Matching Items (35)
Filtering by

Clear all filters

152195-Thumbnail Image.png
Description
Topological insulators with conducting surface states yet insulating bulk states have generated a lot of interest amongst the physics community due to their varied characteristics and possible applications. Doped topological insulators have presented newer physical states of matter where topological order co&ndashexists; with other physical properties (like magnetic order). The

Topological insulators with conducting surface states yet insulating bulk states have generated a lot of interest amongst the physics community due to their varied characteristics and possible applications. Doped topological insulators have presented newer physical states of matter where topological order co&ndashexists; with other physical properties (like magnetic order). The electronic states of these materials are very intriguing and pose problems and the possible solutions to understanding their unique behaviors. In this work, we use Electron Energy Loss Spectroscopy (EELS) – an analytical TEM tool to study both core&ndashlevel; and valence&ndashlevel; excitations in Bi2Se3 and Cu(doped)Bi2Se3 topological insulators. We use this technique to retrieve information on the valence, bonding nature, co-ordination and lattice site occupancy of the undoped and the doped systems. Using the reference materials Cu(I)Se and Cu(II)Se we try to compare and understand the nature of doping that copper assumes in the lattice. And lastly we utilize the state of the art monochromated Nion UltraSTEM 100 to study electronic/vibrational excitations at a record energy resolution from sub-nm regions in the sample.
ContributorsSubramanian, Ganesh (Author) / Spence, John (Thesis advisor) / Jiang, Nan (Committee member) / Chen, Tingyong (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2013
151514-Thumbnail Image.png
Description
Dealloying, the selective dissolution of an elemental component from an alloy, is an important corrosion mechanism and a technological significant means to fabricate nanoporous structures for a variety of applications. In noble metal alloys, dealloying proceeds above a composition dependent critical potential, and bi-continuous structure evolves "simultaneously" as a result

Dealloying, the selective dissolution of an elemental component from an alloy, is an important corrosion mechanism and a technological significant means to fabricate nanoporous structures for a variety of applications. In noble metal alloys, dealloying proceeds above a composition dependent critical potential, and bi-continuous structure evolves "simultaneously" as a result of the interplay between percolation dissolution and surface diffusion. In contrast, dealloying in alloys that show considerable solid-state mass transport at ambient temperature is largely unexplored despite its relevance to nanoparticle catalysts and Li-ion anodes. In my dissertation, I discuss the behaviors of two alloy systems in order to elucidate the role of bulk lattice diffusion in dealloying. First, Mg-Cd alloys are chosen to show that when the dealloying is controlled by bulk diffusion, a new type of porosity - negative void dendrites will form, and the process mirrors electrodeposition. Then, Li-Sn alloys are studied with respect to the composition, particle size and dealloying rate effects on the morphology evolution. Under the right condition, dealloying of Li-Sn supported by percolation dissolution results in the same bi-continuous structure as nanoporous noble metals; whereas lattice diffusion through the otherwise "passivated" surface allows for dealloying with no porosity evolution. The interactions between bulk diffusion, surface diffusion and dissolution are revealed by chronopotentiometry and linear sweep voltammetry technics. The better understanding of dealloying from these experiments enables me to construct a brief review summarizing the electrochemistry and morphology aspects of dealloying as well as offering interpretations to new observations such as critical size effect and encased voids in nanoporous gold. At the end of the dissertation, I will describe a preliminary attempt to generalize the morphology evolution "rules of dealloying" to all solid-to-solid interfacial controlled phase transition process, demonstrating that bi-continuous morphologies can evolve regardless of the nature of parent phase.
ContributorsChen, Qing (Author) / Sieradzki, Karl (Thesis advisor) / Friesen, Cody (Committee member) / Buttry, Daniel (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2013
153370-Thumbnail Image.png
Description
Membrane-based gas separation is promising for efficient propylene/propane (C3H6/C3H8) separation with low energy consumption and minimum environment impact. Two microporous inorganic membrane candidates, MFI-type zeolite membrane and carbon molecular sieve membrane (CMS) have demonstrated excellent thermal and chemical stability. Application of these membranes into C3H6/C3H8 separation has not been well

