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This dissertation is on the study of structural and optical properties of some III-V and II-VI compound semiconductors. The first part of this dissertation is a study of the deformation mechanisms associated with nanoindentation and nanoscratching of InP, GaN, and ZnO crystals. The second part is an investigation of some

This dissertation is on the study of structural and optical properties of some III-V and II-VI compound semiconductors. The first part of this dissertation is a study of the deformation mechanisms associated with nanoindentation and nanoscratching of InP, GaN, and ZnO crystals. The second part is an investigation of some fundamental issues regarding compositional fluctuations and microstructure in GaInNAs and InAlN alloys. In the first part, the microstructure of (001) InP scratched in an atomic force microscope with a small diamond tip has been studied as a function of applied normal force and crystalline direction in order to understand at the nanometer scale the deformation mechanisms in the zinc-blende structure. TEM images show deeper dislocation propagation for scratches along <110> compared to <100>. High strain fields were observed in <100> scratches, indicating hardening due to locking of dislocations gliding on different slip planes. Reverse plastic flow have been observed in <110> scratches in the form of pop-up events that result from recovery of stored elastic strain. In a separate study, nanoindentation-induced plastic deformation has been studied in c-, a-, and m-plane ZnO single crystals and c-plane GaN respectively, to study the deformation mechanism in wurtzite hexagonal structures. TEM results reveal that the prime deformation mechanism is slip on basal planes and in some cases, on pyramidal planes, and strain built up along particular directions. No evidence of phase transformation or cracking was observed in both materials. CL imaging reveals quenching of near band-edge emission by dislocations. In the second part, compositional inhomogeneity in quaternary GaInNAs and ternary InAlN alloys has been studied using TEM. It is shown that exposure to antimony during growth of GaInNAs results in uniform chemical composition in the epilayer, as antimony suppresses the surface mobility of adatoms that otherwise leads to two-dimensional growth and elemental segregation. In a separate study, compositional instability is observed in lattice-matched InAlN films grown on GaN, for growth beyond a certain thickness. Beyond 200 nm of thickness, two sub-layers with different indium content are observed, the top one with lower indium content.
ContributorsHuang, Jingyi (Author) / Ponce, Fernando A. (Thesis advisor) / Carpenter, Ray W (Committee member) / Smith, David J. (Committee member) / Yu, Hongbin (Committee member) / Treacy, Michael Mj (Committee member) / Arizona State University (Publisher)
Created2013
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Description
High electron mobility transistors (HEMTs) based on Group III-nitride heterostructures have been characterized by advanced electron microscopy methods including off-axis electron holography, nanoscale chemical analysis, and electrical measurements, as well as other techniques. The dissertation was organized primarily into three topical areas: (1) characterization of near-gate defects in electrically stressed

