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Description
Two dimensional (2D) Janus Transition Metal Dichalcogenides (TMDs) are a new class of atomically thin polar materials. In these materials, the top and the bottom atomic layer are made of different chalcogen atoms. To date, several theoretical studies have shown that a broken mirror symmetry induces a colossal electrical field

Two dimensional (2D) Janus Transition Metal Dichalcogenides (TMDs) are a new class of atomically thin polar materials. In these materials, the top and the bottom atomic layer are made of different chalcogen atoms. To date, several theoretical studies have shown that a broken mirror symmetry induces a colossal electrical field in these materials, which leads to unusual quantum properties. Despite these new properties, the current knowledge in their synthesis is limited only through two independent studies; both works rely on high-temperature processing techniques and are specific to only one type of 2D Janus material - MoSSe. Therefore, there is an urgent need for the development of a new synthesis method to (1) Extend the library of Janus class materials. (2) Improve the quality of 2D crystals. (3) Enable the synthesis of Janus heterostructures. The central hypothesis in this work is that the processing temperature of 2D Janus synthesis can be significantly lowered down to room temperatures by using reactive hydrogen and sulfur radicals while stripping off selenium atoms from the 2D surface. To test this hypothesis, a series of controlled growth studies were performed, and several complementary characterization techniques were used to establish a process–structure-property relationship. The results show that the newly proposed approach, namely Selective Epitaxy and Atomic Replacement (SEAR), is effective in reducing the growth temperature down to ambient conditions. The proposed technique benefits in achieving highly crystalline 2D Janus layers with an excellent optical response. Further studies herein show that this technique can form highly sophisticated lateral and vertical heterostructures of 2D Janus layers. Overall results establish an entirely new growth technique for 2D Janus.layers, which pave ways for the realization of exciting quantum effects in these materials such as Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) state, Majorana fermions, and topological p-wave superconductors.
ContributorsSayyad, Mohammed Yasir (Author) / Tongay, Sefaattin (Thesis advisor) / Crozier, Peter (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2020
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Description
The realization of Silicon based photonic devices will enable much faster data transmission than is possible today using the current electronics based devices. Group IV alloys germanium tin (GeSn) and silicon germanium tin (SiGeSn) have the potential to form an direct bandgap material and thus, they are promising candidates to

The realization of Silicon based photonic devices will enable much faster data transmission than is possible today using the current electronics based devices. Group IV alloys germanium tin (GeSn) and silicon germanium tin (SiGeSn) have the potential to form an direct bandgap material and thus, they are promising candidates to develop a Si compatible light source and advance the field of silicon photonics. However, the growth of the alloys is challenging as it requires low temperature growth and proper strain management in the films during growth to prevent tin segregation. In order to satisfy these criteria, various research groups have developed novel chemical vapor deposition (CVD) reactors to deposit the films. While these reactors have been highly successful in depositing high crystal quality high Sn concentration films, they are generally expensive set-ups which utilize several turbomolecular/cryogenic pumps and/or load-lock systems. An more economical process than the state-of-the art to grow group IV materials will be highly valuable. Thus, the work presented in this dissertation was focused on deposition of group IV semiconductor thin films using simplified plasma enhanced CVD (PECVD) reactors.

Two different in-house assembled PECVD reactor systems, namely Reactor No. 1 and 2, were utilized to deposit Ge, GeSn and SiGeSn thin films. PECVD technique was used as plasma assistance allows for potentially depositing the films at growth temperatures lower than those of conventional CVD. Germane (GeH4) and Digermane (Ge2H6) were used as the Ge precursor while Disilane (Si2H6) and tin chloride (SnCl4) were used as the precursors for Si and Sn respectively. The growth conditions such as growth temperature, precursor flow rates, precursor partial pressures, and chamber pressure were varied in a wide range to optimize the growth conditions for the films. Polycrystalline Ge films and SiGeSn films with an Sn content upto 8% were deposited using Reactor No. 1 and 2. Development of epitaxial Ge buffers and GeSn films was accomplished using a modified Reactor No. 2 at temperatures <400oC without the aid of ultra-high vacuum conditions or a high temperature substrate pre-deposition bake thereby leading to a low economic and thermal budget for the deposition process.
ContributorsVanjaria, Jignesh (Author) / Yu, Hongbin (Thesis advisor) / Arjunan, Arul C (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Satisfying the ever-increasing demand for electricity while maintaining sustainability and eco-friendliness has become a key challenge for humanity. Around 70% of energy is rejected as heat from different sectors. Thermoelectric energy harvesting has immense potential to convert this heat into electricity in an environmentally friendly manner. However, low efficiency and

