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Description
Infrared photodetectors, used in applications for sensing and imaging, such as military target recognition, chemical/gas detection, and night vision enhancement, are predominantly comprised of an expensive II-VI material, HgCdTe. III-V type-II superlattices (SLs) have been studied as viable alternatives for HgCdTe due to the SL advantages over HgCdTe: greater control of the alloy composition, resulting in more uniform materials and cutoff wavelengths across the wafer; stronger bonds and structural stability; less expensive substrates, i.e., GaSb; mature III-V growth and processing technologies; lower band-to-band tunneling due to larger electron effective masses; and reduced Auger recombination enabling operation at higher temperatures and longer wavelengths. However, the dark current of InAs/Ga1-xInxSb SL detectors is higher than that of HgCdTe detectors and limited by Shockley-Read-Hall (SRH) recombination rather than Auger recombination. This dissertation work focuses on InAs/InAs1-xSbx SLs, another promising alternative for infrared laser and detector applications due to possible lower SRH recombination and the absence of gallium, which simplifies the SL interfaces and growth processes. InAs/InAs1-xSbx SLs strain-balanced to GaSb substrates were designed for the mid- and long-wavelength infrared (MWIR and LWIR) spectral ranges and were grown using MOCVD and MBE by various groups. Detailed characterization using high-resolution x-ray diffraction, atomic force microscopy, photoluminescence (PL), and photoconductance revealed the excellent structural and optical properties of the MBE materials. Two key material parameters were studied in detail: the valence band offset (VBO) and minority carrier lifetime. The VBO between InAs and InAs1-xSbx strained on GaSb with x = 0.28 - 0.41 was best described by Qv = ÄEv/ÄEg = 1.75 ± 0.03. Time-resolved PL experiments on a LWIR SL revealed a lifetime of 412 ns at 77 K, one order of magnitude greater than that of InAs/Ga1-xInxSb LWIR SLs due to less SRH recombination. MWIR SLs also had 100's of ns lifetimes that were dominated by radiative recombination due to shorter periods and larger wave function overlaps. These results allow InAs/InAs1-xSbx SLs to be designed for LWIR photodetectors with minority carrier lifetimes approaching those of HgCdTe, lower dark currents, and higher operating temperatures.
ContributorsSteenbergen, Elizabeth H (Author) / Zhang, Yong-Hang (Thesis advisor) / Brown, Gail J. (Committee member) / Vasileska, Dragica (Committee member) / Johnson, Shane R. (Committee member) / Arizona State University (Publisher)
Created2012
Description
Recently a new materials platform consisting of semiconductors grown on GaSb and InAs substrates with lattice constants close to 6.1 A was proposed by our group for various electronic and optoelectronic applications. This materials platform consists of both II-VI (MgZnCdHg)(SeTe) and III-V (InGaAl)(AsSb) compound semiconductors, which have direct bandgaps spanning the entire energy spectrum from far-IR (~0 eV) up to UV (~3.4 eV). The broad range of bandgaps and material properties make it very attractive for a wide range of applications in optoelectronics, such as solar cells, laser diodes, light emitting diodes, and photodetectors. Moreover, this novel materials system potentially offers unlimited degrees of freedom for integration of electronic and optoelectronic devices onto a single substrate while keeping the best possible materials quality with very low densities of misfit dislocations. This capability is not achievable with any other known lattice-matched semiconductors on any available substrate. In the 6.1-A materials system, the semiconductors ZnTe and GaSb are almost perfectly lattice-matched with a lattice mismatch of only 0.13%. Correspondingly, it is expected that high quality ZnTe/GaSb and GaSb/ZnTe heterostructures can be achieved with very few dislocations generated during growth. To fulfill the task, their MBE growth and material properties are carefully investigated. High quality ZnTe layers grown on various III-V substrates and GaSb grown on ZnTe are successfully achieved using MBE. It is also noticed that ZnTe and GaSb have a type-I band-edge alignment with large band offsets (delta_Ec=0.934 eV, delta_Ev=0.6 eV), which provides strong confinement for both electrons and holes. Furthermore, a large difference in refractive index is found between ZnTe and GaSb (2.7 and 3.9, respectively, at 0.7 eV), leading to excellent optical confinement of the guided optical modes in planar semiconductor lasers or distributed Bragg reflectors (DBR) for vertical-cavity surface-emitting lasers. Therefore, GaSb/ZnTe double-heterostructure and ZnTe/GaSb DBR structure are suitable for use in light emitting devices. In this thesis work, experimental demonstration of these structures with excellent structural and optical properties is reported. During the exploration on the properties of various ZnTe heterostructures, it is found that residual tensile strains exist in the thick ZnTe epilayers when they are grown on GaAs, InP, InAs and GaSb substrates. The presence of tensile strains is due to the difference in