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- All Subjects: Materials Science
- Creators: Smith, David J.
Description
Ordered mesoporous materials have tunable pore sizes between 2 and 50 nm and are characterized by ordered pore structures and high surface areas (~1000 m2/g). This makes them particularly favorable for a number of membrane applications such as protein separation, polymer extrusion, nanowire fabrication and membrane reactors. These membranes can be fabricated as top-layers on macroporous supports or as embedded membranes in a dense matrix. The first part of the work deals with the hydrothermal synthesis and water-vapor/oxygen separation properties of supported MCM-48 and a new Al-MCM-48 type membrane for potential use in air conditioning systems. Knudsen-type permeation is observed in these membranes. The combined effect of capillary condensation and the aluminosilicate matrix resulted in the highest separation factor (142) in Al-MCM-48 membranes, with a water vapor permeance of 6×10-8mol/m2Pas. The second part focuses on synthesis of embedded mesoporous silica membranes with helically ordered pores by a novel Counter Diffusion Self-Assembly (CDSA) method. This method is an extension of the interfacial synthesis method for fiber synthesis using tetrabutylorthosilicate (TBOS) and cetyltrimethylammonium bromide (CTAB) as the silica source and surfactant respectively. The initial part of this study determined the effect of TBOS height and humidity on fiber formation. From this study, the range of TBOS heights for best microscopic and macroscopic ordering were established. Next, the CDSA method was used to successfully synthesize membranes, which were characterized to have good support plugging and an ordered pore structure. Factors that influence membrane synthesis and plug microstructure were determined. SEM studies revealed the presence of gaps between the plugs and support pores, which occur due to shrinking of the plug on drying. Development of a novel liquid deposition method to seal these defects constituted the last part of this work. Post sealing, excess silica was removed by etching with hydrofluoric acid. Membrane quality was evaluated at each step using SEM and gas permeation measurements. After surfactant removal by liquid extraction, the membranes exhibited an O2 permeance of 1.65x10-6mol/m2.Pa.s and He/O2 selectivity of 3.30. The successful synthesis of this membrane is an exciting new development in the area of ordered mesoporous membrane technology.
ContributorsSeshadri, Shriya (Author) / Lin, Jerry Y. S. (Thesis advisor) / Dai, Lenore (Committee member) / Rege, Kaushal (Committee member) / Smith, David J. (Committee member) / Vogt, Bryan (Committee member) / Arizona State University (Publisher)
Created2011
Description
III-nitride alloys are wide band gap semiconductors with a broad range of applications in optoelectronic devices such as light emitting diodes and laser diodes. Indium gallium nitride light emitting diodes have been successfully produced over the past decade. But the progress of green emission light emitting devices has been limited by the incorporation of indium in the alloy, mainly due to phase separation. This difficulty could be addressed by studying the growth and thermodynamics of these alloys. Knowledge of thermodynamic phase stabilities and of pressure - temperature - composition phase diagrams is important for an understanding of the boundary conditions of a variety of growth techniques. In this dissertation a study of the phase separation of indium gallium nitride is conducted using a regular solution model of the ternary alloy system. Graphs of Gibbs free energy of mixing were produced for a range of temperatures. Binodal and spinodal decomposition curves show the stable and unstable regions of the alloy in equilibrium. The growth of gallium nitride and indium gallium nitride was attempted by the reaction of molten gallium - indium alloy with ammonia at atmospheric pressure. Characterization by X-ray diffraction, photoluminescence, and secondary electron microscopy show that the samples produced by this method contain only gallium nitride in the hexagonal phase. The instability of indium nitride at the temperatures required for activation of ammonia accounts for these results. The photoluminescence spectra show a correlation between the intensity of a broad green emission, related to native defects, and indium composition used in the molten alloy. A different growth method was used to grow two columnar-structured gallium nitride films using ammonium chloride and gallium as reactants and nitrogen and ammonia as carrier gasses. Investigation by X-ray diffraction and spatially-resolved cathodoluminescence shows the film grown at higher temperature to be primarily hexagonal with small quantities of cubic crystallites, while the one grown at lower temperature to be pure hexagonal. This was also confirmed by low temperature photoluminescence measurements. The results presented here show that cubic and hexagonal crystallites can coexist, with the cubic phase having a much sharper and stronger luminescence. Controlled growth of the cubic phase GaN crystallites can be of use for high efficiency light detecting and emitting devices. The ammonolysis of a precursor was used to grow InGaN powders with different indium composition. High purity hexagonal GaN and InN were obtained. XRD spectra showed complete phase separation for samples with x < 30%, with ~ 9% indium incorporation in the 30% sample. The presence of InGaN in this sample was confirmed by PL measurements, where luminescence from both GaN and InGaN band edge are observed. The growth of higher indium compositions samples proved to be difficult, with only the presence of InN in the sample. Nonetheless, by controlling parameters like temperature and time may lead to successful growth of this III-nitride alloy by this method.
