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Description
Liquid-liquid interfaces serve as ideal 2-D templates on which solid particles can self-assemble into various structures. These self-assembly processes are important in fabrication of micron-sized devices and emulsion formulation. At oil/water interfaces, these structures can range from close-packed aggregates to ordered lattices. By incorporating an ionic liquid (IL) at the interface, new self-assembly phenomena emerge. ILs are ionic compounds that are liquid at room temperature (essentially molten salts at ambient conditions) that have remarkable properties such as negligible volatility and high chemical stability and can be optimized for nearly any application. The nature of IL-fluid interfaces has not yet been studied in depth. Consequently, the corresponding self-assembly phenomena have not yet been explored. We demonstrate how the unique molecular nature of ILs allows for new self-assembly phenomena to take place at their interfaces. These phenomena include droplet bridging (the self-assembly of both particles and emulsion droplets), spontaneous particle transport through the liquid-liquid interface, and various gelation behaviors. In droplet bridging, self-assembled monolayers of particles effectively "glue" emulsion droplets to one another, allowing the droplets to self-assembly into large networks. With particle transport, it is experimentally demonstrated the ILs overcome the strong adhesive nature of the liquid-liquid interface and extract solid particles from the bulk phase without the aid of external forces. These phenomena are quantified and corresponding mechanisms are proposed. The experimental investigations are supported by molecular dynamics (MD) simulations, which allow for a molecular view of the self-assembly process. In particular, we show that particle self-assembly depends primarily on the surface chemistry of the particles and the non-IL fluid at the interface. Free energy calculations show that the attractive forces between nanoparticles and the liquid-liquid interface are unusually long-ranged, due to capillary waves. Furthermore, IL cations can exhibit molecular ordering at the IL-oil interface, resulting in a slight residual charge at this interface. We also explore the transient IL-IL interface, revealing molecular interactions responsible for the unusually slow mixing dynamics between two ILs. This dissertation, therefore, contributes to both experimental and theoretical understanding of particle self-assembly at IL based interfaces.
ContributorsFrost, Denzil (Author) / Dai, Lenore L (Thesis advisor) / Torres, César I (Committee member) / Nielsen, David R (Committee member) / Squires, Kyle D (Committee member) / Rege, Kaushal (Committee member) / Arizona State University (Publisher)
Created2013
Description
In this dissertation, the interface chemistry and electronic structure of plasma-enhanced atomic layer deposited (PEALD) dielectrics on GaN are investigated with x-ray and ultraviolet photoemission spectroscopy (XPS and UPS). Three interrelated issues are discussed in this study: (1) PEALD dielectric growth process optimization, (2) interface electronic structure of comparative PEALD dielectrics on GaN, and (3) interface electronic structure of PEALD dielectrics on Ga- and N-face GaN. The first study involved an in-depth case study of PEALD Al2O3 growth using dimethylaluminum isopropoxide, with a special focus on oxygen plasma effects. Saturated and self-limiting growth of Al2O3 films were obtained with an enhanced growth rate within the PEALD temperature window (25-220 ºC). The properties of Al2O3 deposited at various temperatures were characterized to better understand the relation between the growth parameters and film properties. In the second study, the interface electronic structures of PEALD dielectrics on Ga-face GaN films were measured. Five promising dielectrics (Al2O3, HfO2, SiO2, La2O3, and ZnO) with a range of band gap energies were chosen. Prior to dielectric growth, a combined wet chemical and in-situ H2/N2 plasma clean process was employed to remove the carbon contamination and prepare the surface for dielectric deposition. The surface band bending and band offsets were measured by XPS and UPS for dielectrics on GaN. The trends of the experimental band offsets on GaN were related to the dielectric band gap energies. In addition, the experimental band offsets were near the calculated values based on the charge neutrality level model. The third study focused on the effect of the polarization bound charge of the Ga- and N-face GaN on interface electronic structures. A surface pretreatment process consisting of a NH4OH wet chemical and an in-situ NH3 plasma treatment was applied to remove carbon contamination, retain monolayer oxygen coverage, and potentially passivate N-vacancy related defects. The surface band bending and polarization charge compensation of Ga- and N-face GaN were investigated. The surface band bending and band offsets were determined for Al2O3, HfO2, and SiO2 on Ga- and N-face GaN. Different dielectric thicknesses and post deposition processing were investigated to understand process related defect formation and/or reduction.
