Matching Items (90)
Description
Nanoporous materials, with pore sizes less than one nanometer, have been incorporated as filler materials into state-of-the-art polyamide-based thin-film composite membranes to create thin-film nanocomposite (TFN) membranes for reverse osmosis (RO) desalination. However, these TFN membranes have inconsistent changes in desalination performance as a result of filler incorporation. The nano-sized filler’s transport role for enhancing water permeability is unknown: specifically, there is debate around the individual transport contributions of the polymer, nanoporous particle, and polymer/particle interface. Limited studies exist on the pressure-driven water transport mechanism through nanoporous single-crystal nanoparticles. An understanding of the nanoporous particles water transport role in TFN membranes will provide a better physical insight on the improvement of desalination membranes.
This dissertation investigates water permeation through single-crystal molecular sieve zeolite A particles in TFN membranes in four steps. First, the meta-analysis of nanoporous materials (e.g., zeolites, MOFs, and graphene-based materials) in TFN membranes demonstrated non-uniform water-salt permselectivity performance changes with nanoporous fillers. Second, a systematic study was performed investigating different sizes of non-porous (pore-closed) and nanoporous (pore-opened) zeolite particles incorporated into conventionally polymerized TFN membranes; however, the challenges of particle aggregation, non-uniform particle dispersion, and possible particle leaching from the membranes limit analysis. Third, to limit aggregation and improve dispersion on the membrane, a TFN-model membrane synthesis recipe was developed that immobilized the nanoparticles onto the support membranes surface before the polymerization reaction. Fourth, to quantify the possible water transport pathways in these membranes, two different resistance models were employed.
The experimental results show that both TFN and TFN-model membranes with pore-opened particles have higher water permeance compared to those with pore-closed particles. Further analysis using the resistance in parallel and hybrid models yields that water permeability through the zeolite pores is smaller than that of the particle/polymer interface and higher than the water permeability of the pure polymer. Thus, nanoporous particles increase water permeability in TFN membranes primarily through increased water transport at particle/polymer interface. Because solute rejection is not significantly altered in our TFN and TFN-model systems, the results reveal that local changes in the polymer region at the polymer/particle interface yield high water permeability.
This dissertation investigates water permeation through single-crystal molecular sieve zeolite A particles in TFN membranes in four steps. First, the meta-analysis of nanoporous materials (e.g., zeolites, MOFs, and graphene-based materials) in TFN membranes demonstrated non-uniform water-salt permselectivity performance changes with nanoporous fillers. Second, a systematic study was performed investigating different sizes of non-porous (pore-closed) and nanoporous (pore-opened) zeolite particles incorporated into conventionally polymerized TFN membranes; however, the challenges of particle aggregation, non-uniform particle dispersion, and possible particle leaching from the membranes limit analysis. Third, to limit aggregation and improve dispersion on the membrane, a TFN-model membrane synthesis recipe was developed that immobilized the nanoparticles onto the support membranes surface before the polymerization reaction. Fourth, to quantify the possible water transport pathways in these membranes, two different resistance models were employed.
The experimental results show that both TFN and TFN-model membranes with pore-opened particles have higher water permeance compared to those with pore-closed particles. Further analysis using the resistance in parallel and hybrid models yields that water permeability through the zeolite pores is smaller than that of the particle/polymer interface and higher than the water permeability of the pure polymer. Thus, nanoporous particles increase water permeability in TFN membranes primarily through increased water transport at particle/polymer interface. Because solute rejection is not significantly altered in our TFN and TFN-model systems, the results reveal that local changes in the polymer region at the polymer/particle interface yield high water permeability.
