ASU Electronic Theses and Dissertations
This collection includes most of the ASU Theses and Dissertations from 2011 to present. ASU Theses and Dissertations are available in downloadable PDF format; however, a small percentage of items are under embargo. Information about the dissertations/theses includes degree information, committee members, an abstract, supporting data or media.
In addition to the electronic theses found in the ASU Digital Repository, ASU Theses and Dissertations can be found in the ASU Library Catalog.
Dissertations and Theses granted by Arizona State University are archived and made available through a joint effort of the ASU Graduate College and the ASU Libraries. For more information or questions about this collection contact or visit the Digital Repository ETD Library Guide or contact the ASU Graduate College at gradformat@asu.edu.
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- Genre: Doctoral Dissertation
Description
Traditional approaches to modeling microgrids include the behavior of each inverter operating in a particular network configuration and at a particular operating point. Such models quickly become computationally intensive for large systems. Similarly, traditional approaches to control do not use advanced methodologies and suffer from poor performance and limited operating range. In this document a linear model is derived for an inverter connected to the Thevenin equivalent of a microgrid. This model is then compared to a nonlinear simulation model and analyzed using the open and closed loop systems in both the time and frequency domains. The modeling error is quantified with emphasis on its use for controller design purposes. Control design examples are given using a Glover McFarlane controller, gain sched- uled Glover McFarlane controller, and bumpless transfer controller which are compared to the standard droop control approach. These examples serve as a guide to illustrate the use of multi-variable modeling techniques in the context of robust controller design and show that gain scheduled MIMO control techniques can extend the operating range of a microgrid. A hardware implementation is used to compare constant gain droop controllers with Glover McFarlane controllers and shows a clear advantage of the Glover McFarlane approach.
ContributorsSteenis, Joel (Author) / Ayyanar, Raja (Thesis advisor) / Mittelmann, Hans (Committee member) / Tsakalis, Konstantinos (Committee member) / Tylavsky, Daniel (Committee member) / Arizona State University (Publisher)
Created2013
Description
A clean and sustainable alternative to fossil fuels is solar energy. For efficient use of solar energy to be realized, artificial systems that can effectively capture and convert sunlight into a usable form of energy have to be developed. In natural photosynthesis, antenna chlorophylls and carotenoids capture sunlight and transfer the resulting excitation energy to the photosynthetic reaction center (PRC). Small reorganization energy, λ and well-balanced electronic coupling between donors and acceptors in the PRC favor formation of a highly efficient charge-separated (CS) state. By covalently linking electron/energy donors to acceptors, organic molecular dyads and triads that mimic natural photosynthesis were synthesized and studied. Peripherally linked free base phthalocyanine (Pc)-fullerene (C60) and a zinc (Zn) phthalocyanine-C60 dyads were synthesized. Photoexcitation of the Pc moiety resulted in singlet-singlet energy transfer to the attached C60, followed by electron transfer. The lifetime of the CS state was 94 ps. Linking C60 axially to silicon (Si) Pc, a lifetime of the CS state of 4.5 ns was realized. The exceptionally long-lived CS state of the SiPc-C60 dyad qualifies it for applications in solar energy conversion devices. A secondary electron donor was linked to the dyad to obtain a carotenoid (Car)-SiPc-C60 triad and ferrocene (Fc)-SiPc-C60 triad. Excitation of the SiPc moiety resulted in fast electron transfer from the Car or Fc secondary electron donors to the C60. The lifetime of the CS state was 17 ps and 1.2 ps in Car-SiPc-C60 and Fc-SiPc-C60, respectively. In Chapter 3, an efficient synthetic route that yielded regioselective oxidative porphyrin dimerization is presented. Using Cu2+ as the oxidant, meso-β doubly-connected fused porphyrin dimers were obtained in very high yields. Removal of the copper from the macrocycle affords a free base porphyrin dimer. This allows for exchange of metals and provides a route to a wider range of metallporphyrin dimers. In Chapter 4, the development of an efficient and an expedient route to bacteriopurpurin synthesis is discussed. Meso-10,20- diformylation of porphyrin was achieved and one-pot porphyrin diacrylate synthesis and cyclization to afford bacteriopurpurin was realized. The bacteriopurpurin had a reduction potential of - 0.85 V vs SCE and λmax, 845 nm.
