Group III-A nitrides (GaN, AlN, InN and alloys) are materials of considerable contemporary interest and currently enable a wide variety of optoelectronic and high-power, high-frequency electronic applications. All of these applications utilize device structures that employ a single or multiple hetero-junctions, with material compositions varying across the interface. For example, the workhorse of GaN based electronic devices is the high electron mobility transistor (HEMT) which is usually composed of an AlGaN/GaN hetero-junction, where a two-dimensional electron gas (2DEG) is formed due to differences in polarization between the two layers. In addition to such hetero-junctions in the same material family, formation of hetero-interfaces in nitrides begins right from the epitaxy of the very first layer due to the lack of native substrates for their growth. The consequences of such "dissimilar" hetero-junctions typically manifest as large defect densities at this interface which in turn gives rise to defective films. Additionally, if the substrate is also a semiconductor, the electrical properties at such dissimilar semiconductor-nitride hetero-junctions are particularly important in terms of their influence on the performance of nitride devices. Nevertheless, the large defect densities at such dissimilar 3D-3D semiconductor interfaces, which translate into more trap states, also prevents them from being used as active device layers to say nothing of reliability considerations arising because of these defects. Recently, the advent of 2D materials such as graphene and MoS2 has opened up avenues for Van der Waal’s epitaxy of these layered films with practically any other material. Such defect-free integration enables dissimilar semiconductor hetero-junctions to be used as active device layers with carrier transport across the 2D-3D hetero-interface. This thesis deals with hetero-epitaxial growth platforms for reducing defect densities, and the material and electrical properties of dissimilar hetero-junctions with the group III-A nitride material system.

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The addition of hexagonal boron nitride (h-BN) has introduced a comprehensive reinforcing effect to the mechanical and electrochemical properties of commercial concrete, including fiber reinforced concrete (FRC) and steel fiber reinforced concrete (SFRC). Although this has been proven effective and applicable, further investigation and study is still required to optimize the strengthen result which will involve the exfoliation of h-BN into single-layered nano sheet, improving the degree of dispersion and dispersion uniformity of h-BN into concrete matrix. There is currently no direct method to test the degree of dispersion of non-conductive particles, including h-BN, in concrete matrix, therefore it is necessary to obtain an analogous quantification method like SEM, etc. The reinforcing mechanism on concrete, including FRC and SFRC is now attracting a great number of interest thanks to the huge potential of application and vast demand across the world. This study briefly describes the reinforcing mechanism brought by h-BN. In this study, different samples under varied conditions were prepared according to the addition of h-BN and dispersant to build a parallel comparison. Characterization is mainly focused on their mechanical properties, corrosive performance and SEM analysis of the cross-section of post-failure samples.

Glasses and ceramics offer several unique characteristics over polymers or metals. However, they suffer from a shortcoming due to their brittle nature, falling short in terms of fracture toughness and mechanical strength. The aim of this work is to reinforce borosilicate glass matrix with reinforcements to increase the fracture toughness and strength of the glass. Boron nitride nanomaterials, i.e. nanotubes and nanosheets have been used as possible reinforcements for the borosilicate glass matrix. The tasks of the thesis are many fold which include: 1. Reinforcement of commercially derived and morphologically different (bamboo like and cylinder like) boron nitride nanotubes in borosilicate glass with the concentration of 0 wt%, 2.5 wt% and 5 wt% by ball milling process. Same process was repeated with reinforcing cleaned boron nitride nanotubes (after acid purification) into the borosilicate glass with similar concentrations. 2. Production of boron nitride nanosheets using liquid exfoliation technique to produce high quality and high aspect ratio nanosheets. These boron nitride nanosheets were reinforced in the borosilicate glass matrix with concentrations of 0 wt%, 2.5 wt% and 5 wt% by ball milling process. The samples were consolidated using spark plasma sintering. These composites were studied in details in terms of material analysis like thermo-gravimetric analysis, detailed scanning electron microscopy and transmission electron microscopy for the quality of reinforcements etc.; microstructure analysis which include the detailed study of the composite powder samples, the densities of bulk composite samples etc; mechanical properties which include fracture toughness, flexural strength, micro-hardness, Young’s modulus etc. and; tribological properties like scratch resistance and wear resistance. Cleaning process of boron nitride nanotubes lead to reduction in the Fe content (present in boron nitride nanotubes during their production as a catalyst) by ~54%. This leads to an improvement of ~30% of fracture toughness measured by chevron notch technique for 5 wt% boron nitride nanotubes reinforced borosilicate glass. It also contributed to the improvement of scratch resistance by ~26% for the 5 wt% boron nitride nanotubes reinforced borosilicate glass matrix. On the other hand, boron nitride nanosheets were successfully produced using liquid exfoliation technique with average length was ~0.5 µm and thickness of the nanosheets was between 4-30 layers. It accounted to an improvement of ~45% for both fracture toughness and flexural strength by reinforcing 5 wt% of boron nitride nanosheets. The wear rates reduced by ~3 times while the coefficient of friction was reduced by ~23% for 5 wt% boron nitride nanosheets reinforcements. Resulting improvements in fracture toughness and flexural strength in the composite materials were observed due to high interfacial bonding between the boron nitride nanomaterials and borosilicate glass matrix resulting in efficient load transfer. Several toughening and strengthening mechanisms like crack bridging, crack deflection and significant pull-out were observed in the matrix. It was also observed that the 2D reinforcement served as more promising candidate for reinforcements compared to 1D reinforcements. It was due to several geometrical advantages like high surface area, rougher surface morphology, and better hindrance in two dimensions rather than just one dimension in nanotubes.

