Ultra high temperature ceramics (UHTC) are candidate materials for high temperature applications such as leading edges for hypersonic flight vehicles, thermal protection systems for spacecraft, and rocket nozzle throat inserts due to their extremely high melting points. Tantalum and Niobium Carbide (TaC and NbC), with melting points of 3950°C and 3600°C, respectively, have high resistivity to chemical attack, making them ideal candidates for the harsh environments UHTCs are to be used in. The major setbacks to the implementation of UHTC materials for these applications are the difficulty in consolidating to full density as well as their low fracture toughness. In this study, small amounts of sintering additive were used to enhance the densification and Graphene Nanoplatelets (GNP) were dispersed in the ceramic composites to enhance the fracture toughness. While the mechanisms of toughening of GNP addition to ceramics have been previously documented, this study focused on the anisotropy of the mechanisms. Spark plasma sintering was used to consolidate both bulk GNP pellets and near full relative density TaC-NbC ceramic composites with the addition of both sintering aid and GNP and resulted in an aligned GNP orientation perpendicular to the SPS pressing axis that allowed the anisotropy to be studied. In situ high load indentation was performed that allowed real time viewing of the deformation mechanisms for enhanced analysis. The total energy dissipation when indenting the bulk GNP pellet in the in-plane GNP direction was found to be 270% greater than in the out-of-plane orientation due to the resulting deformation mechanisms that occurred. In GNP reinforced TaC-NbC composites, the projected residual damaged area as a result of indentation was 89% greater when indenting on the surface of the sintered compact (out-of-plane GNP orientation) than when indenting in the orthogonal direction (in-plane GNP orientation) which is further evidence to the anisotropy of the GNP reinforcement.

Sneak path current is a significant remaining obstacle to the utilization of large crossbar arrays for non-volatile memories and other applications of memristors. A two-terminal selector device with an extremely large current-voltage nonlinearity and low leakage current could solve this problem. We present here a Ag/oxide-based threshold switching (TS) device with attractive features such as high current-voltage nonlinearity (~1010), steep turn-on slope (less than 1 mV/dec), low OFF-state leakage current (~10-14 A), fast turn ON/OFF speeds (<75/250 ns), and good endurance (>108 cycles). The feasibility of using this selector with a typical memristor has been demonstrated by physically integrating them into a multilayered 1S1R cell. Structural analysis of the nanoscale crosspoint device suggests that elongation of a Ag nanoparticle under voltage bias followed by spontaneous reformation of a more spherical shape after power off is responsible for the observed threshold switching of the device. Such mechanism has been quantitatively verified by the Ag nanoparticle dynamics simulation based on thermal diffusion assisted by bipolar electrode effect and interfacial energy minimization.

Understanding the mechanisms that control the mechanical behavior of microscale actuators is necessary to design an actuator that responds to an applied actuation force with the desired behavior. Micro actuators which employ a diaphragm supported by torsional hinges which deform during actuation are used in many applications where device stability and reliability are critical. The material response to the stress developed within the hinge during actuation controls how the actuator will respond to the actuating force. A fully recoverable non-linear viscoelastic response has been observed in electrostatically driven micro actuators employing torsional hinges of silicon covered with thin metal films. The viscoelastic response occurs over a time period of 50 minutes at an operating temperature of 35°C. This viscoelastic phenomenon is similar to that reported in articles addressing anelastic behavior associated with viscous grain boundary slippage and dislocation bowing. In order to investigate this viscoelastic response as a function of metal film composition and thickness, bi-layer torsional hinge actuators consisting of Si with a deposited metal layer were designed to exhibit similar stress levels as the electrostatically driven micro actuators. The test devices were fabricated using common semiconductor fabrication techniques. The actuators were micromachined by deep etching 100mm diameter, 425µm thick, double side polished, single crystal (100) wafers to create a 4.5µm thick device layer. Subsequent etching of the device layer released the fixed-fixed torsional hinge test actuators. Physical vapor depositions of Au, Al and Al-Ti in two different thicknesses (100nm, and 150nm) were deposited in order to investigate the impact of metal film thickness and composition on the viscoelastic response. Grain sizes of the deposited films were estimated using backscattered electron images. Rotational actuation of the test actuators was achieved by using a modified Ambios XP-1 surface profiler that applies a constant force of 0.28mN while measuring the displacement of the actuator with respect to time. The viscoelastic response was observed in the test devices with Au and Al thin films indicating that this phenomenon is attributable to the stresses induced on the torsional hinge. Results indicate that the viscoelastic response was not observed in AlTi thin films consisting of 0.3at% titanium. Two theoretical models are presented that discuss the mechanism associated with the viscoelastic response as well as a method for inhibiting these mechanisms by the addition of an alloying element to form a second phase precipitate.

