In the age of 5th and upcoming 6th generation fighter aircraft one key proponent of these impressive machines is the inclusion of stealth. This inclusion is demonstrated by thoughtful design pertaining to the shape of the aircraft and rigorous material selection. Both criteria aim to minimize the radar cross section of these aircraft over a wide bandwidth of frequencies corresponding to an ever-evolving field of radar technology. Stealth is both an offensive and defensive capability meaning that service men and women depend on this feature to carry out their missions, and to return home safely. The goal of this paper is to introduce a novel method to designing disordered two-phase composites with desired electromagnetic properties. This task is accomplished by employing the spatial point correlation function, specifically at the two-point level. Effective at describing the dispersion of phases within a two-phase system, the two-point correlation function serves as a statistical function that becomes a realizable target for heterogeneous composites. Simulated annealing is exercised to reconstruct two-phase composite microstructures that initially do not match their target function, followed by two separate experiments aimed at studying the impact of the provided inputs on its outcome. Once conditions for reconstructing highly accurate microstructures are identified, modifications are made to the target function to extract and compare dielectric constants associated with each microstructure. Both the real and imaginary components, which respectively affect wave propagation and attenuation, of the dielectric constants are plotted to illustrate their behavior with increasing wavenumber. Conclusions suggest that favorable values of the complex dielectric constant can be reverse-engineered via careful consideration of the two-point correlation function. Subsequently, corresponding microstructures of the composite can be simulated and then produced through 3-D printing for testing and practical applications.

Covalent organic frameworks (COFs) are a recently discovered class of nanoporous polymeric materials with ultra-high specific surface areas, which makes them highly attractive for applications in nanofiltration, gas capture and storage, and catalysis. However, the macroscopic morphology of COFs is maintained by relatively weak physical interactions between crystallites, which limits the applications of COFs where they may experience significant physical stresses. Herein, fillers are added to three-dimensional TAPB-PDA COF aerogels synthesized to improve the mechanical strength and functionality through the formation of a composite material by physically implanting the fillers in the macropores present in the gel network. Boron nitride loading is shown to double the Young’s modulus of the aerogel, from 11 kPa to 22 kPa, at 20 relative weight percent loading, while only causing a 10% decrease in accessible nanoporous surface area, normalized to the mass of COF in the sample. Poly(acrylic acid) added at 5 relative weight percent loading and crosslinked increases the Young’s modulus to 21 kPa and simultaneously increases the elastic limit of the aerogel from 10% to 65% strain, while inducing a 38% decrease in accessible nanoporous surface area, normalized to the mass of COF in the sample. This work demonstrates the potential for macroscopic composites with COFs forming the majority phase of the material, showing the possibility for mechanical reinforcement without significant hinderance of the adsorbent functionality of the material.

Layered oxyhalide magnetic materials have recently emerged as one of the most promising material systems in the field of spintronics and quantum devices because of their large optical anisotropy, magnetic phase transition associated with structural changes, strong antiferromagnetism coupled with weak interlayer bonding and high environmental stability. Despite their attractive magnetic properties and outstanding environmental stability, bottom-up approaches for scalable growth remain limited due to presence of coexisting phases with different stoichiometry in their phase diagram.This work presents the first synthesis of environmentally stable ultra-thin flakes of oxyhalide magnetic CrOCl on Mica and Sapphire substrates using CrCl¬3 and KMnO4 as precursor materials through Atmospheric-Pressure Chemical Vapor Deposition (APCVD) technique in the presence of Argon carrier gas. Comprehensive characterization techniques such as Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS) and X-ray Diffraction (XRD) were employed to confirm the stoichiometry and crystallinity of the grown CrOCl flakes. The findings of the work revealed that the quality of the CrOCl flakes depends on the concentration of the oxygen radicals provided by KMnO4 precursor and substrate temperature. Moreover, morphology and the phase of the material are strongly affected by a variety of factors such as the carrier gas flow rate, the growth time, and the growth temperature. Overall, this work expands the fundamental understanding of the bottom-up growth mechanisms involved in synthesizing such materials thereby contributing to the expansion of the library of stable magnetic oxides with potential applications in advanced technological devices.

