nitrogen atoms. High contents of pyridinic and graphitic N are critical for high catalytic performance. This work suggests that carbon-based materials can be outstanding alternatives to traditional metal-based electrocatalysts when their microstructures and surface chemistries are properly tailored.

Nanomagnetic devices have been projected as an alternative to transistor-based switching devices due to their non-volatility and potentially superior energy-efficiency. The energy efficiency is enhanced by the use of straintronics which involves the application of a voltage to a piezoelectric layer to generate a strain which is ultimately transferred to an elastically coupled magnetostrictive nanomaget, causing magnetization rotation. The low energy dissipation and non-volatility characteristics make straintronic nanomagnets very attractive for both Boolean and non-Boolean computing applications. There was relatively little research on straintronic switching in devices built with real nanomagnets that invariably have defects and imperfections, or their adaptation to non-Boolean computing, both of which have been studied in this work. Detailed studies of the effects of nanomagnet material fabrication defects and surface roughness variation (found in real nanomagnets) on the switching process and ultimately device performance of those switches have been performed theoretically. The results of these studies place the viability of straintronics logic (Boolean) and/or memory in question. With a view to analog computing and signal processing, analog spin wave based device operation has been evaluated in the presence of defects and it was found that defects impact their performance, which can be a major concern for the spin wave based device community. Additionally, the design challenge for low barrier nanomagnet which is the building block of binary stochastic neurons based probabilistic computing device in case of real nanomagnets has also been investigated. This study also cast some doubt on the efficacy of probabilistic computing devices. Fortunately, there are some non-Boolean applications based on the collective action of array of nanomagnets which are very forgiving of material defects. One example is image processing using dipole coupled nanomagnets which is studied here and it showed promising result for noise correction and edge enhancement of corrupted pixels in an image. Moreover, a single magneto tunnel junction based microwave oscillator was proposed for the first time and theoretical simulations showed that it is capable of better performance compared to traditional microwave oscillators. The experimental part of this work dealt with spin wave modes excited by surface acoustic waves, studied with time resolved magneto optic Kerr effect (TR-MOKE). New hybrid spin wave modes were observed for the first time. An experiment was carried out to emulate simulated annealing in a system of dipole coupled magnetostrictive nanomagnets where strain served as the simulated annealing agent. This was a promising outcome and it is the first demonstration of the hardware variant of simulated annealing of a many body system based on magnetostrictive nanomagnets. Finally, a giant spin Hall effect actuated surface acoustic wave antenna was demonstrated experimentally. This is the first observation of photon to phonon conversion using spin-orbit torque and although the observed conversion efficiency was poor (1%), it opened the pathway for a new acoustic radiator. These studies complement past work done in the area of straintronics.

We studied the possibility of achieving an order of magnitude reduction in the energy dissipation needed to write bits in perpendicular magnetic tunnel junctions (p-MTJs) by simulating the magnetization dynamics under a combination of resonant surface acoustic waves (r-SAW) and spin-transfer-torque (STT). The magnetization dynamics were simulated using the Landau-Lifshitz-Gilbert equation under macrospin assumption with the inclusion of thermal noise. We studied such r-SAW assisted STT switching of nanomagnets for both in-plane elliptical and circular perpendicular magnetic anisotropy (PMA) nanomagnets and show that while thermal noise affects switching probability in in-plane nanomagnets, the PMA nanomagnets are relatively robust to the effect of thermal noise. In PMA nanomagnets, the resonant magnetization dynamics builds over few 10s of cycles of SAW application that drives the magnetization to precess in a cone with a deflection of ~45⁰ from the perpendicular direction. This reduces the STT current density required to switch the magnetization direction without increasing the STT application time or degrading the switching probability in the presence of room temperature thermal noise. This could lead to a pathway to achieve energy efficient switching of spin-transfer-torque random access memory (STT-RAM) based on p-MTJs whose lateral dimensions can be scaled aggressively despite using materials with low magnetostriction by employing resonant excitation to drive the magnetization away from the easy axis before applying spin torque to achieve a complete reversal.

