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- All Subjects: Materials Science
- Creators: Crozier, Peter
- Creators: Yu, Hongbin
- Member of: ASU Electronic Theses and Dissertations
Description
Fuel cells, particularly solid oxide fuel cells (SOFC), are important for the future of greener and more efficient energy sources. Although SOFCs have been in existence for over fifty years, they have not been deployed extensively because they need to be operated at a high temperature (∼1000 °C), are expensive, and have slow response to changes in energy demands. One important need for commercialization of SOFCs is a lowering of their operating temperature, which requires an electrolyte that can operate at lower temperatures. Doped ceria is one such candidate. For this dissertation work I have studied different types of doped ceria to understand the mechanism of oxygen vacancy diffusion through the bulk. Doped ceria is important because they have high ionic conductivities thus making them attractive candidates for the electrolytes of solid oxide fuel cells. In particular, I have studied how the ionic conductivities are improved in these doped materials by studying the oxygen-vacancy formations and migrations. In this dissertation I describe the application of density functional theory (DFT) and Kinetic Lattice Monte Carlo (KLMC) simulations to calculate the vacancy diffusion and ionic conductivities in doped ceria. The dopants used are praseodymium (Pr), gadolinium (Gd), and neodymium (Nd), all belonging to the lanthanide series. The activation energies for vacancy migration between different nearest neighbor (relative to the dopant) positions were calculated using the commercial DFT code VASP (Vienna Ab-initio Simulation Package). These activation energies were then used as inputs to the KLMC code that I co-developed. The KLMC code was run for different temperatures (673 K to 1073 K) and for different dopant concentrations (0 to 40%). These simulations have resulted in the prediction of dopant concentrations for maximum ionic conductivity at a given temperature.
ContributorsAnwar, Shahriar (Author) / Adams, James B (Thesis advisor) / Crozier, Peter (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2011
Description
As the 3rd generation solar cell, quantum dot solar cells are expected to outperform the first 2 generations with higher efficiency and lower manufacture cost. Currently the main problems for QD cells are the low conversion efficiency and stability. This work is trying to improve the reliability as well as the device performance by inserting an interlayer between the metal cathode and the active layer. Titanium oxide and a novel nitrogen doped titanium oxide were compared and TiOxNy capped device shown a superior performance and stability to TiOx capped one. A unique light anneal effect on the interfacial layer was discovered first time and proved to be the trigger of the enhancement of both device reliability and efficiency. The efficiency was improved by 300% and the device can retain 73.1% of the efficiency with TiOxNy when normal device completely failed after kept for long time. Photoluminescence indicted an increased charge disassociation rate at TiOxNy interface. External quantum efficiency measurement also inferred a significant performance enhancement in TiOxNy capped device, which resulted in a higher photocurrent. X-ray photoelectron spectrometry was performed to explain the impact of light doping on optical band gap. Atomic force microscopy illustrated the effect of light anneal on quantum dot polymer surface. The particle size is increased and the surface composition is changed after irradiation. The mechanism for performance improvement via a TiOx based interlayer was discussed based on a trap filling model. Then Tunneling AFM was performed to further confirm the reliability of interlayer capped organic photovoltaic devices. As a powerful tool based on SPM technique, tunneling AFM was able to explain the reason for low efficiency in non-capped inverted organic photovoltaic devices. The local injection properties as well as the correspondent topography were compared in organic solar cells with or without TiOx interlayer. The current-voltage characteristics were also tested at a single interested point. A severe short-circuit was discovered in non capped devices and a slight reverse bias leakage current was also revealed in TiOx capped device though tunneling AFM results. The failure reason for low stability in normal devices was also discussed comparing to capped devices.
ContributorsYu, Jialin (Author) / Jabbour, Ghassan E. (Thesis advisor) / Alford, Terry L. (Thesis advisor) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2011
Description
There is an inexorable link between structure and stress, both of which require study in order to truly understand the physics of thin films. To further our knowledge of thin films, the relationship between structure and stress development was examined in three separate systems in vacuum. The first was continued copper thin film growth in ultra-high vacuum after adsorption of a sub-monolayer quantity of oxygen. Results showed an increase in compressive stress generation, and theory was proposed to explain the additional compressive stress within the films. The second system explored was the adsorption of carbon monoxide on the platinum {111} surface in vacuum. The experiments displayed a correlation between known structural developments in the adsorbed carbon monoxide adlayer and the surface stress state of the system. The third system consisted of the growth and annealing stresses of ice thin films at cryogenic temperatures in vacuum. It was shown that the growth stresses are clearly linked to known morphology development from literature, with crystalline ice developing compressive and amorphous ice developing tensile stresses respectively, and that amorphous ice films develop additional tensile stresses upon annealing.
