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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
In-situ environmental transmission electron microscopy (ETEM) is a powerful tool for following the evolution of supported metal nanoparticles under different reacting gas conditions at elevated temperatures. The ability to observe the events in real time under reacting gas conditions can provide significant information on the fundamental processes taking place in catalytic materials, from which the performance of the catalyst can be understood. The first part of this dissertation presents the application of in-situ ETEM studies in developing structure-activity relationship in supported metal nanoparticles. In-situ ETEM studies on nanostructures in parallel with ex-situ reactor studies of conversions and selectivities were performed for partial oxidation of methane (POM) to syngas (CO+H2) on Ni/SiO2, Ru/SiO2 and NiRu/SiO2 catalysts. During POM, the gas composition varies along the catalyst bed with increasing temperature. It is important to consider these variations in gas composition in order to design experiments for in-situ ETEM. In-situ ETEM experiments were performed under three different reacting gas conditions. First in the presence of H2, this represents the state of the fresh catalyst for the catalytic reaction. Later in the presence of CH4 and O2 in 2:1 ratio, this is the composition of the reacting gases for the POM reaction and this composition acts as an oxidizing environment. Finally in the presence of CH4, this is the reducing gas. Oxidation and reduction behavior of Ni, Ru and NiRu nanoparticles were followed in an in-situ ETEM under reacting gas conditions and the observations were correlated with the performance of the catalyst for POM. The later part of the dissertation presents a technique for determining the gas compositional analysis inside the in-situ ETEM using electron energy-loss spectroscopy. Techniques were developed to identify the gas composition using both inner-shell and low-loss spectroscopy of EELS. Using EELS, an "operando TEM" technique was successfully developed for detecting the gas phase catalysis inside the ETEM. Overall this research demonstrates the importance of in-situ ETEM studies in understanding the structure-activity relationship in supported-metal catalysts for heterogeneous catalysis application.
ContributorsChenna, Santhosh (Author) / Crozier, Peter A. (Thesis advisor) / Carpenter, Ray (Committee member) / Sieradzki, Karl (Committee member) / Petuskey, William (Committee member) / Arizona State University (Publisher)
Created2011
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
HgCdTe is currently the dominant material for infrared sensing and imaging, and is usually grown on lattice-matched bulk CdZnTe (CZT) substrates. There have been significant recent efforts to identify alternative substrates to CZT as well as alternative detector materials to HgCdTe. In this dissertation research, a wide range of transmission electron microscopy (TEM) imaging and analytical techniques was used in the characterization of epitaxial HgCdTe and related materials and substrates for third generation IR detectors. ZnTe layers grown on Si substrates are considered to be promising candidates for lattice-matched, large-area, and low-cost composite substrates for deposition of II-VI and III-V compound semiconductors with lattice constants near 6.1 Å. After optimizing MBE growth conditions including substrate pretreatment prior to film growth, as well as nucleation and growth temperatures, thick ZnTe/Si films with high crystallinity, low defect density, and excellent surface morphology were achieved. Changes in the Zn/Te flux ratio used during growth were also investigated. Small-probe microanalysis confirmed that a small amount of As was present at the ZnTe/Si interface. A microstructural study of HgCdTe/CdTe/GaAs (211)B and CdTe/GaAs (211)B heterostructures grown using MBE was carried out. High quality MBE-grown CdTe on GaAs(211)B substrates was demonstrated to be a viable composite substrate platform for HgCdTe growth. In addition, analysis of interfacial misfit dislocations and residual strain showed that the CdTe/GaAs interface was fully relaxed. In the case of HgCdTe/CdTe/ GaAs(211)B, thin HgTe buffer layers between HgCdTe and CdTe were also investigated for improving the HgCdTe crystal quality. A set of ZnTe layers epitaxially grown on GaSb(211)B substrates using MBE was studied using high resolution X-ray diffraction (HRXRD) measurements and TEM characterization in order to investigate conditions for defect-free growth. HRXRD results gave critical thickness estimates between 350 nm and 375 nm, in good agreement with theoretical predictions. Moreover, TEM results confirmed that ZnTe layers with thicknesses of 350 nm had highly coherent interfaces and very low dislocation densities, unlike samples with the thicker ZnTe layers.
ContributorsKim, Jae Jin (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha R. (Committee member) / Alford, Terry L. (Committee member) / Crozier, Peter A. (Committee member) / Arizona State University (Publisher)
Created2012
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
Lithium-ion batteries can fail and catch fire when overcharged, exposed to high temperatures or short-circuited due to the highly flammable organic liquid used in the electrolyte. Using inorganic solid electrolyte materials can potentially improve the safety factor. Additionally, nanostructured electrolyte materials may further enhanced performance by taking advantage of their large aspect ratio. In this work, the synthesis of two promising nanostructured solid electrolyte materials was explored. Amorphous lithium niobate nanowires were synthesized through the decomposition of a niobium-containing complex in a structure-directing solvent using a reflux method. Lithium lanthanum titanate was obtained via solid state reaction with titanium oxide nanowires as the titanium precursor, but the nanowire morphology could not be preserved due to high temperature sintering. Hyperbranched potassium lanthanum titanate was synthesized through hydrothermal route. This was the first time that hyperbranched nanowires with perovskite structure were made without any catalyst or substrate. This result has the potential to be applied to other perovskite materials.