<p dir="ltr">Antennas are used to transmit communication signals for many applications including for the navigation of aircraft. To protect the antennas from environmental conditions electromagnetic transparent structures called radomes are used. Advancements in technology have led to the development of hypersonic flight vehicles. These aircraft travel at speeds of Mach 5 and greater subjecting them to extreme environmental conditions. These aircraft require precise navigation making it important to have radome materials that can withstand the extreme conditions of high-speed flight while maintaining transparency to the incoming and outgoing signals of the antenna. Silicon nitride is a ceramic material of interest for high temperature radomes due to its mechanical properties, temperature stability, and satisfactory dielectric properties. Incorporating porosity into silicon nitride further enhances the transmission performance making porous silicon nitride a leading candidate material for high temperature radomes. In this dissertation slip casting with pressureless sintering is proposed as a route to fabricate porous silicon nitride ceramics for radomes. Modification of sintering aids and sintering temperatures are explored as a method to control the amount of porosity. Mechanical properties and dielectric properties of these materials are investigated. </p><p dir="ltr">First, an aqueous silicon nitride suspension developed for slip casting was optimized by investigating the rheological properties, zeta potential, and sedimentation behavior. It was determined that a suspension with 30 vol% solids, 0.5 wt% dispersant (PEI), and a pH of 7 was the optimized condition that resulted in uniform cast parts. This optimized suspension was used to fabricate silicon nitride samples with yttria and alumina sintering aids. An average density of 93% with an average strength of 659 MPa at room temperature and a strength of 472 MPa maintained up to 1200°C was achieved. Dielectric constant and loss tangent were measured on samples with 4-17% porosity to be 5.85-7.70 and <0.02, respectively. </p><p dir="ltr">To create samples with higher levels of porosity and therefore lower dielectric constants the yttria and alumina sintering aids were replaced with ytterbium oxide. Ytterbium oxide assists in forming porous silicon nitride due to the high melting temperature and high viscosity of the resulting glassy phase. Slip cast samples with 5% Yb₂O₃ were sintered at temperatures of 1700-1850°C resulting in porosities of 21-32% and strengths of 267-445 MPa. The dielectric constants of these materials were measured to be 4.56-5.80 with average loss tangents <0.006. The amount of ytterbium oxide was also studied to determine the effects on density, microstructure, mechanical properties, and dielectric properties. Slip-cast samples with 5-15% Yb₂O₃ were made having average porosities of 23-36% and strengths of 275-421 MPa. The dielectric constants of these materials were measured to be 4.13-4.65 with average loss tangents of <0.007. </p><p dir="ltr">Lastly, slip casting using the previously developed and evaluated suspensions was done to fabricate various radome shapes as well as layered structures. The processing method presented in this dissertation shows the potential for fabricating porous silicon nitride for high temperature radome applications with controlled porosity and relatively high strengths.</p>

