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Description
Silicon nanowires were grown epitaxially on Si (100) and (111) surfaces using the Vapor-Liquid-Solid (VLS) mechanism under both thermal and plasma enhanced growth conditions. Nanowire morphology was investigated as a function of temperature, time, disilane partial pressure and substrate preparation. Silicon nanowires synthesized in low temperature plasma typically curved compared

Silicon nanowires were grown epitaxially on Si (100) and (111) surfaces using the Vapor-Liquid-Solid (VLS) mechanism under both thermal and plasma enhanced growth conditions. Nanowire morphology was investigated as a function of temperature, time, disilane partial pressure and substrate preparation. Silicon nanowires synthesized in low temperature plasma typically curved compared to the linear nanowires grown under simple thermal conditions. The nanowires tended bend more with increasing disilane partial gas pressure up to 25 x10-3 mTorr. The nanowire curvature measured geometrically is correlated with the shift of the main silicon peak obtained in Raman spectroscopy. A mechanistic hypothesis was proposed to explain the bending during plasma activated growth. Additional driving forces related to electrostatic and Van der Waals forces were also discussed. Deduced from a systematic variation of a three-step experimental protocol, the mechanism for bending was associated with asymmetric deposition rate along the outer and inner wall of nanowire. The conditions leading to nanowire branching were also examined using a two-step growth process. Branching morphologies were examined as a function of plasma powers between 1.5 W and 3.5 W. Post-annealing thermal and plasma-assisted treatments in hydrogen were compared to understand the influences in the absence of an external silicon source (otherwise supplied by disilane). Longer and thicker nanowires were associated with longer annealing times due to an Ostwald-like ripening effect. The roles of surface diffusion, gas diffusion, etching and deposition rates were examined.
ContributorsJoun, Hee-Joung (Author) / Petuskey, William T. (Thesis advisor) / Drucker, Jeff (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Ge1-ySny alloys represent a new class of photonic materials for integrated optoelectronics on Si. In this work, the electrical and optical properties of Ge1-ySny alloy films grown on Si, with concentrations in the range 0 ≤ y ≤ 0.04, are studied via a variety of methods. The first microelectronic devices

Ge1-ySny alloys represent a new class of photonic materials for integrated optoelectronics on Si. In this work, the electrical and optical properties of Ge1-ySny alloy films grown on Si, with concentrations in the range 0 ≤ y ≤ 0.04, are studied via a variety of methods. The first microelectronic devices from GeSn films were fabricated using newly developed CMOS-compatible protocols, and the devices were characterized with respect to their electrical properties and optical response. The detectors were found to have a detection range that extends into the near-IR, and the detection edge is found to shift to longer wavelengths with increasing Sn content, mainly due to the compositional dependence of the direct band gap E0. With only 2 % Sn, all of the telecommunication bands are covered by a single detector. Room temperature photoluminescence was observed from GeSn films with Sn content up to 4 %. The peak wavelength of the emission was found to shift to lower energies with increasing Sn content, corresponding to the decrease in the direct band gap E0 of the material. An additional peak in the spectrum was assigned to the indirect band gap. The separation between the direct and indirect peaks was found to decrease with increasing Sn concentration, as expected. Electroluminescence was also observed from Ge/Si and Ge0.98Sn0.02 photodiodes under forward bias, and the luminescence spectra were found to match well with the observed photoluminescence spectra. A theoretical expression was developed for the luminescence due to the direct band gap and fit to the data.
ContributorsMathews, Jay (Author) / Menéndez, Jose (Thesis advisor) / Kouvetakis, John (Thesis advisor) / Drucker, Jeffery (Committee member) / Chizmeshya, Andrew (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2011
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Description
This thesis describes the fabrication of several new classes of Ge1-x-ySixSny materials with the required compositions and crystal quality to engineer the band gaps above and below that of elemental Ge (0.8 eV) in the near IR. The work initially focused on Ge1-x-ySixSny (1-5% Sn, 4-20% Si) materials grown on