ContributorsKennedy, Jordan (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Crozier, Peter (Committee member) / Arizona State University (Publisher)
Created2011
Description
The behavior of a solid oxide fuel cell (SOFC) cermet (ceramic-metal composite) anode under reaction conditions depends significantly on the structure, morphology and atomic scale interactions between the metal and the ceramic components. In situ environmental transmission electron microscope (ETEM) is an important tool which not only allows us to perform the basic nanoscale characterization of the anode materials, but also to observe in real-time, the dynamic changes in the anode material under near-reaction conditions. The earlier part of this dissertation is focused on the synthesis and characterization of Pr- and Gd-doped cerium oxide anode materials. A novel spray drying set-up was designed and constructed for preparing nanoparticles of these mixed-oxides and nickel oxide for anode fabrication. X-ray powder diffraction was used to investigate the crystal structure and lattice parameters of the synthesized materials. Particle size distribution, morphology and chemical composition were investigated using transmission electron microscope (TEM). The nanoparticles were found to possess pit-like defects of average size 2 nm after subjecting the spray-dried material to heat treatment at 700 °C for 2 h in air. A novel electron energy-loss spectroscopy (EELS) quantification technique for determining the Pr and Gd concentrations in the mixed oxides was developed. Nano-scale compositional heterogeneity was observed in these materials. The later part of the dissertation focuses mainly on in situ investigations of the anode materials under a H2 environment in the ETEM. Nano-scale changes in the stand-alone ceramic components of the cermet anode were first investigated. Particle size and composition of the individual nanoparticles of Pr-doped ceria (PDC) were found to affect their reducibility in H2 gas. Upon reduction, amorphization of the nanoparticles was observed and was linked to the presence of pit-like defects in the spray-dried material. Investigation of metal-ceramic interactions in the Ni-loaded PDC nanoparticles indicated a localized reduction of Ce in the vicinity of the Ni/PDC interface at 420 °C. Formation of a reduction zone around the interface was attributed to H spillover which was observed directly in the ETEM. Preliminary results on the fabrication of model SOFCs and in situ behavior of Ni/Gd-doped ceria anodes have been presented.
ContributorsSharma, Vaneet (Author) / Crozier, Peter A. (Thesis advisor) / Sharma, Renu (Thesis advisor) / Adams, James B (Committee member) / Dey, Sandwip (Committee member) / Arizona State University (Publisher)
Created2011
Description
Thin films of ever reducing thickness are used in a plethora of applications and their performance is highly dependent on their microstructure. Computer simulations could then play a vital role in predicting the microstructure of thin films as a function of processing conditions. FACET is one such software tool designed by our research group to model polycrystalline thin film growth, including texture evolution and grain growth of polycrystalline films in 2D. Several modifications to the original FACET code were done to enhance its usability and accuracy. Simulations of sputtered silver thin films are presented here with FACET 2.0 with qualitative and semi-quantitative comparisons with previously published experimental results. Comparisons of grain size, texture and film thickness between simulations and experiments are presented which describe growth modes due to various deposition factors like flux angle and substrate temperature. These simulations provide reasonable agreement with the experimental data over a diverse range of process parameters. Preliminary experiments in depositions of Silver films are also attempted with varying substrates and thickness in order to generate complementary experimental and simulation studies of microstructure evolution. Overall, based on the comparisons, FACET provides interesting insights into thin film growth processes, and the effects of various deposition conditions on thin film structure and microstructure. Lastly, simple molecular dynamics simulations of deposition on bi-crystals are attempted for gaining insight into texture based grain competition during film growth. These simulations predict texture based grain coarsening mechanisms like twinning and grain boundary migration that have been commonly reported in FCC films.