ContributorsCay Durgun, Pinar (Author) / Lind, Mary Laura (Thesis advisor) / Lin, Jerry Y. S. (Committee member) / Green, Matthew D. (Committee member) / Seo, Dong K. (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2018
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
Description
This dissertation presents research findings regarding the exploitation of localized surface plasmon (LSP) of epitaxial Ag islands as a means to enhance the photoluminescence (PL) of Germanium (Ge) quantum dots (QDs). The first step of this project was to investigate the growth of Ag islands on Si(100). Two distinct families of Ag islands have been observed. “Big islands” are clearly faceted and have basal dimensions in the few hundred nm to μm range with a variety of basal shapes. “Small islands” are not clearly faceted and have basal diameters in the 10s of nm range. Big islands form via a nucleation and growth mechanism, and small islands form via precipitation of Ag contained in a planar layer between the big islands that is thicker than the Stranski-Krastanov layer existing at room-temperature.
The pseudodielectric functions of epitaxial Ag islands on Si(100) substrates were investigated with spectroscopic ellipsometry. Comparing the experimental pseudodielectric functions obtained for Si with and without Ag islands clearly identifies a plasmon mode with its dipole moment perpendicular to the surface. This observation is confirmed using a simulation based on the thin island film (TIF) theory. Another mode parallel to the surface may be identified by comparing the experimental pseudodielectric functions with the simulated ones from TIF theory. Additional results suggest that the LSP energy of Ag islands can be tuned from the ultra-violet to the infrared range by an amorphous Si (α-Si) cap layer.
Heterostructures were grown that incorporated Ge QDs, an epitaxial Si cap layer and Ag islands grown atop the Si cap layer. Optimum growth conditions for distinct Ge dot ensembles and Si cap layers were obtained. The density of Ag islands grown on the Si cap layer depends on its thickness. Factors contributing to this effect may include the average strain and Ge concentration on the surface of the Si cap layer.
The effects of the Ag LSP on the PL of Ge coherent domes were investigated for both α-Si capped and bare Ag islands. For samples with low-doped substrates, the LSPs reduce the Ge dot-related PL when the Si cap layer is below some critical thickness and have no effect on the PL when the Si cap layer is above the critical thickness. For samples grown on highly-doped wafers, the LSP of bare Ag islands enhanced the PL of Ge QDs by ~ 40%.
The pseudodielectric functions of epitaxial Ag islands on Si(100) substrates were investigated with spectroscopic ellipsometry. Comparing the experimental pseudodielectric functions obtained for Si with and without Ag islands clearly identifies a plasmon mode with its dipole moment perpendicular to the surface. This observation is confirmed using a simulation based on the thin island film (TIF) theory. Another mode parallel to the surface may be identified by comparing the experimental pseudodielectric functions with the simulated ones from TIF theory. Additional results suggest that the LSP energy of Ag islands can be tuned from the ultra-violet to the infrared range by an amorphous Si (α-Si) cap layer.
Heterostructures were grown that incorporated Ge QDs, an epitaxial Si cap layer and Ag islands grown atop the Si cap layer. Optimum growth conditions for distinct Ge dot ensembles and Si cap layers were obtained. The density of Ag islands grown on the Si cap layer depends on its thickness. Factors contributing to this effect may include the average strain and Ge concentration on the surface of the Si cap layer.
The effects of the Ag LSP on the PL of Ge coherent domes were investigated for both α-Si capped and bare Ag islands. For samples with low-doped substrates, the LSPs reduce the Ge dot-related PL when the Si cap layer is below some critical thickness and have no effect on the PL when the Si cap layer is above the critical thickness. For samples grown on highly-doped wafers, the LSP of bare Ag islands enhanced the PL of Ge QDs by ~ 40%.
ContributorsKong, Dexin (Author) / Drucker, Jeffery (Thesis advisor) / Chen, Tingyong (Committee member) / Ros, Robert (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2015
Description
Photocatalytic water splitting is a promising technique to produce H2 fuels from water using sustainable solar energy. To better design photocatalysts, the understanding of charge transfer at surfaces/interfaces and the corresponding structure change during the reaction is very important. Local structural and chemical information on nanoparticle surfaces or interfaces can be achieved through characterizations on transmission electron microscopy (TEM). Emphasis should be put on materials structure changes during the reactions in their “working conditions”. Environmental TEM with in situ light illumination system allows the photocatalysts to be studied under light irradiation when exposed to H2O vapor. A set of ex situ and in situ TEM characterizations are carried out on typical types of TiO2 based photocatalysts. The observed structure changes during the reaction are correlated with the H2 production rate for structure-property relationships.