thermal expansion coefficients between the epilayers and the substrates. The defect densities in these ZnTe layers become lower as the ZnTe layer thickness increases. Growth of high quality GaSb on ZnTe can be achieved using a temperature ramp during growth. The influence of temperature ramps with different ramping rates in the optical properties of GaSb layer is studied, and the samples grown with a temperature ramp from 360 to 470 C at a rate of 33 C/min show the narrowest bound exciton emission peak with a full width at half maximum of 15 meV. ZnTe/GaSb DBR structures show excellent reflectivity properties in the mid-infrared range. A peak reflectance of 99% with a wide stopband of 480 nm centered at 2.5 um is measured from a ZnTe/GaSb DBR sample of only 7 quarter-wavelength pairs.
ContributorsFan, Jin (Author) / Zhang, Yong-Hang (Thesis advisor) / Smith, David (Committee member) / Yu, Hongbin (Committee member) / Menéndez, Jose (Committee member) / Johnson, Shane (Committee member) / Arizona State University (Publisher)
Created2012
Description
As the world energy demand increases, semiconductor devices with high energy conversion efficiency become more and more desirable. The energy conversion consists of two distinct processes, namely energy generation and usage. In this dissertation, novel multi-junction solar cells and light emitting diodes (LEDs) are proposed and studied for high energy conversion efficiency in both processes, respectively. The first half of this dissertation discusses the practically achievable energy conversion efficiency limit of solar cells. Since the demonstration of the Si solar cell in 1954, the performance of solar cells has been improved tremendously and recently reached 41.6% energy conversion efficiency. However, it seems rather challenging to further increase the solar cell efficiency. The state-of-the-art triple junction solar cells are analyzed to help understand the limiting factors. To address these issues, the monolithically integrated II-VI and III-V material system is proposed for solar cell applications. This material system covers the entire solar spectrum with a continuous selection of energy bandgaps and can be grown lattice matched on a GaSb substrate. Moreover, six four-junction solar cells are designed for AM0 and AM1.5D solar spectra based on this material system, and new design rules are proposed. The achievable conversion efficiencies for these designs are calculated using the commercial software package Silvaco with real material parameters. The second half of this dissertation studies the semiconductor luminescence refrigeration, which corresponds to over 100% energy usage efficiency. Although cooling has been realized in rare-earth doped glass by laser pumping, semiconductor based cooling is yet to be realized. In this work, a device structure that monolithically integrates a GaAs hemisphere with an InGaAs/GaAs quantum-well thin slab LED is proposed to realize cooling in semiconductor. The device electrical and optical performance is calculated. The proposed device then is fabricated using nine times photolithography and eight masks. The critical process steps, such as photoresist reflow and dry etch, are simulated to insure successful processing. Optical testing is done with the devices at various laser injection levels and the internal quantum efficiency, external quantum efficiency and extraction efficiency are measured.
ContributorsWu, Songnan (Author) / Zhang, Yong-Hang (Thesis advisor) / Menéndez, Jose (Committee member) / Ponce, Fernando (Committee member) / Belitsky, Andrei (Committee member) / Schroder, Dieter (Committee member) / Arizona State University (Publisher)
Created2010
Description
Modulated nanostructures are short-range periodic composition fluctuations observed in metals, semiconductors, and ceramic alloys and have an important effect on the mechanical, electrical, and magnetic properties of the materials. Their presence is often attributed to spinodal decomposition. In the past, such modulations have been analyzed using X-ray diffraction, electron diffraction, and diffraction contrast imaging techniques. The investigations gave useful information about the spatial distribution of the modulations but nothing about the composition fluctuation of the modulated structure. In this study, the composition amplitude of the fluctuations was directly measured using STEM Imaging and atomic resolution spectroscopy in small unit cell Au-Pt and Cu-Ti alloys. With the development of field emission sources, aberration correctors, and ADF imaging for STEM microscopes, measuring the amplitude of the modulation directly and examining the diffused interface is possible.Au-Pt alloys, featuring a nearly symmetrical solid-state miscibility gap, and a Cu-Ti alloy with an asymmetrical metastable miscibility gap were chosen for investigation. Three Au-Pt alloys of different compositions were analyzed at a specific temperature for varying aging times. The study successfully employed atomic resolution energy dispersive X-ray spectroscopy (EDS) for Au-Pt alloys and atomic resolution electron energy loss spectroscopy (EELS) for Cu-Ti alloys to measure composition variation and diffused interfaces across modulations.
