Matching Items (75)
Description
A theoretical study of a three-dimensional (3D) N/S interface with arbitrary spin
polarization and interface geometry is presented. The 3D model gives the same intrinsic
spin polarization and superconducting gap dependence as the 1D model. This
demonstrates that the 1D model can be use to t 3D data.
Using this model, a Heusler alloy is investigated. Andreev reflection measurements
show that the spin polarization is 80% in samples sputtered on unheated MgO(100)
substrates and annealed at high temperatures. However, the spin polarization is
considerably smaller in samples deposited on heated substrates.
Ferromagnetic FexSix alloys have been proposed as potential spin injectors into
silicon with a substantial spin polarization. Andreev Reflection Spectroscopy (ARS) is
utilized to determine the spin polarization of both amorphous and crystalline Fe65Si35
alloys. The amorphous phase has a significantly higher spin polarization than that of
the crystalline phase.
In this thesis, (1111) Fe SmO0:82F0:18FeAs and Pb superconductors are used to
measure the spin polarization of a highly spin-polarized material, La0:67Sr0:33MnO3.
Both materials yield the same intrinsic spin polarization, therefore, Fe-superconductors
can be used in ARS. Based on the behavior of the differential conductance for highly
spin polarized LSMO and small polarization of Au, it can be concluded that the Fe-Sc
is not a triplet superconductor.
Zero bias anomaly (ZBA), in point contact Andreev reflection (PCAR), has been
utilized as a characteristic feature to reveal many novel physics. Complexities at a
normal metal/superconducting interface often cause nonessential ZBA-like features,
which may be mistaken as ZBA. In this work, it is shown that an extrinsic ZBA,
which is due to the contact resistance, cannot be suppressed by a highly spin-polarized
current while a nonessential ZBA cannot be affected the contact resistance.
Finally, Cu/Cu multilayer GMR structures were fabricated and the GMR% measured
at 300 K and 4.5 K gave responses of 63% and 115% respectively. Not only
do the GMR structures have a large enhancement of resistance, but by applying an
external magnetic eld it is shown that, unlike most materials, the spin polarization
can be tuned to values of 0.386 to 0.415 from H = 0 kOe to H = 15 kOe.
polarization and interface geometry is presented. The 3D model gives the same intrinsic
spin polarization and superconducting gap dependence as the 1D model. This
demonstrates that the 1D model can be use to t 3D data.
Using this model, a Heusler alloy is investigated. Andreev reflection measurements
show that the spin polarization is 80% in samples sputtered on unheated MgO(100)
substrates and annealed at high temperatures. However, the spin polarization is
considerably smaller in samples deposited on heated substrates.
Ferromagnetic FexSix alloys have been proposed as potential spin injectors into
silicon with a substantial spin polarization. Andreev Reflection Spectroscopy (ARS) is
utilized to determine the spin polarization of both amorphous and crystalline Fe65Si35
alloys. The amorphous phase has a significantly higher spin polarization than that of
the crystalline phase.
In this thesis, (1111) Fe SmO0:82F0:18FeAs and Pb superconductors are used to
measure the spin polarization of a highly spin-polarized material, La0:67Sr0:33MnO3.
Both materials yield the same intrinsic spin polarization, therefore, Fe-superconductors
can be used in ARS. Based on the behavior of the differential conductance for highly
spin polarized LSMO and small polarization of Au, it can be concluded that the Fe-Sc
is not a triplet superconductor.
Zero bias anomaly (ZBA), in point contact Andreev reflection (PCAR), has been
utilized as a characteristic feature to reveal many novel physics. Complexities at a
normal metal/superconducting interface often cause nonessential ZBA-like features,
which may be mistaken as ZBA. In this work, it is shown that an extrinsic ZBA,
which is due to the contact resistance, cannot be suppressed by a highly spin-polarized
current while a nonessential ZBA cannot be affected the contact resistance.
Finally, Cu/Cu multilayer GMR structures were fabricated and the GMR% measured
at 300 K and 4.5 K gave responses of 63% and 115% respectively. Not only
do the GMR structures have a large enhancement of resistance, but by applying an
external magnetic eld it is shown that, unlike most materials, the spin polarization
can be tuned to values of 0.386 to 0.415 from H = 0 kOe to H = 15 kOe.
ContributorsGifford, Jessica Anna (Author) / Chen, Tingyong (Thesis advisor) / Bennett, Peter (Committee member) / Nemanich, Robert (Committee member) / Tsen, Kong-Thon (Committee member) / Arizona State University (Publisher)
Created2015
Description
Group-IV semiconductor alloys are of interest for Si-integrated optoelectronic applications due to the band gap tunability and enhanced optical capabilities that can be achieved through compositional tuning. This work advances the field by presenting a systematic study of the optical and electronic properties of Ge1-ySny and analogous Ge1-x-ySixSny alloys.
