The Virtual Chemical Vapor Deposition (CVD) Process Development Project provides the context for the two areas of the research presented in this dissertation. The first area, generally referred to as feedback in this dissertation, focuses on student learning and the interactions of students and instructors that take place in the project, specifically focused on characterizing feedback and determining the influence of feedback as student teams progress towards completing the project. The characteristics of feedback found in this project are presented within a situative perspective using the analytical framework of episodes. The characteristics include: a list and categorization of episode themes, the structure and flow of episodes during the coaching session, the sub-structure present within individual episodes, and the types of feedback present. This dissertation shows how these characteristics frame participation in a community of practice and can be used as tools to scaffold instructor feedback in project-based learning. Episodes analysis is also used to investigate how feedback on professional skills can help to enculturate students into a community of practice and influence their fluency with professional skills and engagement in more technical activities. The second area examines the spread of this innovative project from its home institution to other institutions. In this area an analysis of the spread of the Virtual CVD Process Development Project in the high school setting is presented. The project was found to provide versatility for instructors and afford student learning in the areas of motivation, cognition, and epistemological beliefs. These two areas inform each other. As the project is assessed at different institutions, it is continually improved and the sensitivity of different aspects of the project is explored, e.g., the aspects of the project that are crucial to maintain effectiveness are identified. One of these aspects is the feedback that takes place in the project. As the project is further examined at the home institution in depth, more can be learned about the best ways it can be delivered. This information informs scaffolding that then can be provided to faculty at other institutions such that they can attend to crucial aspects of the project in the most efficient, effective manner, improving not only the probability of successful adaptation, but also the likelihood that the project will further diffuse to other institutions. / Graduation date: 2013

The objective of this dissertation is to shed light on the physical properties of InN epilayers grown by High-Pressure Chemical Vapor Deposition (HPCVD) for optical device applications. Physical properties of HPCVD grown InN layers were investigated by X-ray diffraction, Raman scattering, infrared reflection spectroscopies, and atomic force microscopy. The dependencies of physical properties as well as surface morphologies of InN layers grown either directly on sapphire substrates or on GaN/sapphire templates on varied growth conditions were studied. The effect of crucial growth parameters such as growth pressure, V/III molar ratio, precursor pulse separation, substrate material, and mass transport along the flow direction on the optical and structural properties, as well as on the surface morphologies were investigated separately. At present, growth of high-quality InN material by conventional growth techniques is limited due to low dissociation temperature of InN (~600 ºC) and large difference in the partial pressures of TMI and NH3 precursors. In this research, HPCVD technique, in which ambient nitrogen is injected into reaction zone at super-atmospheric growth pressures, was utilized to suppress surface dissociation of InN at high temperatures. At high pressures, long-range and short-range orderings indicate that c-lattice constant is shorter and E2(high) mode frequency is higher than those obtained from low-pressure growth techniques, revealing that InN structure compressed either due to a hydrostatic pressure during the growth or thermal contraction during the annealing. Although the influence of varied growth parameters usually exhibit consistent correlation between long-range and short-range crystalline orderings, inconsistent correlation of these indicate inclination of InN anisotropy. InN layers, grown directly on α-sapphire substrates, exhibit InN (1 0 1) Bragg reflex. This might be due to a high c/a ratio of sapphire-grown InN epilayers compared to that of GaN/sapphire-grown InN epilayers. Optical analysis indicates that free carrier concentration, ne, in the range of 1–50 × 1018 cm–3 exhibits consistent tendency with longitudinal-optic phonon. However, for high ne values, electrostatic forces dominate over inter-atomic forces, and consistent tendency between ne and LO phonon disappears. Structural results reveal that growth temperature increases ~6.6 ºC/bar and V/III ratio affects indium migration and/or evaporation. The growth temperature and V/III ratio of InN thin films are optimized at ~850 ºC and 2400 molar ratio, respectively. Although high in-plane strain and c/a ratio values are obtained for sapphire-grown epilayers, FWHM values of long-range and short-range orderings and free carrier concentration value are still lower than those of GaN/sapphire-grown epilayers. Finally, vibrational and optical properties of chalcopyrite ZGP crystal on the (001), (110), and (10) crystalline planes were investigated by Raman scattering and infrared (IR) reflection spectroscopies. Raman scattering exhibits a nonlinear polarizability on the c-plane, and a linear polarizability on the a- and b-planes of ZGP crystal. Also, birefringence of ZGP crystal was calculated from the hydrostatic pressure difference between (110) and (10) crystalline planes for mid-frequency B2(LO) mode.