In Au-Pt alloys, it was shown that the wavelength, as well as the composition amplitude of the modulations, increases as the alloy is aged for a longer time. Non-uniform distribution of wavelength and composition amplitude of modulated structures was observed across the samples. Results shows competitive growth mechanisms occurring in nanostructures with a range of wavelengths/amplitudes. Composition of Au-rich and Pt-rich regions deviates significantly from equilibrium at the selected temperature, more aging is necessary to observe coherency loss. Similarly, in Cu-Ti alloys, variations in wavelengths and composition amplitude of modulations were observed, along with clustering and ordering reactions. Ordering was specifically noted in Ti-rich regions of the alloy aged for an extended period. Diffused interfaces were observed in both alloy systems rather than chemically sharp interfaces, and the contrast in HAADF STEM images in both systems was predominantly influenced by strain effects. Hence utilizing HAADF STEM for composition measurement of modulations is impractical due to the impact of strain on HAADF intensity, specifically due to surface relaxation effects.
ContributorsSawant, Ronit Prasad (Author) / Carpenter, Ray (Thesis advisor) / Treacy, Michael (Committee member) / Crozier, Peter (Committee member) / Liu, Jingyue (Committee member) / Arizona State University (Publisher)
Created2024
Description
Ge1-xSnx and SiyGe1-x-ySnx materials are being researched intensively for applications in infra-red optoelectronic devices. Due to their direct band gap these materials may in-fact be the enabling factor in the commercial realization of silicon photonics/group IV photonics and the integration of nanophotonics with nanoelectronics. However the synthesis of these meta-stable semiconductor alloys, with a range of Sn-compositions, remains the primary technical challenge. Highly specialized epitaxial growth methods must be employed to produce single crystal layers which have sufficient quality for optoelectronic device applications. Up to this point these methods have been unfavorable from a semiconductor manufacturing perspective. In this work the growth of high-quality Si-Ge-Sn epitaxial alloys on Ge-buffered Si (100) using an industry-standard reduced pressure chemical vapor deposition reactor and a cost-effective chemistry is demonstrated. The growth kinetics are studied in detail in-order to understand the factors influencing layer composition, morphology, and defectivity. In doing so breakthrough GeSn materials and device results are achieved including methods to overcome the limits of Sn-incorporation and the realization of low-defect and strain-relaxed epitaxial layers with up to 20% Sn.
P and n-type doping methods are presented in addition to the production of SiGeSn ternary alloys. Finally optically stimulated lasing in thick GeSn layers and SiGeSn/GeSn multiple quantum wells is demonstrated. Lasing wavelengths ranging from 2-3 µm at temperatures up to 180K are realized in thick layers. Whereas SiGeSn/GeSn multiple quantum wells on a strain-relaxed GeSn buffers have enabled the first reported SiGeSn/GeSn multiple quantum well laser operating up to 80K with threshold power densities as low as 33 kW/cm2.
P and n-type doping methods are presented in addition to the production of SiGeSn ternary alloys. Finally optically stimulated lasing in thick GeSn layers and SiGeSn/GeSn multiple quantum wells is demonstrated. Lasing wavelengths ranging from 2-3 µm at temperatures up to 180K are realized in thick layers. Whereas SiGeSn/GeSn multiple quantum wells on a strain-relaxed GeSn buffers have enabled the first reported SiGeSn/GeSn multiple quantum well laser operating up to 80K with threshold power densities as low as 33 kW/cm2.
