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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,

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
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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

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
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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
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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

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
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Description
In engineering, buckling is mechanical instability of walls or columns under compression and usually is a problem that engineers try to prevent. In everyday life buckles (wrinkles) on different substrates are ubiquitous -- from human skin to a rotten apple they are a commonly observed phenomenon. It seems that buckles

In engineering, buckling is mechanical instability of walls or columns under compression and usually is a problem that engineers try to prevent. In everyday life buckles (wrinkles) on different substrates are ubiquitous -- from human skin to a rotten apple they are a commonly observed phenomenon. It seems that buckles with macroscopic wavelengths are not technologically useful; over the past decade or so, however, thanks to the widespread availability of soft polymers and silicone materials micro-buckles with wavelengths in submicron to micron scale have received increasing attention because it is useful for generating well-ordered periodic microstructures spontaneously without conventional lithographic techniques. This thesis investigates the buckling behavior of thin stiff films on soft polymeric substrates and explores a variety of applications, ranging from optical gratings, optical masks, energy harvest to energy storage. A laser scanning technique is proposed to detect micro-strain induced by thermomechanical loads and a periodic buckling microstructure is employed as a diffraction grating with broad wavelength tunability, which is spontaneously generated from a metallic thin film on polymer substrates. A mechanical strategy is also presented for quantitatively buckling nanoribbons of piezoelectric material on polymer substrates involving the combined use of lithographically patterning surface adhesion sites and transfer printing technique. The precisely engineered buckling configurations provide a route to energy harvesters with extremely high levels of stretchability. This stiff-thin-film/polymer hybrid structure is further employed into electrochemical field to circumvent the electrochemically-driven stress issue in silicon-anode-based lithium ion batteries. It shows that the initial flat silicon-nanoribbon-anode on a polymer substrate tends to buckle to mitigate the lithiation-induced stress so as to avoid the pulverization of silicon anode. Spontaneously generated submicron buckles of film/polymer are also used as an optical mask to produce submicron periodic patterns with large filling ratio in contrast to generating only ~100 nm edge submicron patterns in conventional near-field soft contact photolithography. This thesis aims to deepen understanding of buckling behavior of thin films on compliant substrates and, in turn, to harness the fundamental properties of such instability for diverse applications.
ContributorsMa, Teng (Author) / Jiang, Hanqing (Thesis advisor) / Yu, Hongyu (Committee member) / Yu, Hongbin (Committee member) / Poon, Poh Chieh Benny (Committee member) / Rajagopalan, Jagannathan (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Inductors are fundamental components that do not scale well. Their physical limitations to scalability along with their inherent losses make them the main obstacle in achieving monolithic system-on-chip platform (SoCP). For past decades researchers focused on integrating magnetic materials into on-chip inductors in the quest of achieving high inductance density

Inductors are fundamental components that do not scale well. Their physical limitations to scalability along with their inherent losses make them the main obstacle in achieving monolithic system-on-chip platform (SoCP). For past decades researchers focused on integrating magnetic materials into on-chip inductors in the quest of achieving high inductance density and quality factor (QF). The state of the art on-chip inductor is made of an enclosed magnetic thin-film around the current carrying wire for maximum flux amplification. Though the integration of magnetic materials results in enhanced inductor characteristics, this approach has its own challenges and limitations especially in power applications. The current-induced magnetic field (HDC) drives the magnetic film into its saturation state. At saturation, inductance and QF drop to that of air-core inductors, eliminating the benefits of integrating magnetic materials. Increasing the current carrying capability without substantially sacrificing benefits brought on by the magnetic material is an open challenge in power applications. Researchers continue to address this challenge along with the continuous improvement in inductance and QF for RF and power applications.

In this work on-chip inductors incorporating magnetic Co-4%Zr-4%Ta -8%B thin films were fabricated and their characteristics were examined under the influence of an externally applied DC magnetic field. It is well established that spins in magnetic materials tend to align themselves in the same direction as the applied field. The resistance of the inductor resulting from the ferromagnetic film can be changed by manipulating the orientation of magnetization. A reduction in resistance should lead to decreases in losses and an enhancement in the QF. The effect of externally applied DC magnetic field along the easy and hard axes was thoroughly investigated. Depending on the strength and orientation of the externally applied field significant improvements in QF response were gained at the expense of a relative reduction in inductance. Characteristics of magnetic-based inductors degrade with current-induced stress. It was found that applying an externally low DC magnetic field across the on-chip inductor prevents the degradation in inductance and QF responses. Examining the effect of DC magnetic field on current carrying capability under low temperature is suggested.
ContributorsKhdour, Mahmoud (Author) / Yu, Hongbin (Thesis advisor) / Pan, George (Committee member) / Goryll, Michael (Committee member) / Bearat, Hamdallah (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa

Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2*-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set of experiments in C4dMImTf solicited water as the proton donor for oxygen reduction in an approximation of the aqueous alkaline case. The water content was varied between extremely dry (<0.1 mol% H2O) and saturated (approximately 15.8 mol% H2O}). As the water content increased so too did the extent of oxygen reduction eventually approach two electrons on both Pt and GC. However, additional water led to a linear increase in the Tafel slope under enhanced mass transport conditions up to the point of 10 mol% water. This inhibition of oxygen adsorption is the result of the interaction between superoxide and water and more specifically is proposed to be associated with decomposition of theC4dMIm+ cation by hydroxide at the elevated temperatures required for the experiment. Oxygen reduction on both Pt and GC follows Nernstian behavior as the water content is increased. Separate mechanisms for oxygen reduction on Pt and GC are proposed based on the nature of the Nernstian response in these systems.
ContributorsZeller, Robert August (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Buttry, Daniel (Committee member) / Arizona State University (Publisher)
Created2011
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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