As society moves to reduce the effects of climate change, there is a growing needfor the use of polymer science in technologies to mitigate the emission of carbon dioxide. Networks containing quaternary ammonium groups with corresponding HCO3 ions providing the mobile counter-charge in the networks have been reported to capture carbon dioxide directly from the atmosphere through a moisture swing mechanism, among other mechanisms. In this work, microstructural analysis of synthesized polystyrene-based anion exchange networks is conducted using known characterization techniques to better understand if variations in sorbent microstructure adjust the distances between the quaternary ammonium groups. Additional surface morphology studies of these sorbents are conducted. X-Ray Diffraction (XRD) spectra reveal the amorphous structure of these polymers and the ability to adjust the distance between quaternary ammonium groups by introducing different spacer groups and various anions into the networks, which may affect the spontaneity of the CO2 to chemisorb to these sorbents. However, Wide Angle X-Ray Scattering (WAXS) conflicts with the XRD data, indicating a change in distance between these groups is not achieved. Additionally, WAXS data indicates an ability to increase the homogeneity of structure in these materials by introducing larger counterions into the networks. Small Angle X-Ray Scattering (SAXS) reveals no obvious large morphological features in these sorbents, which is supported by Scanning Electron Microscopy (SEM) images. In conclusion, XRD and WAXS experiments exhibit conflicting data regarding the ability to adjust the distances between the quaternary ammonium groups in these networks. Proposed actions to resolve this conflict are presented. Finally, SEM sheds light on particle size and morphological features of these materials.

Diamond transistors are promising as high-power and high-frequency devices having higher efficiencies than conventional transistors. Diamond possesses superior electronic properties, such as a high bandgap (5.47 eV), high breakdown voltage (>10 MV cm−1 ), high electron and hole mobilities [4500 and 3800 cm2 V−1 · s−1, respectively], high electron and hole saturation velocities (1.5 × 107 and 1.05 × 107 cm s−1, respectively), and high thermal conductivity [22 W cm−1 · K−1], compared to conventional semiconductors. Reportedly, the diamond field-effect transistors (FETs) have shown transition frequencies (fT) of 45 and 70 GHz, maximum oscillation frequency (fmax) of 120 GHz, and radiofrequency (RF) power densities of 2.1 and 3.8 W mm−1 at 1 GHz. A two-dimensional-hole-gas (2DHG) surface channel forms on H-diamond by transfer doping from adsorbates/dielectrics in contact with H-diamond surface. However, prior studies indicate that charge transfer at the dielectric/ H-diamond interface could result in relatively low mobility attributed to interface scattering from the transferred negative charge to acceptor region. H-terminated diamond exhibits a negative electron affinity (NEA) of -1.1 to -1.3 eV, which is crucial to enable charge transfer doping. To overcome these limitations modulation doping, that is, selective doping, that leads to spatial separation of the MoO3 acceptor layer from the hole channel on H-diamond has been proposed. Molybdenum oxide (MoO3) was used as dielectric as it has electron affinity of 5.9eV and could align its conduction band minimum (CBM) below the valence band maximum (VBM) of H-terminated diamond. The band alignment provides the driving potential for charge transfer. Hafnium oxide (HfO2) was used as interfacial layer since it is a high-k oxide insulator (∼25), having large Eg (5.6 eV), high critical breakdown field, and high thermal stability. This study presents photoemission measurements of the electronic band alignments of the MoO3/HfO2/H-diamond layer structure to gain insight into the driving potential for the negative charge transfer and the location of the negative charges near the interface, in the HfO2 layer or in the MoO3 layer. The diamond hole concentration, mobility, and sheet resistance were characterized for MoO3/HfO2/H-Diamond with HfO2 layers of 0, 2 and 4 nm thickness.

Doping is the cornerstone of Semiconductor technology, enabling the functionalities of modern digital electronics. Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have tunable direct bandgaps, strong many-body interactions, and promising applications in future quantum information sciences, optoelectronic, spintronic, and valleytronic devices. However, their wafer-scale synthesis and precisely controllable doping are challenging. Moreover, there is no fixed framework to identify the doping concentration, which impedes their process integration for future commercialization. This work utilizes the Neutron Transmutation Doping technique to control the doping uniformly and precisely in TMDCs. Rhenium and Tin dopants are introduced in Tungsten- and Indium-based Chalcogenides, respectively. Fine-tuning over 0.001% doping level is achieved. Precise analytical techniques such as Gamma spectroscopy and Secondary Ion Mass Spectrometry are used to quantify ultra-low doping levels ranging from 0.005-0.01% with minimal error. Dopants in 2D TMDCs often exhibit a broad stokes-shifted emission, with high linewidths, due to extrinsic effects such as substrate disorder and surface adsorbates. A well-defined bound exciton emission induced by Rhenium dopants in monolayer WSe2 and WS2 at liquid nitrogen temperatures is reported along with specific annealing regimes to minimize the defects induced in the Neutron Transmutation process. This work demonstrates a framework for Neutron Doping in 2D materials, which can be a scalable process for controlling doping and doping-induced effects in 2D materials.