ContributorsMargetis, Joseph (Author) / Zhang, Yong-Hang (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Johnson, Shane (Committee member) / Arizona State University (Publisher)
Created2018
Description
The fuel cell is a promising device that converts the chemical energy directly into the electrical energy without combustion process. However, the slow reaction rate of the oxygen reduction reaction (ORR) necessitates the development of cathode catalysts for low-temperature fuel cells. After a thorough literature review in Chapter 1, the thesis is divided into three parts as given below in Chapters 2-4.
Chapter 2 describes the study on the Pt and Pt-Me (Me: Co, Ni) alloy nanoparticles supported on the pyrolyzed zeolitic imidazolate framework (ZIF) towards ORR. The Co-ZIF and NiCo-ZIF were synthesized by the solvothermal method and then mixed with Pt precursor. After pyrolysis and acid leaching, the PtCo/NC and PtNiCo/NC were evaluated in proton exchange membrane fuel cells (PEMFC). The peak power density exhibited > 10% and 15% for PtCo/NC and PtNiCo/NC, respectively, compared to that with commercial Pt/C catalyst under identical test conditions.
Chapter 3 is the investigation of the oxygen vacancy (OV) effect in a-MnO2 as a cathode catalyst for alkaline membrane fuel cells (AMFC). The a-MnO2 nanorods were synthesized by hydrothermal method and heated at 300, 400 and 500 ℃ in the air to introduce the OV. The 400 ℃ treated material showed the best ORR performance among all other samples due to more OV in pure a-MnO2 phase. The optimized AMFC electrode showed ~ 45 mW.cm-2, which was slightly lower than that with commercial Pt/C (~60 mW.cm-2).
Chapter 4 is the density functional theory (DFT) study of the protonation effect and active sites towards ORR on a-MnO2 (211) plane. The theoretically optimized oxygen adsorption and hydroxyl ion desorption energies were ~ 1.55-1.95 eV and ~ 0.98-1.45 eV, respectively, by Nørskov et al.’s calculations. All the configurations showed oxygen adsorption and hydroxyl ion desorption energies were ranging from 0.27 to 1.76 eV and 1.59 to 15.0 eV, respectively. The site which was close to two Mn ions showed the best oxygen adsorption and hydroxyl ion desorption energies improvement with the surface protonation.
Based on the results given in Chapters 1-4, the major findings are summarized in Chapter 5.
Chapter 2 describes the study on the Pt and Pt-Me (Me: Co, Ni) alloy nanoparticles supported on the pyrolyzed zeolitic imidazolate framework (ZIF) towards ORR. The Co-ZIF and NiCo-ZIF were synthesized by the solvothermal method and then mixed with Pt precursor. After pyrolysis and acid leaching, the PtCo/NC and PtNiCo/NC were evaluated in proton exchange membrane fuel cells (PEMFC). The peak power density exhibited > 10% and 15% for PtCo/NC and PtNiCo/NC, respectively, compared to that with commercial Pt/C catalyst under identical test conditions.
Chapter 3 is the investigation of the oxygen vacancy (OV) effect in a-MnO2 as a cathode catalyst for alkaline membrane fuel cells (AMFC). The a-MnO2 nanorods were synthesized by hydrothermal method and heated at 300, 400 and 500 ℃ in the air to introduce the OV. The 400 ℃ treated material showed the best ORR performance among all other samples due to more OV in pure a-MnO2 phase. The optimized AMFC electrode showed ~ 45 mW.cm-2, which was slightly lower than that with commercial Pt/C (~60 mW.cm-2).
Chapter 4 is the density functional theory (DFT) study of the protonation effect and active sites towards ORR on a-MnO2 (211) plane. The theoretically optimized oxygen adsorption and hydroxyl ion desorption energies were ~ 1.55-1.95 eV and ~ 0.98-1.45 eV, respectively, by Nørskov et al.’s calculations. All the configurations showed oxygen adsorption and hydroxyl ion desorption energies were ranging from 0.27 to 1.76 eV and 1.59 to 15.0 eV, respectively. The site which was close to two Mn ions showed the best oxygen adsorption and hydroxyl ion desorption energies improvement with the surface protonation.
Based on the results given in Chapters 1-4, the major findings are summarized in Chapter 5.