ContributorsArero, Jaro (Author) / Gust, Devens (Thesis advisor) / Moore, Ana (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2014
Description
Organic optoelectronic devices have remained a research topic of great interest over the past two decades, particularly in the development of efficient organic photovoltaics (OPV) and organic light emitting diodes (OLED). In order to improve the efficiency, stability, and materials variety for organic optoelectronic devices a number of emitting materials, absorbing materials, and charge transport materials were developed and employed in a device setting. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. Two major approaches were taken to enhance the efficiency of small molecule based OPVs: developing material with higher open circuit voltages or improved device structures which increased short circuit current. To explore the factors affecting the open circuit voltage (VOC) in OPVs, molecular structures were modified to bring VOC closer to the effective bandgap, ∆EDA, which allowed the achievement of 1V VOC for a heterojunction of a select Ir complex with estimated exciton energy of only 1.55eV. Furthermore, the development of anode interfacial layer for exciton blocking and molecular templating provide a general approach for enhancing the short circuit current. Ultimately, a 5.8% PCE was achieved in a single heterojunction of C60 and a ZnPc material prepared in a simple, one step, solvent free, synthesis. OLEDs employing newly developed deep blue emitters based on cyclometalated complexes were demonstrated. Ultimately, a peak EQE of 24.8% and nearly perfect blue emission of (0.148,0.079) was achieved from PtON7dtb, which approaches the maximum attainable performance from a blue OLED. Furthermore, utilizing the excimer formation properties of square-planar Pt complexes, highly efficient and stable white devices employing a single emissive material were demonstrated. A peak EQE of over 20% for pure white color (0.33,0.33) and 80 CRI was achieved with the tridentate Pt complex, Pt-16. Furthermore, the development of a series of tetradentate Pt complexes yielded highly efficient and stable single doped white devices due to their halogen free tetradentate design. In addition to these benchmark achievements, the systematic molecular modification of both emissive and absorbing materials provides valuable structure-property relationship information that should help guide further developments in the field.
ContributorsFleetham, Tyler Blain (Author) / Li, Jian (Thesis advisor) / Alford, Terry (Committee member) / Adams, James (Committee member) / Arizona State University (Publisher)
Created2014
Description
The utilization of solar energy requires an efficient means of its storage as fuel. In bio-inspired artificial photosynthesis, light energy can be used to drive water oxidation, but catalysts that produce molecular oxygen from water are required. This dissertation demonstrates a novel complex utilizing earth-abundant Ni in combination with glycine as an efficient catalyst with a modest overpotential of 0.475 ± 0.005 V for a current density of 1 mA/cm2 at pH 11. The production of molecular oxygen at a high potential was verified by measurement of the change in oxygen concentration, yielding a Faradaic efficiency of 60 ± 5%. This Ni species can achieve a current density of 4 mA/cm2 that persists for at least 10 hours. Based upon the observed pH dependence of the current amplitude and oxidation/reduction peaks, the catalysis is an electron-proton coupled process. In addition, to investigate the binding of divalent metals to proteins, four peptides were designed and synthesized with carboxylate and histidine ligands. The binding of the metals was characterized by monitoring the metal-induced changes in circular dichroism spectra. Cyclic voltammetry demonstrated that bound copper underwent a Cu(I)/Cu(II) oxidation/reduction change at a potential of approximately 0.32 V in a quasi-reversible process. The relative binding affinity of Mn(II), Fe(II), Co(II), Ni(II) and Cu(II) to the peptides is correlated with the stability constants of the Irving-Williams series for divalent metal ions. A potential application of these complexes of transition metals with amino acids or peptides is in the development of artificial photosynthetic cells.