Satisfying the ever-increasing demand for electricity while maintaining sustainability and eco-friendliness has become a key challenge for humanity. Around 70% of energy is rejected as heat from different sectors. Thermoelectric energy harvesting has immense potential to convert this heat into electricity in an environmentally friendly manner. However, low efficiency and high manufacturing costs inhibit the widespread application of thermoelectric devices. In this work, an inexpensive solution processing technique and a nanostructuring approach are utilized to create thermoelectric materials. Specifically, the solution-state and solid-state structure of a lead selenide (PbSe) precursor is characterized by different spectroscopic techniques. This precursor has shown promise for preparing thermoelectric lead selenide telluride (PbSexTe1-x) thin films. The precursor was prepared by reacting lead and diphenyl diselenide in different solvents. The characterization reveals the formation of a solvated lead(II) phenylselenolate complex which deepens the understanding of the formation of these precursors. Further, using slightly different chemistry, a low-temperature tin(II) selenide (SnSe) precursor was synthesized and identified as tin(IV) methylselenolate. The low transformation temperature makes it compatible with colloidal PbSe nanocrystals. The colloidal PbSe nanocrystals were chemically treated with a SnSe precursor and subjected to mild annealing to form conductive nanocomposites. Finally, the room temperature thermoelectric characterization of solution-processed PbSexTe1-x thin films is presented. This is followed by a setup development for temperature-dependent measurements and preliminary temperature-dependent measurements on PbSexTe1-x thin films.
ContributorsVartak, Prathamesh Bhalchandra (Author) / Wang, Robert Y. (Thesis advisor) / Wang, Liping (Committee member) / Trovitch, Ryan J. (Committee member) / Tongay, Sefaattin (Committee member) / Goodnick, Stephen M. (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Several ways exist to improve pavement performance over time. One suggestion is to tailor the asphalt pavement mix design according to certain specified specifications, set up by each state agency. Another option suggests the addition of modifiers that are known to improve pavement performance, such as crumb rubber and fibers.

Several ways exist to improve pavement performance over time. One suggestion is to tailor the asphalt pavement mix design according to certain specified specifications, set up by each state agency. Another option suggests the addition of modifiers that are known to improve pavement performance, such as crumb rubber and fibers. Nowadays, improving asphalt pavement structures to meet specific climate conditions is a must. In addition, time and cost are two crucial settings and are very important to consider; these factors sometimes play a huge role in modifying the asphalt mix design needed to be set into place, and therefore alter the desired pavement performance over the expected life span of the structure. In recent studies, some methods refer to predicting pavement performance based on the asphalt mixtures volumetric properties.

In this research, an effort was undertaken to gather and collect most recent asphalt mixtures’ design data and compare it to historical data such as those available in the Long-Term Pavement Performance (LTPP), maintained by the Federal Highway Administration (FHWA). The new asphalt mixture design data was collected from 25 states within the United States and separated according to the four suggested climatic regions. The previously designed asphalt mixture designs in the 1960’s present in the LTPP Database implemented for the test sections were compared with the recently designed pavement mixtures gathered, and pavement performance was assessed using predictive models.

Three predictive models were studied in this research. The models were related to three major asphalt pavement distresses: Rutting, Fatigue Cracking and Thermal Cracking. Once the performance of the asphalt mixtures was assessed, four ranking criteria were developed to support the assessment of the mix designs quality at hand; namely, Low, Satisfactory, Good or Excellent. The evaluation results were reasonable and deemed acceptable. Out of the 48 asphalt mixtures design evaluated, the majority were between Satisfactory and Good.

The evaluation methodology and criteria developed are helpful tools in determining the quality of asphalt mixtures produced by the different agencies. They provide a quick insight on the needed improvement/modification against the potential development of distress during the lifespan of the pavement structure.
ContributorsKaram, Jolina Joseph (Author) / Kaloush, Kamil (Thesis advisor) / Mamlouk, Michael (Thesis advisor) / Ozer, Hasan (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Photocatalytic activity of titanium dioxide (titania or TiO2) offers enormous potential in solving energy and environmental problems. Immobilization of titania nanoparticles on inert substrates is an effective way of utilizing its photocatalytic activity since nanoparticles enable high mass-transport, and immobilization avoids post-treatment separation. For competitive photocatalytic performance, the morphology of