A surface disordering was observed in situ when well-defined anatase TiO2 rhombohedral nanoparticles were exposed to 1 Torr H2O vapor and 10suns light inside the environmental TEM. The disordering is believed to be related to high density of hydroxyl groups formed on surface oxygen vacancies during water splitting reactions.
Pt co-catalyst on TiO2 is able to split pure water producing H2 and O2. The H2 production rate drops during the reaction. Particle size growth during reaction was discovered with Z-contrast images. The particle size growth is believed to be a photo-electro-chemical Ostwald ripening.
Characterizations were also carried out on a more complicated photocatalyst system: Ni/NiO core/shell co-catalyst on TiO2. A decrease of the H2 production rate resulting from photo-corrosion was observed. The Ni is believed to be oxidized to Ni2+ by OH• radicals which are intermediate products of H2O oxidation. The mechanism that the OH• radicals leak into the cores through cracks on NiO shells is more supported by experiments.
Overall this research has done a comprehensive ex situ and in situ TEM characterizations following some typical TiO2 based photocatalysts during reactions. This research has shown the technique availability to study photocatalyst inside TEM in photocatalytic conditions. It also demonstrates the importance to follow structure changes of materials during reactions in understanding deactivation mechanisms.
A surface disordering was observed in situ when well-defined anatase TiO2 rhombohedral nanoparticles were exposed to 1 Torr H2O vapor and 10suns light inside the environmental TEM. The disordering is believed to be related to high density of hydroxyl groups formed on surface oxygen vacancies during water splitting reactions.
Pt co-catalyst on TiO2 is able to split pure water producing H2 and O2. The H2 production rate drops during the reaction. Particle size growth during reaction was discovered with Z-contrast images. The particle size growth is believed to be a photo-electro-chemical Ostwald ripening.
Characterizations were also carried out on a more complicated photocatalyst system: Ni/NiO core/shell co-catalyst on TiO2. A decrease of the H2 production rate resulting from photo-corrosion was observed. The Ni is believed to be oxidized to Ni2+ by OH• radicals which are intermediate products of H2O oxidation. The mechanism that the OH• radicals leak into the cores through cracks on NiO shells is more supported by experiments.
Overall this research has done a comprehensive ex situ and in situ TEM characterizations following some typical TiO2 based photocatalysts during reactions. This research has shown the technique availability to study photocatalyst inside TEM in photocatalytic conditions. It also demonstrates the importance to follow structure changes of materials during reactions in understanding deactivation mechanisms.
ContributorsZhang, Liuxian (Author) / Crozier, Peter (Thesis advisor) / Smith, David (Committee member) / Chan, Candace (Committee member) / Liu, Jingyue (Committee member) / Arizona State University (Publisher)
Created2015
Description
Carbon nanomaterials have caught tremendous attention in the last few decades due to their unique physical and chemical properties. Tremendous effort has been made to develop new synthesis techniques for carbon nanomaterials and investigate their properties for different applications. In this work, carbon nanospheres (CNSs), carbon foams (CF), and single-walled carbon nanotubes (SWNTs) were studied for various applications, including water treatment, energy storage, actuators, and sensors.
A facile spray pyrolysis synthesis technique was developed to synthesize individual CNSs with specific surface area (SSA) up to 1106 m2/g. The hollow CNSs showed adsorption of up to 300 mg rhodamine B dye per gram carbon, which is more than 15 times higher than that observed for conventional carbon black. They were also evaluated as adsorbents for removal of arsenate and selenate from water and displayed good binding to both species, outperforming commercial activated carbons for arsenate removal in pH > 8. When evaluated as supercapacitor electrode materials, specific capacitances of up to 112 F/g at a current density of 0.1 A/g were observed. When used as Li-ion battery anode materials, the CNSs achieved a discharge capacity of 270 mAh/g at a current density of 372 mA/g (1C), which is 4-fold higher than that of commercial graphite anode.