ContributorsHill, Arlinda (Author) / Ponce, Fernando A. (Thesis advisor) / Chamberlin, Ralph V (Committee member) / Sankey, Otto F (Committee member) / Smith, David J. (Committee member) / Tsen, Kong-Thon (Committee member) / Arizona State University (Publisher)
Created2011
Description
HgCdTe is the dominant material currently in use for infrared (IR) focal-plane-array (FPA) technology. In this dissertation, transmission electron microscopy (TEM) was used for the characterization of epitaxial HgCdTe epilayers and HgCdTe-based devices. The microstructure of CdTe surface passivation layers deposited either by hot-wall epitaxy (HWE) or molecular beam epitaxy (MBE) on HgCdTe heterostructures was evaluated. The as-deposited CdTe passivation layers were polycrystalline and columnar. The CdTe grains were larger and more irregular when deposited by HWE, whereas those deposited by MBE were generally well-textured with mostly vertical grain boundaries. Observations and measurements using several TEM techniques showed that the CdTe/HgCdTe interface became considerably more abrupt after annealing, and the crystallinity of the CdTe layer was also improved. The microstructure and compositional profiles of CdTe(211)B/ZnTe/Si(211) heterostructures grown by MBE was investigated. Many inclined {111}-type stacking faults were present throughout the thin ZnTe layer, terminating near the point of initiation of CdTe growth. A rotation angle of about 3.5° was observed between lattice planes of the Si substrate and the final CdTe epilayer. Lattice parameter measurement and elemental profiles indicated that some local intermixing of Zn and Cd had taken place. The average widths of the ZnTe layer and the (Cd, Zn)Te transition region were found to be roughly 6.5 nm and 3.5 nm, respectively. Initial observations of CdTe(211)B/GaAs(211) heterostructures indicated much reduced defect densities near the vicinity of the substrate and within the CdTe epilayers. HgCdTe epilayers grown on CdTe(211)B/GaAs(211) composite substrate were generally of high quality, despite the presence of precipitates at the HgCdTe/CdTe interface. The microstructure of HgCdSe thin films grown by MBE on ZnTe/Si(112) and GaSb(112) substrates were investigated. The quality of the HgCdSe growth was dependent on the growth temperature and materials flux, independent of the substrate. The materials grown at 100°C were generally of high quality, while those grown at 140°C had {111}-type stacking defects and high dislocation densities. For epitaxial growth of HgCdSe on GaSb substrates, better preparation of the GaSb buffer layer will be essential in order to ensure that high-quality HgCdSe can be grown.
