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Description
Nanoholes on the basal plane of graphene can provide abundant mass transport channels and chemically active sites for enhancing the electrochemical performance, making this material highly promising in applications such as supercapacitors, batteries, desalination, molecule or ion detection, and biosensing. However, the current solution-based chemical etching processes to manufacture these nanoholes commonly suffer from low process efficiency, scalability, and controllability, because conventional bulk heating cannot promote the etching reactions. Herein, a novel manufacturing method is developed to address this issue using microwave irradiation to facilitate and control the chemical etching of graphene. In this process, microwave irradiation induces selective heating of graphene in the aqueous solution due to an energy dissipation mechanism coupled with the dielectric and conduction losses. This strategy brings a remarkable reduction of processing time from hour-scale to minute-scale compared to the conventional approaches. By further incorporating microwave pretreatment, it is possible to control the population and area percentage of the in-plane nanoholes on graphene. Theoretical calculations reveal that the nanoholes emerge and grow by a repeating reduction–oxidation process occurring at the edge-sites atoms around vacancy defects on the graphene basal plane. The reduced holey graphene oxide sheets obtained via the microwave-assisted chemical etching method exhibit great potentials in supercapacitors and electrocatalysis. Excellent capacitive performance and electrocatalytic activity are observed in electrochemical measurements. The improvements against the non-holey counterpart are attributed to the enhanced kinetics involving ion diffusion and heterogeneous charge transfer.
ContributorsWang, Dini (Author) / Nian, Qiong (Thesis advisor) / Alford, Terry (Committee member) / Wang, Qing Hua (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2021
Description
Layer-wise extrusion of soft-solid like cement pastes and mortars is commonly used in 3D printing of concrete. Rheological and mechanical characterization of the printable binder for on-demand flow and subsequent structuration is a critical challenge. This research is an effort to understand the mechanics of cementitious binders as soft solids in the fresh state, towards establishing material-process relationships to enhance print quality. This study introduces 3D printable binders developed based on rotational and capillary rheology test parameters, and establish the direct influence of packing coefficients, geometric ratio, slip velocities, and critical print velocities on the extrudate quality. The ratio of packing fraction to the square of average particle diameter (0.01-0.02), and equivalent microstructural index (5-20) were suitable for printing, and were directly related to the cohesion and extrusional yield stress of the material. In fact, steady state pressure for printing (30-40 kPa) is proportional to the extrusional yield stress, and increases with the geometric ratio (0-60) and print velocity (5-50 mm/s). Higher print velocities results in higher wall shear stresses and was exponentially related to the slip layer thickness (estimated between 1-5μ), while the addition of superplasticizers improve the slip layer thickness and the extrudate flow. However, the steady state pressure and printer capacity limits the maximum print velocity while the deadzone length limits the minimum velocity allowable (critical velocity regime) for printing. The evolution of buildability with time for the fresh state mortars was characterized with digital image correlation using compressive strain and strain rate in printed layers. The fresh state characteristics (interlayer and interfilamentous) and process parameters (layer height and fiber dimensions) influence the hardened mechanical properties. A lower layer height generally improves the mechanical properties and slight addition of fiber (up to 0.3% by volume) results in a 15-30% increase in the mechanical properties. 3D scanning and point-cloud analysis was also used to assess the geometric tolerance of a print based on mean error distances, print accuracy index, and layer-wise percent overlap. The research output will contribute to a synergistic material-process design and development of test methods for printability in the context of 3D printing of concrete.