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Gallium Nitride (GaN) and its alloys with InN and AlN, the III-nitrides, are of interest for a variety of high power-high frequency electronics and optoelectronics applications. However, unlike Si and GaAs technology that have been developed on native substrates, III-nitride devices have been developed on non-native substrates such as Si, sapphire and SiC. This is because bulk cheap native III-nitride substrates are unavailable. Among the known substrates, III-nitride technology development on Si is desirable because of its large substrate size and low cost. However, the large lattice and thermal expansion mismatch between the III-nitrides films and Si substrate leads to a high level of dislocations, 1010 cm-2, and tensile stress which results in cracking. For successful integration of crack free and low dislocation density GaN on Si various kinds of transition layer schemes are used that help to incorporate a compressive growth stress to neutralize the tensile thermal mismatch stresses and also to reduce dislocation densities to levels required by devices. These transition schemes, ranging from 400 nm to 7 m, involve the use of graded AlGaN layers, high/low temperature interlayers and superlattices. The aim of the research described in this thesis was a systematic comparison of the different transition layer schemes currently used with the objective of increasing the efficiency of integrating device quality, crack free, low dislocation density, <109 cm-2, GaN with Si. A metal organic chemical vapor deposition equipped with an in-situ stress monitor was used for growth. Transmission electron microscopy was used for quantitative measurement of dislocation density. The research shows, for the first time, that all transition layer optimization depends critically on the Si surface made available for growth of the first AlN layer. It needs to be optimally cleaned such that it is oxide free and smooth. A quantitative TEM comparison of various currently used transition layer schemes shows that while they have interesting mechanistic differences, they are not very different in their dislocation reduction efficiency. All of them yield a final dislocation density in a probe GaN layer of 1-3×109 cm-2. In contrast, a combination of Si doping and compressive growth stress has a synergistic effect on dislocation reduction. A simple 210 nm transition layer based on this understanding, the lowest reported yet, yields GaN layers that are crack free and have lower <1x109 cm-2 dislocation density, than those obtained by the aforementioned more complicated schemes. High electron mobility transistor characteristics performance on the probe GaN layers obtained on these transition layers supports the structural observations above.

Interstitial carbides and nitrides of early transition metals in Groups IV-VI exhibit platinum-like behavior which makes them a promising candidate to replace noble metals in a wide variety of reactions. Most synthetic methods used to prepare these materials lead to bulk or micron size powder which limits their use in reactions in particular in catalytic applications. Attempts toward the production of transition metal carbide and nitride nanoparticles in a sustainable, simple and cheap manner have been rapidly increasing. In this thesis, a new approach was presented to prepare nano-scale transition metal carbides and nitrides of group IV-VI with a size as small as 3 nm through the reaction of transition metal precursor with mesoporous graphitic carbon nitride (mpg-C3N4) that not only provides confined spaces for nanoparticles formation but also acts as a chemical source of nitrogen and carbon. The produced nanoparticles were characterized by powder X-ray diffraction (XRD), temperature-programmed reaction with mass spectroscopy (MS), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The effects of the reaction temperature, the ratio of the transition metal precursor to the reactive template (mpg-C3N4), and the selection of the carrier gas (Ar, N2, and NH3) on the resultant crystal phases and structures were investigated. The results indicated that different tantalum phases with cubic structure, TaN, Ta2CN, and TaC, can be formed under a flow of nitrogen by changing the reaction temperatures. Two forms of tantalum nitride, namely TaN and Ta3N5, were selectively formed under N2 and NH3 flow, respectively. Significantly, the formation of TaC, Ta2CN, and TaN can be controlled by altering the weight ratio of the C3N4 template relative to the Ta precursor at 1573 K under a flow of nitrogen where high C3N4/Ta precursor ratio generally resulted in high carbide content rather than nitride. In addition, the reactivity of the transition metals of group IV-VI with the reactive template was investigated under a flow of N2 at different temperatures in the range of 1023 to 1573 K while keeping the weight ratio constant at 1:1. The results show that Ti, V, Nb, Ta, and Cr reacted with mpg-C3N4 at 1023 K to form nitride phase with face centered cubic structure. The nitride phase destabilized at higher temperature ≥1223 K through the reaction with the remaining carbon residue originated from the decomposition of the template to form carbonitride and carbide phases. Whereas, Mo and W produce a hexagonal structure of carbide irrespective of the applying reaction temperature. The tendency to form transition metal nitrides and carbides at 1023 K was strongly driven by the free energy of formation. The observed trend indicates that the free energy of formation of nitride is relatively lower for group IV and V transition metals, whereas the carbide phase is thermodynamically more favorable for group VI, in particular for Mo and W. The thermal stability of nitride decreases at high temperature due to the evolution of nitrogen gas. The electrocatalytic activities of the produced nanoparticles were tested for hydrogen evolution reaction in acid media and the results demonstrated that molybdenum carbide nanoparticles exhibited the highest HER current with over potential of 100 mV vs. RHE, among the samples prepared in this study. This result is attributed to the sufficiently small particle size (8 nm on average) and accordingly high surface area (308 m2 g-1). Also, the graphitized carbon layer with a thickness of 1 nm on its surface formed by this synthesis provides excellent electron pathway to the catalyst which will improve the rate of electron transfer reaction.