The fundamental direct and indirect band gaps of Ge1-ySny materials are measured by room temperature photoluminescence in samples containing 0 ≤ y ≤ 0.11 and a transition to direct gap materials is found to occur at yc = 0.087. This result is enabled by the development of sample growth and processing protocols that produce high-quality materials epitaxially on Ge-buffered Si(100) substrates. Strategies to optimize the optical performance are explored by varying the film thickness, thermal and surface treatments, and n-type doping. The electrical and optical properties of diodes based on these materials are characterized by current-voltage, optical responsivity, and electroluminescence measurements. These show improved optical performance near yc with tunable emission out to 2500 nm. Measuring the carrier lifetimes in devices with strain relaxed and fully strained interfaces show significantly longer lifetimes in the fully strained case.
The direct and indirect band gaps of Sn-rich (y > x) Ge1-x-ySixSny materials are measured by room temperature photoluminescence on optimized samples. These data confirm a transition to direct gap materials occurs for the ternary alloy as well. Devices based on compositions 0.02 ≤ x ≤ 0.10 and 0.03 ≤ y ≤ 0.11 are characterized by current-voltage, optical responsivity, and electroluminescence measurements and show competitive performance with analogous devices based on Ge1-ySny materials. A detailed study of the direct gap in Ge1-xSix alloys gives parameters crucial en route to a global description of the Ge1-x-ySixSny fundamental band gaps.
Archetypal laser device designs on Si are explored by fabricating degenerate pn junction diodes and highly doped waveguide devices based on high-quality Ge1-ySny materials. The diodes showed tunnel-like current-voltage characteristics and tailored electroluminescence based on the doping profile. The waveguides demonstrate emission under optical stimulation.
The fundamental direct and indirect band gaps of Ge1-ySny materials are measured by room temperature photoluminescence in samples containing 0 ≤ y ≤ 0.11 and a transition to direct gap materials is found to occur at yc = 0.087. This result is enabled by the development of sample growth and processing protocols that produce high-quality materials epitaxially on Ge-buffered Si(100) substrates. Strategies to optimize the optical performance are explored by varying the film thickness, thermal and surface treatments, and n-type doping. The electrical and optical properties of diodes based on these materials are characterized by current-voltage, optical responsivity, and electroluminescence measurements. These show improved optical performance near yc with tunable emission out to 2500 nm. Measuring the carrier lifetimes in devices with strain relaxed and fully strained interfaces show significantly longer lifetimes in the fully strained case.
The direct and indirect band gaps of Sn-rich (y > x) Ge1-x-ySixSny materials are measured by room temperature photoluminescence on optimized samples. These data confirm a transition to direct gap materials occurs for the ternary alloy as well. Devices based on compositions 0.02 ≤ x ≤ 0.10 and 0.03 ≤ y ≤ 0.11 are characterized by current-voltage, optical responsivity, and electroluminescence measurements and show competitive performance with analogous devices based on Ge1-ySny materials. A detailed study of the direct gap in Ge1-xSix alloys gives parameters crucial en route to a global description of the Ge1-x-ySixSny fundamental band gaps.
Archetypal laser device designs on Si are explored by fabricating degenerate pn junction diodes and highly doped waveguide devices based on high-quality Ge1-ySny materials. The diodes showed tunnel-like current-voltage characteristics and tailored electroluminescence based on the doping profile. The waveguides demonstrate emission under optical stimulation.
ContributorsGallagher, James Dennis (Author) / Menéndez, Jose (Thesis advisor) / Kouvetakis, John (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2015
Description
Cubic boron nitride (c-BN) has potential for electronic applications as an electron emitter and serving as a base material for diodes, transistors, etc. However, there has been limited research on c-BN reported, and many of the electronic properties of c-BN and c-BN interfaces have yet to be reported. This dissertation focused on probing thin film c-BN deposited via plasma enhanced chemical vapor deposition (PECVD) with in situ photoelectron spectroscopy (PES). PES measurements were used to characterize the electronic properties of c-BN films and interfaces with vacuum and diamond. First, the interface between c-BN and vacuum were characterized with ultraviolet PES (UPS). UPS measurements indicated that as-deposited c-BN, H2 plasma treated c-BN, and annealed c-BN post H2 plasma treatment exhibited negative electron affinity surfaces. A dipole model suggested dipoles from H-terminated N surface sites were found to be responsible for the NEA surface. Then, Si was introduced into c-BN films to realize n-type doped c-BN. The valence structure and work function of c-BN:Si films were characterized with XPS and UPS measurements. Measurements were unable to confirm n-type character, and it is concluded that silicon nitride formation was the primary effect for the observations. Finally, XPS measurements were employed to measure the band offsets at the c-BN/diamond interface. Measurements indicated the valence band maximum (VBM) of c-BN was positioned ~0.8 eV above the VBM of diamond.
