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- All Subjects: Materials Science
- Creators: Smith, David J.
Description
Integrated oxide/semiconductor heterostructures have attracted intense interest for device applications which require sharp interfaces and controlled defects. The research of this dissertation has focused on the characterization of perovskite oxide/oxide and oxide/semiconductor heterostructures, and the analysis of interfaces and defect structures, using scanning transmission electrom microscopy (STEM) and related techniques.
The SrTiO3/Si system was initially studied to develop a basic understanding of the integration of perovskite oxides with semiconductors, and successful integration with abrupt interfaces was demonstrated. Defect analysis showed no misfit dislocations but only anti-phase boundaries (APBs) in the SrTiO3 (STO) films. Similar defects were later observed in other perovskite oxide heterostructures.
Ferroelectric BaTiO3 (BTO) thin films deposited directly onto STO substrates, or STO buffer layers with Ge substrates, were grown by molecular beam epitaxy (MBE) in order to control the polarization orientation for field-effect transistors (FETs). STEM imaging and elemental mapping by electron energy-loss spectroscopy (EELS) showed structurally and chemically abrupt interfaces, and the BTO films retained the c-axis-oriented tetragonal structure for both BTO/STO and BTO/STO/Ge heterostructures. The polarization displacement in the BTO films of TiN/BTO/STO heterostructures was investigated. The Ti4+ atomic column displacements and lattice parameters were measured directly using HAADF images. A polarization gradient, which switched from upwards to downwards, was observed in the BTO thin film, and evidence was found for positively-charged oxygen vacancies.
Heterostructures grown on Ge substrates by atomic layer deposition (ALD) were characterized and compared with MBE-grown samples. A two-step process was needed to overcome interlayer reaction at the beginning of ALD growth. A-site-rich oxide films with thicknesses of at least 2-nm had to be deposited and then crystallized before initiating deposition of the following perovskite oxide layer in order to suppress the formation of amorphous oxide layers on the Ge surface. BTO/STO/Ge, BTO/Ge, SrHfTiO3/Ge and SrZrO3/Ge thin films with excellent crystallinity were grown using this process.
Metal-insulator-metal (MIM) heterostructures were fabricated as ferroelectric capacitors and then electrically stressed to the point of breakdown to correlate structural changes with electrical and physical properties. BaTiO3 on Nb:STO was patterned with different top metal electrodes by focused-ion-beam milling, Au/Ni liftoff, and an isolation-defined approach.
The SrTiO3/Si system was initially studied to develop a basic understanding of the integration of perovskite oxides with semiconductors, and successful integration with abrupt interfaces was demonstrated. Defect analysis showed no misfit dislocations but only anti-phase boundaries (APBs) in the SrTiO3 (STO) films. Similar defects were later observed in other perovskite oxide heterostructures.
Ferroelectric BaTiO3 (BTO) thin films deposited directly onto STO substrates, or STO buffer layers with Ge substrates, were grown by molecular beam epitaxy (MBE) in order to control the polarization orientation for field-effect transistors (FETs). STEM imaging and elemental mapping by electron energy-loss spectroscopy (EELS) showed structurally and chemically abrupt interfaces, and the BTO films retained the c-axis-oriented tetragonal structure for both BTO/STO and BTO/STO/Ge heterostructures. The polarization displacement in the BTO films of TiN/BTO/STO heterostructures was investigated. The Ti4+ atomic column displacements and lattice parameters were measured directly using HAADF images. A polarization gradient, which switched from upwards to downwards, was observed in the BTO thin film, and evidence was found for positively-charged oxygen vacancies.
Heterostructures grown on Ge substrates by atomic layer deposition (ALD) were characterized and compared with MBE-grown samples. A two-step process was needed to overcome interlayer reaction at the beginning of ALD growth. A-site-rich oxide films with thicknesses of at least 2-nm had to be deposited and then crystallized before initiating deposition of the following perovskite oxide layer in order to suppress the formation of amorphous oxide layers on the Ge surface. BTO/STO/Ge, BTO/Ge, SrHfTiO3/Ge and SrZrO3/Ge thin films with excellent crystallinity were grown using this process.