Membrane-based gas separation is promising for efficient propylene/propane (C3H6/C3H8) separation with low energy consumption and minimum environment impact. Two microporous inorganic membrane candidates, MFI-type zeolite membrane and carbon molecular sieve membrane (CMS) have demonstrated excellent thermal and chemical stability. Application of these membranes into C3H6/C3H8 separation has not been well investigated. This dissertation presents fundamental studies on membrane synthesis, characterization and C3H6/C3H8 separation properties of MFI zeolite membrane and CMS membrane.

MFI zeolite membranes were synthesized on α-alumina supports by secondary growth method. Novel positron annihilation spectroscopy (PAS) techniques were used to non-destructively characterize the pore structure of these membranes. PAS reveals a bimodal pore structure consisting of intracrystalline zeolitic micropores of ~0.6 nm in diameter and irregular intercrystalline micropores of 1.4 to 1.8 nm in size for the membranes. The template-free synthesized membrane exhibited a high permeance but a low selectivity in C3H6/C3H8 mixture separation.

CMS membranes were synthesized by coating/pyrolysis method on mesoporous γ-alumina support. Such supports allow coating of thin, high-quality polymer films and subsequent CMS membranes with no infiltration into support pores. The CMS membranes show strong molecular sieving effect, offering a high C3H6/C3H8 mixture selectivity of ~30. Reduction in membrane thickness from 500 nm to 300 nm causes an increase in C3H8 permeance and He/N2 selectivity, but a decrease in the permeance of He, N2 and C3H6 and C3H6/C3H8 selectivity. This can be explained by the thickness dependent chain mobility of the polymer film resulting in final carbon membrane of reduced pore size with different effects on transport of gas of different sizes, including possible closure of C3H6-accessible micropores.

CMS membranes demonstrate excellent C3H6/C3H8 separation performance over a wide range of feed pressure, composition and operation temperature. No plasticization was observed at a feed pressure up to 100 psi. The permeation and separation is mainly controlled by diffusion instead of adsorption. CMS membrane experienced a decline in permeance, and an increase in selectivity over time under on-stream C3H6/C3H8 separation. This aging behavior is due to the reduction in effective pore size and porosity caused by oxygen chemisorption and physical aging of the membrane structure.
ContributorsMa, Xiaoli (Author) / Lin, Jerry (Thesis advisor) / Alford, Terry (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2015
156109-Thumbnail Image.png
Description
Photocatalytic water splitting has been proposed as a promising way of generating carbon-neutral fuels from sunlight and water. In one approach, water decomposition is enabled by the use of functionalized nano-particulate photocatalyst composites. The atomic structures of the photocatalysts dictate their electronic and photonic structures, which are controlled by synthesis

Photocatalytic water splitting has been proposed as a promising way of generating carbon-neutral fuels from sunlight and water. In one approach, water decomposition is enabled by the use of functionalized nano-particulate photocatalyst composites. The atomic structures of the photocatalysts dictate their electronic and photonic structures, which are controlled by synthesis methods and may alter under reaction conditions. Characterizing these structures, especially the ones associated with photocatalysts’ surfaces, is essential because they determine the efficiencies of various reaction steps involved in photocatalytic water splitting. Due to its superior spatial resolution, (scanning) transmission electron microscopy (STEM/TEM), which includes various imaging and spectroscopic techniques, is a suitable tool for probing materials’ local atomic, electronic and optical structures. In this work, techniques specific for the study of photocatalysts are developed using model systems.

Nano-level structure-reactivity relationships as well as deactivation mechanisms of Ni core-NiO shell co-catalysts loaded on Ta2O5 particles are studied using an aberration-corrected TEM. It is revealed that nanometer changes in the shell thickness lead to significant changes in the H2 production. Also, deactivation of this system is found to be related to a photo-driven process resulting in the loss of the Ni core.