ContributorsRairkar, Asit (Author) / Adams, James B (Thesis advisor) / Krause, Stephen (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2011
Description
With increasing demand for System on Chip (SoC) and System in Package (SiP) design in computer and communication technologies, integrated inductor which is an essential passive component has been widely used in numerous integrated circuits (ICs) such as in voltage regulators and RF circuits. In this work, soft ferromagnetic core material, amorphous Co-Zr-Ta-B, was incorporated into on-chip and in-package inductors in order to scale down inductors and improve inductors performance in both inductance density and quality factor. With two layers of 500 nm Co-Zr-Ta-B films a 3.5X increase in inductance and a 3.9X increase in quality factor over inductors without magnetic films were measured at frequencies as high as 1 GHz. By laminating technology, up to 9.1X increase in inductance and more than 5X increase in quality factor (Q) were obtained from stripline inductors incorporated with 50 nm by 10 laminated films with a peak Q at 300 MHz. It was also demonstrated that this peak Q can be pushed towards high frequency as far as 1GHz by a combination of patterning magnetic films into fine bars and laminations. The role of magnetic vias in magnetic flux and eddy current control was investigated by both simulation and experiment using different patterning techniques and by altering the magnetic via width. Finger-shaped magnetic vias were designed and integrated into on-chip RF inductors improving the frequency of peak quality factor from 400 MHz to 800 MHz without sacrificing inductance enhancement. Eddy current and magnetic flux density in different areas of magnetic vias were analyzed by HFSS 3D EM simulation. With optimized magnetic vias, high frequency response of up to 2 GHz was achieved. Furthermore, the effect of applied magnetic field on on-chip inductors was investigated for high power applications. It was observed that as applied magnetic field along the hard axis (HA) increases, inductance maintains similar value initially at low fields, but decreases at larger fields until the magnetic films become saturated. The high frequency quality factor showed an opposite trend which is correlated to the reduction of ferromagnetic resonant absorption in the magnetic film. In addition, experiments showed that this field-dependent inductance change varied with different patterned magnetic film structures, including bars/slots and fingers structures. Magnetic properties of Co-Zr-Ta-B films on standard organic package substrates including ABF and polyimide were also characterized. Effects of substrate roughness and stress were analyzed and simulated which provide strategies for integrating Co-Zr-Ta-B into package inductors and improving inductors performance. Stripline and spiral inductors with Co-Zr-Ta-B films were fabricated on both ABF and polyimide substrates. Maximum 90% inductance increase in hundreds MHz frequency range were achieved in stripline inductors which are suitable for power delivery applications. Spiral inductors with Co-Zr-Ta-B films showed 18% inductance increase with quality factor of 4 at frequency up to 3 GHz.
ContributorsWu, Hao (Author) / Yu, Hongbin (Thesis advisor) / Bakkaloglu, Bertan (Committee member) / Cao, Yu (Committee member) / Chickamenahalli, Shamala (Committee member) / Arizona State University (Publisher)
Created2013
Description
Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown that capacities comparable to graphite can be obtained for up to 10 cycles and lower capacities can be obtained for up to 20 cycles. Unlike bulk silicon, the clathrate structure does not undergo excessive volume change upon lithium intercalation, and therefore, the crystal structure is morphologically stable over many cycles. X-ray diffraction of the clathrate after cycling showed that crystallinity is intact, indicating that the clathrate does not collapse during reversible intercalation with lithium ions. Electrochemical potential spectroscopy obtained from the cycling data showed that there is an absence of formation of lithium-silicide, which is the product of lithium alloying with diamond cubic silicon. Type II silicon clathrate, NaxSi136, consists of silicon making up the framework structure and sodium (guest) atoms occupying the interstitial spaces. These clathrates showed very high capacities during their first intercalation cycle, in the range of 3,500 mAh/g, but then deteriorated during subsequent cycles. X-ray diffraction after one cycle showed the absence of clathrate phase and the presence of lithium-silicide, indicating the disintegration of clathrate structure. This could explain the silicon-like cycling behavior of Type II clathrates.
ContributorsRaghavan, Rahul (Author) / Chan, Candace K. (Thesis advisor) / Crozier, Peter (Committee member) / Petuskey, William T (Committee member) / Arizona State University (Publisher)
Created2013
Description
There has been much interest in photoelectrochemical conversion of solar energy in recent years due to its potential for low-–cost, sustainable and renewable production of fuels. Despite the huge potential, there are still a number of technical barriers due to the many constraints needed in order to drive photoelectrochemical reactions such as overall water splitting and the identification of efficient and effective semiconductor materials. To this end, the search for novel semiconductors that can act as light absorbers is still needed. The copper hydroxyphosphate mineral libethenite (CHP), which has a chemical formula of Cu2(OH)PO4, has been recently shown to be active for photocatalytic degradation of methylene blue under UV-–irradiation, indicating that photo-excited electrons and holes can effectively be generated and separated in this material. However, CHP has not been well studied and many of its fundamental electrochemical and photoelectrochemical properties are still unknown. In this work, the synthesis of different morphologies of CHP using hydrothermal synthesis and precipitation methods were explored. Additionally, a preliminary investigation of the relevant fundamental characteristics such as the bandgap, flatband potential, band diagram, electrochemical and photoelectrochemical properties for CHP was performed. Better understanding of the properties of this material may lead to the development of improved catalysts and photocatalysts from natural sources.