Post-combustion CO2 capture is a promising approach for complementing other strategies to mitigate climate change. Liquid absorption is currently used to capture CO2 from post-combustion flue gases. However, the high energy cost required to regenerate the liquid absorbents is a major drawback for this process. As a result, solid sorbents have been investigated extensively in recent years as alternative media to capture CO2 from flue gases. For example, metal organic frameworks (MOFs) are nanoporous materials that have high surface areas, large pore volumes, and flexible designs. A large number of MOFs, however, suffer from 1) low CO2 adsorption capacity at low pressure, which is the typical condition for flue gases, 2) degradation upon exposure to water present in flue gases, and 3) low selectivity of CO2 when present in a mixture of gases. Zeolitic Imidazolate Frameworks (ZIFs) are heavily investigated MOFs for CO2 sorption applications because they have better selectivity for CO2 compared to other MOFs and are resistant to degradation in water due to their hydrophobic nature. However, ZIFs (e.g., ZIF-8) investigated for CO2 sorption applications are typically produced using toxic solvents and their CO2 sorption capacity is drastically lower than other types of MOFs. Post-synthesis modifications with amine functional groups have been known to increase CO2 sorption capacity and selectivity within nanoporous materials. For ZIFs, previous research showed that sufficient loading with linear polyethyleneimine increased their CO2 sorption capacity. Therefore, the objectives of this research were to a) investigate the CO2 sorption capacity of ZIF-8 synthesized by solvothermal methods that use more eco-friendly solvents (e.g., methanol and water) and b) introduce post-synthetic modifications to ZIF-8 using branched polyethyleneimine (bPEI) to enhance its sorption capacity. A custom quartz crystal microbalance (QCM) system was assembled and used to measure the CO2 sorption capacity of unmodified and bPEI-modified ZIF-8 sorbent. The tests were conducted at 0.3 - 1 bar. The results showed that the unmodified ZIF-8 synthesized in methanol (ZIF-8-MeOH) had comparable crystal structure, thermal stability, surface area, and chemical properties to that of literature (Ta et.al 2018). ZIF-8-MeOH had a surface area of 1300 m2/g and a CO2 sorption capacity of 0.85 mmol CO2/g ZIF-8 @ 1 bar. This surface area and sorption capacity are comparable to those of ZIF-8 made in dimethylformamide (DMF). Therefore, ZIF-8-MeOH proved to be a worthy candidate MOF for replacing the ZIF-8 made in DMF for CO2 capture research. Water-based ZIF-8 was also synthesized in this study; however, its CO2 sorption capacity was not tested because it exhibited a significantly lower surface area (732 m2/g) compared to that of ZIF-8-MeOH. Modification of the ZIF-8-MeOH with bPEI resulted in a decrease in its CO2 sorption capacity. This undesired outcome is likely a result of insufficient bPEI load (mass attached), on ZIF-8-MeOH (~ 10% w/w) combined with the surface area lost (~ 770 m2/g) due to bPEI blocking some of the ZIF-8-MeOH pores. Therefore, the bPEI load attained in this study was not enough to compensate for the loss of surface area of the modified ZIF-8 and thus, the CO2 sorption capacity decreased. Future investigations should enhance the post-synthetic modification by increasing the loading of amine functional groups onto the eco-friendlier ZIF-8-MeOH used in this study.