ContributorsAmbadi Omanakuttan Nair, Sooraj Kumar (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam (Committee member) / Mobasher, Barzin (Committee member) / Hoover, Christian (Committee member) / Chawla, Nikhilesh (Committee member) / Arizona State University (Publisher)
Created2021
Description
High-pressure science has been advancing rapidly in the past several decades due to its potential to access bond engineering and lattice reconstruction. Thanks to the development of pressure devices and advanced in-situ probing technics, it is possible to probe structural phase transitions as well as materials’ optical, electrical, and magnetic properties under extreme pressure, which will in turn help explain new emerging materials’ phases and phenomena. As one of the most popular high-pressure devices, the diamond anvil cell has been used to control the crystal structure and interatomic spacing of materials by applying high pressure while accessing their material properties in-situ. In this dissertation, advanced spectroscopy techniques combined with diamond anvil cells are used to help determine how emergent quantum materials behave under high pressure. A comprehensive summary is offered on the synthesis, characterization, and high-pressure studies of various low-dimensional material systems, such as 2D Ruddlesden-Popper hybrid lead bromide perovskites (CH3(CH2)3NH3)2(CH3NH3)nPbnBr3n+1, (n = 1 and n = 2); guanidinium based lead iodides (2D Gua2PbI4 and 1D GuaPbI3), in which researchers discovered extraordinary luminescent properties and extremely high quantum conversion efficiency; 2D Janus MoSSe and WSSe monolayers, in which the mirror symmetry is broken and an electrical field is built in due to different electronegativity of the top and bottom atom layers; and 2D tellurene, which possess a large potential application in optoelectronic devices and sensors. In combination with the density function theory simulations of such collaborators as Dr. Can Ataca (organic–inorganic halide perovskite), Dr. Arunima K. Singh (tellurene), and Dr. Houlong Zhuang (Janus), this study offers comprehensive and detailed insights into the fundamental physics and mechanics of how crystal structure and band structure evolve at high pressure, discovering new phases, understanding the phase transition mechanism, and determining optoelectronic device applications.
ContributorsLi, Han (Author) / Tongay, Sefaattin ST (Thesis advisor) / Botana, Antia Sanchez (Committee member) / Singh, Arunima K. (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2021
Description
Crystalline silicon covers more than 85% of the global photovoltaics industry and has sustained a nearly 30% year-over-year growth rate. Continued cost and capital expenditure (CAPEX) reductions are needed to sustain this growth. Using thin silicon wafers well below the current industry standard of 160 µm can reduce manufacturing cost, CAPEX, and levelized cost of electricity. Additionally, thinner wafers enable more flexible and lighter module designs, making them more compelling in market segments like building-integrated photovoltaics, portable power, aerospace, and automotive industries. Advanced architectures and superior surface passivation schemes are needed to enable the use of very thin silicon wafers. Silicon heterojunction (SHJ) and SHJ with interdigitated back contact solar cells have demonstrated open-circuit voltages surpassing 720 mV and the potential to surpass 25% conversion efficiency. These factors have led to an increasing interest in exploring SHJ solar cells on thin wafers. In this work, the passivation capability of the thin intrinsic hydrogenated amorphous silicon layer is improved by controlling the deposition temperature and the silane-to-hydrogen dilution ratio. An effective way to parametrize surface recombination is by using surface saturation current density and a very low surface saturation density is achieved on textured wafers for wafer thicknesses ranging between 40 and 180 µm which is an order of magnitude lesser compared to the prevalent industry standards. Implied open-circuit voltages over 760 mV were accomplished on SHJ structures deposited on n-type silicon wafers with thicknesses below 50 µm. An analytical model is also described for a better understanding of the variation of the recombination fractions for varying substrate thicknesses. The potential of using very thin wafers is also established by manufacturing SHJ solar cells, using industrially pertinent processing steps, on 40 µm thin standalone wafers while achieving maximum efficiency of 20.7%. It is also demonstrated that 40 µm thin SHJ solar cells can be manufactured using these processes on large areas. An analysis of the percentage contribution of current, voltage, and resistive losses are also characterized for the SHJ devices fabricated in this work for varying substrate thicknesses.