ContributorsYang, Ting (Author) / Chan, Candace K. (Thesis advisor) / Crozier, Peter A. (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2012
Description
A system for illuminating a sample in situ with visible and UV light inside a transmission electron microscope was devised to study photocatalysts. There are many factors which must be considered when designing and building such a system. These include both mechanical, optical, and electron optical considerations. Some of the restrictions posed by the electron microscope column are significant, and care must be taken not to degrade the microscope's electron optical performance, or to unduly restrict the other current capabilities of the microscope. The nature of these various design considerations is discussed in detail. A description of the system that has been added to the microscope at ASU, an FEI Tecnai F20 environmental transmission electron microscope is also given. The system includes a high brightness broadband light source with optical filters, a fiber to guide the light to the sample, and a system for precisely aligning the fiber tip. The spatial distribution and spectrum of the light reaching the sample has been characterized, and is described in detail.
ContributorsMiller, Benjamin (Author) / Crozier, Peter A. (Thesis advisor) / McCartney, Martha (Committee member) / Rez, Peter (Committee member) / Arizona State University (Publisher)
Created2012
Description
The research of this dissertation has involved the nanoscale quantitative characterization of patterned magnetic nanostructures and devices using off-axis electron holography and Lorentz microscopy. The investigation focused on different materials of interest, including monolayer Co nanorings, multilayer Co/Cu/Py (Permalloy, Ni81Fe19) spin-valve nanorings, and notched Py nanowires, which were fabricated via a standard electron-beam lithography (EBL) and lift-off process. Magnetization configurations and reversal processes of Co nanorings, with and without slots, were observed. Vortex-controlled switching behavior with stepped hysteresis loops was identified, with clearly defined onion states, vortex states, flux-closure (FC) states, and Omega states. Two distinct switching mechanisms for the slotted nanorings, depending on applied field directions relative to the slot orientations, were attributed to the vortex chirality and shape anisotropy. Micromagnetic simulations were in good agreement with electron holography observations of the Co nanorings, also confirming the switching field of 700-800 Oe. Co/Cu/Py spin-valve slotted nanorings exhibited different remanent states and switching behavior as a function of the different directions of the applied field relative to the slots. At remanent state, the magnetizations of Co and Py layers were preferentially aligned in antiparallel coupled configuration, with predominant configurations in FC or onion states. Two-step and three-step hysteresis loops were quantitatively determined for nanorings with slots perpendicular, or parallel to the applied field direction, respectively, due to the intrinsic coercivity difference and interlayer magnetic coupling between Co and Py layers. The field to reverse both layers was on the order of ~800 Oe. Domain-wall (DW) motion within Py nanowires (NWs) driven by an in situ magnetic field was visualized and quantified. Different aspects of DW behavior, including nucleation, injection, pinning, depinning, relaxation, and annihilation, occurred depending on applied field strength. A unique asymmetrical DW pinning behavior was recognized, depending on DW chirality relative to the sense of rotation around the notch. The transverse DWs relaxed into vortex DWs, followed by annihilation in a reversed field, which was in agreement with micromagnetic simulations. Overall, the success of these studies demonstrated the capability of off-axis electron holography to provide valuable insights for understanding magnetic behavior on the nanoscale.
ContributorsHe, Kai (Author) / McCartney, Martha R. (Thesis advisor) / Smith, David J. (Thesis advisor) / Chamberlin, Ralph V. (Committee member) / Crozier, Peter A. (Committee member) / Drucker, Jeff (Committee member) / Arizona State University (Publisher)
Created2010
Description
The two-dimensional electron gas (2DEG) at SrTiO3-based oxide interfaces has been extensively studied recently for its high carrier density, high electron mobility, superconducting, ferromagnetic, ferrroelectric and magnetoresistance properties, with possible application for all-oxide devices. Understanding the mechanisms behind the 2DEG formation and factors affecting its properties is the primary objective of this dissertation.
Advanced electron microscopy techniques, including aberration-corrected electron microscopy and electron energy-loss spectroscopy (EELS) with energy-loss near-edge structure (ELNES) analysis, were used to characterize the interfaces. Image and spectrum data-processing algorithms, including subpixel atomic position measurement, and novel outlier detection by oversampling, subspace division based EELS background removal and bias-free endmember extraction algorithms for hyperspectral unmixing and mapping were heavily used. Results were compared with density functional theory (DFT) calculations for theoretical explanation.