Metal-insulator-metal (MIM) heterostructures were fabricated as ferroelectric capacitors and then electrically stressed to the point of breakdown to correlate structural changes with electrical and physical properties. BaTiO3 on Nb:STO was patterned with different top metal electrodes by focused-ion-beam milling, Au/Ni liftoff, and an isolation-defined approach.
ContributorsWu, Hsinwei (Author) / Smith, David J. (Thesis advisor) / Mccartney, Martha R (Thesis advisor) / Alford, Terry (Committee member) / Bertoni, Mariana (Committee member) / Arizona State University (Publisher)
Created2018
Description
With the high demand for faster and smaller wireless communication devices, manufacturers have been pushed to explore new materials for smaller and faster transistors. One promising class of transistors is high electron mobility transistors (HEMT). AlGaAs/GaAs HEMTs have been shown to perform well at high power and high frequencies. However, AlGaN/GaN HEMTs have been gaining more attention recently due to their comparatively higher power densities and better high frequency performance. Nevertheless, these devices have experienced truncated lifetimes. It is assumed that reducing defect densities in these materials will enable a more direct study of the failure mechanisms in these devices. In this work we present studies done to reduce interfacial oxygen at N-polar GaN/GaN interfaces, growth conditions for InAlN barrier layer, and microanalysis of a partial InAlN-based HEMT. Additionally, the depth of oxidation of an InAlN layer on a gate-less InAlN/GaN metal oxide semiconductor HEMT (MOSHEMT) was investigated. Measurements of electric fields in AlGaN/GaN HEMTs with and without field plates are also presented.
ContributorsMcConkie, Thomas O. (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha (Committee member) / Ponce, Fernando A. (Committee member) / Saraniti, Marco (Committee member) / Arizona State University (Publisher)
Created2018
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
This dissertation describes the characterization of optoelectronic and electronic materials being considered for next generation semiconductor devices, primarily using electron microscopy techniques. The research included refinement of growth parameters for optimizing material quality, and investigation of heterostructured interfaces. The results provide better understanding of the fundamental materials science and should lead to future improvements in device applications.
A microstructural study of tin selenide and tin manganese selenide thin films grown by molecular beam epitaxy (MBE) on GaAs (111)B substrates with different Se:Sn flux ratios and Mn concentrations was carried out. Low flux ratios lead to highly defective films, mostly consisting of SnSe, whereas higher flux ratios gave higher quality, single-phase SnSe2. The ternary (Sn,Mn)Se films evolved quasi-coherently, as the Mn concentration increased, from SnSe2 into a complex lattice, and then into MnSe with 3D rock-salt structure. These structural transformations should underlie the evolution of magnetic properties of this ternary system reported earlier in the literature.
II-VI/III-V compound semiconductor heterostructures have been characterized for growth in both single- and dual-chamber MBE systems. Three groups of lattice-matched materials have been investigated: i) 5.65Å materials based on GaAs, ii) 6.1Å materials based on InAs or GaSb, and iii) 6.5Å materials based on InSb. High quality II-VI materials grown on III-V substrates were demonstrated for ZnTe/GaSb and CdTe/InSb. III-V materials grown on II-VI buffer layers present additional challenges and were grown with varying degrees of success. InAsSb quantum wells in between ZnTe barriers were nearly defect-free, but showed 3D island growth. All other materials demonstrated flat interfaces, despite low growth temperature, but with stacking faults in the II-VI materials.
Femtosecond laser-induced defects (LIDs) in silicon solar cells were characterized using a variety of electron microscopy techniques. Scanning electron microscope (SEM) images showed that the intersections of laser lines, finger and busbar intersections, exhibited LIDs with the potential to shunt the contacts. SEM and transmission electron microscope (TEM) images correlated these LIDs with ablated c-Si and showed these defects to come in two sizes ~40nm and ~.5µm. The elemental profiles across defective and non-defective regions were found using energy dispersive x-ray spectroscopy.