With the ever-advancing technology, there is an incessant need for reliable electrochemical energy storage (EES) components that can provide desired energy and power. At the forefront of EES systems are electrochemical capacitors (ECs), also known as supercapacitors that typically have higher power and superior cycle longevity but lower energy densities than their battery counterparts. One of the routes to achieve higher energy density for ECs is using the hybrid EC configuration, which typically utilizes a redox electrode coupled with a counter double-layer type electrode. In this dissertation, both scale-up (coin-cell type) as well as scale-down (on-chip miniaturized) hybrid ECs were designed, constructed and evaluated. The first part of the dissertation comprised material identification, syntheses, and electrochemical analyses. Lithium titanate-anatase titanium oxide (Li4Ti5O12-TiO2) composites were synthesized via electrostatic spray deposition (ESD) and characterized in both half-cell and full-cell assembly against lithium and nanostructured carbon based counter electrodes, respectively. The second redox type material studied for hybrid electrochemical capacitors was ESD derived manganese oxide (MnOx). The MnOx electrodes exhibited a high gravimetric capacitance of 225F g-1 in aqueous media. Further improvement in the rate handling of the MnOx electrodes was achieved by using CNT additives. The MnOx-CNT composites were tested in full-cell assembly against activated carbon counter electrodes and tested for different anode and cathode mass ratios in order to achieve the best energy-power tradeoff, which was the second major goal of the dissertation. The optimized hybrid capacitor was able to deliver a high specific energy density of 30.3 Wh kg-1 and a maximal power density of 4kW kg-1. The last part of the dissertation focused on a scale-down miniaturized hybrid microsupercapacitor; an interdigitated electrode design was adopted in order to shorten the ion-transport pathway, and MnOx and reduced graphene oxide (rGO) were chosen as the redox and double layer components, respectively. The hybrid microsupercapacitor was able to deliver a high stack energy density of 1.02 mWh cm-3 and a maximal stack power density of 3.44 W cm-3, both of which are comparable with thin-film batteries and commercial supercapacitor in terms of volumetric energy and power densities.

In the nanoscale metrology industry, there is a need for low-cost instruments, which have the ability to probe the structrure and elemental composition of thin films. This dissertation, describes the research performed to design and simulate a miniature Cylindrical Mirror Analyzer, (CMA), and Auger Electron Spectrometer, (AES). The CMA includes an integrated coaxial thermionic electron source. Electron optics simulations were performed using the Finite Element Method, (FEM), software COMSOL. To address the large Secondary Electron, (SE), noise, inherent in AES spectra, this research also included experiments to create structures in materials, which were intended to suppress SE backgound noise in the CMA. Laser Beam Machining, (LBM), of copper substrates was used to create copper pillars with very high surface areas, which were designed to supress SE’s. The LBM was performed with a Lumera SUPER RAPID‐HE model Neodymium Vanadate laser. The laser has a peak output power of 30 megawatts, has a 5x lens and a spot size of 16 μm. The laser wavelength is in the infrared at 1064 nm, a pulse width of 15 picoseconds, and pulse repetition rate up to 100 kHz. The spectrometer used in this research is intended for use when performing chemical analysis of the surface of bulk materials and thin films. It is applicable for metrology of thin films, as low as 0.4 nm in thickness, without the need to perform destructive sample thinning, which is required in Scanning Tranmission Electron Microscopy, (STEM). The spectrometer design is based on the well known and widely used coaxial cylinder capacitor design known as the Cylindrical Mirror Analyzer, (CMA). The coaxial tube arrangement of the CMA allows for placing an electron source,which is mounted in the center of the inner cylinder of the spectrometer. Simulation of the electron source with an Einzel Lens was also performed. In addtion, experiments with thin film coatings and Laser Beam Machining to supress Secondary Electron emission noise within the Auger electron spectrum were completed. Design geometry for the miniature CMA were modeled using Computer Aided Design, (CAD). Fixed Boundary Conditions, (BC), were applied and the geometry was then meshed for FEM. The electrostatic potential was then solved using the Poisson equation at each point. Having found the solution to the electrostatic potentials, electron flight simulations were performed and compared with the analytical solution. From several commercially available FEM modeling packages, COMSOL Multiphysics was chosen as the research platform for modeling of the spectrometer design. The CMA in this design was reduced in size by a factor of 4 to 5. This enabled mounting the CMA on a 2 ¾ in flange compared to the commercial PHI model 660 CMA which mounts onto a 10 in flange. Results from the Scanning Electron Microscopy measurements of the Secondary Electron emission characteristics of the LBM electron suppressor will also be presented.