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
This work investigates in-situ stress evolution of interfacial and bulk processes in electrochemical systems, and is divided into two projects. The first project examines the electrocapillarity of clean and CO-covered electrodes. It also investigates surface stress evolution during electro-oxidation of CO at Pt{111}, Ru/Pt{111} and Ru{0001} electrodes. The second project

This work investigates in-situ stress evolution of interfacial and bulk processes in electrochemical systems, and is divided into two projects. The first project examines the electrocapillarity of clean and CO-covered electrodes. It also investigates surface stress evolution during electro-oxidation of CO at Pt{111}, Ru/Pt{111} and Ru{0001} electrodes. The second project explores the evolution of bulk stress that occurs during intercalation (extraction) of lithium (Li) and formation of a solid electrolyte interphase during electrochemical reduction (oxidation) of Li at graphitic electrodes. Electrocapillarity measurements have shown that hydrogen and hydroxide adsorption are compressive on Pt{111}, Ru/Pt{111}, and Ru{0001}. The adsorption-induced surface stresses correlate strongly with adsorption charge. Electrocatalytic oxidation of CO on Pt{111} and Ru/Pt{111} gives a tensile surface stress. A numerical method was developed to separate both current and stress into background and active components. Applying this model to the CO oxidation signal on Ru{0001} gives a tensile surface stress and elucidates the rate limiting steps on all three electrodes. The enhanced catalysis of Ru/Pt{111} is confirmed to be bi-functional in nature: Ru provides adsorbed hydroxide to Pt allowing for rapid CO oxidation. The majority of Li-ion batteries have anodes consisting of graphite particles with polyvinylidene fluoride (PVDF) as binder. Intercalation of Li into graphite occurs in stages and produces anisotropic strains. As batteries have a fixed size and shape these strains are converted into mechanical stresses. Conventionally staging phenomena has been observed with X-ray diffraction and collaborated electrochemically with the potential. Work herein shows that staging is also clearly observed in stress. The Li staging potentials as measured by differential chronopotentiometry and stress are nearly identical. Relative peak heights of Li staging, as measured by these two techniques, are similar during reduction, but differ during oxidation due to non-linear stress relaxation phenomena. This stress relaxation appears to be due to homogenization of Li within graphite particles rather than viscous flow of the binder. The first Li reduction wave occurs simultaneously with formation of a passivating layer known as the solid electrolyte interphase (SEI). Preliminary experiments have shown the stress of SEI formation to be tensile (~+1.5 MPa).
ContributorsMickelson, Lawrence (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Buttry, Daniel (Committee member) / Venables, John (Committee member) / Arizona State University (Publisher)
Created2011
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Description
In this work, I worked on the synthesis and characterization of nanowires and belts, grown using different materials, in Chemical Vapor Deposition (CVD) system with catalytic growth method. Through this thesis, I utilized the Photoluminescence (PL), Secondary Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS) and X-ray diffraction (XRD) analyses to

In this work, I worked on the synthesis and characterization of nanowires and belts, grown using different materials, in Chemical Vapor Deposition (CVD) system with catalytic growth method. Through this thesis, I utilized the Photoluminescence (PL), Secondary Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS) and X-ray diffraction (XRD) analyses to find out the properties of Erbium Chloride Silicate (ECS) and two segment CdS-CdSe samples. In the first part of my research, growth of very new material, Erbium Chloride Silicate (ECS), in form of core/shell Si/ECS and pure ECS nanowires, was demonstrated. This new material has very fascinating properties for new Si based photonic devices. The Erbium density in those nanowires is which is very high value compared to the other Erbium doped materials. It was shown that the luminescence peaks of ECS nanowires are very sharp and stronger than their counterparts. Furthermore, both PL and XRD peaks get sharper and stronger as growth temperature increases and this shows that crystalline quality of ECS nanowires gets better with higher temperature. In the second part, I did a very detail research for growing two segment axial nanowires or radial belts and report that the structure type mostly depends on the growth temperature. Since our final step is to create white light LEDs using single axial nanowires which have three different regions grown with distinct materials and give red, green and blue colors simultaneously, we worked on growing CdS-CdSe nanowires or belts for the first step of our aim. Those products were successfully grown and they gave two luminescence peaks with maximum 160 nm wavelength separation depending on the growth conditions. It was observed that products become more likely belt once the substrate temperature increases. Also, dominance between VLS and VS is very critical to determine the shape of the products and the substitution of CdS by CdSe is very effective; hence, CdSe growth time should be chosen accordingly. However, it was shown two segmented products can be synthesized by picking the right conditions and with very careful analyses. We also demonstrated that simultaneous two colors lasing from a single segmented belt structures is possible with strong enough-pumping-power.
ContributorsTurkdogan, Sunay (Author) / Ning, Cun-Zheng (Thesis advisor) / Tao, Meng (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2012