A microstructural study of tin selenide and tin manganese selenide thin films grown by molecular beam epitaxy (MBE) on GaAs (111)B substrates with different Se:Sn flux ratios and Mn concentrations was carried out. Low flux ratios lead to highly defective films, mostly consisting of SnSe, whereas higher flux ratios gave higher quality, single-phase SnSe2. The ternary (Sn,Mn)Se films evolved quasi-coherently, as the Mn concentration increased, from SnSe2 into a complex lattice, and then into MnSe with 3D rock-salt structure. These structural transformations should underlie the evolution of magnetic properties of this ternary system reported earlier in the literature.
II-VI/III-V compound semiconductor heterostructures have been characterized for growth in both single- and dual-chamber MBE systems. Three groups of lattice-matched materials have been investigated: i) 5.65Å materials based on GaAs, ii) 6.1Å materials based on InAs or GaSb, and iii) 6.5Å materials based on InSb. High quality II-VI materials grown on III-V substrates were demonstrated for ZnTe/GaSb and CdTe/InSb. III-V materials grown on II-VI buffer layers present additional challenges and were grown with varying degrees of success. InAsSb quantum wells in between ZnTe barriers were nearly defect-free, but showed 3D island growth. All other materials demonstrated flat interfaces, despite low growth temperature, but with stacking faults in the II-VI materials.
Femtosecond laser-induced defects (LIDs) in silicon solar cells were characterized using a variety of electron microscopy techniques. Scanning electron microscope (SEM) images showed that the intersections of laser lines, finger and busbar intersections, exhibited LIDs with the potential to shunt the contacts. SEM and transmission electron microscope (TEM) images correlated these LIDs with ablated c-Si and showed these defects to come in two sizes ~40nm and ~.5µm. The elemental profiles across defective and non-defective regions were found using energy dispersive x-ray spectroscopy.
ContributorsTracy, Brian David (Author) / Smith, David J. (Thesis advisor) / Bennett, Peter A (Committee member) / Drucker, Jeffery (Committee member) / Mccartney, Martha R (Committee member) / Zhang, Yong-Hang (Committee member) / Arizona State University (Publisher)
Created2018
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
InAs/InAsSb type-II superlattices (T2SLs) can be considered as potential alternatives for conventional HgCdTe photodetectors due to improved uniformity, lower manufacturing costs with larger substrates, and possibly better device performance. This dissertation presents a comprehensive study on the structural, optical and electrical properties of InAs/InAsSb T2SLs grown by Molecular Beam Epitaxy.
The effects of different growth conditions on the structural quality were thoroughly investigated. Lattice-matched condition was successfully achieved and material of exceptional quality was demonstrated.
After growth optimization had been achieved, structural defects could hardly be detected, so different characterization techniques, including etch-pit-density (EPD) measurements, cathodoluminescence (CL) imaging and X-ray topography (XRT), were explored, in attempting to gain better knowledge of the sparsely distributed defects. EPD revealed the distribution of dislocation-associated pits across the wafer. Unfortunately, the lack of contrast in images obtained by CL imaging and XRT indicated their inability to provide any quantitative information about defect density in these InAs/InAsSb T2SLs.
The nBn photodetectors based on mid-wave infrared (MWIR) and long-wave infrared (LWIR) InAs/InAsSb T2SLs were fabricated. The significant difference in Ga composition in the barrier layer coupled with different dark current behavior, suggested the possibility of different types of band alignment between the barrier layers and the absorbers. A positive charge density of 1.8 × 1017/cm3 in the barrier of MWIR nBn photodetector, as determined by electron holography, confirmed the presence of a potential well in its valence band, thus identifying type-II alignment. In contrast, the LWIR nBn photodetector was shown to have type-I alignment because no sign of positive charge was detected in its barrier.
Capacitance-voltage measurements were performed to investigate the temperature dependence of carrier densities in a metal-oxide-semiconductor (MOS) structure based on MWIR InAs/InAsSb T2SLs, and a nBn structure based on LWIR InAs/InAsSb T2SLs. No carrier freeze-out was observed in either sample, indicating very shallow donor levels. The decrease in carrier density when temperature increased was attributed to the increased density of holes that had been thermally excited from localized states near the oxide/semiconductor interface in the MOS sample. No deep-level traps were revealed in deep-level transient spectroscopy temperature scans.