In order to improve the efficiency of various optical surfaces, optical coatings are used. Optical coating is a process of depositing a thin layer of a material on an optical component such as mirror or lens to change reflectance or transmittance. There are two main types of coatings namely / reflective and antireflective (AR) Coatings. Reflective and antireflective coatings have long been developed for a variety of applications in all aspects of use / for optical and electro-optical systems in telecommunications, medicine, military products and space applications. In this thesis, the main properties of reflective and antireflective coatings, the thin film deposition techniques, suitable coating materials for space applications, space environment effects on coating materials and coating design examples which are developed using MATLAB for space applications will be discussed.

ABSTRACT HYDROGEN STORAGE IN MAGNESIUM BASED THIN FILMS Akyildiz, Hasan Ph.D., Department of Metallurgical and Materials Engineering Supervisor : Prof. Dr. Tayfur &Ouml / zt&uuml / rk Co-Supervisor : Prof. Dr. Macit &Ouml / zenbas October 2010, 146 pages A study was carried out for the production of Mg-based thin films which can absorb and desorb hydrogen near ambient conditions, with fast kinetics. For this purpose, two deposition units were constructed / one high vacuum (HV) and the other ultra high vacuum (UHV) deposition system. The HV system was based on a pyrex bell jar and had two independent evaporation sources. The unit was used to deposit films of Mg, Mg capped with Pd and Au-Pd as well as Mg-Cu both in co-deposited and multilayered form within a thickness range of 0.4 to 1.5 &mu / m. The films were crystalline with columnar grains having some degree of preferred orientation. In terms of hydrogen storage properties, Mg/Pd system yielded the most favorable results. These films could desorb hydrogen at temperatures not greater than 473 K. The study on crystalline thin films has further shown that there is a narrow temperature window for useful hydrogenation of thin films, the upper limit of which is determined by the intermetallic formation. The UHV deposition system had four independent evaporation sources and incorporated substrate cooling by circulating cooled nitrogen gas through the substrate holder. Thin films of Mg-Cu were produced in this unit via co-evaporation technique to provide concentrations of 5, 10 and 15 at. % Cu. The films were 250-300 nm thick, capped with a thin layer of Pd, i.e. 5-25 nm. The deposition was yielded nanocrystalline or amorphous Mg-Cu thin films depending on the substrate temperature. At 298 K, the films were crystalline, the structure being refined with the increase in Cu content. At 223 K, the films were amorphous, except for Mg:Cu=95:5. The hydrogen sorption of the films was followed by resistance measurements, with the samples heated isochronally, initially under hydrogen and then under vacuum. The resistance data have shown that hydrogen sorption behaviour of thin films was improved by size refinement, and further by amorphization. Among the films deposited, amorphous Mg:Cu=85:15 alloy could absorb hydrogen at room temperature and could desorb it at 223 K (50 &ordm / C), with fast kinetics.

Interference filters are multilayer thin film devices. They use interference effects between the incident and reflected radiation waves at each layer interface to select wavelengths. The production of interference filters depend on the precise deposition of thin material layers on substrates which have suitable optical properties. In this thesis, the main target is to design and produce two optical filters (short-pass filter and long-pass filter) for the CCDs that will be used in the electronics of a space camera. By means of these filters, it is possible to take image in different bands (RGB and NIR) by identical two CCDs. The filters will be fabricated by plasma ion-assisted deposition technique.

This thesis describes the design, fabrication and characterization of AlGaN/GaN Heterostructure Field E ect Transistors (HFETs) grown by a Metal Organic Chemical Vapor Deposition (MOCVD) on sapphire substrates. The objective of this research is to develop AlGaN/GaN power devices with high breakdown voltage (greater than 1 kV) and low turn-on resistance. Various characteristics such as current drive (Idss), transconductance (gm) and threshold voltage (Vth) have also been measured and the results have been discussed. Two major challenges with the development of high breakdown voltage AlGaN/GaN HFETs in the past have been high material defect density and non-optimized fabrication technologies which gives rise to bu er leakage and surface leakage, respectively. In this thesis, mesa isolation, ohmic and gate metal contacts, and passivation techniques, have been discussed to improve the performance of these power transistors in terms of low contact resistance and low gate leakage. The relationship between breakdown voltage and Rds(ON)A with respect to the gate-drain length (Lgd) is also discussed. First, unit cell devices were designed (two-fingered cells with Wg = 100, 300, 400 m) and characterized, and then they were extended to form large area devices (upto Wg = 40 mm). The design goals were classied into three parts: - High Breakdown Voltage: This was achieved by designing devices with variations in Lgd, - Low turn-on resistance: This was achieved by optimizing the annealing temperatures as well as incorporating additional thick metal pads, as well as optimizing the passivation etch recipe, - Low Gate Leakage: The gate leakage was reduced signicantly by using a gate metal with a larger barrier height. All devices with Lgd larger than 10 m exhibited excellent breakdown voltage characteristics of over 800 V, and it progressed as the Lgd increased. The turn-on resistance was also reduced signicantly below 20 m-cm2, for devices with Lgd = 15, 25, and 20 m. The gate leakage was measured for all devices upto 200 V, and was in the range of 10-100 nA, which is one of the best values reported for multi-ngered devices with Lgd in the range of 2.4-5 mm. Some of the key challenges faced in fabrication were determining a better gate metal layer to reduce gate leakage, optimizing the passivation via etch recipe, and reducing surface leakage.