A microfluidic reactor for synthesizing cadmium selenide (CdSe) quantum dots (QDs) was synthesized out of a silicon wafer and Pyrex glass. Microfabrication techniques were used to etch channels into the silicon wafer. Holes were wet-drilled into the Pyrex glass using a diamond-tip drill bit. The Pyrex wafer was anodically bonded to the etched silicon wafer to enclose the microfluidic reactor. Conditions for anodic bonding were created by exposing the stacked substrates to 300V at ~350oC under 5.46N of force. A syringe containing a room temperature CdSe solution was interfaced to the microfluidic reactor by using Poly (dimethylsiloxane) (PDMS) as an interface. The reactor was placed on a hot plate at 225oC, creating thermodynamic conditions for the QD chemical reaction to occur within the etched channels. Tygon® tubing transported solutions in and out of the microfluidic reactor. The CdSe solution was injected into the reactor by a syringe pump at an injection rate of 5 mL/hr, with a channel length of 2.5 cm. While in the microfluidic channels, QD residence time of approximately 30 seconds was sufficient enough for nucleation and growth of QDs to occur. The QD size was characterized by fluorescence full-width-half-maximum (FWHM), which is directly proportional to size distribution. The FWHM of the QDs synthesized was 38 nm, with a peak wavelength of 492 nm. By controlling combinations of pump rate and channel length, a range of QD sizes was able to be consistently synthesized through the microfluidic reactor with significant repeatability and reproducibility.

Piezoelectric materials in the forms of both bulk and thin-film have been widely used as actuators and sensors due to their electromechanical coupling. The characterization of piezoelectric materials plays an important role in determining device performance and reliability. Instrumented indentation is a promising method for probing mechanical as well as electrical properties of piezoelectric materials. The use of instrumented indentation to characterize the properties of piezoelectric materials requires analytical relations. Finite element methods are used to analyze the indentation of piezoelectric materials under different mechanical and electrical boundary conditions. For indentation of a piezoelectric half space, a three-dimensional finite element model is used due to the anisotropy and geometric nonlinearity. The analysis is focused on the effect of angle between poling direction and indentation-loading direction on indentation responses. For the indentation by a flat-ended cylindrical indenter, both insulating indenter and conducting indenter without a prescribed electric potential are considered. The results reveal that both the indentation load and the magnitude of the indentation-induced potential at the contact center increase linearly with the indentation depth. For the indentation by an insulating Berkovich indenter, both frictionless and frictional contact between the indenter and indented surface are considered. The results show the indentation load is proportional to the square of the indentation depth, while the indentation-induced potential at the contact center is proportional to the indentation depth. Spherical indentation of piezoelectric thin films is analyzed in an axisymmetric finite element model, in which the poling direction is anti-parallel to the indentation-loading direction. Six different combinations of electrical boundary conditions are considered for a thin film perfectly bonded to a rigid substrate under the condition of the contact radius being much larger than the film thickness. The indentation load is found to be proportional to the square of the indentation depth. To analyze the decohesion problem between a piezoelectric film and an elastic substrate, a traction-separation law is used to control the interfacial behavior between a thin film and an electrically grounded elastic substrate. The discontinuous responses at the initiation of interfacial decohesion are found to depend on interface and substrate properties.

Lung cancer is one of the leading causes of cancer deaths in the United States. Radiation and chemotherapy are conventional treatments, but they result in serious side effects and the probability of tumor recurrence remains high. Therefore, there is an increasing need to enhance the efficacy of conventional treatments. Magnetic nanoparticles have been previously studied for a variety of applications such as magnetic resonance imaging contrast agents, anemia treatment, magnetic cell sorting and magnetically mediated hyperthermia (MMH). In this work, dextran coated iron oxide nanoparticles were developed and functionalized with peptides to target the nanoparticles to either the extracellular matrix (ECM) of tumor tissue or to localize the nanoparticles in subcellular regions after cell uptake. The magnetic nanoparticles were utilized for a variety of applications. First, heating properties of the nanoparticles were utilized to administer hyperthermia treatments combined with chemotherapy. The nanoparticles were functionalized with peptides to target fibrinogen in the ECM and extensively characterized for their physicochemical properties, and MMH combined with chemotherapy was able to enhance the toxicity of chemotherapy. The second application of the nanoparticles was magnetically mediated energy delivery. This treatment does not result in a bulk temperature rise upon actuation of the nanoparticles by an alternating magnetic field (AMF) but rather results in intracellular damage via friction from Brownian rotation or nanoscale heating effects from Neél relaxations. The nanoparticles were functionalized with a cell penetrating peptide to facilitate cell uptake and lysosomal escape. The intracellular effects of the internalized nanoparticles alone and with activation by an AMF were evaluated. Iron concentrations in vivo are highly regulated as excess iron can catalyze the formation of the hydroxyl radical through Fenton chemistry. Although often a concern of using iron oxide nanoparticles for therapeutic applications, these inherent toxicities were harnessed and utilized to enhance radiation therapy. Therefore, the third application of magnetic nanoparticles was their ability to catalyze reactive oxygen species formation and increase efficacy of radiation. Overall, iron oxide nanoparticles have a variety of cancer therapy applications and are a promising class of materials for increasing efficacy and reducing the side effects of conventional cancer treatments.