The effects of different growth conditions on the structural quality were thoroughly investigated. Lattice-matched condition was successfully achieved and material of exceptional quality was demonstrated.
After growth optimization had been achieved, structural defects could hardly be detected, so different characterization techniques, including etch-pit-density (EPD) measurements, cathodoluminescence (CL) imaging and X-ray topography (XRT), were explored, in attempting to gain better knowledge of the sparsely distributed defects. EPD revealed the distribution of dislocation-associated pits across the wafer. Unfortunately, the lack of contrast in images obtained by CL imaging and XRT indicated their inability to provide any quantitative information about defect density in these InAs/InAsSb T2SLs.
The nBn photodetectors based on mid-wave infrared (MWIR) and long-wave infrared (LWIR) InAs/InAsSb T2SLs were fabricated. The significant difference in Ga composition in the barrier layer coupled with different dark current behavior, suggested the possibility of different types of band alignment between the barrier layers and the absorbers. A positive charge density of 1.8 × 1017/cm3 in the barrier of MWIR nBn photodetector, as determined by electron holography, confirmed the presence of a potential well in its valence band, thus identifying type-II alignment. In contrast, the LWIR nBn photodetector was shown to have type-I alignment because no sign of positive charge was detected in its barrier.
Capacitance-voltage measurements were performed to investigate the temperature dependence of carrier densities in a metal-oxide-semiconductor (MOS) structure based on MWIR InAs/InAsSb T2SLs, and a nBn structure based on LWIR InAs/InAsSb T2SLs. No carrier freeze-out was observed in either sample, indicating very shallow donor levels. The decrease in carrier density when temperature increased was attributed to the increased density of holes that had been thermally excited from localized states near the oxide/semiconductor interface in the MOS sample. No deep-level traps were revealed in deep-level transient spectroscopy temperature scans.
ContributorsShen, Xiaomeng (Author) / Zhang, Yong-Hang (Thesis advisor) / Smith, David J. (Thesis advisor) / Alford, Terry (Committee member) / Goryll, Michael (Committee member) / Mccartney, Martha R (Committee member) / Arizona State University (Publisher)
Created2015
Description
In this dissertation research, conventional and aberration-corrected (AC) transmission electron microscopy (TEM) techniques were used to evaluate the structural and compositional properties of thin-film semiconductor compounds/alloys grown by molecular beam epitaxy for infrared photo-detection. Imaging, diffraction and spectroscopy techniques were applied to TEM specimens in cross-section geometry to extract information about extended structural defects, chemical homogeneity and interface abruptness. The materials investigated included InAs1-xBix alloys grown on GaSb (001) substrates, InAs/InAs1-xSbx type-II superlattices grown on GaSb (001) substrates, and CdTe-based thin-film structures grown on InSb (001) substrates.
The InAsBi dilute-bismide epitaxial films were grown on GaSb (001) substrates at relatively low growth temperatures. The films were mostly free of extended defects, as observed in diffraction-contrast images, but the incorporation of bismuth was not homogeneous, as manifested by the lateral Bi-composition modulation and Bi-rich surface droplets. Successful Bi incorporation into the InAs matrix was confirmed using lattice expansion measurements obtained from misfit strain analysis of high-resolution TEM (HREM) images.
Analysis of averaged intensity line profiles in HREM and scanning TEM (STEM) images of the Ga-free InAs/InAs1-xSbx type-II strained superlattices indicated slight variations in layer thickness across the superlattice stack. The interface abruptness was evaluated using misfit strain analysis of AC-STEM images, electron energy-loss spectroscopy and 002 dark-field imaging. The compositional profiles of antimony across the superlattices were fitted to a segregation model and revealed a strong antimony segregation probability.
The CdTe/MgxCd1-xTe double-heterostructures were grown with Cd overflux in a dual-chamber molecular beam epitaxy with an ultra-high vacuum transfer loadlock. Diffraction-contrast images showed that the growth temperature had a strong impact on the structural quality of the epilayers. Very abrupt CdTe/InSb interfaces were obtained for epilayers grown at the optimum temperature of 265 °C, and high-resolution imaging using AC-STEM revealed an interfacial transition region with a width of a few monolayers and smaller lattice spacing than either CdTe or InSb.