Photocatalytic activity of titanium dioxide (titania or TiO2) offers enormous potential in solving energy and environmental problems. Immobilization of titania nanoparticles on inert substrates is an effective way of utilizing its photocatalytic activity since nanoparticles enable high mass-transport, and immobilization avoids post-treatment separation. For competitive photocatalytic performance, the morphology of the substrate can be engineered to enhance mass-transport and light accessibility. In this work, two types of fiber architectures (i.e., dispersed polymer/titania phase or D-phase, and multi-phase polymer-core/composite-shell fibers or M-phase) were explored as effective substrate solutions for anchoring titania. These fibers were fabricated using a low-cost and scalable fiber spinning technique. Polymethyl methacrylate (PMMA) was selected as the substrate material due to its ultraviolet (UV) transparency and stability against oxidative radicals. The work systematically investigates the influence of the fiber porosity on mass-transport and UV light scattering. The properties of the fabricated fiber systems were characterized by scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), UV-vis spectrophotometry (UV-vis), and mechanical analysis. The photocatalytic performance was characterized by monitoring the decomposition of methylene blue (MB) under UV (i.e., 365 nm) light. Fabrication of photocatalytic support structures was observed to be an optimization problem where porosity improved mass transport but reduced UV accessibility. The D-phase fibers demonstrated the highest MB degradation rate (i.e., 0.116 min-1) due to high porosity (i.e., 33.2 m2/g). The M-phase fibers reported a better degradation rate compared to a D-phase fibers due to higher UV accessibility efficiency.
ContributorsKanth, Namrata (Author) / Song, Kenan (Thesis advisor) / Tongay, Sefaattin (Thesis advisor) / Kannan, Arunachala Mada (Committee member) / Arizona State University (Publisher)
Created2020
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Description
The chemical, structural, and electrical properties of niobium-silicon, niobium-germanium, and YBCO-dielectric interfaces are characterized. Reduction in the concentration of interfacial defects in these structures can improve the performance of (i) many devices including low-loss coplanar, microstrip, and stripline microwave resonators used in next-generation cryogenic communication, sensor, and quantum information technologies

The chemical, structural, and electrical properties of niobium-silicon, niobium-germanium, and YBCO-dielectric interfaces are characterized. Reduction in the concentration of interfacial defects in these structures can improve the performance of (i) many devices including low-loss coplanar, microstrip, and stripline microwave resonators used in next-generation cryogenic communication, sensor, and quantum information technologies and (ii) layers used in device isolation, inter-wiring dielectrics, and passivation in microwave and Josephson junction circuit fabrication.

Methods were developed to synthesize amorphous-Ge (a-Ge) and homoepitaxial-Si dielectric thin-films with loss tangents of 1–2×10 -6 and 0.6–2×10 -5 at near single-photon powers and sub-Kelvin temperatures (≈40 mK), making them potentially a better choice over undoped silicon and sapphire substrates used in quantum devices. The Nb/Ge interface has 20 nm of chemical intermixing, which is reduced by a factor of four using 10 nm Ta diffusion layers. Niobium coplanar resonators using this structure exhibit reduced microwave losses.

The nature and concentration of defects near Nb-Si interfaces prepared with commonly-used Si surface treatments were characterized. All samples have H, C, O, F, and Cl in the Si within 50 nm of the interface, and electrically active defects with activation energies of 0.147, 0.194, 0.247, 0.339, and 0.556 eV above the valence band maximum (E vbm ), with concentrations dominated by a hole trap at E vbm +0.556 eV (presumably Nb Si ). The optimum surface treatment is an HF etch followed by an in-situ 100 eV Ar ion mill. RCA etches, and higher energy ion milling processes increase the concentration of electrically active defects.

A thin SrTiO 3 buffer layer used in YBa 2 Cu 3 O 7-δ superconductor/high-performance Ba(Zn 1/3 Ta 2/3 )O 3 and Ba(Cd 1/3 Ta 2/3 )O 3 microwave dielectric trilayers improves the structural quality of the layers and results in 90 K superconductor critical temperatures. This advance enables the production of more compact high-temperature superconductor capacitors, inductors, and microwave microstrip and stripline devices.
ContributorsKopas, Cameron Joseph (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry L. (Committee member) / Carpenter, Ray W (Committee member) / Williams, Peter (Committee member) / Arizona State University (Publisher)
Created2020
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Description
A new nanoparticle deposition technique, Aerosol Impaction-Driven Assembly (AIDA), was extensively characterized for material structures and properties. Aerogel films can be deposited directly onto a substrate with AIDA without the long aging and drying steps in the sol-gel method. Electron microscopy, pore size analysis, thermal conductivity, and optical measurements show

