Thesis (M.Phil.)--Hong Kong University of Science and Technology, 2005. / Includes bibliographical references (leaves 69-70). Also available in electronic version.

Thesis (Ph. D.)--West Virginia University, 2001. / Title from document title page. Document formatted into pages; contains xvi, 217, 2 p. : ill. (some col.). Vita. Includes abstract. Includes bibliographical references (p. 198-207).

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This thesis mainly aims at application of principles of engineering technology in the field of molecular beam epitaxy (MBE). MBE is a versatile technique for growing epitaxial thin films of semiconductors and metals by impinging molecular beams of atoms onto a heated substrate under ultra-high vacuum (UHV) conditions. Here, a LabVIEW® (laboratory virtual instrument engineering workbench) software (National Instruments Corp., http://www.ni.com/legal/termsofuse/unitedstates/usH) program is developed that would form the basis of a real-time control system that would transform MBE into a true-production technology. Growth conditions can be monitored in real-time with the help of reflection high energy electron diffraction (RHEED) technique. The period of one RHEED oscillation corresponds exactly to the growth of one monolayer of atoms of the semiconductor material. The PCI-1409 frame grabber card supplied by National Instruments is used in conjunction with the LabVIEW software to capture the RHEED images and capture the intensity of RHEED oscillations. The intensity values are written to a text file and plotted in the form of a graph. A fast Fourier transform of these oscillations gives the growth rate of the epi-wafer being grown. All the data being captured by the LabVIEW program can be saved to file forming a growth pedigree for future use. Unattended automation can be achieved by designing a control system that monitors the growth in real-time and compares it with the data recorded from the LabVIEW program from the previous growth and adjusts the growth parameters automatically thereby growing accurate device structures.

Semi-conductor industry relies heavily on silicon (Si). However, Si is not a direct-band gap semi-conductor. Consequently, Si does not possess great versatility for multi-functional applications in comparison with the direct band-gap III-V semi-conductors such as GaAs. To bridge this gap, what is ideally required is a semi-conductor material system that is based on silicon, but has significantly greater versatility. While sparsely studied, the semi-conducting silicides material systems offer great potential. Thus, I focused on the growth and structural characterization of ruthenium silicide and osmium silicide material systems. I also characterized iron silicon germanide films using extended x-ray absorption fine structure (EXAFS) to reveal phase, semi-conducting behavior, and to calculate nearest neighbor distances. The choice of these silicides material systems was due to their theoretically predicted and/or experimentally reported direct band gaps. However, the challenge was the existence of more than one stable phase/stoichiometric ratio of these materials. In order to possess the greatest control over the growth process, molecular beam epitaxy (MBE) has been employed. Structural and film quality comparisons of as-grown versus annealed films of ruthenium silicide are presented. Structural characterization and film quality of MBE grown ruthenium silicide and osmium silicide films via in situ and ex situ techniques have been done using reflection high energy electron diffraction, scanning tunneling microscopy, atomic force microscopy, cross-sectional scanning electron microscopy, x-ray photoelectron spectroscopy, and micro Raman spectroscopy. This is the first attempt, to the best of our knowledge, to grow osmium silicide thin films on Si(100) via the template method and compare it with the regular MBE growth method. The pros and cons of using the MBE template method for osmium silicide growth are discussed, as well as the structural differences of the as-grown versus annealed films. Future perspectives include further studies on other semi-conducting silicides material systems in terms of growth optimization and characterization.