The InAsBi dilute-bismide epitaxial films were grown on GaSb (001) substrates at relatively low growth temperatures. The films were mostly free of extended defects, as observed in diffraction-contrast images, but the incorporation of bismuth was not homogeneous, as manifested by the lateral Bi-composition modulation and Bi-rich surface droplets. Successful Bi incorporation into the InAs matrix was confirmed using lattice expansion measurements obtained from misfit strain analysis of high-resolution TEM (HREM) images.
Analysis of averaged intensity line profiles in HREM and scanning TEM (STEM) images of the Ga-free InAs/InAs1-xSbx type-II strained superlattices indicated slight variations in layer thickness across the superlattice stack. The interface abruptness was evaluated using misfit strain analysis of AC-STEM images, electron energy-loss spectroscopy and 002 dark-field imaging. The compositional profiles of antimony across the superlattices were fitted to a segregation model and revealed a strong antimony segregation probability.
The CdTe/MgxCd1-xTe double-heterostructures were grown with Cd overflux in a dual-chamber molecular beam epitaxy with an ultra-high vacuum transfer loadlock. Diffraction-contrast images showed that the growth temperature had a strong impact on the structural quality of the epilayers. Very abrupt CdTe/InSb interfaces were obtained for epilayers grown at the optimum temperature of 265 °C, and high-resolution imaging using AC-STEM revealed an interfacial transition region with a width of a few monolayers and smaller lattice spacing than either CdTe or InSb.
ContributorsLu, Jing (Author) / Smith, David J. (Thesis advisor) / Alford, Terry L. (Committee member) / Crozier, Peter A. (Committee member) / McCartney, Martha R. (Committee member) / Zhang, Yong-Hang (Committee member) / Arizona State University (Publisher)
Created2017
Description
Ordered mesoporous materials have tunable pore sizes between 2 and 50 nm and are characterized by ordered pore structures and high surface areas (~1000 m2/g). This makes them particularly favorable for a number of membrane applications such as protein separation, polymer extrusion, nanowire fabrication and membrane reactors. These membranes can be fabricated as top-layers on macroporous supports or as embedded membranes in a dense matrix. The first part of the work deals with the hydrothermal synthesis and water-vapor/oxygen separation properties of supported MCM-48 and a new Al-MCM-48 type membrane for potential use in air conditioning systems. Knudsen-type permeation is observed in these membranes. The combined effect of capillary condensation and the aluminosilicate matrix resulted in the highest separation factor (142) in Al-MCM-48 membranes, with a water vapor permeance of 6×10-8mol/m2Pas. The second part focuses on synthesis of embedded mesoporous silica membranes with helically ordered pores by a novel Counter Diffusion Self-Assembly (CDSA) method. This method is an extension of the interfacial synthesis method for fiber synthesis using tetrabutylorthosilicate (TBOS) and cetyltrimethylammonium bromide (CTAB) as the silica source and surfactant respectively. The initial part of this study determined the effect of TBOS height and humidity on fiber formation. From this study, the range of TBOS heights for best microscopic and macroscopic ordering were established. Next, the CDSA method was used to successfully synthesize membranes, which were characterized to have good support plugging and an ordered pore structure. Factors that influence membrane synthesis and plug microstructure were determined. SEM studies revealed the presence of gaps between the plugs and support pores, which occur due to shrinking of the plug on drying. Development of a novel liquid deposition method to seal these defects constituted the last part of this work. Post sealing, excess silica was removed by etching with hydrofluoric acid. Membrane quality was evaluated at each step using SEM and gas permeation measurements. After surfactant removal by liquid extraction, the membranes exhibited an O2 permeance of 1.65x10-6mol/m2.Pa.s and He/O2 selectivity of 3.30. The successful synthesis of this membrane is an exciting new development in the area of ordered mesoporous membrane technology.