This dissertation addresses the synthesis mechanism of mesoporous titania thin films with 2D Hexagonal Close Packed (HCP) cylindrical nanopores by an evaporation-induced self-assembly (EISA) method with Pluronic surfactants P123 and F127 as structure directing agents, and their applications in photovoltaics and lithium ion batteries. To provide orthogonal alignment of the pores, surface modification of substrates with crosslinked surfactant has been used to provide a chemically neutral surface. GISAXS studies show not only that aging at 4°C facilitates ordered mesostructure development, but also that aging at this temperature helps to provide orthogonal orientation of the cylindrical micelles which assemble into an ordered mesophase directly by a disorder-order transition. These films provide pores with 8-9 nm diameter, which is precisely the structure expected to provide short carrier diffusion length and high hole conductivity required for efficient bulk heterojunction solar cells. In addition, anatase titania is a n-type semiconductor with a band gap of +3.2 eV. Therefore, titania readily absorbs UV light with a wavelength below 387 nm. Because of this, these titania films can be used as window layers with a p-type semiconductor incorporated into the pores and at the top surface of the device to synthesize a photovoltaic cell. The pores provide opportunities to increase the surface area for contact between the two semiconductors, to align a p-type semiconductor at the junction, and to induce quantum confinement effects. These titania films with hexagonal phase are infiltrated with a hole conducting polymer, poly(3-hexylthiophene) (P3HT), in order to create a p-n junctions for organic-inorganic hybrid solar cells, by spin coating followed by thermal annealing. This assembly is hypothesized to give better photovoltaic performance compared to disordered or bicontinuous cubic nanopore arrangements; confinement in cylindrical nanopores is expected to provide isolated, regioregular “wires” of conjugated polymers with tunable optoelectronic properties, such as improved hole conductivity over that in bicontinuous cubic structure. The kinetics of infiltration into the pores show that maximum infiltration occurs within less than one hour in these films, and give materials with improved photovoltaic performance relative to planar TiO2/P3HT assemblies. These oriented mesoporous titania films are also used to develop an inorganic solar cell by depositing CdTe at the top using the Close Spaced Sublimation (CSS) technique. A power conversion efficiency of 5.53% is measured for heterostructures built using mesoporous titania films, which is significantly enhanced relative to planar TiO2/CdTe devices and prior reports in the literature. These mesoporous titania films have a great potential in inorganic solar cell development and can potentially replace CdS window layers which are conventionally used in inorganic CdS-CdTe solar cells. The last part of the dissertation addresses layer-by-layer synthesis to increase the thickness of mesoporous titania films with vertically oriented 2D-HCP nanopores, and their use in lithium ion batteries as negative electrodes because of advantages such as good cycling stability, small volume expansion (~3%) during intercalation/extraction and high discharge voltage plateau. The high surface area and small wall thickness of these titania films provide excellent lithium ion insertion and reduced Li-ion diffusion length, resulting in stable capacities as high as 200-250 mAh/g over 200 cycles.