ContributorsYang, Jialing (Author) / Nemanich, Robert J (Thesis advisor) / Chen, Tingyong (Committee member) / Peng, Xihong (Committee member) / Ponce, Fernando (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2014
Description
A method for evaluating the integrity of geosynthetic elements of a waste containment system subject to seismic loading is developed using a large strain finite difference numerical computer program. The method accounts for the effect of interaction between the geosynthetic elements and the overlying waste on seismic response and allows for explicit calculation of forces and strains in the geosynthetic elements. Based upon comparison of numerical results to experimental data, an elastic-perfectly plastic interface model is demonstrated to adequately reproduce the cyclic behavior of typical geomembrane-geotextile and geomembrane-geomembrane interfaces provided the appropriate interface properties are used. New constitutive models are developed for the in-plane cyclic shear behavior of textured geomembrane/geosynthetic clay liner (GMX/GCL) interfaces and GCLs. The GMX/GCL model is an empirical model and the GCL model is a kinematic hardening, isotropic softening multi yield surface plasticity model. Both new models allows for degradation in the cyclic shear resistance from a peak to a large displacement shear strength. The ability of the finite difference model to predict forces and strains in a geosynthetic element modeled as a beam element with zero moment of inertia sandwiched between two interface elements is demonstrated using hypothetical models of a heap leach pad and two typical landfill configurations. The numerical model is then used to conduct back analyses of the performance of two lined municipal solid waste (MSW) landfills subjected to strong ground motions in the Northridge earthquake. The modulus reduction "backbone curve" employed with the Masing criterion and 2% Rayleigh damping to model the cyclic behavior of MSW was established by back-analysis of the response of the Operating Industries Inc. landfill to five different earthquakes, three small magnitude nearby events and two larger magnitude distant events. The numerical back analysis was able to predict the tears observed in the Chiquita Canyon Landfill liner system after the earthquake if strain concentrations due to seams and scratches in the geomembrane are taken into account. The apparent good performance of the Lopez Canyon landfill geomembrane and the observed tension in the overlying geotextile after the Northridge event was also successfully predicted using the numerical model.
ContributorsArab, Mohamed G (Author) / Kavazanjian, Edward (Thesis advisor) / Zapata, Claudia (Committee member) / Houston, Sandra (Committee member) / Arizona State University (Publisher)
Created2011
Description
In this dissertation, in-situ X-ray and ultraviolet photoemission spectroscopy have been employed to study the interface chemistry and electronic structure of potential high-k gate stack materials. In these gate stack materials, HfO2 and La2O3 are selected as high-k dielectrics, VO2 and ZnO serve as potential channel layer materials. The gate stack structures have been prepared using a reactive electron beam system and a plasma enhanced atomic layer deposition system. Three interrelated issues represent the central themes of the research: 1) the interface band alignment, 2) candidate high-k materials, and 3) band bending, internal electric fields, and charge transfer. 1) The most highlighted issue is the band alignment of specific high-k structures. Band alignment relationships were deduced by analysis of XPS and UPS spectra for three different structures: a) HfO2/VO2/SiO2/Si, b) HfO2-La2O3/ZnO/SiO2/Si, and c) HfO2/VO2/ HfO2/SiO2/Si. The valence band offset of HfO2/VO2, ZnO/SiO2 and HfO2/SiO2 are determined to be 3.4 ± 0.1, 1.5 ± 0.1, and 0.7 ± 0.1 eV. The valence band offset between HfO2-La2O3 and ZnO was almost negligible. Two band alignment models, the electron affinity model and the charge neutrality level model, are discussed. The results show the charge neutrality model is preferred to describe these structures. 2) High-k candidate materials were studied through comparison of pure Hf oxide, pure La oxide, and alloyed Hf-La oxide films. An issue with the application of pure HfO2 is crystallization which may increase the leakage current in gate stack structures. An issue with the application of pure La2O3 is the presence of carbon contamination in the film. Our study shows that the alloyed Hf-La oxide films exhibit an amorphous structure along with reduced carbon contamination. 3) Band bending and internal electric fields in the gate stack structure were observed by XPS and UPS and indicate the charge transfer during the growth and process. The oxygen plasma may induce excess oxygen species with negative charges, which could be removed by He plasma treatment. The final HfO2 capping layer deposition may reduce the internal potential inside the structures. The band structure was approaching to a flat band condition.
ContributorsZhu, Chiyu (Author) / Nemanich, Robert (Thesis advisor) / Chamberlin, Ralph (Committee member) / Chen, Tingyong (Committee member) / Ponce, Fernando (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2012
Description
Integrated oxide/semiconductor heterostructures have attracted intense interest for device applications which require sharp interfaces and controlled defects. The research of this dissertation has focused on the characterization of perovskite oxide/oxide and oxide/semiconductor heterostructures, and the analysis of interfaces and defect structures, using scanning transmission electrom microscopy (STEM) and related techniques.
The SrTiO3/Si system was initially studied to develop a basic understanding of the integration of perovskite oxides with semiconductors, and successful integration with abrupt interfaces was demonstrated. Defect analysis showed no misfit dislocations but only anti-phase boundaries (APBs) in the SrTiO3 (STO) films. Similar defects were later observed in other perovskite oxide heterostructures.