High electron mobility transistors (HEMTs) based on Group III-nitride heterostructures have been characterized by advanced electron microscopy methods including off-axis electron holography, nanoscale chemical analysis, and electrical measurements, as well as other techniques. The dissertation was organized primarily into three topical areas: (1) characterization of near-gate defects in electrically stressed AlGaN/GaN HEMTs, (2) microstructural and chemical analysis of the gate/buffer interface of AlN/GaN HEMTs, and (3) studies of the impact of laser-liftoff processing on AlGaN/GaN HEMTs. The electrical performance of stressed AlGaN/GaN HEMTs was measured and the devices binned accordingly. Source- and drain-side degraded, undegraded, and unstressed devices were then prepared via focused-ion-beam milling for examination. Defects in the near-gate region were identified and their correlation to electrical measurements analyzed. Increased gate leakage after electrical stressing is typically attributed to "V"-shaped defects at the gate edge. However, strong evidence was found for gate metal diffusion into the barrier layer as another contributing factor. AlN/GaN HEMTs grown on sapphire substrates were found to have high electrical performance which is attributed to the AlN barrier layer, and robust ohmic and gate contact processes. TEM analysis identified oxidation at the gate metal/AlN buffer layer interface. This thin a-oxide gate insulator was further characterized by energy-dispersive x-ray spectroscopy and energy-filtered TEM. Attributed to this previously unidentified layer, high reverse gate bias up to −30 V was demonstrated and drain-induced gate leakage was suppressed to values of less than 10−6 A/mm. In addition, extrinsic gm and ft * LG were improved to the highest reported values for AlN/GaN HEMTs fabricated on sapphire substrates. Laser-liftoff (LLO) processing was used to separate the active layers from sapphire substrates for several GaN-based HEMT devices, including AlGaN/GaN and InAlN/GaN heterostructures. Warpage of the LLO samples resulted from relaxation of the as-grown strain and strain arising from dielectric and metal depositions, and this strain was quantified by both Newton's rings and Raman spectroscopy methods. TEM analysis demonstrated that the LLO processing produced no detrimental effects on the quality of the epitaxial layers. TEM micrographs showed no evidence of either damage to the ~2 μm GaN epilayer generated threading defects.
ContributorsJohnson, Michael R. (Author) / Mccartney, Martha R (Thesis advisor) / Smith, David J. (Committee member) / Goodnick, Stephen (Committee member) / Shumway, John (Committee member) / Chen, Tingyong (Committee member) / Arizona State University (Publisher)
Created2012
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Description
HgCdTe is currently the dominant material for infrared sensing and imaging, and is usually grown on lattice-matched bulk CdZnTe (CZT) substrates. There have been significant recent efforts to identify alternative substrates to CZT as well as alternative detector materials to HgCdTe. In this dissertation research, a wide range of transmission

HgCdTe is currently the dominant material for infrared sensing and imaging, and is usually grown on lattice-matched bulk CdZnTe (CZT) substrates. There have been significant recent efforts to identify alternative substrates to CZT as well as alternative detector materials to HgCdTe. In this dissertation research, a wide range of transmission electron microscopy (TEM) imaging and analytical techniques was used in the characterization of epitaxial HgCdTe and related materials and substrates for third generation IR detectors. ZnTe layers grown on Si substrates are considered to be promising candidates for lattice-matched, large-area, and low-cost composite substrates for deposition of II-VI and III-V compound semiconductors with lattice constants near 6.1 Å. After optimizing MBE growth conditions including substrate pretreatment prior to film growth, as well as nucleation and growth temperatures, thick ZnTe/Si films with high crystallinity, low defect density, and excellent surface morphology were achieved. Changes in the Zn/Te flux ratio used during growth were also investigated. Small-probe microanalysis confirmed that a small amount of As was present at the ZnTe/Si interface. A microstructural study of HgCdTe/CdTe/GaAs (211)B and CdTe/GaAs (211)B heterostructures grown using MBE was carried out. High quality MBE-grown CdTe on GaAs(211)B substrates was demonstrated to be a viable composite substrate platform for HgCdTe growth. In addition, analysis of interfacial misfit dislocations and residual strain showed that the CdTe/GaAs interface was fully relaxed. In the case of HgCdTe/CdTe/ GaAs(211)B, thin HgTe buffer layers between HgCdTe and CdTe were also investigated for improving the HgCdTe crystal quality. A set of ZnTe layers epitaxially grown on GaSb(211)B substrates using MBE was studied using high resolution X-ray diffraction (HRXRD) measurements and TEM characterization in order to investigate conditions for defect-free growth. HRXRD results gave critical thickness estimates between 350 nm and 375 nm, in good agreement with theoretical predictions. Moreover, TEM results confirmed that ZnTe layers with thicknesses of 350 nm had highly coherent interfaces and very low dislocation densities, unlike samples with the thicker ZnTe layers.
ContributorsKim, Jae Jin (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha R. (Committee member) / Alford, Terry L. (Committee member) / Crozier, Peter A. (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Electromigration in metal interconnects is the most pernicious failure mechanism in semiconductor integrated circuits (ICs). Early electromigration investigations were primarily focused on aluminum interconnects for silicon-based ICs. An alternative metallization compatible with gallium arsenide (GaAs) was required in the development of high-powered radio frequency (RF) compound semiconductor devices operating at