In addition, a special form of monochromated electron energy-loss spectroscopy (EELS), the so-called aloof beam EELS, is used to probe surface electronic states as well as light-particle interactions from model oxide nanoparticles. Surface states associated with hydrate species are analyzed using spectral simulations based on a dielectric theory and a density of states model. Geometry-induced optical-frequency resonant modes are excited using fast electrons in catalytically relevant oxides. Combing the spectral features detected in experiments with classical electrodynamics simulations, the underlying physics involved in this excitation process and the various influencing factors of the modes are investigated.

Finally, an in situ light illumination system is developed for an aberration-corrected environmental TEM to enable direct observation of atomic structural transformations of model photocatalysts while they are exposed to near reaction conditions.
ContributorsLiu, Qianlang (Author) / Crozier, Peter A. (Thesis advisor) / Chan, Candace (Committee member) / Buttry, Daniel (Committee member) / Liu, Jingyue (Committee member) / Nemanich, Robert (Committee member) / Arizona State University (Publisher)
Created2018
156155-Thumbnail Image.png
Description
This work demonstrates a capable reverse pulse deposition methodology to influence gap fill behavior inside microvia along with a uniform deposit in the fine line patterned regions for substrate packaging applications. Interconnect circuitry in IC substrate packages comprises of stacked microvia that varies in depth from 20µm to 100µm with

This work demonstrates a capable reverse pulse deposition methodology to influence gap fill behavior inside microvia along with a uniform deposit in the fine line patterned regions for substrate packaging applications. Interconnect circuitry in IC substrate packages comprises of stacked microvia that varies in depth from 20µm to 100µm with an aspect ratio of 0.5 to 1.5 and fine line patterns defined by photolithography. Photolithography defined pattern regions incorporate a wide variety of feature sizes including large circular pad structures with diameter of 20µm - 200µm, fine traces with varying widths of 3µm - 30µm and additional planar regions to define a IC substrate package. Electrodeposition of copper is performed to establish the desired circuit. Electrodeposition of copper in IC substrate applications holds certain unique challenges in that they require a low cost manufacturing process that enables a void-free gap fill inside the microvia along with uniform deposition of copper on exposed patterned regions. Deposition time scales to establish the desired metal thickness for such packages could range from several minutes to few hours. This work showcases a reverse pulse electrodeposition methodology that achieves void-free gap fill inside the microvia and uniform plating in FLS (Fine Lines and Spaces) regions with significantly higher deposition rates than traditional approaches. In order to achieve this capability, systematic experimental and simulation studies were performed. A strong correlation of independent parameters that govern the electrodeposition process such as bath temperature, reverse pulse plating parameters and the ratio of electrolyte concentrations is shown to the deposition kinetics and deposition uniformity in fine patterned regions and gap fill rate inside the microvia. Additionally, insight into the physics of via fill process is presented with secondary and tertiary current simulation efforts. Such efforts lead to show “smart” control of deposition rate at the top and bottom of via to avoid void formation. Finally, a parametric effect on grain size and the ensuing copper metallurgical characteristics of bulk copper is also shown to enable high reliability substrate packages for the IC packaging industry.
ContributorsGanesan, Kousik (Author) / Tasooji, Amaneh (Thesis advisor) / Manepalli, Rahul (Committee member) / Alford, Terry (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2018
156366-Thumbnail Image.png
Description
It is well known that the overall performance of a solar cell is limited by the worst performing areas of the device. These areas are usually micro and nano-scale defects inhomogenously distributed throughout the material. Mitigating and/or engineering these effects is necessary to provide a path towards increasing the efficiency

It is well known that the overall performance of a solar cell is limited by the worst performing areas of the device. These areas are usually micro and nano-scale defects inhomogenously distributed throughout the material. Mitigating and/or engineering these effects is necessary to provide a path towards increasing the efficiency of state-of-the-art solar cells. The first big challenge is to identify the nature, origin and impact of such defects across length scales that span multiple orders of magnitude, and dimensions (time, temperature etc.). In this work, I present a framework based on correlative X-ray microscopy and big data analytics to identify micro and nanoscale defects and their impact on material properties in CuIn1-xGaxSe2 (CIGS) solar cells.