ContributorsLi, Man (Author) / Chan, Candace K. (Thesis advisor) / O'Connell, Michael (Committee member) / Crozier, Peter (Committee member) / Arizona State University (Publisher)
Created2013
Description
Integrated photonics requires high gain optical materials in the telecom wavelength range for optical amplifiers and coherent light sources. Erbium (Er) containing materials are ideal candidates due to the 1.5 μm emission from Er3+ ions. However, the Er density in typical Er-doped materials is less than 1 x 1020 cm-3, thus limiting the maximum optical gain to a few dB/cm, too small to be useful for integrated photonics applications. Er compounds could potentially solve this problem since they contain much higher Er density. So far the existing Er compounds suffer from short lifetime and strong upconversion effects, mainly due to poor quality of crystals produced by various methods of thin film growth and deposition. This dissertation explores a new Er compound: erbium chloride silicate (ECS, Er3(SiO4)2Cl ) in the nanowire form, which facilitates the growth of high quality single crystals. Growth methods for such single crystal ECS nanowires have been established. Various structural and optical characterizations have been carried out. The high crystal quality of ECS material leads to a long lifetime of the first excited state of Er3+ ions up to 1 ms at Er density higher than 1022 cm-3. This Er lifetime-density product was found to be the largest among all Er containing materials. A unique integrating sphere method was developed to measure the absorption cross section of ECS nanowires from 440 to 1580 nm. Pump-probe experiments demonstrated a 644 dB/cm signal enhancement from a single ECS wire. It was estimated that such large signal enhancement can overcome the absorption to result in a net material gain, but not sufficient to compensate waveguide propagation loss. In order to suppress the upconversion process in ECS, Ytterbium (Yb) and Yttrium (Y) ions are introduced as substituent ions of Er in the ECS crystal structure to reduce Er density. While the addition of Yb ions only partially succeeded, erbium yttrium chloride silicate (EYCS) with controllable Er density was synthesized successfully. EYCS with 30 at. % Er was found to be the best. It shows the strongest PL emission at 1.5 μm, and thus can be potentially used as a high gain material.
ContributorsYin, Leijun (Author) / Ning, Cun-Zheng (Thesis advisor) / Chamberlin, Ralph (Committee member) / Yu, Hongbin (Committee member) / Menéndez, Jose (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2013
Description
This dissertation is on the study of structural and optical properties of some III-V and II-VI compound semiconductors. The first part of this dissertation is a study of the deformation mechanisms associated with nanoindentation and nanoscratching of InP, GaN, and ZnO crystals. The second part is an investigation of some fundamental issues regarding compositional fluctuations and microstructure in GaInNAs and InAlN alloys. In the first part, the microstructure of (001) InP scratched in an atomic force microscope with a small diamond tip has been studied as a function of applied normal force and crystalline direction in order to understand at the nanometer scale the deformation mechanisms in the zinc-blende structure. TEM images show deeper dislocation propagation for scratches along <110> compared to <100>. High strain fields were observed in <100> scratches, indicating hardening due to locking of dislocations gliding on different slip planes. Reverse plastic flow have been observed in <110> scratches in the form of pop-up events that result from recovery of stored elastic strain. In a separate study, nanoindentation-induced plastic deformation has been studied in c-, a-, and m-plane ZnO single crystals and c-plane GaN respectively, to study the deformation mechanism in wurtzite hexagonal structures. TEM results reveal that the prime deformation mechanism is slip on basal planes and in some cases, on pyramidal planes, and strain built up along particular directions. No evidence of phase transformation or cracking was observed in both materials. CL imaging reveals quenching of near band-edge emission by dislocations. In the second part, compositional inhomogeneity in quaternary GaInNAs and ternary InAlN alloys has been studied using TEM. It is shown that exposure to antimony during growth of GaInNAs results in uniform chemical composition in the epilayer, as antimony suppresses the surface mobility of adatoms that otherwise leads to two-dimensional growth and elemental segregation. In a separate study, compositional instability is observed in lattice-matched InAlN films grown on GaN, for growth beyond a certain thickness. Beyond 200 nm of thickness, two sub-layers with different indium content are observed, the top one with lower indium content.
ContributorsHuang, Jingyi (Author) / Ponce, Fernando A. (Thesis advisor) / Carpenter, Ray W (Committee member) / Smith, David J. (Committee member) / Yu, Hongbin (Committee member) / Treacy, Michael Mj (Committee member) / Arizona State University (Publisher)
Created2013