ContributorsShi, Xuan, Ph.D (Author) / Kannan, Arunachalanadar Mada (Thesis advisor) / Liu, Jingyue (Committee member) / Nam, Changho (Committee member) / Peng, Xihong (Committee member) / Arizona State University (Publisher)
Created2019
Description
Compound semiconductors tend to be more ionic if the cations and anions are further apart in atomic columns, such as II-VI compared to III-V compounds, due in part to the greater electronegativity difference between group-II and group-VI atoms. As the electronegativity between the atoms increases, the materials tend to have more insulator-like properties, including higher energy band gaps and lower indices of refraction. This enables significant differences in the optical and electronic properties between III-V, II-VI, and IV-VI semiconductors. Many of these binary compounds have similar lattice constants and therefore can be grown epitaxially on top of each other to create monolithic heterovalent and heterocrystalline heterostructures with optical and electronic properties unachievable in conventional isovalent heterostructures.
Due to the difference in vapor pressures and ideal growth temperatures between the different materials, precise growth methods are required to optimize the structural and optical properties of the heterovalent heterostructures. The high growth temperatures of the III-V materials can damage the II-VI barrier layers, and therefore a compromise must be found for the growth of high-quality III-V and II-VI layers in the same heterostructure. In addition, precise control of the interface termination has been shown to play a significant role in the crystal quality of the different layers in the structure. For non-polar orientations, elemental fluxes of group-II and group-V atoms consistently help to lower the stacking fault and dislocation density in the II-VI/III-V heterovalent heterostructures.
This dissertation examines the epitaxial growth of heterovalent and heterocrystalline heterostructures lattice-matched to GaAs, GaSb, and InSb substrates in a single-chamber growth system. The optimal growth conditions to achieve alternating layers of III-V, II-VI, and IV-VI semiconductors have been investigated using temperature ramps, migration-enhanced epitaxy, and elemental fluxes at the interface. GaSb/ZnTe distributed Bragg reflectors grown in this study significantly outperform similar isovalent GaSb-based reflectors and show great promise for mid-infrared applications. Also, carrier confinement in GaAs/ZnSe quantum wells was achieved with a low-temperature growth technique for GaAs on ZnSe. Additionally, nearly lattice-matched heterocrystalline PbTe/CdTe/InSb heterostructures with strong infrared photoluminescence were demonstrated, along with virtual (211) CdZnTe/InSb substrates with extremely low defect densities for long-wavelength optoelectronic applications.
Due to the difference in vapor pressures and ideal growth temperatures between the different materials, precise growth methods are required to optimize the structural and optical properties of the heterovalent heterostructures. The high growth temperatures of the III-V materials can damage the II-VI barrier layers, and therefore a compromise must be found for the growth of high-quality III-V and II-VI layers in the same heterostructure. In addition, precise control of the interface termination has been shown to play a significant role in the crystal quality of the different layers in the structure. For non-polar orientations, elemental fluxes of group-II and group-V atoms consistently help to lower the stacking fault and dislocation density in the II-VI/III-V heterovalent heterostructures.
This dissertation examines the epitaxial growth of heterovalent and heterocrystalline heterostructures lattice-matched to GaAs, GaSb, and InSb substrates in a single-chamber growth system. The optimal growth conditions to achieve alternating layers of III-V, II-VI, and IV-VI semiconductors have been investigated using temperature ramps, migration-enhanced epitaxy, and elemental fluxes at the interface. GaSb/ZnTe distributed Bragg reflectors grown in this study significantly outperform similar isovalent GaSb-based reflectors and show great promise for mid-infrared applications. Also, carrier confinement in GaAs/ZnSe quantum wells was achieved with a low-temperature growth technique for GaAs on ZnSe. Additionally, nearly lattice-matched heterocrystalline PbTe/CdTe/InSb heterostructures with strong infrared photoluminescence were demonstrated, along with virtual (211) CdZnTe/InSb substrates with extremely low defect densities for long-wavelength optoelectronic applications.