This thesis describes the fabrication of several new classes of Ge1-x-ySixSny materials with the required compositions and crystal quality to engineer the band gaps above and below that of elemental Ge (0.8 eV) in the near IR. The work initially focused on Ge1-x-ySixSny (1-5% Sn, 4-20% Si) materials grown on Ge(100) via gas-source epitaxy of Ge4H10, Si4H10 and SnD4. Both intrinsic and doped layers were produced with defect-free microstructure and viable thickness, allowing the fabrication of high-performance photodetectors. These exhibited low ideality factors, state-of-the-art dark current densities and adjustable absorption edges between 0.87 and 1.03 eV, indicating that the band gaps span a significant range above that of Ge. Next Sn-rich Ge1-x-ySixSny alloys (2-4% Si and 4-10% Sn) were fabricated directly on Si and were found to show significant optical emission using photoluminescence measurements, indicating that the alloys have direct band gaps below that of pure Ge in the range of 0.7-0.55 eV. A series of Sn-rich Ge1-x-ySixSny analogues (y>x) with fixed 3-4% Si content and progressively increasing Sn content in the 4-10% range were then grown on Ge buffered Si platforms for the purpose of improving the material's crystal quality. The films in this case exhibited lower defect densities than those grown on Si, allowing a meaningful study of both the direct and indirect gaps. The results show that the separation of the direct and indirect edges can be made smaller than in Ge even for non-negligible 3-4% Si content, confirming that with a suitable choice of Sn compositions the ternary Ge1-x-ySixSny reproduces all features of the electronic structure of binary Ge1-ySny, including the sought-after indirect-to-direct gap cross over. The above synthesis of optical quality Ge1-x-ySixSny on virtual Ge was made possible by the development of high quality Ge-on-Si buffers via chemical vapor deposition of Ge4H10. The resultant films exhibited structural and electrical properties significantly improved relative to state-of-the-art results obtained using conventional approaches. It was found that pure Ge4H10 facilitates the control of residual doping and enables p-i-n devices whose dark currents are not entirely determined by defects and whose zero-bias collection efficiencies are higher than those obtained from samples fabricated using alternative Ge-on-Si approaches.
ContributorsXu, Chi (Author) / Kouvetakis, John (Thesis advisor) / Menéndez, Jose (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Drucker, Jeffrey (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2013
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Description
The thesis studies new methods to fabricate optoelectronic Ge1-ySny/Si(100) alloys and investigate their photoluminescence (PL) properties for possible applications in Si-based photonics including IR lasers. The work initially investigated the origin of the difference between the PL spectrum of bulk Ge, dominated by indirect gap emission, and the PL spectrum

The thesis studies new methods to fabricate optoelectronic Ge1-ySny/Si(100) alloys and investigate their photoluminescence (PL) properties for possible applications in Si-based photonics including IR lasers. The work initially investigated the origin of the difference between the PL spectrum of bulk Ge, dominated by indirect gap emission, and the PL spectrum of Ge-on-Si films, dominated by direct gap emission. It was found that the difference is due to the supression of self-absorption effects in Ge films, combined with a deviation from quasi-equilibrium conditions in the conduction band of undoped films. The latter is confirmed by a model suggesting that the deviation is caused by the shorter recombination lifetime in the films relative to bulk Ge. The knowledge acquired from this work was then utilized to study the PL properties of n-type Ge1-ySny/Si (y=0.004-0.04) samples grown via chemical vapor deposition of Ge2H6/SnD4/P(GeH3)3. It was found that the emission intensity (I) of these samples is at least 10x stronger than observed in un-doped counterparts and that the Idir/Iind ratio of direct over indirect gap emission increases for high-Sn contents due to the reduced gamma-L valley separation, as expected. Next the PL investigation was expanded to samples with y=0.05-0.09 grown via a new method using the more reactive Ge3H8 in place of Ge2H6. Optical quality, 1-um thick Ge1-ySny/Si(100) layers were produced using Ge3H10/SnD4 and found to exhibit strong, tunable PL near the threshold of the direct-indirect bandgap crossover. A byproduct of this study was the development of an enhanced process to produce Ge3H8, Ge4H10, and Ge5H12 analogs for application in ultra-low temperature deposition of Group-IV semiconductors. The thesis also studies synthesis routes of an entirely new class of semiconductor compounds and alloys described by Si5-2y(III-V)y (III=Al, V= As, P) comprising of specifically designed diamond-like structures based on a Si parent lattice incorporating isolated III-V units. The common theme of the two thesis topics is the development of new mono-crystalline materials on ubiquitous silicon platforms with the objective of enhancing the optoelectronic performance of Si and Ge semiconductors, potentially leading to the design of next generation optical devices including lasers, detectors and solar cells.
ContributorsGrzybowski, Gordon (Author) / Kouvetakis, John (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Menéndez, Jose (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Group IV alloy films exhibit the ability to tune both band structure and lattice parameters and have recently attracted attention for their potential applications in Si-photonics and photovoltaics. In this work, several new approaches to produce these alloys directly on Si(100) and Ge(100) wafers are developed. For photovoltaics, use of

