Theses and Dissertations
This collection includes both ASU Theses and Dissertations, submitted by graduate students, and the Barrett, Honors College theses submitted by undergraduate students.
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Description
Diamond transistors are promising as high-power and high-frequency devices having higher efficiencies than conventional transistors. Diamond possesses superior electronic properties, such as a high bandgap (5.47 eV), high breakdown voltage (>10 MV cm−1 ), high electron and hole mobilities [4500 and 3800 cm2 V−1 · s−1, respectively], high electron and hole saturation velocities (1.5 × 107 and 1.05 × 107 cm s−1, respectively), and high thermal conductivity [22 W cm−1 · K−1], compared to conventional semiconductors. Reportedly, the diamond field-effect transistors (FETs) have shown transition frequencies (fT) of 45 and 70 GHz, maximum oscillation frequency (fmax) of 120 GHz, and radiofrequency (RF) power densities of 2.1 and 3.8 W mm−1 at 1 GHz. A two-dimensional-hole-gas (2DHG) surface channel forms on H-diamond by transfer doping from adsorbates/dielectrics in contact with H-diamond surface. However, prior studies indicate that charge transfer at the dielectric/ H-diamond interface could result in relatively low mobility attributed to interface scattering from the transferred negative charge to acceptor region. H-terminated diamond exhibits a negative electron affinity (NEA) of -1.1 to -1.3 eV, which is crucial to enable charge transfer doping. To overcome these limitations modulation doping, that is, selective doping, that leads to spatial separation of the MoO3 acceptor layer from the hole channel on H-diamond has been proposed. Molybdenum oxide (MoO3) was used as dielectric as it has electron affinity of 5.9eV and could align its conduction band minimum (CBM) below the valence band maximum (VBM) of H-terminated diamond. The band alignment provides the driving potential for charge transfer. Hafnium oxide (HfO2) was used as interfacial layer since it is a high-k oxide insulator (∼25), having large Eg (5.6 eV), high critical breakdown field, and high thermal stability. This study presents photoemission measurements of the electronic band alignments of the MoO3/HfO2/H-diamond layer structure to gain insight into the driving potential for the negative charge transfer and the location of the negative charges near the interface, in the HfO2 layer or in the MoO3 layer. The diamond hole concentration, mobility, and sheet resistance were characterized for MoO3/HfO2/H-Diamond with HfO2 layers of 0, 2 and 4 nm thickness.
ContributorsDeshmukh, Aditya Vilasrao (Author) / Nemanich, Robert J. (Thesis advisor) / Alford, Terry (Committee member) / Yang, Sui (Committee member) / Arizona State University (Publisher)
Created2024
Description
ABSTRACT
Large-pore metal-organic framework (MOF) membranes offer potential in a number of gas and liquid separations due to their wide and selective adsorption capacities. A key characteristic of a number of MOF and zeolitic imidazolate framework (ZIF) membranes is their highly selective adsorption capacities for CO2. These membranes offer very tangible potential to separate CO2 in a wide array of industrially relevant separation processes, such as the separation from CO2 in flue gas emissions, as well as the sweetening of methane.
By virtue of this, the purpose of this dissertation is to synthesize and characterize two linear large-pore MOF membranes, MOF-5 and ZIF-68, and to study their gas separation properties in binary mixtures of CO¬2/N2 and CO2/CH4. The three main objectives researched are as follows. The first is to study the pervaporation behavior and stability of MOF-5; this is imperative because although MOF-5 exhibits desirable adsorption and separation characteristics, it is very unstable in atmospheric conditions. In determining its stability and behavior in pervaporation, this material can be utilized in conditions wherein atmospheric levels of moisture can be avoided. The second objective is to synthesize, optimize and characterize a linear, more stable MOF membrane, ZIF-68. The final objective is to study in tandem the high-pressure gas separation behavior of MOF-5 and ZIF-68 in binary gas systems of both CO2/N2 and CO2/CH4.
Continuous ZIF-68 membranes were synthesized via the reactive seeding method and the modified reactive seeding method. These membranes, as with the MOF-5 membranes synthesized herein, both showed adherence to Knudsen diffusion, indicating limited defects. Organic solvent experiments indicated that MOF-5 and ZIF-68 were stable in a variety of organic solvents, but both showed reductions in permeation flux of the tested molecules. These reductions were attributed to fouling and found to be cumulative up until a saturation of available bonding sites for molecules was reached and stable pervaporation permeances were reached for both. Gas separation behavior for MOF-5 showed direct dependence on the CO2 partial pressure and the overall feed pressure, while ZIF-68 did not show similar behavior. Differences in separation behavior are attributable to orientation of the ZIF-68 membranes.