Piezoelectric materials are widely used for sensors, actuators and trasducers. Traditionally, piezoelectric applications are dominated by multicomponent oxide ferroelectrics such as lead zirconate titanate (PZT), which have the advantage of high piezoelectric coefficients. Recently, one-dimensional piezoelectric nanostructures such as nanowires of zinc oxide (ZnO) and gallium nitride (GaN) has gained a lot of attention due to their combined piezoelectric and semiconducting properties. The focus of this thesis is to study the processing and electric properties of such piezoelectric thin films and nanostructures for various applications. There is an increasing interest to form thin films of multicomponent ferroelectric oxides such as PZT on three-dimensional structures for charge storage and MEMS applications. Traditional vapor phase deposition techniques of PZT offer poor conformality over threedimensional surfaces due to their reactant transport mechanisms. As an alternative, solgel synthesis may provide new process possibilities to overcome this hurdle but the film quality is usually inferior, and the yield data was usually reported for small device areas. The first part of this study is dedicated to the characterization of the electric properties and yield of PZT thin film derived from the sol-gel process. PZT thin films with good electric property and high yield over a large area have been fabricated. La doping was found to double the breakdown field due to donor doping effect. LaNiO3 thin films that can be coated on a three-dimensional surface have been synthesized by an all-nitrate based sol-gel route, and the feasibility to form a conformal coating over a three-dimensional surface by solution coating techniques has been demonstrated. ZnO and GaN micro/nanowires are promising piezoelectric materials for energy harvesting and piezotronic device applications. The second part of this study is focused on the growth of ZnO and GaN micro/nanowires by physical vapor deposition techniques. The morphology and chemical compositions are revealed by electron microscopy. Utilizing the as-grown ZnO nanowires, single nanowire based photocell has been fabricated, and its performance was studied in terms of its response time, repeatability, excitation position and polarization dependence upon He-Cd UV-laser illumination. The excitation position dependence was attributed to the competition of two opposite photo- and thermoelectric currents originated from the two junctions. The excitation polarization dependence was attributed to the difference in optical properties due to crystallographic anisotropy. Employing the as-grown GaN nanowires, single nanowire based strain sensor is demonstrated, and its behavior is discussed in terms of the effect of strain-induced piezopotential on the Schottky barrier height.

Combustion chemical vapor deposition (combustion CVD) is a thin film deposition process that uses a flame created by the ignition of an aerosol containing precursors dissolved in a flammable solvent. Combustion CVD is a relatively new technique for creating thin film oxide coatings. Combustion CVD has been successfully used to deposit high quality thin oxide films for potential applications such as thermal barrier coatings, dielectric thin films, composite interlayer coatings, etc. The present work involved developing the optimum parameters for deposition of thin films of yttria-stabilized zirconia (YSZ), alumina (Al₂O₃), and YSZ-alumina composites followed by a determination of the mechanical properties of the films (measured using nanoindentation) as a function of composition. The optimized parameters for deposition of YSZ, alumina, and YSZ-alumina composites onto single crystal a-plane alumina involved using an organic liquid as the flammable solvent and Y 2-ethylhexanoate, Zr 2-ethylhexanoate and Al acetylacetonate as the metal precursors at a 0.002 M concentration delivered at 4 ml/min at flame temperatures of 155 ℃ and substrate temperatures of 105 ℃. The resulting films were grown with deposition rates of ~ 1.5 μm/hr. Measurement of the mechanical properties (hardness, elastic modulus and fracture toughness) of the films was performed using a mechanical properties microprobe called the Nanoindenter®. In order to obtain valid results from nanoindentation, the combustion CVD films were optimized for minimum surface roughness and grown to a thickness of approximately 0.8 μm. With the penetration depth of the indenter at approximately 150 nm, the 800 nm thickness of the film made influences of the substrate on the measurements negligible. The hardnesses and elastic moduli of the YSZ-alumina films did not vary with the composition of the film. The fracture toughness, however, did show a dependence on the composition. It was found that second phase particles of alumina grown into a YSZ matrix increased the fracture toughness of the films (on average, 1.76 MPa• m⁰.⁵ for 100% YSZ to 2.49 MPa• m⁰.⁵ for 70 mol% YSZ/30 mol% alumina). Similarly, second phase particles of YSZ grown into an alumina matrix also increased the fracture toughness (on average, 2.20 MPa• m⁰.⁵ for 100% alumina to 2.45 MPa• m⁰.⁵ for 37.2 mol% YSZ/62.8 mol% alumina). Modeling of the fracture toughness of the YSZ-alumina films was successfully achieved by using the following toughening mechanisms: crack deflection from the second phase particles, grain bridging around the particles, and residual stress from the CTE mismatch between the film and the substrate and between the second phase particles and the matrix of the film.