Electromigration in metal interconnects is the most pernicious failure mechanism in semiconductor integrated circuits (ICs). Early electromigration investigations were primarily focused on aluminum interconnects for silicon-based ICs. An alternative metallization compatible with gallium arsenide (GaAs) was required in the development of high-powered radio frequency (RF) compound semiconductor devices operating at higher current densities and elevated temperatures. Gold-based metallization was implemented on GaAs devices because it uniquely forms a very low resistance ohmic contact and gold interconnects have superior electrical and thermal conductivity properties. Gold (Au) was also believed to have improved resistance to electromigration due to its higher melting temperature, yet electromigration reliability data on passivated Au interconnects is scarce and inadequate in the literature. Therefore, the objective of this research was to characterize the electromigration lifetimes of passivated Au interconnects under precisely controlled stress conditions with statistically relevant quantities to obtain accurate model parameters essential for extrapolation to normal operational conditions. This research objective was accomplished through measurement of electromigration lifetimes of large quantities of passivated electroplated Au interconnects utilizing high-resolution in-situ resistance monitoring equipment. Application of moderate accelerated stress conditions with a current density limited to 2 MA/cm2 and oven temperatures in the range of 300°C to 375°C avoided electrical overstress and severe Joule-heated temperature gradients. Temperature coefficients of resistance (TCRs) were measured to determine accurate Joule-heated Au interconnect film temperatures. A failure criterion of 50% resistance degradation was selected to prevent thermal runaway and catastrophic metal ruptures that are problematic of open circuit failure tests. Test structure design was optimized to reduce resistance variation and facilitate failure analysis. Characterization of the Au microstructure yielded a median grain size of 0.91 ìm. All Au lifetime distributions followed log-normal distributions and Black's model was found to be applicable. An activation energy of 0.80 ± 0.05 eV was measured from constant current electromigration tests at multiple temperatures. A current density exponent of 1.91 was extracted from multiple current densities at a constant temperature. Electromigration-induced void morphology along with these model parameters indicated grain boundary diffusion is dominant and the void nucleation mechanism controlled the failure time.
ContributorsKilgore, Stephen (Author) / Adams, James (Thesis advisor) / Schroder, Dieter (Thesis advisor) / Krause, Stephen (Committee member) / Gaw, Craig (Committee member) / Arizona State University (Publisher)
Created2013
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Description
The research described in this dissertation involved the use of transmission electron microscopy (TEM) to characterize II-VI and III-V compound semiconductor quantum dots (QDs) and dilute-nitride alloys grown by molecular beam epitaxy (MBE) and intended for photovoltaic applications. The morphology of CdTe QDs prepared by the post-annealing MBE method were

The research described in this dissertation involved the use of transmission electron microscopy (TEM) to characterize II-VI and III-V compound semiconductor quantum dots (QDs) and dilute-nitride alloys grown by molecular beam epitaxy (MBE) and intended for photovoltaic applications. The morphology of CdTe QDs prepared by the post-annealing MBE method were characterized by various microscopy techniques including high-resolution transmission electron microscopy (HR-TEM), and high-angle annular-dark-field scanning transmission electron microscopy (HAADF-STEM). Extensive observations revealed that the of QD shapes were not well-defined, and the QD size and spatial distribution were not determined by the amount of CdTe deposition. These results indicated that the formation of II-VI QDs using a post-annealing treatment did not follow the conventional growth mechanism for III-V and IV-IV materials. The structural properties of dilute-nitride GaAsNx films grown using plasma-assisted MBE were characterized by TEM and HAADF-STEM. A significant amount of the nitrogen incorporated into the dilute nitride films was found to be interstitial, and that fluctuations in local nitrogen composition also occurred during growth. Post-growth partial relaxation of strain resulted in the formation of {110}-oriented microcracks in the sample with the largest substitutional nitrogen composition. Single- and multi-layered InAs QDs grown on GaAsSb/GaAs composite substrates were investigated using HR-TEM and HAADF-STEM. Correlation between the structural and optoelectronic properties revealed that the GaAsSb barrier layers had played an important role in tuning the energy-band alignments but without affecting the overall structural morphology. However, according to both XRD measurement and electron microscopy the densities of dislocations increased as the number of QD layers built up. An investigation of near-wetting layer-free InAs QDs incorporated with AlAs/GaAs spacer layers was carried out. The microscopy observations revealed that both embedded and non-embedded near-wetting layer-free InAs QDs did not have well-defined shapes unlike conventional InAs QDs. According to AFM analysis and plan-view TEM characterization, the InAs QDs incorporated with spacer layers had smaller dot density and more symmetrical larger sizes with an apparent bimodal size distribution (two distinct families of large and small dots) in comparison with conventional InAs QDs grown without any spacer layer.
ContributorsTang, Dinghao (Author) / Smith, David J. (Thesis advisor) / Crozier, Peter A. (Committee member) / Liu, Jingyue (Committee member) / Mccartney, Martha R (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Organic optoelectronic devices have remained a research topic of great interest over the past two decades, particularly in the development of efficient organic photovoltaics (OPV) and organic light emitting diodes (OLED). In order to improve the efficiency, stability, and materials variety for organic optoelectronic devices a number of emitting materials,