Large-pore metal-organic framework (MOF) membranes offer potential in a number of gas and liquid separations due to their wide and selective adsorption capacities. A key characteristic of a number of MOF and zeolitic imidazolate framework (ZIF) membranes is their highly selective adsorption capacities for CO2. These membranes offer very tangible potential to separate CO2 in a wide array of industrially relevant separation processes, such as the separation from CO2 in flue gas emissions, as well as the sweetening of methane.
By virtue of this, the purpose of this dissertation is to synthesize and characterize two linear large-pore MOF membranes, MOF-5 and ZIF-68, and to study their gas separation properties in binary mixtures of CO¬2/N2 and CO2/CH4. The three main objectives researched are as follows. The first is to study the pervaporation behavior and stability of MOF-5; this is imperative because although MOF-5 exhibits desirable adsorption and separation characteristics, it is very unstable in atmospheric conditions. In determining its stability and behavior in pervaporation, this material can be utilized in conditions wherein atmospheric levels of moisture can be avoided. The second objective is to synthesize, optimize and characterize a linear, more stable MOF membrane, ZIF-68. The final objective is to study in tandem the high-pressure gas separation behavior of MOF-5 and ZIF-68 in binary gas systems of both CO2/N2 and CO2/CH4.
Continuous ZIF-68 membranes were synthesized via the reactive seeding method and the modified reactive seeding method. These membranes, as with the MOF-5 membranes synthesized herein, both showed adherence to Knudsen diffusion, indicating limited defects. Organic solvent experiments indicated that MOF-5 and ZIF-68 were stable in a variety of organic solvents, but both showed reductions in permeation flux of the tested molecules. These reductions were attributed to fouling and found to be cumulative up until a saturation of available bonding sites for molecules was reached and stable pervaporation permeances were reached for both. Gas separation behavior for MOF-5 showed direct dependence on the CO2 partial pressure and the overall feed pressure, while ZIF-68 did not show similar behavior. Differences in separation behavior are attributable to orientation of the ZIF-68 membranes.
ContributorsKasik, Alexandra Marie (Author) / Lin, Jerry (Thesis advisor) / Tasooji, Amaneh (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2015
Description
Membrane-based gas separation is promising for efficient propylene/propane (C3H6/C3H8) separation with low energy consumption and minimum environment impact. Two microporous inorganic membrane candidates, MFI-type zeolite membrane and carbon molecular sieve membrane (CMS) have demonstrated excellent thermal and chemical stability. Application of these membranes into C3H6/C3H8 separation has not been well investigated. This dissertation presents fundamental studies on membrane synthesis, characterization and C3H6/C3H8 separation properties of MFI zeolite membrane and CMS membrane.
MFI zeolite membranes were synthesized on α-alumina supports by secondary growth method. Novel positron annihilation spectroscopy (PAS) techniques were used to non-destructively characterize the pore structure of these membranes. PAS reveals a bimodal pore structure consisting of intracrystalline zeolitic micropores of ~0.6 nm in diameter and irregular intercrystalline micropores of 1.4 to 1.8 nm in size for the membranes. The template-free synthesized membrane exhibited a high permeance but a low selectivity in C3H6/C3H8 mixture separation.
CMS membranes were synthesized by coating/pyrolysis method on mesoporous γ-alumina support. Such supports allow coating of thin, high-quality polymer films and subsequent CMS membranes with no infiltration into support pores. The CMS membranes show strong molecular sieving effect, offering a high C3H6/C3H8 mixture selectivity of ~30. Reduction in membrane thickness from 500 nm to 300 nm causes an increase in C3H8 permeance and He/N2 selectivity, but a decrease in the permeance of He, N2 and C3H6 and C3H6/C3H8 selectivity. This can be explained by the thickness dependent chain mobility of the polymer film resulting in final carbon membrane of reduced pore size with different effects on transport of gas of different sizes, including possible closure of C3H6-accessible micropores.
CMS membranes demonstrate excellent C3H6/C3H8 separation performance over a wide range of feed pressure, composition and operation temperature. No plasticization was observed at a feed pressure up to 100 psi. The permeation and separation is mainly controlled by diffusion instead of adsorption. CMS membrane experienced a decline in permeance, and an increase in selectivity over time under on-stream C3H6/C3H8 separation. This aging behavior is due to the reduction in effective pore size and porosity caused by oxygen chemisorption and physical aging of the membrane structure.