ContributorsLassise, Maxwell Brock (Author) / Zhang, Yong-Hang (Thesis advisor) / Smith, David J. (Committee member) / Johnson, Shane R (Committee member) / Mccartney, Martha R (Committee member) / Arizona State University (Publisher)
Created2019
Description
Among the alternative processes for the traditional distillation, adsorption and membrane separations are the two most promising candidates and metal-organic frameworks (MOFs) are the new material candidate as adsorbent or membrane due to their high surface area, various pore sizes, and highly tunable framework functionality. This dissertation presents an investigation of the formation process of MOF membrane, framework defects, and two-dimensional (2D) MOFs, aiming to explore the answers for three critical questions: (1) how to obtain a continuous MOF membrane, (2) how defects form in MOF framework, and (3) how to obtain isolated 2D MOFs. To solve the first problem, the accumulated protons in the MOF synthesis solution is proposed to be the key factor preventing the continuous growth among Universitetet I Oslo-(UiO)-66 crystals. The hypothesis is verified by the growth reactivation under the addition of deprotonating agent. As long as the protons were sufficiently coordinated by the deprotonating agent, the continuous growth of UiO-66 is guaranteed. Moreover, the modulation effect can impact the coordination equilibrium so that an oriented growth of UiO-66 film was achieved in membrane structures. To find the answer for the second problem, the defect formation mechanism in UiO-66 was investigated and the formation of missing-cluster (MC) defects is attributed to the partially-deprotonated ligands. Experimental results show the number of MC defects is sensitive to the addition of deprotonating agent, synthesis temperature, and reactant concentration. Pore size distribution allows an accurate and convenient characterization of the defects. Results show that these defects can cause significant deviations of its pore size distribution from the perfect crystal. The study of the third questions is based on the established bi-phase synthesis method, a facile synthesis method is adopted for the production of high quality 2D MOFs in large scale. Here, pyridine is used as capping reagent to prevent the interplanar hydrogen bond formation. Meanwhile, formic acid and triethylamine as modulator and deprotonating agent to balance the anisotropic growth, crystallinity, and yield in the 2D MOF synthesis. As a result, high quality 2D zinc-terephthalic acid (ZnBDC) and copper-terephthalic acid (CuBDC) with extraordinary aspect ratio samples were successfully synthesized.
ContributorsShan, Bohan (Author) / Mu, Bin (Thesis advisor) / Forzani, Erica (Committee member) / Dai, Lenore (Committee member) / Lin, Jerry (Committee member) / Liu, Jingyue (Committee member) / Arizona State University (Publisher)
Created2019
Description
Non-stoichiometric oxides play a critical role in many catalytic, energy, and sensing technologies, providing the ability to reversibly exchange oxygen with the ambient environment through the creation and annihilation of surface oxygen vacancies. Oxygen exchange at the surfaces of these materials is strongly influenced by atomic structure, which varies significantly across nanoparticle surfaces. The studies presented herein elucidate the relationship between surface structure behaviors and oxygen exchange reactions on ceria (CeO2) catalyst materials. In situ aberration-corrected transmission electron microscopy (AC-TEM) techniques were developed and employed to correlate dynamic atomic-level structural heterogeneities to local oxygen vacancy activity.
A model Ni/CeO2 catalyst was used to probe the role of a ceria support during hydrocarbon reforming reactions, and it was revealed that carbon formation was inhibited on Ni metal nanoparticles due to the removal of lattice oxygen from the ceria support and subsequent oxidation of adsorbed decomposed hydrocarbon products. Atomic resolution observations of surface oxygen vacancy creation and annihilation were performed on CeO2 nanoparticle surfaces using a novel time-resolved in situ AC-TEM approach. Cation displacements were found to be related to oxygen vacancy creation and annihilation, and the most reactive surface oxygen sites were identified by monitoring the frequency of cation displacements. In addition, the dynamic evolution of CeO2 surface structures was characterized with high temporal resolution AC-TEM imaging, which resulted in atomic column positions and occupancies to be determined with a combination of spatial precision and temporal resolution that had not previously been achieved. As a result, local lattice expansions and contractions were observed on ceria surfaces, which were likely related to cyclic oxygen vacancy activity. Finally, local strain fields on CeO2 surfaces were quantified, and it was determined that local strain enhanced the ability of a surface site to create oxygen vacancies. Through the characterization of dynamic surface structures with advanced AC-TEM techniques, an improvement in the fundamental understanding of how ceria surfaces influence and control oxygen exchange reactions was obtained.
