Thesis (Ph. D.)--University of Texas at Austin, 2000. / Vita. Includes bibliographical references (leaves 141-150). Available also in a digital version from Dissertation Abstracts.

Thesis (M.S.)--Ohio University, November, 2001. / Title from PDF t.p.

Thesis (Ph. D.)--University of Texas at Austin, 2000. / Vita. Includes bibliographical references (leaves 156-165). Available also in a digital version from Dissertation Abstracts.

Thesis (Ph. D.)--University of Texas at Austin, 1999. / Vita. Includes bibliographical references (leaves 129-137). Available also in a digital version from Dissertation Abstracts.

Thesis (Ph.D.)--Ohio University, March, 2003. / Title from PDF t.p. Includes bibliographical references (leaves 147-151)

Zinc oxide (ZnO) is a II-VI semiconductor material that offers tremendous potential as a light emitter in the blue-to-UV range. It has a wurtzite structure, and a direct band gap that can be tuned from 3.0 to 4.0 eV by alloying with Cd or Mg, respectively. In this work, ZnO thin films were grown by metalorganic chemical vapor deposition (MOCVD) on n-Si 2 ° off (100), amorphous glass, n-GaAs (100), and c-plane sapphire substrates. Diethyl zinc (DEZn) and tert-butanol (TBOH) were chosen as precursors. For the first time, Second Harmonic Generation Imaging was applied to the mapping of ZnO epilayers. The images obtained highlighted the polycrystalline character of the thin films, and provided insight as to the growth mode of ZnO on Si. The influence of substrate temperature on the structural properties of the epilayers was investigated by X-ray diffraction and optical microscopy. Grain sizes as high as 54 nm were measured. The optimum temperature range for this system proved to be 450 – 500 °C. The influence of the VI:II ratio during growth on the optical properties of the epilayers was studied by UV-vis-near IR spectroscopy. The lowest Urbach tail E0 parameter was measured for material grown at a VI:II ratio of 18:1. The films’ free electron concentration was shown to decrease by over two orders of magnitude, from 1019 to 1017 cm-3, as the VI:II ratio increased from 10 to 60:1. This decrease in carrier concentration with rising VI:II ratio was paralleled to the surge at 12 K of a photoluminescence (PL) emission band characteristic of p-type ZnO. The band gap energies extracted from room temperature transmission spectra ranged between 3.35 and 3.38 eV, in agreement with the value of 3.35 eV measured by room temperature PL. Moreover, variable temperature PL spectra were recorded between 12 and 298 K on ZnO grown on Si. The 12 K spectrum was dominated by a donor-bound exciton (D°X) at 3.36 eV, while the 298 K scan displayed strong free exciton emission (FX) at 3.29 eV. The width of the D°X band proved to be as narrow as 7 meV. The intensity ratio between the room temperature near-band edge emission and the defect-related green band was as high as 28:1, highlighting the optical quality of the layers deposited in this work. The electrical properties of the thin films were studied by Hall measurements (van der Pauw configuration), and a maximum room temperature mobility of 11 cm2/Vs was recorded. Furthermore, a palladium (Pd) Schottky barrier diode on ZnO was fabricated. The barrier height and ideality factor were calculated from current–voltage measurements to be 0.83 eV and 1.6, respectively. The capacitance–voltage curve of the diode yielded a carrier concentration in the depletion region of 8·1017 cm-3. This study has shown that the optical and electrical properties of ZnO depend strongly on the growth conditions employed. A suitable choice of growth parameters can yield high quality ZnO that may be used for various devices. Keywords: Hall, MOCVD, optical spectroscopy, photoluminescence, Schottky barrier diode, SH Imaging, X-ray diffraction, ZnO.