Synchrotron based X-ray Fluorescence (XRF) and X-ray Beam Induced Current (XBIC) are used to study the effect that compositional variations, between grains and at grain boundaries, have on CIGS device properties. An experimental approach is presented to correcting XRF and XBIC quantification of CIGS thin film solar cells. When applying XRF and XBIC to study low and high gallium CIGS devices, it was determined that increased copper and gallium at grain boundaries leads to increased collection efficiency at grain boundaries in low gallium absorbers. However, composition variations were not correlated with changes in collection efficiency in high gallium absorbers, despite the decreased collection efficiency observed at grain boundaries.

Understanding the nature and impact of these defects is only half the battle; controlling or mitigating their impact is the next challenge. This requires a thorough understanding of the origin of these defects and their kinetics. For such a study, a temperature and atmosphere controlled in situ stage was developed. The stage was utilized to study CIGS films during a rapid thermal growth process. Comparing composition variations across different acquisition times and growth temperatures required the implementation of machine learning techniques, including clustering and classification algorithms. From the analysis, copper was determined to segregate the faster than indium and gallium, and clustering techniques showed consistent elemental segregation into copper rich and copper poor regions. Ways to improve the current framework and new applications are also discussed.
ContributorsWest, Bradley (Author) / Bertoni, Mariana I (Thesis advisor) / Verebelyi, Darren (Committee member) / Holman, Zachary (Committee member) / Rose, Volker (Committee member) / Arizona State University (Publisher)
Created2018
156166-Thumbnail Image.png
Description
The electronic states of semiconductor interfaces have significant importance for semiconductor device performance, especially due to the continuing miniaturization of device technology.

The application of ultra high vacuum (UHV) enables the preparation and characterization of fresh and cleaned interfaces. In a UHV environment, photoemission spectroscopy (PES) provides a non-destructive method to

The electronic states of semiconductor interfaces have significant importance for semiconductor device performance, especially due to the continuing miniaturization of device technology.

The application of ultra high vacuum (UHV) enables the preparation and characterization of fresh and cleaned interfaces. In a UHV environment, photoemission spectroscopy (PES) provides a non-destructive method to measure the electronic band structure, which is a crucial component of interface properties.

In this dissertation, three semiconductor interfaces were studies to understand different effects on electronic states. The interfaces studied were freshly grown or pre-treated under UHV. Then in-situ PES measurements, including x-ray photoemission spectroscopy (XPS) and ultra-violet photoemission spectroscopy (UPS), were conducted to obtain electronic states information.

First, the CdTe/InSb (100) heterointerface was employed as a model interface for II-VI and III-V heterojunctions. It was suggested that an interface layer formed, which consisted of In-Te bonding. The non-octal bonding between In and Te atoms has donor-like behavior, which was proposed to result in an electron accumulation layer in InSb. A type-I heterointerface was observed. Second, Cu/ZnO interfaces were studied to understand the interface bonding and the role of polarization on ZnO interfaces. It was shown that on O-face ZnO (0001) and PEALD ZnO, copper contacts had ohmic behavior. However, on Zn-face ZnO (0001), a 0.3 eV Schottky barrier height was observed. The lower than expected barrier heights were attributed to oxygen vacancies introduced by Cu-O bonding during interface formation. In addition, it is suggested that the different barrier heights on two sides of ZnO (0001) are caused by the different behavior for the ZnO (0001) faces. Last, a pulse mode deposition method was applied for P-doped diamond growth on (100) diamond surfaces. Pretreatment effects were studied. It is suggested that an O/H plasma treatment or a short period of H-plasma and CH4/H2 plasma could yield a higher growth rate. PES measurements were conducted on H-terminated intrinsic diamond surface and P-doped/intrinsic diamond (100) interfaces. It was suggested that electronic states near the valence band maximum caused Fermi level pinning effects, independent of the diamond doping.
ContributorsWang, Xingye (Author) / Nemanich, Robert J (Thesis advisor) / Chan, Candace (Committee member) / Ponce, Fernando (Committee member) / Holman, Zachary (Committee member) / Arizona State University (Publisher)
Created2018
156128-Thumbnail Image.png
Description
Polycrystalline magnetite thin films were deposited on large area polymer substrates using aqueous solution based spin-spray deposition (SSD). This technique involved the hydrolysis of precursor salt solutions at low temperatures (70-100°C). The fundamental mechanisms and pathways in crystallization and evolution of the film microstructures were studied as a function of