A new nanoparticle deposition technique, Aerosol Impaction-Driven Assembly (AIDA), was extensively characterized for material structures and properties. Aerogel films can be deposited directly onto a substrate with AIDA without the long aging and drying steps in the sol-gel method. Electron microscopy, pore size analysis, thermal conductivity, and optical measurements show the nanoparticle (NP) films to be similar to typical silica aerogel. Haze of nanoparticle films modeled as scattering sites correlates strongly with pore size distribution. Supporting evidence was obtained from particle sizes and aggregates using electron microscopy and small-angle X-ray scattering. NP films showed interlayers of higher porosity and large aggregates formed by tensile film stress.

To better understand film stress and NP adhesion, chemical bonding analyses were performed for samples annealed up to 900 °C. Analysis revealed that about 50% of the NP surfaces are functionalized by hydroxyl (-OH) groups, providing for hydrogen bonding. Ellipsometric porosimetry was used to further understand the mechanical properties by providing a measure of strain upon capillary pressure from filling pores. Upon annealing to 200 °C, the films lost water resulting in closer bonding of NPs and higher Young’s modulus. Upon further annealing up to 900 °C, the films lost hydroxyl bonds while gaining siloxane bonds, reducing Young’s modulus. The application of ellipsometric porosimetry to hydrophilic coatings brings into question the validity of pore size distribution calculations for materials that hold onto water molecules and result in generally smaller calculated pore sizes.

Doped hydrogenated microcrystalline silicon was grown on crystalline silicon NPs, as a test case of an application for NP films to reduce parasitic absorption in silicon heterojunction solar cells. Parasitic absorption of blue light could be reduced because microcrystalline silicon has a mix of direct and indirect bandgap, giving lower blue absorption than amorphous silicon. Using Ultraviolet Raman spectroscopy, the crystallinity of films as thin as 13 nm was determined rapidly (in 1 minute) and non-destructively. A mono-layer of nanocrystals was applied as seeds for p-doped microcrystalline silicon growth and resulted in higher crystallinity films. Applications of the method could be explored for other nanocrystalline materials.
ContributorsCarpenter, Joe Victor (Author) / Holman, Zachary C (Thesis advisor) / Bertoni, Mariana I (Committee member) / Chan, Candace K. (Committee member) / Smith, David J. (Committee member) / Arizona State University (Publisher)
Created2020
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Description
AA 7XXX alloys are used extensively in aircraft and naval structures due to their excellent strength to weight ratio. These alloys are often exposed to harsh corrosive environments and mechanical stresses that can compromise their reliability in service. They are also coupled with fasteners that are composed of different materials

AA 7XXX alloys are used extensively in aircraft and naval structures due to their excellent strength to weight ratio. These alloys are often exposed to harsh corrosive environments and mechanical stresses that can compromise their reliability in service. They are also coupled with fasteners that are composed of different materials such as Titanium alloys. Such dissimilar metal contact facilitates galvanic and crevice corrosion, which can further reduce their lifetimes. Despite decades of research in the area, the confluence of mechanical, microstructural, and electrochemical aspects of damage is still unclear. Traditionally, 2D and destructive methods have often been employed to study the corrosion and cracking behavior in these systems which can be severely limiting and lead to inaccurate conclusions. This dissertation is aimed at comprehensively studying the corrosion and cracking behavior of these systems using time-dependent 3D microstructural characterization, as well as correlative microscopy. The microstructural evolution of corrosion in AA 7075 was studied using a combination of potentiodynamic polarization, X-ray Computed Tomography (XCT) and Transmission X-ray Microscopy (TXM). In both experiments, a strong emphasis was placed on studying localized corrosion attack at constituent particles and intergranular corrosion. With an understanding of the alloy’s corrosion behavior, a dissimilar alloy couple comprising AA 7075 / Ti-6Al-4V was then investigated. Ex situ and in situ x-ray microtomography was used extensively to investigate the evolution of pitting corrosion and corrosion fatigue in AA 7075 plates fastened separately with Ti-6Al-4V screws and rivets. The 4D tomography combined with the extensive fractography yielded valuable information pertaining the preferred sites of pit initiation, crack initiation and growth in these complex geometries. The use of correlative microscopy-based methodologies yielded multimodal characterization results that provided a unique and seminal insight on corrosion mechanisms in these materials.
ContributorsNiverty, Sridhar (Author) / Chawla, Nikhilesh (Thesis advisor) / Liu, Yongming (Committee member) / Ankit, Kumar (Committee member) / Xiao, Xianghui (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Precursors of carbon fibers include rayon, pitch, and polyacrylonitrile fibers that can be heat-treated for high-strength or high-modulus carbon fibers. Among them, polyacrylonitrile has been used most frequently due to its low viscosity for easy processing and excellent performance for high-end applications. To further explore polyacrylonitrile-based fibers for better precursors,