ContributorsBalaji, Pradeep (Author) / Bowden, Stuart (Thesis advisor) / Alford, Terry (Thesis advisor) / Goryll, Michael (Committee member) / Augusto, Andre (Committee member) / Arizona State University (Publisher)
Created2021
Description
Automation has become a staple in high volume manufacturing, where the consistency and quality of a product carries as much importance as the quantity produced. The Aerospace Industry has a vested interest in expanding the application of automation beyond simply manufacturing. In this project, the process of systems engineering has been applied to the Conceptual Design Phase of product development; specifically, the Preliminary Structural Design of a Composite wing for an Unmanned Air Vehicle (UAV). Automated structural analysis can be used to develop a composite wing structure that can be directly rendered in Computer Aided Drafting (CAD) and validated using Finite Element Analysis (FEA). This concept provides the user with the ability to quickly iterate designs and demonstrates how different the “optimal light weight” composite structure must look for UAV systems of varied weight, range, and flight maneuverability.
ContributorsBlair, Martin Caceres (Author) / Takahashi, Timothy (Thesis advisor) / Murthy, Raghavendra (Committee member) / Perez, Ruben (Committee member) / Arizona State University (Publisher)
Created2021
Description
Wide bandgap semiconductors are of much current interest due to their superior electrical properties. This dissertation describes electron microscopy characterization of GaN-on-GaN structures for high-power vertical device applications. Unintentionally-doped (UID) GaN layers grown homoepitaxially via metal-organic chemical vapor deposition on freestanding GaN substrates, were subjected to dry etching, and layers of UID-GaN/p-GaN were over-grown. The as-grown and regrown heterostructures were examined in cross-section using transmission electron microscopy (TEM). Two different etching treatments, fast-etch-only and multiple etches with decreasing power, were employed. The fast-etch-only devices showed GaN-on-GaN interface at etched location, and low device breakdown voltages were measured (~ 45-95V). In comparison, no interfaces were visible after multiple etching steps, and the corresponding breakdown voltages were much higher (~1200-1270V). These results emphasized importance of optimizing surface etching techniques for avoiding degraded device performance.
The morphology of GaN-on-GaN devices after reverse-bias electrical stressing to breakdown was investigated. All failed devices had irreversible structural damage, showing large surface craters (~15-35 microns deep) with lengthy surface cracks. Cross-sectional TEM of failed devices showed high densities of threading dislocations (TDs) around the cracks and near crater surfaces. Progressive ion-milling across damaged devices revealed high densities of TDs and the presence of voids beneath cracks: these features were not observed in unstressed devices. The morphology of GaN substrates grown by hydride vapor-phase epitaxy (HVPE) and by ammonothermal methods were correlated with reverse-bias results. HVPE substrates showed arrays of surface features when observed by X-ray topography (XRT). All fabricated devices that overlapped with these features had typical reverse-bias voltages less than 100V at a leakage current limit of 10-6 A. In contrast, devices not overlapping with such features reached voltages greater than 300V. After etching, HVPE substrate surfaces showed defect clusters and macro-pits, whereas XRT images of ammonothermal substrate revealed no visible features. However, some devices fabricated on ammonothermal substrate failed at low voltages. Devices on HVPE and ammonothermal substrates with low breakdown voltages showed crater-like surface damage and revealed TDs (~25µm deep) and voids; such features were not observed in devices reaching higher voltages. These results should assist in developing protocols to fabricate reliable high-voltage devices.