Group IV alloy films exhibit the ability to tune both band structure and lattice parameters and have recently attracted attention for their potential applications in Si-photonics and photovoltaics. In this work, several new approaches to produce these alloys directly on Si(100) and Ge(100) wafers are developed. For photovoltaics, use of Ge-buffered Si(100) wafers as a low cost platform for epitaxy of In1-xGaxAs layers was explored. The results indicate that this approach has promise for transitioning from bulk Ge platforms to virtual substrates for a significant cost reduction. The electrical and optical properties of Ge and Ge1-ySny layers produced using several different techniques were explored via fabrication of high performance heterostructure photodiodes. First, a new CVD approach to Ge-like materials was developed in which germanium is alloyed with very small amounts of tin. These alloys exhibited no significant difference in their structural properties or band gap compared to pure Ge, however superior photo response and reduced dark currents were observed from fabricated devices relative to pure Ge on Si reference diodes. Additionally, pure Ge/Si(100) photodiodes were fabricated using layers grown via reactions of Ge4H10 on Si(100) and found to exhibit low dark current densities with high collection efficiencies. Ge1-x-ySixSny materials represent the newest member of group IV alloy family. The ability to decouple the lattice constant and the band gap in this system has led to strong interest both for strain/confinement layers in quantum well structures, and as the possible "missing" 1 eV junction in multijunction photovoltaics. Recent progress in this field has allowed for the first time growth, fabrication and measurement of novel photodiodes based on Ge1-x-ySixSny. This work presents the material, electrical and optical properties of Ge1-x-ySixSny layers and photodiodes grown directly on Ge and Si wafers using two different synthetic approaches. A series of photodiodes containing Sn concentrations from 1-5%, all lattice matched to Ge, was fabricated. The devices exhibited low dark current densities with high collection efficiencies as required for photovoltaics. By measuring the photoresponse, tunable band gaps ranging from 0.85 eV to 1.02 eV were observed.
ContributorsBeeler, Richard (Author) / Kouvetakis, John (Thesis advisor) / Menéndez, Jose (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2012
Description
The study of the mechanical behavior of nanocrystalline metals using microelectromechanical systems (MEMS) devices lies at the intersection of nanotechnology, mechanical engineering and material science. The extremely small grains that make up nanocrystalline metals lead to higher strength but lower ductility as compared to bulk metals. Effects of strain-rate dependence

The study of the mechanical behavior of nanocrystalline metals using microelectromechanical systems (MEMS) devices lies at the intersection of nanotechnology, mechanical engineering and material science. The extremely small grains that make up nanocrystalline metals lead to higher strength but lower ductility as compared to bulk metals. Effects of strain-rate dependence on the mechanical behavior of nanocrystalline metals are explored. Knowing the strain rate dependence of mechanical properties would enable optimization of material selection for different applications and lead to lighter structural components and enhanced sustainability.
ContributorsHall, Andrea Paulette (Author) / Rajagopalan, Jagannathan (Thesis director) / Liao, Yabin (Committee member) / Barrett, The Honors College (Contributor) / Mechanical and Aerospace Engineering Program (Contributor)
Created2014-05
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Description
This paper investigates Surface Mechanical Attrition Treatment (SMAT) and the influence of treatment temperature and initial sample surface finish on the corrosion resistance of 7075-T651 aluminum alloy. Ambient SMAT was performed on AA7075 samples polished to 80-grit initial surface roughness. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) tests were used