Precursors of carbon fibers include rayon, pitch, and polyacrylonitrile fibers that can be heat-treated for high-strength or high-modulus carbon fibers. Among them, polyacrylonitrile has been used most frequently due to its low viscosity for easy processing and excellent performance for high-end applications. To further explore polyacrylonitrile-based fibers for better precursors, in this study, carbon nanofillers were introduced in the polymer matrix to examine their reinforcement effects and influences on carbon fiber performance. Two-dimensional graphene nanoplatelets were mainly used for the polymer reinforcement and one-dimensional carbon nanotubes were also incorporated in polyacrylonitrile as a comparison. Dry-jet wet spinning was used to fabricate the composite fibers. Hot-stage drawing and heat-treatment were used to evolve the physical microstructures and molecular morphologies of precursor and carbon fibers. As compared to traditionally used random dispersions, selective placement of nanofillers was effective in improving composite fiber properties and enhancing mechanical and functional behaviors of carbon fibers. The particular position of reinforcement fillers with polymer layers was enabled by the in-house developed spinneret used for fiber spinning. The preferential alignment of graphitic planes contributed to the enhanced mechanical and functional behaviors than those of dispersed nanoparticles in polyacrylonitrile composites. The high in-plane modulus of graphene and the induction to polyacrylonitrile molecular carbonization/graphitization were the motivation for selectively placing graphene nanoplatelets between polyacrylonitrile layers. Mechanical tests, scanning electron microscopy, thermal, and electrical properties were characterized. Applications such as volatile organic compound sensing and pressure sensing were demonstrated.
ContributorsFranklin, Rahul Joseph (Author) / Song, Kenan (Thesis advisor) / Jiao, Yang (Thesis advisor) / Liu, Yongming (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Single drop impact of liquid on a static powder bed was studied to investigate the granule formation mechanism, droplet penetration time, the characterization of granules (morphology, surface structure and internal structure), as well as the formation regime map. Water was used as the liquid and two pharmaceutical powders, microcrystalline cellulose

Single drop impact of liquid on a static powder bed was studied to investigate the granule formation mechanism, droplet penetration time, the characterization of granules (morphology, surface structure and internal structure), as well as the formation regime map. Water was used as the liquid and two pharmaceutical powders, microcrystalline cellulose (MCC) and acetaminophen (APAP), were mixed to make heterogeneous powder beds. The complete drop impact and penetration was recorded by a high-speed camera. Two granule formation mechanisms identified previously occurred: Spreading and Tunneling. Spreading occurred for mixtures of large particle sizes, while Tunneling started to occur when the particle sizes of the mixtures decreased. With an increase of APAP concentration, the overall drop penetration time increased, which was in good agreement with previous literature. The granule morphology, surface structure, and internal structure were characterized by a prism method with image analysis, scanning electron microscope, and X-ray microtomography, respectively. The Spreading mechanism produced flat disks with porous internal structures, while the Tunneling mechanism produced round granules with dense internal structures. Granules that were formed via a hybrid of the mechanisms, Spreading/Tunneling, were hybrid granules, with some dense areas and some porous areas. The results of the granule content uniformity from UV-vis spectrometry revealed that with the increase of APAP proportion, the overall uniformity was compromised for mixtures with fine ingredients, while the content was much more uniform for coarse mixtures. It is believed that the mean particle size of the powder bed is the predominant factor in influencing the formation mechanism, drop penetration time, and granule properties, while the content uniformity is affected by both the particle sizes and the mixture hydrophobicity.
ContributorsGao, Tianxiang (Author) / Emady, Heather N (Thesis advisor) / Chawla, Nikhilesh (Committee member) / Jiao, Yang (Committee member) / Pradhan, Shankali (Committee member) / Oka, Sarang (Committee member) / Arizona State University (Publisher)
Created2020