This study focuses on the growth and characterization of epitaxial InAs and InAs1-xSbx. Layers are grown on InAs, GaAs and GaSb substrates by metalorganic vapour phase epitaxy, using trimethylindium, trimethylantimony and arsine as precursors. The growth parameters (V/III ratio, Sb vapour phase compositions) are varied in the temperature range from 500 ºC to 700 ºC, in order to study the influence of these parameters on the structural, optical and electrical properties of the materials. The layers were assessed by X-ray diffraction, electron and optical microscopy, photoluminescence and Hall measurements. Furthermore, the influence of hydrogenation and annealing on the electrical and optical properties of GaSb was investigated. It is shown that the growth temperature and the V/III ratio play a vital role in the resulting surface morphology of homoepitaxial and heteroepitaxial InAs layers. Growth at low temperatures is found to promote three-dimensional growth in both cases, with improvements in the surface morphologies observed for higher growth temperatures. All the investigated epilayers are n-type. It is shown that the electrical properties of heteroepitaxial InAs epilayers are complicated by a competition between bulk conduction and conduction due to a surface accumulation and an interface layer. The low temperature photoluminescence spectra of homoepitaxial InAs are dominated by two transitions. These are identified as band-to-band/excitonic and donor-acceptor recombination. The incorporation efficiency of antimony (Sb) into InAs1-xSbx is dependent on the growth temperature and the V/III ratio. Under the growth conditions used in this study, the incorporation efficiency of Sb is controlled by the thermal stability of the two constituent binaries (i.e. InAs and InSb). Changes in the low temperature photoluminescence spectra are detected with increasing x. From temperature and laser power dependent measurements, the highest energy line is attributed to band-to-band/excitonic recombination, while the peak appearing approximately 15 meV below this line is assigned to donor-acceptor recombination. The origin of an additional “moving” peak observed for higher Sb mole fraction x is tentatively attributed to quasi-donor-acceptor-recombination, arising from increased impurity/defect concentrations and a higher compensation ratio in the material. However, the unusual behaviour of this peak may also be ascribed to the presence of some degree of ordering in InAsSb. The exposure of a semiconductor to a hydrogen plasma usually leads to the passivation of shallow and deep centres, thereby removing their electrical and optical activity. In this study, the passivation and thermal stability of the native acceptor in p-type GaSb is also investigated. It is shown that this acceptor can be passivated, where after improvements in the electrical and optical properties of GaSb are observed. Upon annealing the passivated samples above 300 °C, the acceptor is reactivated.