Design and synthesis of porous organic polymers have attracted considerable attentions during the past decade due to their wide range of applications in gas storage, gas separation, energy conversion, and catalysis. Porous organic polymers can be pre-synthetically and post-synthetically functionalized with a wide variety of functionalities for desirable applications. Along these pursuits, we introduced new synthetic strategies for preparation of porous organic polymers for selective CO2 capture. Porous azo-linked polymers (ALPs) were synthesized by an oxidative reaction of amine-based monomers using copper(I) as a catalyst which leads to azo-linkage formation. ALPs exhibit high surface areas of up to 1200 m2 g-1 and have high chemical and thermal stabilities. The nitrogen atoms of the azo group can act as Lewis bases and the carbon atom of CO2 can act as a Lewis acid. Therefore, ALPs show high CO2 uptake capacities due to this Lewis acid-based interaction. The potential applications of ALPs for selective CO2 capture from flue gas, natural gas, and landfill gas under pressure-swing and vacuum swing separation settings were studied. Due to their high CO2 uptake capacity, selectivity, regenerability, and working capacity, ALPs are among the best porous organic frameworks for selective CO2 capture. In our second project, a new bis(imino)pyridine-linked porous polymer (BIPLP-1) was synthesized and post-synthetically functionalized with Cu(BF4)2 for highly selective CO2 capture. BIPLP-1 was synthesized via a condensation reaction between 2,6-pyridinedicarboxaldehyde and 1,3,5-tris(4-aminophenyl)benzene, wherein the bis(imino)pyridine linkages are formed in-situ during polymerization. The functionalization of the polymer with Cu(BF4)2 was achieved by treatment of the polymer with a solution of Cu(BF4)2 via complexation of copper cations with bis(imino)pyridine moieties of the polymer. BF4- ions can act Lewis base and CO2 can act as a Lewis acid; and therefore, the functionalized polymer shows high binding affinity for CO2 due to this Lewis acid-based interaction. The functionalization of the pores with Cu(BF4)2 resulted in a significant enhancement in CO2 binding energy, CO2 uptake capacity, and CO2 selectivity values. Due to high reactivity of bis(imino)pyridines toward transitions metals, BIPLP-1 can be post-synthetically functionalized with a wide variety of inorganic species for CO2 separation and catalytic applications.

Research in future generation computing is focused on reducing energy dissipation while maintaining the switching speed in a binary operation to continue the current trend of increasing transistor-density according to Moore’s law. Unlike charge-based CMOS technology, spin-based nanomagnetic technology, based on switching bistable magnetization of single domain shape-anisotropic nanomagnets, has the potential to achieve ultralow energy dissipation due to the fact that no charge motion is directly involved in switching. However, switching of magnetization has not been any less dissipative than switching transistors because most magnet switching schemes involve generating a current to produce a magnetic field, or spin transfer torque or domain wall motion to switch magnetization. Current-induced switching invariably dissipates an exorbitant amount of energy in the switching circuit that nullifies any energy advantage that a magnet may have over a transistor. Magnetoelastic switching (switching the magnetization of a magnetostrictive magnet with voltage generated stress) is an unusual switching paradigm where the dissipation turns out to be merely few hundred kT per switching event – several orders of magnitude less than that encountered in current-based switching. A fundamental obstacle, though, is to deterministically switch the magnetization of a nanomagnet between two stable states that are mutually anti-parallel with stress alone. In this work, I have investigated ways to mitigate this problem. One popular approach to flip the magnetizations of a nanomagnet is to pass a spin polarized current through it that transfers spin angular moment from the current to the electrons in the magnet, thereby switching their spins and ultimately the magnet’s magnetization. This approach – known as spin transfer torque (STT) – is very dissipative because of the enormous current densities needed to switch magnets, We, therefore, devised a mixed mode technique to switch magnetization with a combination of STT and stress to gain both energy efficiency from stress and deterministic 180o switching from STT. This approach reduces the total energy dissipation by roughly one order of magnitude. We then extended this idea to find a way to deterministically flip magnetization with stress alone. Sequentially applying stresses along two skewed axes, a complete 180o switching can be achieved. These results have been verified with stochastic Landau-Lifshitz-Gilbert simulation in the presence of thermal noise. The 180o switching makes it possible to develop a genre of magneto-elastic memory where bits are written entirely with voltage generated stress with no current flow. They are extremely energy-efficient. In addition to memory devices, a universal NAND logic device has been proposed which satisfies all the essential characteristics of a Boolean logic gate. It is non-volatile unlike transistor based logic gates in the sense that that gate can process binary inputs and store the output (result) in the magnetization states of magnets, thereby doubling as both logic and memory. Such dual role elements can spawn non-traditional non-von-Neumann architectures without the processor and memory partition that reduces energy efficiency and introduces additional errors. A bit comparator is also designed, which happens to be all straintronic, yet reconfigurable. Moreover, a straintronic spin neuron is designed for neural computing architecture that dissipates orders of magnitude less energy than its CMOS based counterparts. Finally, an experiment has been performed to demonstrate a complete 180o switching of magnetization in a shape anisotropic magnetostrictive Co nanomagnet using voltage generated stress. The device is synthesized with nano-fabrication techniques namely electron beam lithography, electron beam evaporation, and lift off. The experimental results vindicate our proposal of applying sequential stress along two skewed axes to reverse magnetization with stress and therefore, provide a firm footing to magneto-elastic memory technology.