Carbon foams were synthesized using direct pyrolysis and had SSA up to 2340 m2/g. When used as supercapacitor electrode materials, a specific capacitance up to 280 F/g was achieved at current density of 0.1 A/g and remained as high as 207 F/g, even at a high current density of 10 A/g.
A printed walking robot was made from common plastic films and coatings of SWNTs. The solid-state thermal bimorph actuators were multifunctional energy transducers powered by heat, light, or electricity. The actuators were also investigated for photo/thermal detection. Electrochemical actuators based on MnO2 were also studied for potential underwater applications.
SWNTs were also used to fabricate printable electrodes for trace Cr(VI) detection, which displayed sensitivity up to 500 nA/ppb for Cr(VI). The limit of detection was shown to be as low as 5 ppb. A flow detection system based on CNT/printed electrodes was also demonstrated.
A facile spray pyrolysis synthesis technique was developed to synthesize individual CNSs with specific surface area (SSA) up to 1106 m2/g. The hollow CNSs showed adsorption of up to 300 mg rhodamine B dye per gram carbon, which is more than 15 times higher than that observed for conventional carbon black. They were also evaluated as adsorbents for removal of arsenate and selenate from water and displayed good binding to both species, outperforming commercial activated carbons for arsenate removal in pH > 8. When evaluated as supercapacitor electrode materials, specific capacitances of up to 112 F/g at a current density of 0.1 A/g were observed. When used as Li-ion battery anode materials, the CNSs achieved a discharge capacity of 270 mAh/g at a current density of 372 mA/g (1C), which is 4-fold higher than that of commercial graphite anode.
Carbon foams were synthesized using direct pyrolysis and had SSA up to 2340 m2/g. When used as supercapacitor electrode materials, a specific capacitance up to 280 F/g was achieved at current density of 0.1 A/g and remained as high as 207 F/g, even at a high current density of 10 A/g.
A printed walking robot was made from common plastic films and coatings of SWNTs. The solid-state thermal bimorph actuators were multifunctional energy transducers powered by heat, light, or electricity. The actuators were also investigated for photo/thermal detection. Electrochemical actuators based on MnO2 were also studied for potential underwater applications.
SWNTs were also used to fabricate printable electrodes for trace Cr(VI) detection, which displayed sensitivity up to 500 nA/ppb for Cr(VI). The limit of detection was shown to be as low as 5 ppb. A flow detection system based on CNT/printed electrodes was also demonstrated.
ContributorsWang, Chengwei, Ph.D (Author) / Chan, Candace K. (Thesis advisor) / Tongay, Sefaattin (Committee member) / Wang, Qing Hua (Committee member) / Seo, Dong (Committee member) / Arizona State University (Publisher)
Created2015
Description
This thesis presents systematic studies on angle dependent Raman and Photoluminescence (PL) of a new class of layered materials, Transition Metal Trichalcogenides (TMTCs), which are made up of layers possessing anisotropic structure within the van-der-Waals plane. The crystal structure of individual layer of MX3 compounds consists of aligned nanowire like 1D chains running along the b-axis direction. The work focuses on the growth of two members of this family - ZrS3 and TiS3 - through Chemical Vapor Transport Method (CVT), with consequent angle dependent Raman and PL studies which highlight their in-plane optically anisotropic properties. Results highlight that the optical properties of few-layer flakes are highly anisotropic as evidenced by large PL intensity variation with polarization direction (in ZrS3) and an intense variation in Raman intensity with variation in polarization direction (in both ZrS3 and TiS3).