Ferroelectric BaTiO3 (BTO) thin films deposited directly onto STO substrates, or STO buffer layers with Ge substrates, were grown by molecular beam epitaxy (MBE) in order to control the polarization orientation for field-effect transistors (FETs). STEM imaging and elemental mapping by electron energy-loss spectroscopy (EELS) showed structurally and chemically abrupt interfaces, and the BTO films retained the c-axis-oriented tetragonal structure for both BTO/STO and BTO/STO/Ge heterostructures. The polarization displacement in the BTO films of TiN/BTO/STO heterostructures was investigated. The Ti4+ atomic column displacements and lattice parameters were measured directly using HAADF images. A polarization gradient, which switched from upwards to downwards, was observed in the BTO thin film, and evidence was found for positively-charged oxygen vacancies.
Heterostructures grown on Ge substrates by atomic layer deposition (ALD) were characterized and compared with MBE-grown samples. A two-step process was needed to overcome interlayer reaction at the beginning of ALD growth. A-site-rich oxide films with thicknesses of at least 2-nm had to be deposited and then crystallized before initiating deposition of the following perovskite oxide layer in order to suppress the formation of amorphous oxide layers on the Ge surface. BTO/STO/Ge, BTO/Ge, SrHfTiO3/Ge and SrZrO3/Ge thin films with excellent crystallinity were grown using this process.
Metal-insulator-metal (MIM) heterostructures were fabricated as ferroelectric capacitors and then electrically stressed to the point of breakdown to correlate structural changes with electrical and physical properties. BaTiO3 on Nb:STO was patterned with different top metal electrodes by focused-ion-beam milling, Au/Ni liftoff, and an isolation-defined approach.
The SrTiO3/Si system was initially studied to develop a basic understanding of the integration of perovskite oxides with semiconductors, and successful integration with abrupt interfaces was demonstrated. Defect analysis showed no misfit dislocations but only anti-phase boundaries (APBs) in the SrTiO3 (STO) films. Similar defects were later observed in other perovskite oxide heterostructures.
Ferroelectric BaTiO3 (BTO) thin films deposited directly onto STO substrates, or STO buffer layers with Ge substrates, were grown by molecular beam epitaxy (MBE) in order to control the polarization orientation for field-effect transistors (FETs). STEM imaging and elemental mapping by electron energy-loss spectroscopy (EELS) showed structurally and chemically abrupt interfaces, and the BTO films retained the c-axis-oriented tetragonal structure for both BTO/STO and BTO/STO/Ge heterostructures. The polarization displacement in the BTO films of TiN/BTO/STO heterostructures was investigated. The Ti4+ atomic column displacements and lattice parameters were measured directly using HAADF images. A polarization gradient, which switched from upwards to downwards, was observed in the BTO thin film, and evidence was found for positively-charged oxygen vacancies.
Heterostructures grown on Ge substrates by atomic layer deposition (ALD) were characterized and compared with MBE-grown samples. A two-step process was needed to overcome interlayer reaction at the beginning of ALD growth. A-site-rich oxide films with thicknesses of at least 2-nm had to be deposited and then crystallized before initiating deposition of the following perovskite oxide layer in order to suppress the formation of amorphous oxide layers on the Ge surface. BTO/STO/Ge, BTO/Ge, SrHfTiO3/Ge and SrZrO3/Ge thin films with excellent crystallinity were grown using this process.
Metal-insulator-metal (MIM) heterostructures were fabricated as ferroelectric capacitors and then electrically stressed to the point of breakdown to correlate structural changes with electrical and physical properties. BaTiO3 on Nb:STO was patterned with different top metal electrodes by focused-ion-beam milling, Au/Ni liftoff, and an isolation-defined approach.
ContributorsWu, Hsinwei (Author) / Smith, David J. (Thesis advisor) / Mccartney, Martha R (Thesis advisor) / Alford, Terry (Committee member) / Bertoni, Mariana (Committee member) / Arizona State University (Publisher)
Created2018
Description
The goal of this paper was to do an analysis of two-dimensional unsplit mass and momentum conserving Finite Volume Methods for Advection for Volume of Fluid Fields with interfaces and validating their rates of convergence. Specifically three unsplit transport methods and one split transport method were amalgamated individually with four Piece-wise Linear Reconstruction Schemes (PLIC) i.e. Unsplit Eulerian Advection (UEA) by Owkes and Desjardins (2014), Unsplit Lagrangian Advection (ULA) by Yang et al. (2010), Split Lagrangian Advection (SLA) by Scardovelli and Zaleski (2003) and Unsplit Averaged Eulerian-Lagrangian Advection (UAELA) with two Finite Difference Methods by Parker and Youngs (1992) and two Error Minimization Methods by Pilliod Jr and Puckett (2004). The observed order of accuracy was first order in all cases except when unsplit methods and error minimization methods were used consecutively in each iteration, which resulted in second-order accuracy on the shape error convergence. The Averaged Unsplit Eulerian-Lagrangian Advection (AUELA) did produce first-order accuracy but that was due to a temporal error in the numerical setup. The main unsplit methods, Unsplit Eulerian Advection (UEA) and Unsplit Lagrangian Advection (ULA), preserve mass and momentum and require geometric clipping to solve two-phase fluid flows. The Unsplit Lagrangian Advection (ULA) can allow for small divergence in the velocity field perhaps saving time on the iterative solver of the variable coefficient Poisson System.