ContributorsSeshadri, Shriya (Author) / Lin, Jerry Y. S. (Thesis advisor) / Dai, Lenore (Committee member) / Rege, Kaushal (Committee member) / Smith, David J. (Committee member) / Vogt, Bryan (Committee member) / Arizona State University (Publisher)
Created2011
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
Multifunctional oxide thin-films grown on silicon and several oxide substrates have been characterized using High Resolution (Scanning) Transmission Electron Microscopy (HRTEM), Energy-Dispersive X-ray Spectroscopy (EDX), and Electron Energy-Loss Spectroscopy (EELS). Oxide thin films grown on SrTiO3/Si pseudo-substrate showed the presence of amorphised SrTiO3 (STO) at the STO/Si interface. Oxide/oxide interfaces were observed to be atomically clean with very few defects.
Al-doped SrTiO3 thin films grown on Si were of high crystalline quality. The Ti/O ratio estimated from EELS line scans revealed that substitution of Ti by Al created associated O vacancies. The strength of the crystal field in STO was measured using EELS, and decreased by ~1.0 eV as Ti4+ was substituted by Al3+. The damping of O-K EELS peaks confirmed the rise in oxygen vacancies. For Co-substituted STO films grown on Si, the EDS and EELS spectra across samples showed Co doping was quite random. The substitution of Ti4+ with Co3+ or Co2+ created associated oxygen vacancies for charge balance. Presence of oxygen vacancies was also confirmed by shift of Ti-L EELS peaks towards lower energy by ~0.4 eV. The crystal-field strength decreased by ~0.6 eV as Ti4+ was partially substituted by Co3+ or Co2+.
Spinel Co3O4 thin films grown on MgAl2O4 (110) were observed to have excellent crystalline quality. The structure of the Co3O4/MgAl2O4 interface was determined using HRTEM and image simulations. It was found that MgAl2O4 substrate is terminated with Al and oxygen. Stacking faults and associated strain fields in spinel Co3O4 were found along [111], [001], and [113] using Geometrical Phase Analysis.
NbO2 films on STO (111) were observed to be tetragonal with lattice parameter of 13.8 Å and NbO films on LSAT (111) were observed to be cubic with lattice parameter of 4.26 Å. HRTEM showed formation of high quality NbOx films and excellent coherent interface. HRTEM of SrAl4 on LAO (001) confirmed an island growth mode. The SrAl4 islands were highly crystalline with excellent epitaxial registry with LAO. By comparing HRTEM images with image simulations, the interface structure was determined to consist of Sr-terminated SrAl4 (001) on AlO2-terminated LAO (001).
Al-doped SrTiO3 thin films grown on Si were of high crystalline quality. The Ti/O ratio estimated from EELS line scans revealed that substitution of Ti by Al created associated O vacancies. The strength of the crystal field in STO was measured using EELS, and decreased by ~1.0 eV as Ti4+ was substituted by Al3+. The damping of O-K EELS peaks confirmed the rise in oxygen vacancies. For Co-substituted STO films grown on Si, the EDS and EELS spectra across samples showed Co doping was quite random. The substitution of Ti4+ with Co3+ or Co2+ created associated oxygen vacancies for charge balance. Presence of oxygen vacancies was also confirmed by shift of Ti-L EELS peaks towards lower energy by ~0.4 eV. The crystal-field strength decreased by ~0.6 eV as Ti4+ was partially substituted by Co3+ or Co2+.
Spinel Co3O4 thin films grown on MgAl2O4 (110) were observed to have excellent crystalline quality. The structure of the Co3O4/MgAl2O4 interface was determined using HRTEM and image simulations. It was found that MgAl2O4 substrate is terminated with Al and oxygen. Stacking faults and associated strain fields in spinel Co3O4 were found along [111], [001], and [113] using Geometrical Phase Analysis.
NbO2 films on STO (111) were observed to be tetragonal with lattice parameter of 13.8 Å and NbO films on LSAT (111) were observed to be cubic with lattice parameter of 4.26 Å. HRTEM showed formation of high quality NbOx films and excellent coherent interface. HRTEM of SrAl4 on LAO (001) confirmed an island growth mode. The SrAl4 islands were highly crystalline with excellent epitaxial registry with LAO. By comparing HRTEM images with image simulations, the interface structure was determined to consist of Sr-terminated SrAl4 (001) on AlO2-terminated LAO (001).
ContributorsDhamdhere, Ajit (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha R. (Committee member) / Chamberlin, Ralph (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2015