ContributorsShammas, Joseph (Author) / Nemanich, Robert J (Thesis advisor) / Ponce, Fernando (Committee member) / Chen, Tingyong (Committee member) / Chamberlin, Ralph (Committee member) / Arizona State University (Publisher)
Created2016
Description
Nanoscale semiconductors with their unique properties and potential applications have been a focus of extensive research in recent years. There are many ways in which semiconductors change the world with computers, cell phones, and solar panels, and nanoscale semiconductors having a promising potential to expand the efficiency, reduce the cost, and improve the flexibility and durability of their design. In this study, theoretical quantum mechanical simulations were performed on several different nanoscale semiconductor materials, including graphene/phosphorene nanoribbons and group III-V nanowires. First principles density functional theory (DFT) was used to study the electronic and structural properties of these nanomaterials in their fully relaxed and strained states. The electronic band gap, effective masses of charge carriers, electronic orbitals, and density of states were most commonly examined with strain, both from intrinsic and external sources. For example, armchair graphene nanoribbons (AGNR) were found to have unprecedented band gap-strain dependence. Phosphorene nanoribbons (PNRs) demonstrate a different behavior, including a chemical scissors effect, and studies revealed a strong relationship between passivation species and band gap tunability. Unlike the super mechanical flexibility of AGNRs and PNRs which can sustain incredible strain, modest yet large strain was applied to group III-V nanowires such as GaAs/InAs. The calculations showed that a direct and indirect band gap transition occurs at some critical strains and the origination of these gap transitions were explored in detail. In addition to the pure nanowires, GaAs/InAs core/shell heterostructure nanowires were also studied. Due to the lattice mismatch between GaAs and InAs, the intrinsic strain in the core/shell nanowires demonstrates an interesting behavior on tuning the electronic properties. This interesting behavior suggests a mechanical way to exert compressive strain on nanowires experimentally, and can create a finite quantum confinement effect on the core.
ContributorsCopple, Andrew (Author) / Peng, Xihong (Thesis advisor) / Chan, Candace (Committee member) / Chizmeshya, Andrew (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2016
Description
Conductance fluctuations associated with quantum transport through quantumdot systems are currently understood to depend on the nature of the corresponding classical dynamics, i.e., integrable or chaotic. There are a couple of interesting phenomena about conductance fluctuation and quantum tunneling related to geometrical shapes of graphene systems. Firstly, in graphene quantum-dot systems, when a magnetic field is present, as the Fermi energy or the magnetic flux is varied, both regular oscillations and random fluctuations in the conductance can occur, with alternating transitions between the two. Secondly, a scheme based on geometrical rotation of rectangular devices to effectively modulate the conductance fluctuations is presented. Thirdly, when graphene is placed on a substrate of heavy metal, Rashba spin-orbit interaction of substantial strength can occur. In an open system such as a quantum dot, the interaction can induce spin polarization. Finally, a problem using graphene systems with electron-electron interactions described by the Hubbard Hamiltonian in the setting of resonant tunneling is investigated.
Another interesting problem in quantum transport is the effect of disorder or random impurities since it is inevitable in real experiments. At first, for a twodimensional Dirac ring, as the disorder density is systematically increased, the persistent current decreases slowly initially and then plateaus at a finite nonzero value, indicating remarkable robustness of the persistent currents, which cannot be discovered in normal metal and semiconductor rings. In addition, in a Floquet system with a ribbon structure, the conductance can be remarkably enhanced by onsite disorder.
Recent years have witnessed significant interest in nanoscale physical systems, such as semiconductor supperlattices and optomechanical systems, which can exhibit distinct collective dynamical behaviors. Firstly, a system of two optically coupled optomechanical cavities is considered and the phenomenon of synchronization transition associated with quantum entanglement transition is discovered. Another useful issue is nonlinear dynamics in semiconductor superlattices caused by its key potential application lies in generating radiation sources, amplifiers and detectors in the spectral range of terahertz. In such a system, transition to multistability, i.e., the emergence of multistability with chaos as a system parameter passes through a critical point, is found and argued to be abrupt.
Another interesting problem in quantum transport is the effect of disorder or random impurities since it is inevitable in real experiments. At first, for a twodimensional Dirac ring, as the disorder density is systematically increased, the persistent current decreases slowly initially and then plateaus at a finite nonzero value, indicating remarkable robustness of the persistent currents, which cannot be discovered in normal metal and semiconductor rings. In addition, in a Floquet system with a ribbon structure, the conductance can be remarkably enhanced by onsite disorder.