ContributorsPeri, Prudhvi Ram (Author) / Smith, David J. (Thesis advisor) / Alford, Terry (Committee member) / Mccartney, Martha R (Committee member) / Nemanich, Robert (Committee member) / Zhao, Yuji (Committee member) / Arizona State University (Publisher)
Created2021
Description
Two-dimensional (2D) materials have nanometer-scale thickness in one dimension but macroscopic sizes in the other two dimensions and have unique physical and chemical properties that arise from this dimensionality. For example, atomically thin forms of semiconducting materials like transition metal dichalcogenides (TMDs) have attracted significant attention for electric and optical device applications due to their tunable bandgaps. Most 2D materials are derived from layered materials with weak van der Waals (vdW) bonds between layers, but more recently, non-vdW materials with stronger bonds and non-layered structures have also been formed into nanosheets. Because of their aspect ratios, surface chemistry plays a substantial role in both vdW- and non-vdW-derived 2D materials, and involves intercalation and exfoliation, surface modification and functionalization, which contribute to their use in diverse applications. In this thesis, the materials chemistry of nanosheets from both vdW and non-vdW materials has been studied. First, this work demonstrates the covalent functionalization of a new rising 2D material in the TMDs family, palladium diselenide (PdSe2), which has a layer-dependent bandgap and is much more stable in air than many other 2D materials. Aryl diazonium salts were used to functionalize monolayer PdSe2 nanosheets, and the reaction kinetics were studied as a function of reaction time and concentrations. Raman spectroscopy suggests the structure of PdSe2 is undisturbed after functionalization, which will expand its future applications in areas like electronics, sensors, and energy storage.
Next, liquid-phase exfoliation (LPE), an economical, scalable, and efficient method, was used to produce nanosheets of two types of non-vdW materials: metal diborides (MB2) which are a family of ceramic materials with a layered structure, and boron carbide (B4C), a non-layered material with covalent bonding. Quasi-2D nanosheets were formed from eight different metal diborides, with sizes and thicknesses that were found to correlate with the hardness of the bulk compounds. CrB2 nanosheets incorporated into polyvinyl alcohol (PVA) thin films showed enhanced mechanical properties that exceed the specific performance of additives from other 2D materials. Boron carbide, the third hardest known material, has also been successfully exfoliated into ultrathin by LPE. Combined theory and experiment show the rich surface structures of B4C nanosheets.
ContributorsGuo, Yuqi (Author) / Wang, Qing Hua QW (Thesis advisor) / Green, Alexander AG (Committee member) / Jiao, Yang YJ (Committee member) / Arizona State University (Publisher)
Created2021
Description
There is a high demand for customized designs of various types of cement-based materials in order to address specific purposes in the construction field. These demands stem from the need to optimize the cementitious matrix properties and reinforcement choices, especially in high reliability, durability, and performance applications that include infrastructure, energy production, commercial buildings, and may ultimately be extended to low risk/high volume applications such as residential applications. The typical tools required to guide practicing engineers should be based on optimization algorithms that require highly efficient capacity and design alternatives and optimal computational tools. The general case of flexural design of members is an important aspect of design of structural members which can be extended to a variety of applications that include various cross-sections such as rectangular, W-sections, channels, angles, and T sections. The model utilized the simplified linear constitutive response of cement-based composite in compression and tension and extends into a two-segment elastic-plastic, strain softening, hardening, tension-stiffening, and a multi-segment system. The generalized parametric model proposed uses a dimensionless system in the stress-strain materials diagram to formulate piecewise equations for an equilibrium of internal stresses and obtains strain distributions for the closed-form solution of neutral axis location. This would allow for the computation of piecewise moment-curvature response. The number of linear residual stress implemented is flexible to a user to maintain a robust response. In the present approach bilinear, trilinear, and quad-linear models are addressed and a procedure for incorporating additional segments is presented. Moreover, a closed-form solution of moment-curvature can be solved and employed in calculating load-deflection response. The model is adaptable for various types of fiber-reinforced and textile reinforced concrete (FRC, TRC, UHPC, AAC, and Reinforced Concrete). The extensions to cover continuous fiber reinforcement such as textile reinforced concrete (TRC, FRCM) strengthening and repair are addressed. The theoretical model is extended to incorporate the hybrid design (HRC) with continuous rebar with FRC to increase the ductility and ultimate moment capacity. HRC extends the performance of the fiber system to incorporate residual capacity into a serviceability-based design that reduced the reliance on the design based on the limit state. The design chart for HRC and as well as conventional RC has been generated for practicing engineering applications. Results are compared to a large array of data from experimental results conducted at the ASU structural lab facilities and other published literature.