Organic optoelectronic devices have remained a research topic of great interest over the past two decades, particularly in the development of efficient organic photovoltaics (OPV) and organic light emitting diodes (OLED). In order to improve the efficiency, stability, and materials variety for organic optoelectronic devices a number of emitting materials, absorbing materials, and charge transport materials were developed and employed in a device setting. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. Two major approaches were taken to enhance the efficiency of small molecule based OPVs: developing material with higher open circuit voltages or improved device structures which increased short circuit current. To explore the factors affecting the open circuit voltage (VOC) in OPVs, molecular structures were modified to bring VOC closer to the effective bandgap, ∆EDA, which allowed the achievement of 1V VOC for a heterojunction of a select Ir complex with estimated exciton energy of only 1.55eV. Furthermore, the development of anode interfacial layer for exciton blocking and molecular templating provide a general approach for enhancing the short circuit current. Ultimately, a 5.8% PCE was achieved in a single heterojunction of C60 and a ZnPc material prepared in a simple, one step, solvent free, synthesis. OLEDs employing newly developed deep blue emitters based on cyclometalated complexes were demonstrated. Ultimately, a peak EQE of 24.8% and nearly perfect blue emission of (0.148,0.079) was achieved from PtON7dtb, which approaches the maximum attainable performance from a blue OLED. Furthermore, utilizing the excimer formation properties of square-planar Pt complexes, highly efficient and stable white devices employing a single emissive material were demonstrated. A peak EQE of over 20% for pure white color (0.33,0.33) and 80 CRI was achieved with the tridentate Pt complex, Pt-16. Furthermore, the development of a series of tetradentate Pt complexes yielded highly efficient and stable single doped white devices due to their halogen free tetradentate design. In addition to these benchmark achievements, the systematic molecular modification of both emissive and absorbing materials provides valuable structure-property relationship information that should help guide further developments in the field.
ContributorsFleetham, Tyler Blain (Author) / Li, Jian (Thesis advisor) / Alford, Terry (Committee member) / Adams, James (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Organic light emitting diodes (OLEDs) are a promising approach for display and solid state lighting applications. However, further work is needed in establishing the availability of efficient and stable materials for OLEDs with high external quantum efficiency's (EQE) and high operational lifetimes. Recently, significant improvements in the internal quantum efficiency

Organic light emitting diodes (OLEDs) are a promising approach for display and solid state lighting applications. However, further work is needed in establishing the availability of efficient and stable materials for OLEDs with high external quantum efficiency's (EQE) and high operational lifetimes. Recently, significant improvements in the internal quantum efficiency or ratio of generated photons to injected electrons have been achieved with the advent of phosphorescent complexes with the ability to harvest both singlet and triplet excitons. Since then, a variety of phosphorescent complexes containing heavy metal centers including Os, Ni, Ir, Pd, and Pt have been developed. Thus far, the majority of the work in the field has focused on iridium based complexes. Platinum based complexes, however, have received considerably less attention despite demonstrating efficiency's equal to or better than their iridium analogs. In this study, a series of OLEDs implementing newly developed platinum based complexes were demonstrated with efficiency's or operational lifetimes equal to or better than their iridium analogs for select cases.