La production de polyéthylène par la polymérisation de l'éthylène est un procédé industriel de grande importance. L'éthylène, issue de la pétrochimie contient des impuretés d'acétylène (1%), ce qui empoisonne le catalyseur de polymérisation, et donc le besoin d'un catalyseur qui soit sélectif pour hydrogéner l'acétylène en éthylène. Le composé intermétallique Al13Fe4 a été développé par Armbuster et al. en 2012 comme un catalyseur actif et sélectif pour la semi-hydrogénation de l'acétylène pour la production de polyéthylène. Il présente une structure cristalline avec des distances interatomiques Fe-Fe élevées et un faible nombre de coordination des atomes de fer, qui tombe sous le concept de "site isolation principle". Ce composé est également intéressant en raison de son faible coût (sans métaux nobles par rapport à Pd /Al2O3 catalyseurs industriels) et une faible toxicité. Cependant, il a été produit sous la forme de poudre non supportée par la méthode Czochralski ce qui limite son utilisation dans le domaine du génie catalytique. Dans ce contexte, supporter le catalyseur présente de nombreux avantages comme la facilité de séparation du catalyseur hétérogène à partir du mélange réactionnel obtenue par une variété de procédés telle que la filtration par exemple. Un autre avantage des catalyseurs supportés est la plus grande surface exposée du catalyseur ou dispersion. Etant donné que la catalyse est une réaction de surface, maximiser la surface d'un catalyseur, en le dispersant sur le support améliorera / optimisera l'activité catalytique. Les procédés de "chimie douce" dénommés Metal Organic Chemical Vapor Deposition (MOCVD) et Metal Organic Deposition (MOD) sont réputés pour être efficaces et économiquement compétitifs pour déposer des nanoparticules ou des films minces, à partir de précurseurs moléculaires appropriés. Notre travail vise donc à développer Al13Fe4 sous forme de films ou de nanoparticules supportées par MOCVD. La première étape pour atteindre cet objectif est le développement des précurseurs moléculaires d'aluminium métallique et de fer, dans des conditions compatibles suivies par codépôt ou dépôt séquentiel des deux précurseurs de Fe et Al pour former le composé intermétallique dans la bonne stœchiométrie. Parmi les nombreux précurseurs d'Al, le diméthyl ethylaminealane (DMEAA, [AlH3(NMe2Et)]) est utilisé en raison de sa pression de vapeur importante et des températures de dépôt faibles. En outre, l'absence de liaisons Al-O et Al-C conduit à la production de films sans impuretés carbone et oxygène. Cependant, des précurseurs moléculaires de fer pour le dépôt pour MOCVD de films de fer purs sont rares et moins développés. En dehors du pentacarbonyle de fer qui produit des films de fer pur, amidinates et guanidinates sont utilisés comme précurseurs de fer. Cependant, l'oxygène et des carbures sont présents dans des pourcentages élevés. Ainsi, l'objectif principal de ce travail de thèse est de concevoir et de synthétiser de nouveaux complexes moléculaires de fer qui servent de précurseurs pour la MOCVD. Dans ce travail, des nanoparticules de composé intermétallique Al13Fe4 sont préparées par réduction en solution et des films par dépôt séquentiel MOCVD en utilisant DMEAA et Fe(CO)5 en tant que précurseurs moléculaires. Les propriétés catalytiques ont été étudiées et ont montré d'une activité très peu active dans la réaction d'hydrogénation de l'acétylène: moins de 1% avant de se désactiver rapidement. La régénération sous hydrogène ou sous oxygène n'a qu'une faible restauration de l'activité. Les tests catalytiques ont été encore étendus à Al13Fe4 poudre préparée par réduction en solution ainsi que Al13Fe4 en poudre commerciale et a constaté que Al13Fe4 était non catalytiquement actif sous toutes ses formes (dans nos conditions de réaction) / Polyethylene production from the polymerization of ethylene is an industrial process of great importance. Ethylene stream for the polymerization of polyethylene is produced by the steam cracking of a wide range of hydrocarbon feedstock and usually contains acetylene impurities (1%) which poison the polymerization catalyst. The ethylene steam has to be purified by the selective semi-hydrogenation of acetylene which requires a catalyst with high selectivity to hydrogenate acetylene to ethylene. The intermetallic compound Al13Fe4 was introduced in 2012 by Armbuster et al. as an active and selective catalyst for the semi-hydrogenation of acetylene for polyethylene production. It has a crystal structure with high average inter-atomic distances Fe-Fe and a low coordination number of iron atoms, which falls under the concept of "site isolation principle". This compound is also attractive because of its low cost (without any noble metals compared to Pd/Al2O3 industrial catalysts) and low toxicity. However, it has been produced in the form of unsupported powder by the Czochralski method which limits its use in catalytic engineering. In this context, supporting the catalyst presents many advantages as the ease of separation of the heterogeneous catalyst from the reaction mixture. In contrast to homogeneous catalysts in which separation is often costly and difficult, separating the supported heterogeneous catalyst can be achieved by a variety of methods such as filtration for example. Another advantage of supported catalysts is the higher surface area of the catalyst. Since catalysis is a surface reaction, consequently, maximizing the surface area of a catalyst by distributing it over the support will enhance/optimize the catalytic activity.Chemical synthetic routes such as Metal Organic Chemical Vapor Deposition (MOCVD) and Metal Organic Deposition (MOD) referred as “Chimie douce” process are reputed to be flexible and economically competitive methods to prepare nanoparticles or thin films. Our work is thus aimed at developing Al13Fe4 as supported films or nanoparticles by MOCVD and/or MOD. The first step to meet our objective is the development of compatible molecular precursors of metallic aluminum and iron followed by MOCVD or MOD of those precursors to form the intermetallic compound in the good stoichiometry. Among the numerous aluminum MOCVD precursors used in the literature, dimethyl ethylamine alane (DMEAA, [AlH3(NMe2Et)]) is used due to its properties such as high vapor pressure and low deposition temperatures. Moreover, the absence of Al-O and Al-C bonds leads to the production of carbon and oxygen free films. However, iron molecular precursors for the MOCVD of pure iron films are scarce and less developed. Apart from iron pentacarbonyl that produces pure iron films, amidinates and guanidinates are used as iron precursors. However, oxygen and carbides impurities are present in high percentages. Thus the main objective of this Ph-D work is to design and synthesize novel and original iron molecular complexes that serve as precursors for the low temperature MOCVD of iron films. In this Ph-D work, nanoparticles of the intermetallic complex were prepared via solution reduction of novel Fe triazenide precursors and Al metal. Supported films were also prepared via sequential MOCVD by using DMEAA and Fe(CO)5 as molecular precursors. Its catalytic properties have been explored and showed that it is very little active in the hydrogenation reaction of acetylene. Regeneration under hydrogen or oxygen was not very successful and only some activity restored. The catalytic tests have been further extended to Al13Fe4 powder prepared by solution reduction as well as to commercial Al13Fe4 and found that Al13Fe4 was inactive catalytically in all forms (in our conditions of reactions)