This paper investigates Surface Mechanical Attrition Treatment (SMAT) and the influence of treatment temperature and initial sample surface finish on the corrosion resistance of 7075-T651 aluminum alloy. Ambient SMAT was performed on AA7075 samples polished to 80-grit initial surface roughness. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) tests were used to characterize the corrosion behavior of samples before and after SMAT. Electrochemical tests indicated an improved corrosion resistance after application of SMAT process. The observed improvements in corrosion properties are potentially due to microstructural changes in the material surface induced by SMAT which encouraged the formation of a passive oxide layer. Further testing and research are required to understand the corrosion related effects of cryogenic SMAT and initial-surface finish as the COVID-19 pandemic inhibited experimentation plans.
ContributorsDeorio, Jordan Anthony (Author) / Solanki, Kiran (Thesis director) / Rajagopalan, Jagannathan (Committee member) / Mechanical and Aerospace Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05
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Description
In materials science, developing GeSn alloys is major current research interest concerning the production of efficient Group-IV photonics. These alloys are particularly interesting because the development of next-generation semiconductors for ultrafast (terahertz) optoelectronic communication devices could be accomplished through integrating these novel alloys with industry-standard silicon technology. Unfortunately, incorporating a

In materials science, developing GeSn alloys is major current research interest concerning the production of efficient Group-IV photonics. These alloys are particularly interesting because the development of next-generation semiconductors for ultrafast (terahertz) optoelectronic communication devices could be accomplished through integrating these novel alloys with industry-standard silicon technology. Unfortunately, incorporating a maximal amount of Sn into a Ge lattice has been difficult to achieve experimentally. At ambient conditions, pure Ge and Sn adopt cubic (α) and tetragonal (β) structures, respectively, however, to date the relative stability and structure of α and β phase GeSn alloys versus percent composition Sn has not been thoroughly studied. In this research project, computational tools were used to perform state-of-the-art predictive quantum simulations to study the structural, bonding and energetic trends in GeSn alloys in detail over a range of experimentally accessible compositions. Since recent X-Ray and vibrational studies have raised some controversy about the nanostructure of GeSn alloys, the investigation was conducted with ordered, random and clustered alloy models.
By means of optimized geometry analysis, pure Ge and Sn were found to adopt the alpha and beta structures, respectively, as observed experimentally. For all theoretical alloys, the corresponding αphase structure was found to have the lowest energy, for Sn percent compositions up to 90%. However at 50% Sn, the correspondingβ alloy energies are predicted to be only ~70 meV higher. The formation energy of α-phase alloys was found to be positive for all compositions, whereas only two beta formation energies were negative. Bond length distributions were analyzed and dependence on Sn incorporation was found, perhaps surprisingly, not to be directly correlated with cell volume. It is anticipated that the data collected in this project may help to elucidate observed complex vibrational properties in these systems.
ContributorsLiberman-Martin, Zoe Elise (Author) / Chizmeshya, Andrew (Thesis director) / Sayres, Scott (Committee member) / Wolf, George (Committee member) / School of Mathematical and Statistical Sciences (Contributor) / School of Molecular Sciences (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05
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Description
Achieving a viable process for advanced manufacturing of ceramics and metal-ceramic composites is a sought-after goal in a wide range of fields including electronics and sensors for harsh environments, microelectromechanical devices, energy storage materials, and structural materials, among others. In this dissertation, the processing, and manufacturing of ceramics and ceramic