Results suggest that light is efficiently absorbed when E-field of the polarized incident excitation laser is polarized along the chain (b-axis). It is greatly attenuated and absorption is reduced when field is polarized perpendicular to the length of 1D-like chains, as wavelength of the exciting light is much longer than the width of each 1D chain. Observed PL variation with respect to the azimuthal flake angle is similar to what has been previously observed in 1D materials like nanowires. However, in TMTCs, since the 1D chains interact with each other, it gives rise to a unique linear dichroism response that falls between 2D and 1D like behavior. These results not only mark the very first demonstration of high PL polarization anisotropy in 2D systems, but also provide a novel insight into how interaction between adjacent 1D-like chains and the 2D nature of each layer influences the overall optical anisotropy of Quasi-1D materials. The presented results are anticipated to have impact in technologies involving polarized detection, near-field imaging, communication systems, and bio-applications relying on the generation and detection of polarized light.
Results suggest that light is efficiently absorbed when E-field of the polarized incident excitation laser is polarized along the chain (b-axis). It is greatly attenuated and absorption is reduced when field is polarized perpendicular to the length of 1D-like chains, as wavelength of the exciting light is much longer than the width of each 1D chain. Observed PL variation with respect to the azimuthal flake angle is similar to what has been previously observed in 1D materials like nanowires. However, in TMTCs, since the 1D chains interact with each other, it gives rise to a unique linear dichroism response that falls between 2D and 1D like behavior. These results not only mark the very first demonstration of high PL polarization anisotropy in 2D systems, but also provide a novel insight into how interaction between adjacent 1D-like chains and the 2D nature of each layer influences the overall optical anisotropy of Quasi-1D materials. The presented results are anticipated to have impact in technologies involving polarized detection, near-field imaging, communication systems, and bio-applications relying on the generation and detection of polarized light.
ContributorsPant, Anupum (Author) / Tongay, Sefaattin (Thesis advisor) / Alford, Terry Lynn (Committee member) / He, Ximin (Committee member) / Arizona State University (Publisher)
Created2016
Description
The proposed research mainly focuses on employing tunable materials to achieve dynamic control of radiative heat transfer in both far and near fields for thermal management. Vanadium dioxide (VO2), which undergoes a phase transition from insulator to metal at the temperature of 341 K, is one tunable material being applied. The other one is graphene, whose optical properties can be tuned by chemical potential through external bias or chemical doping.
In the far field, a VO2-based metamaterial thermal emitter with switchable emittance in the mid-infrared has been theoretically studied. When VO2 is in the insulating phase, high emittance is observed at the resonance frequency of magnetic polaritons (MPs), while the structure becomes highly reflective when VO2 turns metallic. A VO2-based thermal emitter with tunable emittance is also demonstrated due to the excitation of MP at different resonance frequencies when VO2 changes phase. Moreover, an infrared thermal emitter made of graphene-covered SiC grating could achieve frequency-tunable emittance peak via the change of the graphene chemical potential.
In the near field, a radiation-based thermal rectifier is constructed by investigating radiative transfer between VO2 and SiO2 separated by nanometer vacuum gap distances. Compared to the case where VO2 is set as the emitter at 400 K as a metal, when VO2 is considered as the receiver at 300 K as an insulator, the energy transfer is greatly enhanced due to the strong surface phonon polariton (SPhP) coupling between insulating VO2 and SiO2. A radiation-based thermal switch is also explored by setting VO2 as both the emitter and the receiver. When both VO2 emitter and receiver are at the insulating phase, the switch is at the “on” mode with a much enhanced heat flux due to strong SPhP coupling, while the near-field radiative transfer is greatly suppressed when the emitting VO2 becomes metallic at temperatures higher than 341K during the “off” mode. In addition, an electrically-gated thermal modulator made of graphene covered SiC plates is theoretically studied with modulated radiative transport by varying graphene chemical potential. Moreover, the MP effect on near-field radiative transport has been investigated by spectrally enhancing radiative heat transfer between two metal gratings.