ContributorsZhao, Wenfeng (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha (Committee member) / Carpenter, Ray (Committee member) / Bennett, Peter (Committee member) / Treacy, Michael J. (Committee member) / Arizona State University (Publisher)
Created2011
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 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
Description
Alkali-activated aluminosilicates, commonly known as "geopolymers", are being increasingly studied as a potential replacement for Portland cement. These binders use an alkaline activator, typically alkali silicates, alkali hydroxides or a combination of both along with a silica-and-alumina rich material, such as fly ash or slag, to form a final product with properties comparable to or better than those of ordinary Portland cement. The kinetics of alkali activation is highly dependent on the chemical composition of the binder material and the activator concentration. The influence of binder composition (slag, fly ash or both), different levels of alkalinity, expressed using the ratios of Na2O-to-binders (n) and activator SiO2-to-Na2O ratios (Ms), on the early age behavior in sodium silicate solution (waterglass) activated fly ash-slag blended systems is discussed in this thesis. Optimal binder composition and the n values are selected based on the setting times. Higher activator alkalinity (n value) is required when the amount of slag in the fly ash-slag blended mixtures is reduced. Isothermal calorimetry is performed to evaluate the early age hydration process and to understand the reaction kinetics of the alkali activated systems. The differences in the calorimetric signatures between waterglass activated slag and fly ash-slag blends facilitate an understanding of the impact of the binder composition on the reaction rates. Kinetic modeling is used to quantify the differences in reaction kinetics using the Exponential as well as the Knudsen method. The influence of temperature on the reaction kinetics of activated slag and fly ash-slag blends based on the hydration parameters are discussed. Very high compressive strengths can be obtained both at early ages as well as later ages (more than 70 MPa) with waterglass activated slag mortars. Compressive strength decreases with the increase in the fly ash content. A qualitative evidence of leaching is presented through the electrical conductivity changes in the saturating solution. The impact of leaching and the strength loss is found to be generally higher for the mixtures made using a higher activator Ms and a higher n value. Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) is used to obtain information about the reaction products.
ContributorsChithiraputhiran, Sundara Raman (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniyam D (Committee member) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2012
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 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
Description
The alkali activation of aluminosilicate materials as binder systems derived from industrial byproducts have been extensively studied due to the advantages they offer in terms enhanced material properties, while increasing sustainability by the reuse of industrial waste and byproducts and reducing the adverse impacts of OPC production. Fly ash and ground granulated blast furnace slag are commonly used for their content of soluble silica and aluminate species that can undergo dissolution, polymerization with the alkali, condensation on particle surfaces and solidification. The following topics are the focus of this thesis: (i) the use of microwave assisted thermal processing, in addition to heat-curing as a means of alkali activation and (ii) the relative effects of alkali cations (K or Na) in the activator (powder activators) on the mechanical properties and chemical structure of these systems. Unsuitable curing conditions instigate carbonation, which in turn lowers the pH of the system causing significant reductions in the rate of fly ash activation and mechanical strength development. This study explores the effects of sealing the samples during the curing process, which effectively traps the free water in the system, and allows for increased aluminosilicate activation. The use of microwave-curing in lieu of thermal-curing is also studied in order to reduce energy consumption and for its ability to provide fast volumetric heating. Potassium-based powder activators dry blended into the slag binder system is shown to be effective in obtaining very high compressive strengths under moist curing conditions (greater than 70 MPa), whereas sodium-based powder activation is much weaker (around 25 MPa). Compressive strength decreases when fly ash is introduced into the system. Isothermal calorimetry is used to evaluate the early hydration process, and to understand the reaction kinetics of the alkali powder activated systems. A qualitative evidence of the alkali-hydroxide concentration of the paste pore solution through the use of electrical conductivity measurements is also presented, with the results indicating the ion concentration of alkali is more prevalent in the pore solution of potassium-based systems. The use of advanced spectroscopic and thermal analysis techniques to distinguish the influence of studied parameters is also discussed.