MFI zeolite membranes were synthesized on α-alumina supports by secondary growth method. Novel positron annihilation spectroscopy (PAS) techniques were used to non-destructively characterize the pore structure of these membranes. PAS reveals a bimodal pore structure consisting of intracrystalline zeolitic micropores of ~0.6 nm in diameter and irregular intercrystalline micropores of 1.4 to 1.8 nm in size for the membranes. The template-free synthesized membrane exhibited a high permeance but a low selectivity in C3H6/C3H8 mixture separation.
CMS membranes were synthesized by coating/pyrolysis method on mesoporous γ-alumina support. Such supports allow coating of thin, high-quality polymer films and subsequent CMS membranes with no infiltration into support pores. The CMS membranes show strong molecular sieving effect, offering a high C3H6/C3H8 mixture selectivity of ~30. Reduction in membrane thickness from 500 nm to 300 nm causes an increase in C3H8 permeance and He/N2 selectivity, but a decrease in the permeance of He, N2 and C3H6 and C3H6/C3H8 selectivity. This can be explained by the thickness dependent chain mobility of the polymer film resulting in final carbon membrane of reduced pore size with different effects on transport of gas of different sizes, including possible closure of C3H6-accessible micropores.
CMS membranes demonstrate excellent C3H6/C3H8 separation performance over a wide range of feed pressure, composition and operation temperature. No plasticization was observed at a feed pressure up to 100 psi. The permeation and separation is mainly controlled by diffusion instead of adsorption. CMS membrane experienced a decline in permeance, and an increase in selectivity over time under on-stream C3H6/C3H8 separation. This aging behavior is due to the reduction in effective pore size and porosity caused by oxygen chemisorption and physical aging of the membrane structure.
ContributorsMa, Xiaoli (Author) / Lin, Jerry (Thesis advisor) / Alford, Terry (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2015
Description
Wide bandgap semiconductors are of much current interest due to their superior electrical properties. This dissertation describes electron microscopy characterization of GaN-on-GaN structures for high-power vertical device applications. Unintentionally-doped (UID) GaN layers grown homoepitaxially via metal-organic chemical vapor deposition on freestanding GaN substrates, were subjected to dry etching, and layers of UID-GaN/p-GaN were over-grown. The as-grown and regrown heterostructures were examined in cross-section using transmission electron microscopy (TEM). Two different etching treatments, fast-etch-only and multiple etches with decreasing power, were employed. The fast-etch-only devices showed GaN-on-GaN interface at etched location, and low device breakdown voltages were measured (~ 45-95V). In comparison, no interfaces were visible after multiple etching steps, and the corresponding breakdown voltages were much higher (~1200-1270V). These results emphasized importance of optimizing surface etching techniques for avoiding degraded device performance.
The morphology of GaN-on-GaN devices after reverse-bias electrical stressing to breakdown was investigated. All failed devices had irreversible structural damage, showing large surface craters (~15-35 microns deep) with lengthy surface cracks. Cross-sectional TEM of failed devices showed high densities of threading dislocations (TDs) around the cracks and near crater surfaces. Progressive ion-milling across damaged devices revealed high densities of TDs and the presence of voids beneath cracks: these features were not observed in unstressed devices. The morphology of GaN substrates grown by hydride vapor-phase epitaxy (HVPE) and by ammonothermal methods were correlated with reverse-bias results. HVPE substrates showed arrays of surface features when observed by X-ray topography (XRT). All fabricated devices that overlapped with these features had typical reverse-bias voltages less than 100V at a leakage current limit of 10-6 A. In contrast, devices not overlapping with such features reached voltages greater than 300V. After etching, HVPE substrate surfaces showed defect clusters and macro-pits, whereas XRT images of ammonothermal substrate revealed no visible features. However, some devices fabricated on ammonothermal substrate failed at low voltages. Devices on HVPE and ammonothermal substrates with low breakdown voltages showed crater-like surface damage and revealed TDs (~25µm deep) and voids; such features were not observed in devices reaching higher voltages. These results should assist in developing protocols to fabricate reliable high-voltage devices.
ContributorsPeri, Prudhvi Ram (Author) / Smith, David J. (Thesis advisor) / Alford, Terry (Committee member) / Mccartney, Martha R (Committee member) / Nemanich, Robert (Committee member) / Zhao, Yuji (Committee member) / Arizona State University (Publisher)
Created2021