Recent years have witnessed significant interest in nanoscale physical systems, such as semiconductor supperlattices and optomechanical systems, which can exhibit distinct collective dynamical behaviors. Firstly, a system of two optically coupled optomechanical cavities is considered and the phenomenon of synchronization transition associated with quantum entanglement transition is discovered. Another useful issue is nonlinear dynamics in semiconductor superlattices caused by its key potential application lies in generating radiation sources, amplifiers and detectors in the spectral range of terahertz. In such a system, transition to multistability, i.e., the emergence of multistability with chaos as a system parameter passes through a critical point, is found and argued to be abrupt.
ContributorsYing, Lei (Author) / Lai, Ying-Cheng (Thesis advisor) / Vasileska, Dragica (Committee member) / Chen, Tingyong (Committee member) / Yao, Yu (Committee member) / Arizona State University (Publisher)
Created2016
Description
The initial microstructure of oxide fuel pellets can play a key role in their performance. At low burnups, the transport of fission products has a strong dependence on oxygen content, grain size distribution, porosity and grain boundary (GB) characteristics (crystallography, geometry and topology), all of which, in turn depend on processing conditions. These microstructural features can also affect the fuel densification, thermal conductivity and microstructure evolution inside the reactor. Understanding these effects can provide insight into microstructure evolution of fuels in-pile. In this work, mechanical and ion beam serial sectioning techniques were developed to obtain Electron Backscatter Diffraction (EBSD) data, both in 2-D and 3-D, for depleted UO2+X pellets manufactured under different conditions. The EBSD maps were used to relate processing conditions to microstructural features, with emphasis on special GBs according to the Coincident Site Lattice (CSL) model, as well as correlations between pore size and location in the microstructure. Furthermore, larger grains (at least 2.5 times the average grain size) were observed in all the samples and studied. Results indicate that larger grains, in samples manufactured under different conditions, dominate the overall crystallographic texture and have a fairly strong GB texture. Moreover, it seems that the preferential misorientation axis for these GBs, regardless of the O/M, is {001}. These results might be related to GB energy and structure and, suggest that the mechanism that controls grain growth seems to be independent of both processing conditions and stoichiometry. Additionally, a sample was heat treated to relate grain growth and crystallography. The results indicate that at least two mechanisms were involved. Lengthening of GBs was observed for larger grains. Another mechanism of grain growth was observed, in this case, grains rotate to match a neighboring grain forming a larger grain. In the new grain, the misorientation between the two neighboring grains decreases to less than 5 degrees, forming a new larger grain. The results presented in this work indicate that detailed studies of the initial microstructure of the fuel, with emphasis on the crystallography of grains and GBs could help to give insights on the in-pile microstructural evolution of the fuel.
ContributorsRudman Prieto, Karin (Author) / Peralta, Pedro (Thesis advisor) / Ponce, Fernando (Committee member) / Sieradski, Karl (Committee member) / Arizona State University (Publisher)
Created2014
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
Description
The absorption spectra of metal-centered phthalocyanines (MPc's) have been investigated since the early 1960's. With improved experimental techniques to characterize this class of molecules the band assignments have advanced. The characterization remains difficult with historic disagreements. A new push for characterization came with a wave of interest in using these molecules for absorption/donor molecules in organic photovoltaics. The use of zinc phthalocyanine (ZnPc) became of particular interest, in addition to novel research being done for azaporphyrin analogs of ZnPc.
A theoretical approach is taken to research the excited states of these molecules using time-dependent density functional theory (TDDFT). Most theoretical results for the first excited state in ZnPc are in only limited agreement with experiment (errors near 0.1 eV or higher). This research investigates ZnPc and 10 additional porphyrin analogs. Excited-state properties are predicted for 8 of these molecules using ab initio computational methods and symmetry breaking for accurate time- dependent self-consistent optimization. Franck-Condon analysis is used to predict the Q-band absorption spectra for all 8 of these molecules. This is the first time that Franck-Condon analysis has been reported in absolute units for any of these molecules. The first excited-state energy for ZnPc is found to be the closest to experiment thus far using a range-separated meta-GGA hybrid functional. The theoretical results are used to find a trend in the novel design of new porphyrin analog molecules.
A theoretical approach is taken to research the excited states of these molecules using time-dependent density functional theory (TDDFT). Most theoretical results for the first excited state in ZnPc are in only limited agreement with experiment (errors near 0.1 eV or higher). This research investigates ZnPc and 10 additional porphyrin analogs. Excited-state properties are predicted for 8 of these molecules using ab initio computational methods and symmetry breaking for accurate time- dependent self-consistent optimization. Franck-Condon analysis is used to predict the Q-band absorption spectra for all 8 of these molecules. This is the first time that Franck-Condon analysis has been reported in absolute units for any of these molecules. The first excited-state energy for ZnPc is found to be the closest to experiment thus far using a range-separated meta-GGA hybrid functional. The theoretical results are used to find a trend in the novel design of new porphyrin analog molecules.
ContributorsTheisen, Rebekah (Author) / Adams, James B (Thesis advisor) / Li, Jian (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2014