In addition to demonstrating excellent device performance in OLEDs, platinum based complexes exhibit unique photophysical properties including the ability to form excimer emission capable of generating broad white light emission from a single emitter and the ability to form narrow band emission from a rigid, tetradentate molecular structure for select cases. These unique photophysical properties were exploited and their optical and electrical properties in a device setting were elucidated.

Utilizing the unique properties of a tridentate Pt complex, Pt-16, a highly efficient white device employing a single emissive layer exhibited a peak EQE of over 20% and high color quality with a CRI of 80 and color coordinates CIE(x=0.33, y=0.33). Furthermore, by employing a rigid, tetradentate platinum complex, PtN1N, with a narrow band emission into a microcavity organic light emitting diode (MOLED), significant enhancement in the external quantum efficiency was achieved. The optimized MOLED structure achieved a light out-coupling enhancement of 1.35 compared to the non-cavity structure with a peak EQE of 34.2%. In addition to demonstrating a high light out-coupling enhancement, the microcavity effect of a narrow band emitter in a MOLED was elucidated.
ContributorsEcton, Jeremy David (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Organic light emitting diodes (OLEDs) is a rapidly emerging technology based on organic thin film semiconductors. Recently, there has been substantial investment in their use in displays. In less than a decade, OLEDs have grown from a promising academic curiosity into a multi-billion dollar global industry. At the heart of

Organic light emitting diodes (OLEDs) is a rapidly emerging technology based on organic thin film semiconductors. Recently, there has been substantial investment in their use in displays. In less than a decade, OLEDs have grown from a promising academic curiosity into a multi-billion dollar global industry. At the heart of an OLED are emissive molecules that generate light in response to electrical stimulation. Ideal emitters are efficient, compatible with existing materials, long lived, and produce light predominantly at useful wavelengths. Developing an understanding of the photophysical processes that dictate the luminescent properties of emissive materials is vital to their continued development. Chapter 1 and Chapter 2 provide an introduction to the topics presented and the laboratory methods used to explore them. Chapter 3 discusses a series of tridentate platinum complexes. A synthetic method utilizing microwave irradiation was explored, as well as a study of the effects ligand structure had on the excited state properties. Results and techniques developed in this endeavor were used as a foundation for the work undertaken in later chapters. Chapter 4 introduces a series of tetradentate platinum complexes that share a phenoxy-pyridyl (popy) motif. The new molecular design improved efficiency through increased rigidity and modification of the excited state properties. This class of platinum complexes were markedly more efficient than those presented in Chapter 3, and devices employing a green emitting complex of the series achieved nearly 100% electron-to-photon conversion efficiency in an OLED device. Chapter 5 adapts the ligand structure developed in Chapter 4 to palladium. The resulting complexes exceed reported efficiencies of palladium complexes by an order of magnitude. This chapter also provides the first report of a palladium complex as an emitter in an OLED device. Chapter 6 discusses the continuation of development efforts to include carbazolyl components in the ligand. These complexes possess interesting luminescent properties including ultra-narrow emission and metal assisted delayed fluorescence (MADF) emission.
ContributorsTurner, Eric (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Fluctuation Electron Microscopy (FEM) has become an effective materials' structure characterization technique, capable of probing medium-range order (MRO) that may be present in amorphous materials. Although its sensitivity to MRO has been exercised in numerous studies, FEM is not yet a quantitative technique. The holdup has been the discrepancy

Fluctuation Electron Microscopy (FEM) has become an effective materials' structure characterization technique, capable of probing medium-range order (MRO) that may be present in amorphous materials. Although its sensitivity to MRO has been exercised in numerous studies, FEM is not yet a quantitative technique. The holdup has been the discrepancy between the computed kinematical variance and the experimental variance, which previously was attributed to source incoherence. Although high-brightness, high coherence, electron guns are now routinely available in modern electron microscopes, they have not eliminated this discrepancy between theory and experiment. The main objective of this thesis was to explore, and to reveal, the reasons behind this conundrum.