Instrumented nanoindentation techniques have been widely used in characterizing mechanical behavior of materials in small length scales. For defect-free single crystals under nanoindentation, the onset of elastic-plastic transition is often shown by a sudden displacement burst in the measured load-displacement curve. It is believed to result from the homogeneous dislocation nucleation because the maximum shear stress at the pop-in load approaches the theoretical strength of the material and because statistical measurements agree with a thermally activated process of homogeneous dislocation nucleation. For single crystals with defects, the pop-in is believed to result from the sudden motion of pre-existing dislocations or heterogeneous dislocation nucleation. If the sample is prestrained before nanoindentation tests, a monotonic decrease of the measured pop-in load with respect to the increase of prestrain on Ni and Mo single crystals is observed. A similar trend is also observed that the pop-in load will gradually decrease if the size of indenter tip radius increases. This dissertation presents a systematic modeling endeavor of energetics and kinetics of defect initiation in the stressed volume at small scales. For homogeneous dislocation nucleation, an indentation Schmid factor is determined as the ratio of maximum resolved shear stress to the maximum contact pressure. The orientation-depended nanoindentation pop-in loads are predicted based on the indentation Schmid factor, theoretical strength of the material, indenter radius, and the effective indentation modulus. A good agreement has been reached when comparing the experimental data of nanoindentation tests on NiAl, Mo, and Ni, with different loading orientations to theoretical predictions. Statistical measurements generally confirm the thermal activation model of homogeneous dislocation nucleation, because the extracted dependence of activation energy on resolved shear stress is almost unique for all the indentation directions. For pop-in due to pre-existing defects, the pop-in load is predicted to be dependent on the defect density and the critical strength for heterogeneous dislocation nucleation. The cumulative probability of pop-in loads contains convoluted information from the homogenous dislocation nucleation, which is sensitive to temperature and loading rate, and heterogeneous dislocation nucleation due to the unstable change of existing defect network, which is sensitive to the initial defect distribution.

This work seeks to fabricate, optimize, and characterize nanofibers of cactus Opuntia ficus-indica mucilage and Poly (vinyl alcohol) (PVA) by electrospinning. Mucilage is a neutral mixture of sugars produced by cactus and PVA is a non-toxic, water-soluble, synthetic polymer, which is widely used as a co-spinning agent for polymers. Mucilage was extracted from the cactus pad and prepared for electrospinning by mixing with acetic acid. Two types of PVA were used differentiating in high and low molecular weights. Concentrations of PVA were varied to find an adequate threshold for fiber formation. Changing the ratio of PVA to cactus mucilage produced fibers of different diameter and quality. The optimizations of the parameters used in the electrospinning setup were also a factor in creating quality fibers without deformity. An acceptable PVA to mucilage ratio mixture was reached for the use of the electrospinning process and consistent nanofibers were accomplished with the use of both the low and high molecular weight PVA. The fibers were observed using a Scanning Electron Microscope, Atomic Force Microscopy, and Differential Scanning Calorimetry. In this project we were able to obtain nanofiber meshes made with environmentally friendly materials with fiber diameters raging from 50nm to 7um sized. The produced nanofibers were made in the hope that it can be utilized in the future as an inexpensive, biocompatible, and biodegradable water filtration system.

Reversible circuits are similar to conventional logic circuits except that they are built from reversible gates. In reversible gates, there is a unique, one-to-one mapping between the inputs and outputs, not the case with conventional logic. Also, reversible gates require constant ancilla inputs for reconfiguration of gate functions and garbage outputs that help in keeping reversibility. Reversible circuits hold promise in futuristic computing technologies like quantum computing, quantum dot cellular automata, DNA computing, optical computing, etc. Thus, it is important to minimize parameters such as ancilla and garbage bits, quantum cost and delay in the design of reversible circuits. The first contribution of this dissertation is the design of a new reversible gate namely the TR gate (Thapliyal-Ranganathan) which has the unique structure that makes it ideal for the realization of arithmetic circuits such as adders, subtractors and comparators, efficient in terms of the parameters such as ancilla and garbage bits, quantum cost and delay. The second contribution is the development of design methodologies and a synthesis framework to synthesize reversible data path functional units, such as binary and BCD adders, subtractors, adder-subtractors and binary comparators. The objective behind the proposed design methodologies is to synthesize arithmetic and logic functional units optimizing key metrics such as ancilla inputs, garbage outputs, quantum cost and delay. A library of reversible gates such as the Fredkin gate, the Toffoli gate, the TR gate, etc. was developed by coding in Verilog for use during synthesis. The third contribution of this dissertation is the set of methodologies for the design of reversible sequential circuits such as reversible latches, flip-flops and shift registers. The reversible designs of asynchronous set/reset D latch and the D flip-flop are attempted for the first time. It is shown that the designs are optimal in terms of number of garbage outputs while exploring the best possible values for quantum cost and delay. The other important contributions of this dissertation are the applications of reversible logic as well as a special class of reversible logic called conservative reversible logic towards concurrent (online) and offline testing of single as well as multiple faults in traditional and reversible nanoscale VLSI circuits, based on emerging nanotechnologies such as QCA, quantum computing, etc. Nanoelectronic devices tend to have high permanent and transient faults and thus are susceptible to high error rates. Specific contributions include (i) concurrently testable sequential circuits for molecular QCA based on reversible logic, (ii) concurrently testable QCA-based FPGA, (iii) design of self checking conservative logic gates for QCA, (iv) concurrent multiple error detection in emerging nanotechnologies using reversible logic, (v) two-vectors, all 0s and all 1s, testable reversible sequential circuits.