III-Nitride materials, which consist of AlN, GaN, InN, and their alloys have become the cornerstone of the third generation compound semiconductor. Planar IIINitride materials are commonly grown on sapphire substrates which impose several limitations such as challenging scalability, rigid substrate, and thermal and lattice mismatch between substrate and material. Semiconductor nanowires can help circumvent this problem because of their inherent capability to relieve strain and grow threading dislocation-free without strict lattice matching requirements, enabling growth on unconventional substrates. This thesis aims to investigate the microscopic characteristics of the nanowires and expand on the possibility of using transparent amorphous substrate for III-nitride nanowire devices. In this work, we performed material growth, characterization, and device fabrication of III-nitride nanowires grown using molecular beam epitaxy on unconventional substrates. We first studied the structural imperfections within quantum-disks-in-nanowire structure grown on silicon and discovered how growth condition could affect the macroscopic photoluminescence behavior of nanowires ensemble. To expand our work on unconventional substrates, we also used an amorphous silica-based substrate as a more economical substrate for our nanowire growth. One of the limitations of growing nanowires on an insulating substrate is the added fabrication complexity required to fabricate a working device. Therefore, we attempted to overcome this limitation by 5 investigating various possible GaN nanowire nucleation layers, which exhibits both transparency and conductivity. We employed various nucleation layers, including a thin TiN/Ti layer, indium tin oxide (ITO), and Ti3C2 MXene. The structural, electrical, and optical characterizations of nanowires grown on different nucleation layers are discussed. From our work, we have established several key processes for transparent nanowire device applications. A nanowire LED emitting at ∼590 nm utilizing TiN/Ti interlayer is presented. We have also established the growth process for n-doped GaN nanowires grown on ITO and Ti3C2 MXene with transmittance above 40 % in the visible wavelength, which is useful for practical applications. This work paves the way for future devices utilizing low-cost substrates, enabling further cost reduction in III-nitride device fabrication.

archives@tulane.edu / A cold molecular beam approach has been pioneered to investigate the pyrolysis reactions of triglycerides (TGs) as a function of temperature. Traditionally, an established repertoire of laser techniques is utilized for multiple species present, which has been extensively used for a detailed study of specifically targeted species that are often novel and reactive. Instead, we have applied these methods for the mass characterization of numerous product species as they appeared. Unlike traditional batch reactor studies of pyrolysis, where terminal products are identified and characterized generally using GC/MS methods, herein, product analysis was conducted in real time. Experiments were performed by recording mass spectra as a function of increasing sample temperature. For clearer results and interpretation, most studies employed model TGs containing a single fatty acid, such as oleic or stearic acid. Soft photoionization was conducted using 118 and 266 nm laser-based pulses. Time-of-flight mass spectroscopy (TOF-MS) was conducted after each photoionization pulse. Several novel direct observations include 1) the observation of initial cracking temperatures and the formation of non-aromatic and aromatic products; 2) the determination of key factors for pyrolysis—fatty acid detachment from the glycerol backbone and subsequent fatty acid pyrolysis; 3) the growth of C6 and C7 fragments as an important precursor for following association reactions. The use of 266 nm pulses exclusively facilitated the sensitive and selective photoionization of aromatic products and, thus, the thorough examination of the evolving aromatic products. Unlike the batch reactor studies of terminal products, the molecular beam studies of aromatic products revealed the evolution to a small number of selective and relatively massive polycyclic aromatic hydrocarbons (PAH). It is deduced that in a batch reactor, these undetected products ultimately lead to solids and tars that are difficult to analyze. Our investigation revealed that hydrogen addition showed some effectiveness in inhibiting formation of large / 1 / Ibrahi M. Alhroob

GaAs nanowires (NW) have been grown on Si (111) substrates by the self-assisted vapor-liquid-solid (VLS) mechanism using molecular beam epitaxy (MBE). Substrates were prepared with nano-patterned oxide templates using electron beam lithography (EBL) in order to achieve position controlled NW growth. Early experiments uncovered several key issues with regards to the patterning process. Cross-sectional lamella prepared using the focused-ion beam (FIB) technique were used to study the NW-substrate interface using transmission electron microscopy (TEM). Undesirable growth outcomes were found to be caused in part by an unintended residual layer of oxide. Uniform NW dimensions were then obtained by improving the pattern transfer method. The effects of deposition parameters on the growth results were then explored in further experiments. The first systematic study of the axial and radial growth rates of vertical NWs in the positioned array was conducted. It was proposed that the observed expansion of the Ga droplet in Ga-rich growth conditions results in a slight inverse tapered morphology, promoting significant radial growth. While the growth rates were shown to be approximately constant in time, their measured values were found to increase with increasing pattern pitch and decrease with increasing hole diameter. A phenomenological model was then developed based on the principle of mass conservation. A fit to the experimental data was obtained by calculating the collection of growth material supplied by a secondary flux of both gallium and arsenic species desorbing from the oxide surface between the NWs, subsequently impinging on the liquid droplet and NW sidewalls. The reduction of this contribution due to shading of the incident and scattered flux by neighboring NWs in the array was able to account for the differences in final NW morphologies observed with increasing pattern pitch. This model demonstrates the significant impact of secondary adsorption in patterned self-assisted NW growth. / Thesis / Doctor of Science (PhD)

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