The study was started with an analysis of the speckle statistics of tilted dark-field TEM images obtained from an amorphous carbon sample, which confirmed that the structural ordering is sensitively detected by FEM. This analysis also revealed the inconsistency between predictions of the source incoherence model and the experimentally observed variance.

FEM of amorphous carbon, amorphous silicon and ultra nanocrystalline diamond samples was carried out in an attempt to explore the conundrum. Electron probe and sample parameters were varied to observe the scattering intensity variance behavior. Results were compared to models of probe incoherence, diffuse scattering, atom displacement damage, energy loss events and multiple scattering. Models of displacement decoherence matched the experimental results best.

Decoherence was also explored by an interferometric diffraction method using bilayer amorphous samples, and results are consistent with strong displacement decoherence in addition to temporal decoherence arising from the electron source energy spread and energy loss events in thick samples.

It is clear that decoherence plays an important role in the long-standing discrepancy between experimental FEM and its theoretical predictions.
ContributorsRezikyan, Aram (Author) / Treacy, Michael M.J. (Thesis advisor) / Smith, David J. (Committee member) / McCartney, Martha R. (Committee member) / Rez, Peter (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Off-axis electron holography (EH) has been used to characterize electrostatic potential, active dopant concentrations and charge distribution in semiconductor nanostructures, including ZnO nanowires (NWs) and thin films, ZnTe thin films, Si NWs with axial p-n junctions, Si-Ge axial heterojunction NWs, and Ge/LixGe core/shell NW.

The mean inner potential (MIP) and inelastic

Off-axis electron holography (EH) has been used to characterize electrostatic potential, active dopant concentrations and charge distribution in semiconductor nanostructures, including ZnO nanowires (NWs) and thin films, ZnTe thin films, Si NWs with axial p-n junctions, Si-Ge axial heterojunction NWs, and Ge/LixGe core/shell NW.

The mean inner potential (MIP) and inelastic mean free path (IMFP) of ZnO NWs have been measured to be 15.3V±0.2V and 55±3nm, respectively, for 200keV electrons. These values were then used to characterize the thickness of a ZnO nano-sheet and gave consistent values. The MIP and IMFP for ZnTe thin films were measured to be 13.7±0.6V and 46±2nm, respectively, for 200keV electrons. A thin film expected to have a p-n junction was studied, but no signal due to the junction was observed. The importance of dynamical effects was systematically studied using Bloch wave simulations.

The built-in potentials in Si NWs across the doped p-n junction and the Schottky junction due to Au catalyst were measured to be 1.0±0.3V and 0.5±0.3V, respectively. Simulations indicated that the dopant concentrations were ~1019cm-3 for donors and ~1017 cm-3 for acceptors. The effects of positively charged Au catalyst, a possible n+-n--p junction transition region and possible surface charge, were also systematically studied using simulations.

Si-Ge heterojunction NWs were studied. Dopant concentrations were extracted by atom probe tomography. The built-in potential offset was measured to be 0.4±0.2V, with the Ge side lower. Comparisons with simulations indicated that Ga present in the Si region was only partially activated. In situ EH biasing experiments combined with simulations indicated the B dopant in Ge was mostly activated but not the P dopant in Si. I-V characteristic curves were measured and explained using simulations.

The Ge/LixGe core/shell structure was studied during lithiation. The MIP for LixGe decreased with time due to increased Li content. A model was proposed to explain the lower measured Ge potential, and the trapped electron density in Ge core was calculated to be 3×1018 electrons/cm3. The Li amount during lithiation was also calculated using MIP and volume ratio, indicating that it was lower than the fully lithiated phase.
ContributorsGan, Zhaofeng (Author) / Mccartney, Martha R (Thesis advisor) / Smith, David J. (Thesis advisor) / Drucker, Jeffery (Committee member) / Bennett, Peter A (Committee member) / Arizona State University (Publisher)
Created2015