Achieving a viable process for advanced manufacturing of ceramics and metal-ceramic composites is a sought-after goal in a wide range of fields including electronics and sensors for harsh environments, microelectromechanical devices, energy storage materials, and structural materials, among others. In this dissertation, the processing, and manufacturing of ceramics and ceramic composites are addressed, specifically, a process for three-dimensional (3D) printing of polymer-derived ceramics (PDC), and a process for low-cost manufacturing as well as healing of metal-ceramic composites is demonstrated.Three-dimensional printing of ceramics is enabled by dispensing the preceramic polymer at the tip of a moving nozzle into a gel that can reversibly switch between fluid and solid states, and subsequently thermally cross-linking the entire printed part “at once” while still inside the same gel was demonstrated. The solid gel converts to fluid at the tip of the moving nozzle, allowing the polymer solution to be dispensed and quickly returns to a solid state to maintain the geometry of the printed polymer both during printing and the subsequent high-temperature (160 °C) cross-linking. After retrieving the cross-linked part from the gel, the green body is converted to ceramic by high-temperature pyrolysis. This scalable process opens new opportunities for low-cost and high-speed production of complex three-dimensional ceramic parts and will be widely used for high-temperature and corrosive environment applications, including electronics and sensors, microelectromechanical systems, energy, and structural applications. Metal-ceramic composites are technologically significant as structural and functional materials and are among the most expensive materials to manufacture and repair. Hence, technologies for self-healing metal-ceramic composites are important. Here, a concept to fabricate and heal co-continuous metal-ceramic composites at room temperature were demonstrated. The composites were fabricated by infiltration of metal (here Copper) into a porous alumina preform (fabricated by freeze-casting) through electroplating; a low-temperature and low-cost process for the fabrication of such composites. Additionally, the same electroplating process was demonstrated for healing damages such as grooves and cracks in the original composite, such that the healed composite recovered its strength by more than 80%. Such technology may be expanded toward fully autonomous self-healing structures.
ContributorsMahmoudi, Mohammadreza (Author) / Minary-Jolandan, Majid (Thesis advisor) / Rajagopalan, Jagannathan (Committee member) / Cramer, Corson (Committee member) / Kang, Wonmo (Committee member) / Bhate, Dhruv (Committee member) / Arizona State University (Publisher)
Created2022
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Description
This thesis presents a study of Boron Nitride (BN) and Copper (Cu)/BN multilayer thin films in terms of synthesis, chemical, structural, morphological, and mechanical properties characterization. In this study, the influence of Ar/N₂ flow rate in synthesizing stoichiometric BN thin films via magnetron sputtering was investigated initially. Post magnetron

This thesis presents a study of Boron Nitride (BN) and Copper (Cu)/BN multilayer thin films in terms of synthesis, chemical, structural, morphological, and mechanical properties characterization. In this study, the influence of Ar/N₂ flow rate in synthesizing stoichiometric BN thin films via magnetron sputtering was investigated initially. Post magnetron sputtering, the crystalline nature and B:N stoichiometric ratio of deposited thin films were investigated by X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) respectively. Thicknesses revealed by ellipsometry analysis for nearly stoichiometric B:N thin films and their corresponding deposition times were used for estimating BN interlayer deposition times during the deposition of Cu/BN multilayer thin films. To characterize the microstructure of the synthesized Cu/BN multilayer thin films, XRD and scanning electron microscopy (SEM) have been used. Finally, a comparison of nanoindentation measurements on pure Cu and Cu/BN multilayer thin films having different number of BN interlayers were used for studying the influence of BN interlayers on improving mechanical properties such as hardness and elastic modulus. The results show that the stoichiometry of BN thin films is dependent on the Ar/N₂ flow rate during magnetron sputtering. An optimal Ar/N₂ flow rate of 13:5 during deposition was required to achieve an approximately 1:1 B:N stoichiometry. Grazing incidence and powder XRD analysis on these stoichiometric BN thin films deposited at room temperature did not reveal a phase match when compared to hexagonal boron nitride (h-BN) and cubic boron nitride (c-BN) reference XRD patterns. For a BN thin film deposition time of 5 hours, a thickness of approximately 40 nm was achieved, as revealed by ellipsometry. XRD and microstructure analysis using scanning electron microscopy (SEM) on pure Cu and Cu/BN thin films showed that the Cu grain size in Cu/BN thin films is much finer than pure Cu thin films. Interestingly, nanoindentation measurements on pure Cu and Cu/BN thin films having a similar overall thickness demonstrated that hardness and Young’s modulus of the films were improved significantly when BN interlayers are present.
ContributorsCaner, Sumeyye (Author) / Rajagopalan, Jagannathan (Thesis advisor) / Oswald, Jay (Committee member) / Solanki, Kiran (Committee member) / Arizona State University (Publisher)
Created2023