ContributorsWang, Dong (Author) / Allen, James P. (Thesis advisor) / Ghirlanda, Giovanna (Committee member) / Redding, Kevin (Committee member) / Arizona State University (Publisher)
Created2014
Description
This dissertation examines the nexus of three trends in electricity systems transformations underway worldwide—the scale-up of renewable energy, regionalization, and liberalization. Interdependent electricity systems are being envisioned that require partnership and integration across power disparities. This research explores how actors in the Mediterranean region envisioned a massive scale-up of renewable energy within a single electricity system and market across Europe, North Africa, and the Middle East. It asks: How are regional sociotechnical systems envisioned? What are the anticipated consequences of a system for a region with broad disparities and deep sociopolitical differences? What can be learned about energy justice by examining this vision at multiple scales? A sociotechnical systems framework is used to analyze energy transformations, interweaving the technical aspects with politics, societal effects, and political development issues. This research utilized mixed qualitative methods to analyze Mediterranean electricity transformations at multiple scales, including fieldwork in Morocco and Germany, document analysis, and event ethnography. Each scale—from a global history of concentrating solar power technologies to a small village in Morocco—provides a different lens on the sociotechnical system and its implications for justice. This study updates Thomas Hughes’ Networks of Power, the canonical history of the sociotechnical development of electricity systems, by adding new aspects to sociotechnical electricity systems theory. First, a visioning process now plays a crucial role in guiding innovation and has a lasting influence on the justice outcomes. Second, rather than simply providing people with heat and light, electrical power systems in the 21st century are called upon to address complex integrated solutions. Furthermore, building a sustainable energy system is now a retrofitting agenda, as system builders must graft new infrastructure on top of old systems. Third, the spatial and temporal aspects of sociotechnical energy systems should be amended to account for constructed geography and temporal complexity. Fourth, transnational electricity systems pose new challenges for politics and political development. Finally, this dissertation presents a normative framework for conceptualizing and evaluating energy justice. Multi-scalar, systems-level justice requires collating diverse ideas about energy justice, expanding upon them based on the empirical material, and evaluating them with this framework.
ContributorsMoore, Sharlissa (Author) / Hackett, Ed J. (Thesis advisor) / Minteer, Ben (Committee member) / Parmentier, Mary Jane (Committee member) / Wetmore, Jameson (Committee member) / Arizona State University (Publisher)
Created2015
Description
The main objective of this research is to develop an approach to PV module lifetime prediction. In doing so, the aim is to move from empirical generalizations to a formal predictive science based on data-driven case studies of the crystalline silicon PV systems. The evaluation of PV systems aged 5 to 30 years old that results in systematic predictive capability that is absent today. The warranty period provided by the manufacturers typically range from 20 to 25 years for crystalline silicon modules. The end of lifetime (for example, the time-to-degrade by 20% from rated power) of PV modules is usually calculated using a simple linear extrapolation based on the annual field degradation rate (say, 0.8% drop in power output per year). It has been 26 years since systematic studies on solar PV module lifetime prediction were undertaken as part of the 11-year flat-plate solar array (FSA) project of the Jet Propulsion Laboratory (JPL) funded by DOE. Since then, PV modules have gone through significant changes in construction materials and design; making most of the field data obsolete, though the effect field stressors on the old designs/materials is valuable to be understood. Efforts have been made to adapt some of the techniques developed to the current technologies, but they are too often limited in scope and too reliant on empirical generalizations of previous results. Some systematic approaches have been proposed based on accelerated testing, but no or little experimental studies have followed. Consequently, the industry does not exactly know today how to test modules for a 20 - 30 years lifetime.