Polycrystalline magnetite thin films were deposited on large area polymer substrates using aqueous solution based spin-spray deposition (SSD). This technique involved the hydrolysis of precursor salt solutions at low temperatures (70-100°C). The fundamental mechanisms and pathways in crystallization and evolution of the film microstructures were studied as a function of reactant chemistry and reactor conditions (rotation rate, flow rates etc.). A key feature of this method was the ability to constantly supply fresh solutions throughout deposition. Solution flow due to substrate rotation ensured that reactant depleted solutions were spun off. This imparted a limited volume, near two-dimensional restriction on the growth process. Film microstructure was studied as a function of process parameters such as liquid flow rate, nebulizer configuration, platen rotation rate and solution chemistry. It was found that operating in the micro-droplet regime of deposition was a crucial factor in controlling the microstructure.

Film porosity and substrate adhesion were linked to the deposition rate, which in-turn depended on solution chemistry. Films exhibited a wide variety of hierarchically organized microstructures often spanning length scales from tens-of-nanometers to a few microns. These included anisotropic morphologies such as nanoplates and nanoblades, that were generally unexpected from magnetite (a high symmetry cubic solid). Time resolved studies showed that the reason for complex hierarchy in microstructure was the crystallization via non-classical pathways. SSD of magnetite films involved formation of precursor phases that subsequently underwent solid-state transformations and nanoparticle self-assembly. These precursor phases were identified and possible reaction mechanisms for the formation of magnetite were proposed. A qualitative description of the driving forces for self-assembly was presented.
ContributorsVadari Venkata, Kaushik Sridhar (Author) / Petuskey, William (Thesis advisor) / Carpenter, Ray (Committee member) / McCartney, Martha (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2018
156609-Thumbnail Image.png
Description
Achieving high efficiency in solar cells requires optimal photovoltaics materials for light absorption and as with any electrical device—high-quality contacts. Essentially, the contacts separate the charge carriers—holes at one terminal and electrons at the other—extracting them to an external circuit. For this purpose, the development of passivating and carrier-selective contacts

Achieving high efficiency in solar cells requires optimal photovoltaics materials for light absorption and as with any electrical device—high-quality contacts. Essentially, the contacts separate the charge carriers—holes at one terminal and electrons at the other—extracting them to an external circuit. For this purpose, the development of passivating and carrier-selective contacts that enable low interface defect density and efficient carrier transport is critical for making high-efficiency solar cells. The recent record-efficiency n-type silicon cells with hydrogenated amorphous silicon (a-Si:H) contacts have demonstrated the usefulness of passivating and carrier-selective contacts. However, the use of a-Si:H contacts should not be limited in just n-type silicon cells.

In the present work, a-Si:H contacts for crystalline silicon and cadmium telluride (CdTe) solar cells are developed. First, hydrogen-plasma-processsed a-Si:H contacts are used in n-type Czochralski silicon cell fabrication. Hydrogen plasma treatment is used to increase the Si-H bond density of a-Si:H films and decrease the dangling bond density at the interface, which leads to better interface passivation and device performance, and wider temperature-processing window of n-type silicon cells under full spectrum (300–1200 nm) illumination. In addition, thickness-varied a-Si:H contacts are studied for n-type silicon cells under the infrared spectrum (700–1200 nm) illumination, which are prepared for silicon-based tandem applications.