Contributorspleesudjai, chidchanok (Author) / Mobasher, Barzin (Thesis advisor) / Neithalath, Narayanan (Committee member) / Rajan, Subramaniam (Committee member) / Arizona State University (Publisher)
Created2021
Description
Multifunctional oxide thin-films grown on silicon and several oxide substrates have been characterized using High Resolution (Scanning) Transmission Electron Microscopy (HRTEM), Energy-Dispersive X-ray Spectroscopy (EDX), and Electron Energy-Loss Spectroscopy (EELS). Oxide thin films grown on SrTiO3/Si pseudo-substrate showed the presence of amorphised SrTiO3 (STO) at the STO/Si interface. Oxide/oxide interfaces were observed to be atomically clean with very few defects.
Al-doped SrTiO3 thin films grown on Si were of high crystalline quality. The Ti/O ratio estimated from EELS line scans revealed that substitution of Ti by Al created associated O vacancies. The strength of the crystal field in STO was measured using EELS, and decreased by ~1.0 eV as Ti4+ was substituted by Al3+. The damping of O-K EELS peaks confirmed the rise in oxygen vacancies. For Co-substituted STO films grown on Si, the EDS and EELS spectra across samples showed Co doping was quite random. The substitution of Ti4+ with Co3+ or Co2+ created associated oxygen vacancies for charge balance. Presence of oxygen vacancies was also confirmed by shift of Ti-L EELS peaks towards lower energy by ~0.4 eV. The crystal-field strength decreased by ~0.6 eV as Ti4+ was partially substituted by Co3+ or Co2+.
Spinel Co3O4 thin films grown on MgAl2O4 (110) were observed to have excellent crystalline quality. The structure of the Co3O4/MgAl2O4 interface was determined using HRTEM and image simulations. It was found that MgAl2O4 substrate is terminated with Al and oxygen. Stacking faults and associated strain fields in spinel Co3O4 were found along [111], [001], and [113] using Geometrical Phase Analysis.
NbO2 films on STO (111) were observed to be tetragonal with lattice parameter of 13.8 Å and NbO films on LSAT (111) were observed to be cubic with lattice parameter of 4.26 Å. HRTEM showed formation of high quality NbOx films and excellent coherent interface. HRTEM of SrAl4 on LAO (001) confirmed an island growth mode. The SrAl4 islands were highly crystalline with excellent epitaxial registry with LAO. By comparing HRTEM images with image simulations, the interface structure was determined to consist of Sr-terminated SrAl4 (001) on AlO2-terminated LAO (001).
Al-doped SrTiO3 thin films grown on Si were of high crystalline quality. The Ti/O ratio estimated from EELS line scans revealed that substitution of Ti by Al created associated O vacancies. The strength of the crystal field in STO was measured using EELS, and decreased by ~1.0 eV as Ti4+ was substituted by Al3+. The damping of O-K EELS peaks confirmed the rise in oxygen vacancies. For Co-substituted STO films grown on Si, the EDS and EELS spectra across samples showed Co doping was quite random. The substitution of Ti4+ with Co3+ or Co2+ created associated oxygen vacancies for charge balance. Presence of oxygen vacancies was also confirmed by shift of Ti-L EELS peaks towards lower energy by ~0.4 eV. The crystal-field strength decreased by ~0.6 eV as Ti4+ was partially substituted by Co3+ or Co2+.
Spinel Co3O4 thin films grown on MgAl2O4 (110) were observed to have excellent crystalline quality. The structure of the Co3O4/MgAl2O4 interface was determined using HRTEM and image simulations. It was found that MgAl2O4 substrate is terminated with Al and oxygen. Stacking faults and associated strain fields in spinel Co3O4 were found along [111], [001], and [113] using Geometrical Phase Analysis.