This research study focuses on the behavior of crystalline silicon PV module technology in the dry and hot climatic condition of Tempe/Phoenix, Arizona. A three-phase approach was developed: (1) A quantitative failure modes, effects, and criticality analysis (FMECA) was developed for prioritizing failure modes or mechanisms in a given environment; (2) A time-series approach was used to model environmental stress variables involved and prioritize their effect on the power output drop; and (3) A procedure for developing a prediction model was proposed for the climatic specific condition based on accelerated degradation testing
This research study focuses on the behavior of crystalline silicon PV module technology in the dry and hot climatic condition of Tempe/Phoenix, Arizona. A three-phase approach was developed: (1) A quantitative failure modes, effects, and criticality analysis (FMECA) was developed for prioritizing failure modes or mechanisms in a given environment; (2) A time-series approach was used to model environmental stress variables involved and prioritize their effect on the power output drop; and (3) A procedure for developing a prediction model was proposed for the climatic specific condition based on accelerated degradation testing
ContributorsKuitche, Joseph Mathurin (Author) / Pan, Rong (Thesis advisor) / Tamizhmani, Govindasamy (Thesis advisor) / Montgomery, Douglas C. (Committee member) / Wu, Teresa (Committee member) / Arizona State University (Publisher)
Created2014
Description
Increased global demand for energy has led to prolific use of fossil fuels, which produce and release greenhouse gases, such as carbon dioxide. This increase in atmospheric carbon dioxide affects the global weather system and has been cited as a cause for global warming. For humans to continue to meet demands for energy while reducing greenhouse emission, a sustainable, carbon-neutral energy source must be developed. The sun provides energy for the majority of life on earth, as well as the energy stored in the chemical bonds of fossil fuels. This dissertation investigates systems inspired by the biological mechanism of solar energy capture and storage. In natural photosynthesis, organisms use chlorophyll as a chromophore to absorb the sun's energy. Bio-inspired systems use close analogues like porphyrins and phthalocyanines. In this dissertation, a soluble, semiconducting porphyrin is reported. The polymer was synthesized via a Buchwald-Hartwig style coupling of porphyrin monomers which produced a polyaniline-like chain with porphyrins incorporated into the backbone. Spectroscopic and electrochemical studies were performed, which show evidence of excited state charge transfer and a first oxidation state of 0.58 V (vs SCE). These properties suggest that the polymer could be involved in excited state electron donation to fullerenes and other electron acceptors, which could be beneficial in organic photovoltaics, sensors, and other applications. Molecular dyads and triads capable of charge separation have been studied for decades, and the spectroscopic properties of two novel systems are reported in this dissertation. A peripherally-connected zinc-phthalocyanine-C60 dyad was studied, and showed excited state electron transfer from the phthalocyanine excited state to the C60, with a long-lived charge separated state. An axially-linked carotene-Si-pthalocyanine-C60 triad was studied, showing excited state electron transfer from the phthalocyanine to the C60, but fast recombination before hole transfer can occur to the carotene. Analogues of the electron transport mechanisms used in many biological systems use iron-sulfur clusters to shuttle electrons from donors to acceptors. In this dissertation, the spectroscopic properties of a de novo protein were studied. Nanosecond transient absorption was used to characterize the electron and energy transfer of an excited water-soluble porphyrin to the oxidized [FeS] clusters incorporated in the de novo protein. The triplet state of the porphyrin was strongly quenched with the holo-protein without a rise in porphyrin plus signal, suggesting that only Dexter-type energy transfer occurs between the sensitized porphyrin and the [FeS] clusters.