Applications like integrated circuits, microelectromechanical devices, antennas, sensors, actuators, and metamaterials benefit from heterogeneous material systems made of metallic structures and polymer matrixes. Due to their distinctive shells made of metal and polymer, scaly-foot snails, which are found in the deep ocean, exhibit high strength and temperature resistance. Recent metal deposition fabrication techniques have been used to create a variety of multi-material structures. However, using these complex hybrid processes, it is difficult to build complex 3D structures of heterogeneous material with improved properties, high resolution, and time efficiency. The use of electrical field-assisted heterogeneous material printing (EFA-HMP) technology has shown potential in fabricating metal-composite materials with improved mechanical properties and controlled microstructures. The technology is an advanced form of 3D printing that allows for printing multiple materials with different properties in a single print. This allows for the creation of complex and functional structures that are not possible with traditional 3D printing methods. The development of a photocurable printing solution was carried out that can serve as an electrolyte for charge transfer and further research into the printing solution's curing properties was conducted. A fundamental understanding of the formation mechanism of metallic structures on the polymer matrix was investigated through physics-based multiscale modeling and simulations. The relationship between the metallic structure's morphology, the printing solution's properties, and the printing process parameters was discovered.The thesis aims to investigate the microstructures and electrical properties of metal-composite materials fabricated using EFA-HMP technology and to evaluate the correlation between them. Several samples of metal-composite materials with different microstructures will be fabricated using EFA-HMP technology to accomplish this. The results of this study will provide a better understanding of the relationship between the microstructures and properties of metal-composite materials fabricated using EFA-HMP technology and contribute to the development of new and improved materials in various fields of application. Furthermore, this research will also shed light on the advantages and limitations of EFA-HMP technology in fabricating metal-composite materials and study the correlation between the microstructures and mechanical properties.

In the past decade, 2D materials especially transition metal dichalcogenides (TMDc), have been studied extensively for their remarkable optical and electrical properties arising from their reduced dimensionality. A new class of materials developed based on 2D TMDc that has gained great interest in recent years is Janus crystals. In contrast to TMDc, Janus monolayer consists of two different chalcogen atomic layers between which the transition metal layer is sandwiched. This structural asymmetry causes strain buildup or a vertically oriented electric field to form within the monolayer. The presence of strain brings questions about the materials' synthesis approach, particularly when strain begins to accumulate and whether it causes defects within monolayers.The initial research demonstrated that Janus materials could be synthesized at high temperatures inside a chemical vapor deposition (CVD) furnace. Recently, a new method (selective epitaxy atomic replacement - SEAR) for plasma-based room temperature Janus crystal synthesis was proposed. In this method etching and replacing top layer chalcogen atoms of the TMDc monolayer happens with reactive hydrogen and sulfur radicals. Based on Raman and photoluminescence studies, the SEAR method produces high-quality Janus materials. Another method used to create Janus materials was the pulsed laser deposition (PLD) technique, which utilizes the interaction of sulfur/selenium plume with monolayer to replace the top chalcogen atomic layer in a single step. The goal of this analysis is to characterize microscale defects that appear in 2D Janus materials after they are synthesized using SEAR and PLD techniques. Various microscopic techniques were used for this purpose, as well as to understand the mechanism of defect formation. The main mechanism of defect formation was proposed to be strain release phenomena. Furthermore, different chalcogen atom positions within the monolayer result in different types of defects, such as the appearance of cracks or wrinkles across monolayers. In addition to investigating sample topography, Kelvin probe force microscopy (KPFM) was used to examine its electrical properties to see if the formation of defects impacts work function. Further study directions have been suggested for identifying and characterizing defects and their formation mechanism in the Janus crystals to understand their fundamental properties.

Many important technologies, including electronics, computing, communications, optoelectronics, and sensing, are built on semiconductors. The band gap is a crucial factor in determining the electrical and optical properties of semiconductors. Beyond graphene, newly found two-dimensional (2D) materials have semiconducting bandgaps that range from the ultraviolet in hexagonal boron nitride to the terahertz and mid-infrared in bilayer graphene and black phosphorus, visible in transition metal dichalcogenides (TMDs). These 2D materials were shown to have highly controllable bandgaps which can be controlled by alloying. Only a small number of TMDs and monochalcogenides have been alloyed, though, because alloying compromised the material's Van der Waals (Vdw) property and the stability of the host crystal lattice phase. Phase transition in 2D materials is an interesting phenomenon where work has been done only on few TMDs namely MoTe2, MoS2, TaS2 etc.In order to change the band gaps and move them towards the UV (ultraviolet) and IR (infrared) regions, this work has developed new 2D alloys in InSe by alloying them with S and Te at 10% increasing concentrations. As the concentration of the chalcogens (S and Te) increased past a certain point, a structural phase transition in the alloys was observed. However, pinpointing the exact concentration for phase change and inducing phase change using external stimuli will be a thing of the future. The resulting changes in the crystal structure and band gap were characterized using some basic characterization techniques like scanning electron microscopy (SEM), X-ray Diffraction (XRD), Raman and photoluminescence spectroscopy.