NbO2 films on STO (111) were observed to be tetragonal with lattice parameter of 13.8 Å and NbO films on LSAT (111) were observed to be cubic with lattice parameter of 4.26 Å. HRTEM showed formation of high quality NbOx films and excellent coherent interface. HRTEM of SrAl4 on LAO (001) confirmed an island growth mode. The SrAl4 islands were highly crystalline with excellent epitaxial registry with LAO. By comparing HRTEM images with image simulations, the interface structure was determined to consist of Sr-terminated SrAl4 (001) on AlO2-terminated LAO (001).
ContributorsDhamdhere, Ajit (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha R. (Committee member) / Chamberlin, Ralph (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2015
Description
Biogenic silica nanostructures, derived from diatoms, possess highly ordered porous hierarchical nanostructures and afford flexibility in design in large part due to the availability of a great variety of shapes, sizes, and symmetries. These advantages have been exploited for study of transport phenomena of ions and molecules towards the goal of developing ultrasensitive and selective filters and biosensors. Diatom frustules give researchers many inspiration and ideas for the design and production of novel nanostructured materials. In this doctoral research will focus on the following three aspects of biogenic silica: 1) Using diatom frustule as protein sensor. 2) Using diatom nanostructures as template to fabricate nano metal materials. 3) Using diatom nanostructures to fabricate hybrid platform.
Nanoscale confinement biogenetic silica template-based electrical biosensor assay offers the user the ability to detect and quantify the biomolecules. Diatoms have been demonstrated as part of a sensor. The sensor works on the principle of electrochemical impedance spectroscopy. When specific protein biomarkers from a test sample bind to corresponding antibodies conjugated to the surface of the gold surface at the base of each nanowell, a perturbation of electrical double layer occurs resulting in a change in the impedance.
Diatoms are also a new source of inspiration for the design and fabrication of nanostructured materials. Template-directed deposition within cylindrical nanopores of a porous membrane represents an attractive and reproducible approach for preparing metal nanopatterns or nanorods of a variety of aspect ratios. The nanopatterns fabricated from diatom have the potential of the metal-enhanced fluorescence to detect dye-conjugated molecules.
Another approach presents a platform integrating biogenic silica nanostructures with micromachined silicon substrates in a micro
ano hybrid device. In this study, one can take advantages of the unique properties of a marine diatom that exhibits nanopores on the order of 40 nm in diameter and a hierarchical structure. This device can be used to several applications, such as nano particles separation and detection. This platform is also a good substrate to study cell growth that one can observe the reaction of cell growing on the nanostructure of frustule.
Nanoscale confinement biogenetic silica template-based electrical biosensor assay offers the user the ability to detect and quantify the biomolecules. Diatoms have been demonstrated as part of a sensor. The sensor works on the principle of electrochemical impedance spectroscopy. When specific protein biomarkers from a test sample bind to corresponding antibodies conjugated to the surface of the gold surface at the base of each nanowell, a perturbation of electrical double layer occurs resulting in a change in the impedance.
Diatoms are also a new source of inspiration for the design and fabrication of nanostructured materials. Template-directed deposition within cylindrical nanopores of a porous membrane represents an attractive and reproducible approach for preparing metal nanopatterns or nanorods of a variety of aspect ratios. The nanopatterns fabricated from diatom have the potential of the metal-enhanced fluorescence to detect dye-conjugated molecules.
Another approach presents a platform integrating biogenic silica nanostructures with micromachined silicon substrates in a micro
ano hybrid device. In this study, one can take advantages of the unique properties of a marine diatom that exhibits nanopores on the order of 40 nm in diameter and a hierarchical structure. This device can be used to several applications, such as nano particles separation and detection. This platform is also a good substrate to study cell growth that one can observe the reaction of cell growing on the nanostructure of frustule.
ContributorsLin, Kai-Chun (Author) / Ramakrishna, B.L. (Thesis advisor) / Goryll, Michael (Thesis advisor) / Dey, Sandwip (Committee member) / Prasad, Shalini (Committee member) / Arizona State University (Publisher)
Created2014