ContributorsSchmitz, Robert (Author) / Gust, John D (Thesis advisor) / Jones, Anne K (Committee member) / Buttry, Daniel (Committee member) / Arizona State University (Publisher)
Created2014
Description
A primary motivation of research in photovoltaic technology is to obtain higher efficiency photovoltaic devices at reduced cost of production so that solar electricity can be cost competitive. The majority of photovoltaic technologies are based on p-n junction, with efficiency potential being much lower than the thermodynamic limits of individual technologies and thereby providing substantial scope for further improvements in efficiency. The thesis explores photovoltaic devices using new physical processes that rely on thin layers and are capable of attaining the thermodynamic limit of photovoltaic technology. Silicon heterostructure is one of the candidate technologies in which thin films induce a minority carrier collecting junction in silicon and the devices can achieve efficiency close to the thermodynamic limits of silicon technology. The thesis proposes and experimentally establishes a new theory explaining the operation of silicon heterostructure solar cells. The theory will assist in identifying the optimum properties of thin film materials for silicon heterostructure and help in design and characterization of the devices, along with aiding in developing new devices based on this technology. The efficiency potential of silicon heterostructure is constrained by the thermodynamic limit (31%) of single junction solar cell and is considerably lower than the limit of photovoltaic conversion (~ 80 %). A further improvement in photovoltaic conversion efficiency is possible by implementing a multiple quasi-fermi level system (MQFL). A MQFL allows the absorption of sub band gap photons with current being extracted at a higher band-gap, thereby allowing to overcome the efficiency limit of single junction devices. A MQFL can be realized either by thin epitaxial layers of alternating higher and lower band gap material with nearly lattice matched (quantum well) or highly lattice mismatched (quantum dot) structure. The thesis identifies the material combination for quantum well structure and calculates the absorption coefficient of a MQFl based on quantum well. GaAsSb (barrier)/InAs(dot) was identified as a candidate material for MQFL using quantum dot. The thesis explains the growth mechanism of GaAsSb and the optimization of GaAsSb and GaAs heterointerface.
ContributorsGhosha, Kuṇāla (Author) / Bowden, Stuart (Thesis advisor) / Honsberg, Christiana (Thesis advisor) / Vasileska, Dragica (Committee member) / Goodnick, Stephen (Committee member) / Arizona State University (Publisher)
Created2011
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 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.
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
Description
The Energiewende aims to drastically reduce Germany’s greenhouse gas emissions, without relying on nuclear power, while maintaining a secure and affordable energy supply. Since 2000 the country’s renewable-energy share has increased exponentially, accounting in 2017 for over a third of Germany's gross electricity consumption. This unprecedented achievement is the result of policies, tools, and institutional arrangements intended to steer society to a low-carbon economy. Despite its resounding success in renewable-energy deployment, the Energiewende is not on track to meet its decarbonization goals. Energiewende rules and regulations have generated numerous undesired consequences, and have cost much more than anticipated, a burden borne primarily by energy consumers. Why has the Energiewende not only made energy more expensive, but also failed to bring Germany closer to its decarbonization goals? I analyzed the Energiewende as a complex socio-technical system, examining its legal framework and analyzing the consequences of successive regulations; identifying major political and energy players and the factors that motivated them to pursue socio-technical change; and documenting the political trends and events in which the Energiewende is rooted and which continue to shape it. I analyzed the dynamics and the loopholes that created barriers to transition, pushed the utility sector to the brink of dissolution, and led to such undesirable outcomes as negative wholesale prices and forced exports of electricity to Germany’s European neighbors. Thirty high-level energy experts and stakeholders were interviewed to find out how the best-informed members of German society perceive the Energiewende. Surprisingly, although they were highly critical of the way the transition has unfolded, most were convinced that the transition would eventually succeed. But their definitions of success did not always depend on achieving carbon-mitigation targets. Indeed, Germany jeopardizes the achievement of these targets by changing too many policy and institutional variables at too fast a pace. Good intentions and commitment are not enough to create economies based on intermittent energy sources: they will also require intensive grid expansion and breakthroughs in storage technology. The Energiewende demonstrates starkly that collective action driven by robust political consensus is not sufficient for steering complex socio-technical systems in desired directions.
ContributorsSturm, Christine (Author) / Sarewitz, Daniel (Thesis advisor) / Miller, Clark (Committee member) / Anderies, John (Committee member) / Hirt, Paul (Committee member) / Arizona State University (Publisher)
Created2018