In the far field, a VO2-based metamaterial thermal emitter with switchable emittance in the mid-infrared has been theoretically studied. When VO2 is in the insulating phase, high emittance is observed at the resonance frequency of magnetic polaritons (MPs), while the structure becomes highly reflective when VO2 turns metallic. A VO2-based thermal emitter with tunable emittance is also demonstrated due to the excitation of MP at different resonance frequencies when VO2 changes phase. Moreover, an infrared thermal emitter made of graphene-covered SiC grating could achieve frequency-tunable emittance peak via the change of the graphene chemical potential.
In the near field, a radiation-based thermal rectifier is constructed by investigating radiative transfer between VO2 and SiO2 separated by nanometer vacuum gap distances. Compared to the case where VO2 is set as the emitter at 400 K as a metal, when VO2 is considered as the receiver at 300 K as an insulator, the energy transfer is greatly enhanced due to the strong surface phonon polariton (SPhP) coupling between insulating VO2 and SiO2. A radiation-based thermal switch is also explored by setting VO2 as both the emitter and the receiver. When both VO2 emitter and receiver are at the insulating phase, the switch is at the “on” mode with a much enhanced heat flux due to strong SPhP coupling, while the near-field radiative transfer is greatly suppressed when the emitting VO2 becomes metallic at temperatures higher than 341K during the “off” mode. In addition, an electrically-gated thermal modulator made of graphene covered SiC plates is theoretically studied with modulated radiative transport by varying graphene chemical potential. Moreover, the MP effect on near-field radiative transport has been investigated by spectrally enhancing radiative heat transfer between two metal gratings.
ContributorsYang, Yue (Author) / Wang, Liping (Thesis advisor) / Phelan, Patrick (Committee member) / Wang, Robert (Committee member) / Tongay, Sefaattin (Committee member) / Rykaczewski, Konrad (Committee member) / Arizona State University (Publisher)
Created2016
Description
In this dissertation, the interface chemistry and electronic structure of plasma-enhanced atomic layer deposited (PEALD) dielectrics on GaN are investigated with x-ray and ultraviolet photoemission spectroscopy (XPS and UPS). Three interrelated issues are discussed in this study: (1) PEALD dielectric growth process optimization, (2) interface electronic structure of comparative PEALD dielectrics on GaN, and (3) interface electronic structure of PEALD dielectrics on Ga- and N-face GaN. The first study involved an in-depth case study of PEALD Al2O3 growth using dimethylaluminum isopropoxide, with a special focus on oxygen plasma effects. Saturated and self-limiting growth of Al2O3 films were obtained with an enhanced growth rate within the PEALD temperature window (25-220 ºC). The properties of Al2O3 deposited at various temperatures were characterized to better understand the relation between the growth parameters and film properties. In the second study, the interface electronic structures of PEALD dielectrics on Ga-face GaN films were measured. Five promising dielectrics (Al2O3, HfO2, SiO2, La2O3, and ZnO) with a range of band gap energies were chosen. Prior to dielectric growth, a combined wet chemical and in-situ H2/N2 plasma clean process was employed to remove the carbon contamination and prepare the surface for dielectric deposition. The surface band bending and band offsets were measured by XPS and UPS for dielectrics on GaN. The trends of the experimental band offsets on GaN were related to the dielectric band gap energies. In addition, the experimental band offsets were near the calculated values based on the charge neutrality level model. The third study focused on the effect of the polarization bound charge of the Ga- and N-face GaN on interface electronic structures. A surface pretreatment process consisting of a NH4OH wet chemical and an in-situ NH3 plasma treatment was applied to remove carbon contamination, retain monolayer oxygen coverage, and potentially passivate N-vacancy related defects. The surface band bending and polarization charge compensation of Ga- and N-face GaN were investigated. The surface band bending and band offsets were determined for Al2O3, HfO2, and SiO2 on Ga- and N-face GaN. Different dielectric thicknesses and post deposition processing were investigated to understand process related defect formation and/or reduction.