For the γ-Al2O3/SrTiO3 system, negative-Cs imaging confirmed the formation of crystalline γ-Al2O3. ELNES hyperspectral unmixing combined with DFT calculations revealed that oxygen vacancies, rather than polar discontinuity, were the key to the 2DEG formation. The critical thickness can be explained by shift of the Fermi level due to Ti out diffusion from the substrate to the film.
At the LaTiO3/SrTiO3 interface, aberration-corrected imaging showed crystallinity deterioration in LaTiO3 films a few unit cells away from the interface. ELNES showed that oxygen annealing did not alter the crystallinity but converted Ti3+ near the interface into Ti4+, which explained disappearance of the conductivity.
At the EuO/SrTiO3 interface, both high-resolution imaging and ELNES confirmed EuO formation. ELNES hyperspectral unmixing showed a Ti3+ layer confined to within several unit cells of the interface on the SrTiO3 side, confirming the presence of oxygen vacancies.
At the BaTiO3/SrTiO3 interface, spontaneous polarization and local lattice parameters were measured directly in each unit cell column and compared with oxidation state mapping using ELNES with unit-cell resolution. The unusually large polarization near the interface and the polarization gradient were explained by oxygen vacancies and the piezoelectric effect due to epitaxial strain and strain gradient from relaxation.
Advanced electron microscopy techniques, including aberration-corrected electron microscopy and electron energy-loss spectroscopy (EELS) with energy-loss near-edge structure (ELNES) analysis, were used to characterize the interfaces. Image and spectrum data-processing algorithms, including subpixel atomic position measurement, and novel outlier detection by oversampling, subspace division based EELS background removal and bias-free endmember extraction algorithms for hyperspectral unmixing and mapping were heavily used. Results were compared with density functional theory (DFT) calculations for theoretical explanation.
For the γ-Al2O3/SrTiO3 system, negative-Cs imaging confirmed the formation of crystalline γ-Al2O3. ELNES hyperspectral unmixing combined with DFT calculations revealed that oxygen vacancies, rather than polar discontinuity, were the key to the 2DEG formation. The critical thickness can be explained by shift of the Fermi level due to Ti out diffusion from the substrate to the film.
At the LaTiO3/SrTiO3 interface, aberration-corrected imaging showed crystallinity deterioration in LaTiO3 films a few unit cells away from the interface. ELNES showed that oxygen annealing did not alter the crystallinity but converted Ti3+ near the interface into Ti4+, which explained disappearance of the conductivity.
At the EuO/SrTiO3 interface, both high-resolution imaging and ELNES confirmed EuO formation. ELNES hyperspectral unmixing showed a Ti3+ layer confined to within several unit cells of the interface on the SrTiO3 side, confirming the presence of oxygen vacancies.
At the BaTiO3/SrTiO3 interface, spontaneous polarization and local lattice parameters were measured directly in each unit cell column and compared with oxidation state mapping using ELNES with unit-cell resolution. The unusually large polarization near the interface and the polarization gradient were explained by oxygen vacancies and the piezoelectric effect due to epitaxial strain and strain gradient from relaxation.
ContributorsLu, Sirong (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha R. (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Crozier, Peter A. (Committee member) / Arizona State University (Publisher)
Created2018
Description
As selenium and chromium are toxic even at low levels, it is very necessary to remove them from drinking water with proper ways. In this work, titanium dioxide based photocatalysts were mainly investigated in detail for their photoreduction ability towards selenate and chromate in aqueous environment. Firstly, photoreduction ability of layered double hydroxide (LDH) nanosheets with commercial TiO2 particle hybrid materials was investigated towards selenate or chromate. The results showed that commercial LDH/TiO2 (P90) composite, homemade LDH nanosheets/TiO2 (P90) composite and also in situ LDH/TiO2 (P25) composite all did not indicate significant improvement on photoreduction performance towards selenate or chromate. Secondly, TiO2 nanosheets material was synthesized with TiS2 as precursor via hydrothermal treatment. Morphology of TiO2 nanosheets were characterized by SEM, AFM and TEM. Photodegradation of MB (methylene blue) with TiO2 nanosheets was performed. In the future, first approach is to synthesize visible-light driven LDH photocatalyst NiFe-LDH nanosheets with TiO2 nanosheets hybrid material for selenate removal. Second approach is to use anion intercalation/insertion via electrochemical process to remove anions in drinking water.
ContributorsJing, Hangkun (Author) / Chan, Candace K. (Thesis advisor) / Sieradzki, Karl (Committee member) / Wang, Qinghua (Committee member) / Arizona State University (Publisher)
Created2018