ContributorsAnsari, Adil (M.S.) (Author) / Herrmann, Marcus (Thesis advisor) / Peet, Yulia (Committee member) / Huang, Huei-Ping (Committee member) / Arizona State University (Publisher)
Created2019
Description
The quality of user interface designs largely depends on the aptitude of the designer. The ability to generate mental abstract models and characterize a target user audience helps greatly when conceiving a design. The dry cleaning point-of-sale industry lacks quality user interface designs. These impaired interfaces were compared with textbook design techniques to discover how applicable published interface design concepts are in practice. Four variations of a software package were deployed to end users. Each variation contained different design techniques. Surveyed users responded positively to interface design practices that were consistent and easy to learn. This followed textbook expectations. Users however responded poorly to customization options, an important feature according to textbook material. The study made conservative changes to the four interface variations provided to end-users. A more liberal approach may have yielded additional results.
ContributorsSmith, Andrew David (Author) / Nakamura, Mutsumi (Thesis director) / Gottesman, Aaron (Committee member) / Barrett, The Honors College (Contributor) / Electrical Engineering Program (Contributor)
Created2014-05
Description
I analyzed a non-profit's educational content website called SolarSPELL and proposed to redesign its interface. SolarSPELL is a solar-powered, offline site that can be accessed without wifi. It looks and behaves exactly like a real website. SolarSPELL is used by children and community members in developing countries across the world, including Africa and the Pacific Islands. The original site was not intuitive or easy to use, which deterred users with low technical literacy, lowering its effectiveness and defeating its purpose of providing educational materials to schools in the community, because users were less likely to use it to access educational content. The website was not responsive, meaning that it did not resize well to fit tablet and mobile devices. I redesigned the site's UX based on user feedback and expert advice to create wireframes that improved the site's layout and user flow to make it more intuitive. I pulled user comments from past surveys on the site and designed solutions to each of the user's complaints. I implemented a filter system and a universal search bar to improve the process of finding specific pieces of content. I designed prototypes using Adobe Illustrator to create the visual side of the interface. I designed my wireframes and prototypes with responsiveness in mind, creating versions for desktop, mobile and tablet. I also illustrated banners for the East Africa and Native American versions of the site, featuring landscape and wildlife from the respective regions. This interface redesign will be coded into a working site and distributed to communities around the world.
ContributorsThielen, Bethany Meishal (Author) / Hosman, Laura (Thesis director) / Ralston, Laurel (Committee member) / College of Integrative Sciences and Arts (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
The software element of home and small business networking solutions has failed to keep pace with annual development of newer and faster hardware. The software running on these devices is an afterthought, oftentimes equipped with minimal features, an obtuse user interface, or both. At the same time, this past year has seen the rise of smart home assistants that represent the next step in human-computer interaction with their advanced use of natural language processing. This project seeks to quell the issues with the former by exploring a possible fusion of a powerful, feature-rich software-defined networking stack and the incredible natural language processing tools of smart home assistants. To accomplish these ends, a piece of software was developed to leverage the powerful natural language processing capabilities of one such smart home assistant, the Amazon Echo. On one end, this software interacts with Amazon Web Services to retrieve information about a user's speech patterns and key information contained in their speech. On the other end, the software joins that information with its previous session state to intelligently translate speech into a series of commands for the separate components of a networking stack. The software developed for this project empowers a user to quickly make changes to several facets of their networking gear or acquire information about it with just their language \u2014 no terminals, java applets, or web configuration interfaces needed, thus circumventing clunky UI's or jumping from shell to shell. It is the author's hope that showing how networking equipment can be configured in this innovative way will draw more attention to the current failings of networking equipment and inspire a new series of intuitive user interfaces.
ContributorsHermens, Ryan Joseph (Author) / Meuth, Ryan (Thesis director) / Burger, Kevin (Committee member) / Computer Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
ContributorsEvans, Bartlett R. (Conductor) / Schildkret, David (Conductor) / Glenn, Erica (Conductor) / Concert Choir (Performer) / Chamber Singers (Performer) / ASU Library. Music Library (Publisher)
Created2018-03-16