Second, the a-Si:H contacts are applied to commercial-grade p-type silicon cells, which have much lower bulk carrier lifetimes than the n-type silicon cells. The approach is using gettering and bulk hydrogenation to improve the p-type silicon bulk quality, and then applying a-Si:H contacts to enable excellent surface passivation and carrier transport. This leads to an open-circuit voltage of 707 mV in p-type Czochralski silicon cells, and of 702 mV, the world-record open-circuit voltage in p-type multi-crystalline silicon cells.

Finally, CdTe cells with p-type a-Si:H hole-selective contacts are studied. As a proof of concept, p-type a-Si:H contacts enable achieving the highest reported open-circuit voltages (1.1 V) in mono-crystalline CdTe devices. A comparative study of applying p-type a-Si:H contacts in poly-crystalline CdTe solar cells is performed, resulting in absolute voltage gain of 53 mV over using the standard tellurium contacts.
ContributorsShi, Jianwei (Author) / Holman, Zachary (Thesis advisor) / Bowden, Stuart (Committee member) / Bertoni, Mariana (Committee member) / Goodnick, Stephen (Committee member) / Arizona State University (Publisher)
Created2018
156808-Thumbnail Image.png
Description
In this dissertation, micro-galvanic corrosion effects and passivation behavior of single-phase binary alloys have been studied in order to formulate new insights towards the development of “stainless-like” lightweight alloys. As a lightweight material of interest, Mg-xAl alloys were studied using aqueous free corrosion, atmospheric corrosion, dissolution rate kinetics, and ionic

In this dissertation, micro-galvanic corrosion effects and passivation behavior of single-phase binary alloys have been studied in order to formulate new insights towards the development of “stainless-like” lightweight alloys. As a lightweight material of interest, Mg-xAl alloys were studied using aqueous free corrosion, atmospheric corrosion, dissolution rate kinetics, and ionic liquid dissolution. Polarization and “accelerated” free corrosion studies in aqueous chloride were used to characterize the corrosion behavior and morphology of alloys. Atmospheric corrosion experiments revealed surface roughness and pH evolution behavior in aqueous environment. Dissolution in absence of water using choline-chloride:urea ionic liquid allowed for a simpler dissolution mechanism to be observed, providing additional insights regarding surface mobility of Al. These results were compared with commercial alloy (AZ31B, AM60, and AZ91D) behavior to better elucidate effects associated with secondary phases and intermetallic particles often present in Mg alloys. Aqueous free corrosion, “accelerated” free corrosion and ionic liquid dissolution studies have confirmed Al surface enrichment in a variety of morphologies, including Al-rich platelet and Al nanowire formation. This behavior is attributed to the preferential dissolution of Al as the more “noble” element in the matrix. Inductively-coupled mass spectroscopy was used to measure first-order rate reaction constants for elemental Mg and Al dissolution in aqueous chloride environment to be kMg= 9.419 x 10-6 and kAl = 2.103 x 10-6 for future implementation in kinetic Monte Carlo simulations. To better understand how “stainless-like” passivation may be achieved, Ni-xCr alloys were studied using polarization and potential pulse experiments. The passivation potential, critical current density, and passivation current density were found to decay with increasing Cr composition. The measured average number of monolayers dissolved during passivation was found to be in good agreement with percolation theory, with a fitted 3-D percolation threshold of p_c^3D=0.118 compared with the theoretical value of 0.137. Using these results, possible approaches towards achieving passivation in other systems, including Mg-Al, are discussed.
ContributorsAiello, Ashlee (Author) / Sieradzki, Karl (Thesis advisor) / Buttry, Daniel (Committee member) / Chan, Candace (Committee member) / Crozier, Peter (Committee member) / Arizona State University (Publisher)
Created2018