This thesis comprises detailed experimental and theoretical investigations of the transport properties of one-dimensional nanostructures. Most of the work is dedicated to the exploration of the fascinating effects occurring in single wall carbon nanotubes (SWCNT). These particular nanostructures gained an overwhelming interest in the past two decades due to its outstanding electronic and mechanical features. We have investigated the properties of a novel family of carbon nanostructures, named here as Y-shaped rings. The studies show that they present very interesting quantum interference effects. A high structural stability under tensile strain and elevated temperatures is observed. Within the semi-classical potential adopted, the critical strain values of structure rupture lie in the same range of their pristine SWCNT counterparts. This is directly verified by the first observations of these ring-like structures in a transmission electron microscopy. A merging process of asymmetric into symmetric rings is investigated in-situ under electron beam irradiation at high temperatures. The electronic properties of these systems are theoretically studied using Monte Carlo simulations and environment dependent tight-binding calculations. From our results, we address the possibility of double-slit like interference processes of counter-propagating electron waves in the ring-like structures. The nature of well defined, sharp peaks in the density of states are determined as the discrete eigenenergies of the central loop part. Furthermore, the formation and dispersion of standing waves inside the ring is shown to originate from the quantum-dot like confinement of each branch between the leads. The obtained dispersion relation is shown to be the same occurring in purely one-dimensional quantum dots of similar geometries. Furthermore, Fabry-Perot-like interferences are observed. We established at the IFW a bottom-up processing route to fabricate nanotube based electronic devices. The SWCNTs are grown by chemical vapor deposition and we present a detailed study of the different approaches to obtain individual nanotubes suitable for a successful integration into electronic devices. Wet-chemistry and ultra-thin films as well as ferritin were employed as catalyst particles in the growth of SWCNT samples. By adjusting the optimized process parameters, we can control the obtained yield from thick nanotube forests down to just a couple of free-standing individual SWCNTs. The nanotubes are localized, contacted by standard e-beam lithography and characterized at ambient- as well as liquid helium temperatures. We usually obtain quite transparent contacts and the devices exhibit metallic or a mixed metallic/semiconducting behavior. The well-known memory effect upon gate voltage sweeping as well as single electron tunneling in the Coulomb blockade regime are addressed.