A model Ni/CeO2 catalyst was used to probe the role of a ceria support during hydrocarbon reforming reactions, and it was revealed that carbon formation was inhibited on Ni metal nanoparticles due to the removal of lattice oxygen from the ceria support and subsequent oxidation of adsorbed decomposed hydrocarbon products. Atomic resolution observations of surface oxygen vacancy creation and annihilation were performed on CeO2 nanoparticle surfaces using a novel time-resolved in situ AC-TEM approach. Cation displacements were found to be related to oxygen vacancy creation and annihilation, and the most reactive surface oxygen sites were identified by monitoring the frequency of cation displacements. In addition, the dynamic evolution of CeO2 surface structures was characterized with high temporal resolution AC-TEM imaging, which resulted in atomic column positions and occupancies to be determined with a combination of spatial precision and temporal resolution that had not previously been achieved. As a result, local lattice expansions and contractions were observed on ceria surfaces, which were likely related to cyclic oxygen vacancy activity. Finally, local strain fields on CeO2 surfaces were quantified, and it was determined that local strain enhanced the ability of a surface site to create oxygen vacancies. Through the characterization of dynamic surface structures with advanced AC-TEM techniques, an improvement in the fundamental understanding of how ceria surfaces influence and control oxygen exchange reactions was obtained.
ContributorsLawrence, Ethan Lee (Author) / Crozier, Peter A. (Thesis advisor) / Lin, Jerry (Committee member) / Liu, Jingyue (Committee member) / Petuskey, William (Committee member) / Arizona State University (Publisher)
Created2019
Description
This dissertation describes fundamental studies of hollow carbon nanostructures, which may be used as electrodes for practical energy storage applications such as batteries or supercapacitors. Electron microscopy is heavily utilized for the nanoscale characterization. To control the morphology of hollow carbon nanostructures, ZnO nanowires serve as sacrificial templates. The first part of this dissertation focuses on the optimization of synthesis parameters and the scale-up production of ZnO nanowires by vapor transport method. Uniform ZnO nanowires with 40 nm width can be produced by using 1100 °C reaction temperature and 20 sccm oxygen flow rate, which are the two most important parameters.
The use of ethanol as carbon source with or without water steam provides uniform carbonaceous deposition on ZnO nanowire templates. The amount of as-deposited carbonaceous material can be controlled by reaction temperature and reaction time. Due to the catalytic property of ZnO surface, the thicknesses of carbonaceous layers are typically in nanometers. Different methods to remove the ZnO templates are explored, of which hydrogen reduction at temperatures higher than 700 °C is most efficient. The ZnO templates can also be removed under ethanol environment, but the temperatures need to be higher than 850 °C for practical use.
Characterizations of hollow carbon nanofibers show that the hollow carbon nanostructures have a high specific surface area (>1100 m2/g) with the presence of mesopores (~3.5 nm). The initial data on energy storage as electrodes of electrochemical double layer capacitors show that high specific capacitance (> 220 F/g) can be obtained, which is related to the high surface area and unique porous hollow structure with a thin wall.
The use of ethanol as carbon source with or without water steam provides uniform carbonaceous deposition on ZnO nanowire templates. The amount of as-deposited carbonaceous material can be controlled by reaction temperature and reaction time. Due to the catalytic property of ZnO surface, the thicknesses of carbonaceous layers are typically in nanometers. Different methods to remove the ZnO templates are explored, of which hydrogen reduction at temperatures higher than 700 °C is most efficient. The ZnO templates can also be removed under ethanol environment, but the temperatures need to be higher than 850 °C for practical use.
Characterizations of hollow carbon nanofibers show that the hollow carbon nanostructures have a high specific surface area (>1100 m2/g) with the presence of mesopores (~3.5 nm). The initial data on energy storage as electrodes of electrochemical double layer capacitors show that high specific capacitance (> 220 F/g) can be obtained, which is related to the high surface area and unique porous hollow structure with a thin wall.
ContributorsSong, Yian (Author) / Liu, Jingyue (Committee member) / Smith, David (Committee member) / McCartney, Martha (Committee member) / Chen, Tingyong (Committee member) / Arizona State University (Publisher)
Created2016