ContributorsYang, Jialing (Author) / Nemanich, Robert J (Thesis advisor) / Chen, Tingyong (Committee member) / Peng, Xihong (Committee member) / Ponce, Fernando (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2014
Description
This dissertation presents research findings on the three materials systems: lateral Si nanowires (SiNW), In2Se3/Bi2Se3 heterostructures and graphene. The first part of the thesis was focused on the growth and characterization of lateral SiNW. Lateral here refers to wires growing along the plane of substrate; vertical NW on the other hand grow out of the plane of substrate. It was found, using the Au-seeded vapor – liquid – solid technique, that epitaxial single-crystal SiNW can be grown laterally along Si(111) substrates that have been miscut toward [11− 2]. The ratio of lateral-to-vertical NW was found to increase as the miscut angle increased and as disilane pressure and substrate temperature decreased. Based on this observation, growth parameters were identified whereby all of the deposited Au seeds formed lateral NW. Furthermore, the nanofaceted substrate guided the growth via a mechanism that involved pinning of the trijunction at the liquid/solid interface of the growing nanowire.
Next, the growth of selenide heterostructures was explored. Specifically, molecular beam epitaxy was utilized to grow In2Se3 and Bi2Se3 films on h-BN, highly oriented pyrolytic graphite and Si(111) substrates. Growth optimizations of In2Se3 and Bi2Se3 films were carried out by systematically varying the growth parameters. While the growth of these films was demonstrated on h-BN and HOPG surface, the majority of the effort was focused on growth on Si(111). Atomically flat terraces that extended laterally for several hundred nm, which were separated by single quintuple layer high steps characterized surface of the best In2Se3 films grown on Si(111). These In2Se3 films were suitable for subsequent high quality epitaxy of Bi2Se3 .
The last part of this dissertation was focused on a recently initiated and ongoing study of graphene growth on liquid metal surfaces. The initial part of the study comprised a successful modification of an existing growth system to accommodate graphene synthesis and process development for reproducible graphene growth. Graphene was grown on Cu, Au and AuCu alloys at varioua conditions. Preliminary results showed triangular features on the liquid part of the Cu metal surface. For Au, and AuCu alloys, hexagonal features were noticed both on the solid and liquid parts.
Next, the growth of selenide heterostructures was explored. Specifically, molecular beam epitaxy was utilized to grow In2Se3 and Bi2Se3 films on h-BN, highly oriented pyrolytic graphite and Si(111) substrates. Growth optimizations of In2Se3 and Bi2Se3 films were carried out by systematically varying the growth parameters. While the growth of these films was demonstrated on h-BN and HOPG surface, the majority of the effort was focused on growth on Si(111). Atomically flat terraces that extended laterally for several hundred nm, which were separated by single quintuple layer high steps characterized surface of the best In2Se3 films grown on Si(111). These In2Se3 films were suitable for subsequent high quality epitaxy of Bi2Se3 .
The last part of this dissertation was focused on a recently initiated and ongoing study of graphene growth on liquid metal surfaces. The initial part of the study comprised a successful modification of an existing growth system to accommodate graphene synthesis and process development for reproducible graphene growth. Graphene was grown on Cu, Au and AuCu alloys at varioua conditions. Preliminary results showed triangular features on the liquid part of the Cu metal surface. For Au, and AuCu alloys, hexagonal features were noticed both on the solid and liquid parts.