Eine Reihe wichtiger Wachstums- und Integrationsaspekte von Kohlenstoff-Nanoröhren wurde im Rahmen dieser Arbeit untersucht. Der Schwerpunkt der experimentellen Arbeit lag dabei hauptsächlich bei einschaligen Kohlenstoffnanoröhren (SWCNT). Das große Potential dieser Nanoröhren für Transistor-Anwendungen wurde durch die Herstellung einer Vielzahl funktionierender Bauelemente aus diesen Kohlenstoffnanoröhren mittels relativ einfacher Herstellungsprozesse demonstriert. Ein fundiertes Verständnis für die Abhängigkeiten des Nanoröhrenwachstums von einer Vielzahl an Parametern wurde mit Hilfe mehrerer tausend Wachstumsexperimente gesammelt. Verschiedene Katalysatormetalle, Kohlenstoffquellen und Katalysatorunterlagen wurden detailliert untersucht. Ein Hauptaugenmerk wurde dabei auf eine Reduzierung der Wachstumstemperatur gerichtet. Die niedrige Wachstumstemperatur spielt eine große Rolle für eine möglichst hohe Kompatibilität mit konventionellen Herstellungsverfahren der Silizium-Halbleitertechnik. Ein einfaches phänomenologisches Wachstumsmodell wurde für die Synthese von Nanoröhren mittels katalytisch-chemischer Gasphasen-Abscheidung (CCVD) formuliert. Dieses Modell basiert hauptsächlich auf der Oberflächendiffusion von adsorbierten Kohlenstoffverbindungen entlang der Seitenwände der Nanoröhren sowie auf der Oberfläche der Katalysatorunterlage. Das Modell ist eine wichtige Ergänzung zu dem VLS-Mechanismus. Ein Wachstumsverfahren zur Herstellung von Nanoröhren für niedrigere Temperaturen bis zu 600 °C wurde entwickelt. Experimentell wurde nachgewiesen, dass der Durchmesser des Katalysatorteilchens fast ausschließlich bestimmt, wie viele Schalen eine wachsende Nanoröhre bei geeigneten Wachstumsbedingungen hat. Es wurde zum ersten Mal gezeigt, dass einschalige Kohlenstoffnanoröhren auf Metallelektroden wachsen werden können, insofern eine dünne Aluminiumschicht als Trennschicht verwendet wird. Dadurch können in-situ kontaktierte Nanoröhren einfach hergestellt werden, was deren elektrische Charakterisierung weitaus erleichtert. Mittels stromloser Abscheidung von Nickel oder Palladium aus einer Lösung konnte eine deutliche Verbesserung der Kontaktwiderstände der in-situ-kontaktierten Nanoröhren erreicht werden. Durch Einbettung von Nanoröhren in eine Tantaloxidschicht konnten Transistoren mit einem Dielektrikum mit hoher relativer Dielektrizitätskonstante hergestellt werden. Die Tantaloxidschicht wurde mit einem neu entwickelten Tauchprozess abgeschieden. Erstmalig wurden Transistoren basierend auf Kohlenstoffnanoröhren hergestellt, die relativ hohe Ströme (Milliampere) mit einer Modulation bis zu einem Faktor 500 schalten können. Diese Transistoren beruhen auf einer Parallelschaltung einer großen Anzahl an Nanoröhren. Mit Hilfe der hergestellten Transistoren konnten die Eigenschaften einer großen Zahl von Nanoröhren untersucht werden, wobei große Unterschiede in den elektronischen Eigenschaften von metallischen Nanoröhren, halbleitenden Nanoröhren und Nanoröhren mit einer kleinen Bandlücke beobachtet wurden. / A number of very important growth and integration aspects of carbon nanotubes have been investigated during the course of this thesis. The focus was mainly on single-walled carbon nanotubes. Their potential for transistor applications was demonstrated by the successful fabrication of a variety of devices using rather simple processes. A detailed understanding of the dependence of SWCNT growth on a variety of parameters was obtained as the result of several thousand growth experiments. Various catalyst materials, gaseous carbon sources, and catalyst supports have been investigated. Special attention was paid to a considerable reduction of the growth temperature. A simple phenomenological growth model could be derived for CCVD of SWCNTs taking into account a number of effects observed during the various growth experiments. The model presented is mainly based on the surface diffusion of carbon species along the sidewalls of the carbon nanotubes or on the catalyst support and is an addition to the vapor-liquid-solid (VLS) mechanism. Growth methods for the CCVD synthesis of SWCNTs were developed for temperatures as low as 600 °C. It has been found that the size of the catalyst particle alone determines whether a SWCNT, DWCNT, or MWCNT will nucleate from a specific particle under suitable growth conditions. It could be demonstrated for the first time that SWCNTs can be grown on a variety of conducting materials if the catalyst is separated from the electrode by a thin Al layer. In-situ contacted SWCNTs can be easily obtained that way, largely facilitating the electronic characterization of as-grown SWCNTs. A tremendous improvement of the contacts of in-situ contacted SWCNTs could be achieved by electroless deposition. SWCNT growth on appropriate electrodes allowed the encapsulation of the nanotubes by electroless deposition of Ni and Pd, yielding good and reliable contacts. SWCNT transistors with a high-k dielectric could be fabricated by encapsulation of the nanotube with a tantalum oxide layer. The tantalum oxide was deposited by a newly developed dip-coat process. High-current SWCNT transistors consisting of a large number of SWCNTs in parallel were demonstrated for the first time during this work. Finally, the properties of a large number of CCVD grown SWCNTs have been investigated by electronic transport measurement. Large differences in the electronic transport have been observed for metallic, small band gap semiconducting (SGS), and semiconducting SWCNTs with small diameters.