ContributorsChowdhury, Ussala (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramanium D. (Committee member) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2013
Description
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
Description
Concrete design has recently seen a shift in focus from prescriptive specifications to performance based specifications with increasing demands for sustainable products. Fiber reinforced composites (FRC) provides unique properties to a material that is very weak under tensile loads. The addition of fibers to a concrete mix provides additional ductility and reduces the propagation of cracks in the concrete structure. It is the fibers that bridge the crack and dissipate the incurred strain energy in the form of a fiber-pullout mechanism. The addition of fibers plays an important role in tunnel lining systems and in reducing shrinkage cracking in high performance concretes. The interest in most design situations is the load where cracking first takes place. Typically the post crack response will exhibit either a load bearing increase as deflection continues, or a load bearing decrease as deflection continues. These behaviors are referred to as strain hardening and strain softening respectively. A strain softening or hardening response is used to model the behavior of different types of fiber reinforced concrete and simulate the experimental flexural response. Closed form equations for moment-curvature response of rectangular beams under four and three point loading in conjunction with crack localization rules are utilized. As a result, the stress distribution that considers a shifting neutral axis can be simulated which provides a more accurate representation of the residual strength of the fiber cement composites. The use of typical residual strength parameters by standards organizations ASTM, JCI and RILEM are examined to be incorrect in their linear elastic assumption of FRC behavior. Finite element models were implemented to study the effects and simulate the load defection response of fiber reinforced shotcrete round discrete panels (RDP's) tested in accordance with ASTM C-1550. The back-calculated material properties from the flexural tests were used as a basis for the FEM material models. Further development of FEM beams were also used to provide additional comparisons in residual strengths of early age samples. A correlation between the RDP and flexural beam test was generated based a relationship between normalized toughness with respect to the newly generated crack surfaces. A set of design equations are proposed using a residual strength correction factor generated by the model and produce the design moment based on specified concrete slab geometry.
ContributorsBarsby, Christopher (Author) / Mobasher, Barzin (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Neithalath, Narayanan (Committee member) / Arizona State University (Publisher)
Created2011
Description
The research described in this dissertation has involved the use of transmission electron microcopy (TEM) to characterize the structural properties of II-VI and III-V compound semiconductor heterostructures and superlattices. The microstructure of thick ZnTe epilayers (~2.4 µm) grown by molecular beam epitaxy (MBE) under virtually identical conditions on GaSb, InAs, InP and GaAs (100) substrates were compared using TEM. High-resolution electron micrographs revealed a highly coherent interface for the ZnTe/GaSb sample, and showed extensive areas with well-separated interfacial misfit dislocations for the ZnTe/InAs sample. Lomer edge dislocations and 60o dislocations were commonly observed at the interfaces of the ZnTe/InP and ZnTe/GaAs samples. The amount of residual strain at the interfaces was estimated to be 0.01% for the ZnTe/InP sample and -0.09% for the ZnTe/GaAs sample. Strong PL spectra for all ZnTe samples were observed from 80 to 300 K. High quality GaSb grown by MBE on ZnTe/GaSb (001) virtual substrates with a temperature ramp at the beginning of the GaSb growth has been demonstrated. High-resolution X-ray diffraction (XRD) showed clear Pendellösung thickness fringes from both GaSb and ZnTe epilayers. Cross-section TEM images showed excellent crystallinity and smooth morphology for both ZnTe/GaSb and GaSb/ZnTe interfaces. Plan-view TEM image revealed the presence of Lomer dislocations at the interfaces and threading dislocations in the top GaSb layer. The defect density was estimated to be ~1 x107/cm2. The PL spectra showed improved optical properties when using the GaSb transition layer grown on ZnTe with a temperature ramp. The structural properties of strain-balanced InAs/InAs1-xSbx SLs grown on GaSb (001) substrates by metalorganic chemical vapor deposition (MOCVD) and MBE, have been studied using XRD and TEM. Excellent structural quality of the InAs/InAs1-xSbx SLs grown by MOCVD has been demonstrated. Well-defined ordered-alloy structures within individual InAs1-xSbx layers were observed for samples grown by modulated MBE. However, the ordering disappeared when defects propagating through the SL layers appeared during growth. For samples grown by conventional MBE, high-resolution images revealed that interfaces for InAs1-xSbx grown on InAs layers were sharper than for InAs grown on InAs1-xSbx layers, most likely due to a Sb surfactant segregation effect.
ContributorsOuyang, Lu (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha (Committee member) / Ponce, Fernando (Committee member) / Chamberlin, Ralph (Committee member) / Menéndez, Jose (Committee member) / Arizona State University (Publisher)
Created2012