ContributorsRathi, Somilkumar J (Author) / Drucker, Jeffery (Thesis advisor) / Smith, David (Committee member) / Chen, Tingyong (Committee member) / Arizona State University (Publisher)
Created2014
Description
GaN and AlGaN have shown great potential in next-generation power and RF electronics. However, these devices are limited by reliability issues such as leakage current and current collapse that result from surface and interface states on GaN and AlGaN. This dissertation, therefore, examined these electronic states, focusing on the following two points:
First, the surface electronic state configuration was examined with regards to the polarization bound 1013 charges/cm2 that increases with aluminum content. This large bound charge requires compensation either externally by surface states or internally by the space charge regions as relates to band bending. In this work, band bending was measured after different surface treatments of GaN and AlGaN to determine the effects of specific surface states on the electronic state configuration. Results showed oxygen-terminated N-face GaN, Ga-face GaN, and Ga-face Al0.25Ga0.75N surface were characterized by similar band bending regardless of the polarization bound charge, suggesting a Fermi level pinning state ~0.4-0.8 eV below the conduction band minimum. On oxygen-free Ga-face GaN, Al0.15Ga0.85N, Al0.25Ga0.75N, and Al0.35Ga0.65N, band bending increased slightly with aluminum content and thus did not exhibit the same pinning behavior; however, there was still significant compensating charge on these surfaces (~1013 charges/cm2). This charge is likely related to nitrogen vacancies and/or gallium dangling bonds.
In addition, this wozrk investigated the interface electronic state configuration of dielectric/GaN and AlGaN interfaces with regards to deposition conditions and aluminum content. Specifically, oxygen plasma-enhanced atomic layer deposited (PEALD) was used to deposit SiO2. Growth temperature was shown to influence the film quality, where room temperature deposition produced the highest quality films in terms of electrical breakdown. In addition, the valence band offsets (VBOs) appeared to decrease with the deposition temperature, which likely related to an electric field across the Ga2O3 interfacial layer. VBOs were also determined with respect to aluminum content at the PEALD-SiO2/AlxGa1-xN interface, giving 3.0, 2.9, 2.9, and 2.8 eV for 0%, 15%, 25%, and 35% aluminum content, respectively—with corresponding conduction band offsets of 2.5, 2.2, 1.9, and 1.8 eV. This suggests the largest difference manifests in the conduction band, which is in agreement with the charge neutrality level model.
First, the surface electronic state configuration was examined with regards to the polarization bound 1013 charges/cm2 that increases with aluminum content. This large bound charge requires compensation either externally by surface states or internally by the space charge regions as relates to band bending. In this work, band bending was measured after different surface treatments of GaN and AlGaN to determine the effects of specific surface states on the electronic state configuration. Results showed oxygen-terminated N-face GaN, Ga-face GaN, and Ga-face Al0.25Ga0.75N surface were characterized by similar band bending regardless of the polarization bound charge, suggesting a Fermi level pinning state ~0.4-0.8 eV below the conduction band minimum. On oxygen-free Ga-face GaN, Al0.15Ga0.85N, Al0.25Ga0.75N, and Al0.35Ga0.65N, band bending increased slightly with aluminum content and thus did not exhibit the same pinning behavior; however, there was still significant compensating charge on these surfaces (~1013 charges/cm2). This charge is likely related to nitrogen vacancies and/or gallium dangling bonds.
In addition, this wozrk investigated the interface electronic state configuration of dielectric/GaN and AlGaN interfaces with regards to deposition conditions and aluminum content. Specifically, oxygen plasma-enhanced atomic layer deposited (PEALD) was used to deposit SiO2. Growth temperature was shown to influence the film quality, where room temperature deposition produced the highest quality films in terms of electrical breakdown. In addition, the valence band offsets (VBOs) appeared to decrease with the deposition temperature, which likely related to an electric field across the Ga2O3 interfacial layer. VBOs were also determined with respect to aluminum content at the PEALD-SiO2/AlxGa1-xN interface, giving 3.0, 2.9, 2.9, and 2.8 eV for 0%, 15%, 25%, and 35% aluminum content, respectively—with corresponding conduction band offsets of 2.5, 2.2, 1.9, and 1.8 eV. This suggests the largest difference manifests in the conduction band, which is in agreement with the charge neutrality level model.
ContributorsEller, Brianna (Author) / Nemanich, Robert J (Thesis advisor) / Chowdhury, Srabanti (Committee member) / McCartney, Martha (Committee member) / Ponce, Fernando (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2015