Electrical and optical properties of the (N,Ga)-doped ZnO films have been studied. Three growth regions were identified to obtain ZnO films with different conduction types depending on the N/Ga flux ratio in doping process. The PL spectra show evident competition between neutral-donor bound exciton (D0X) and neutral-acceptor bound exciton (A0X) according to the N/Ga ratio. From the temperature-dependent PL spectra, the nitrogen acceptor level was identified to be about 126 meV in (N,Ga)-doped p-type ZnO. / For nitrogen doping of ZnO thin films, DMHy was used as the nitrogen dopant source. A narrow temperature window from about 500°C to 550°C for efficient nitrogen doping was identified. However, p-type ZnO was not obtained by nitrogen mono-doping, which results from the low solubility of N and the self-compensating effect of native defects, and/or N-induced complexes. By co-doping N with Ga in proper ratios, p-type ZnO films were successfully achieved with a high hole concentration of 3.51 x 1017 --2.41 x 1018cm-3, Hall mobility of 1.1 --4.29 cm2/V-s and resistivity of 0.6 -- 16.2 O cm. But the conduction type critically depends on the growth conditions. Based on the successfully fabrication of (N,Ga)-doped p-type ZnO, a p-ZnO:(N,Ga)/n-ZnO homojunction was fabricated. The I-V measurement shows clear rectifying behavior with a turn-on voltage of about 3.7 V. / Further investigation of the effect of N/Ga doping ratios on the conduction type of ZnO samples reveals that successful doping depends much on engineering a stable local chemical bonding environment. Under mono-doping conditions (via N-Zn4), nitrogen solubility is limited and nitrogen acceptors are readily compensated by native donors and/or N-related donors; under appropriate N/Ga flux ratios, cluster-doping (via Ga-N3O and Ga-N4) can be realized to achieve p-type ZnO; while excessively high N/Ga ratios cause the doped ZnO n-type conductivity again, which may be because that under excessively high N/Ga ratio range, N-Zn4 configuration dominates and thus cause more N-related donors and degrade the ZnO film quality, similar as the mono-doping case. By tuning the N/Ga ratio in doping, it is expected to create appropriate chemical environments to enhance the formation of desired dopant species for stable p-type ZnO. / In this work, Metal-organic chemical vapour deposition (MOCVD) growth of ZnO and its p-type doping have been studied. The group V element N was used as primary dopant to make ZnO p-type. In the growth of ZnO by MOCVD, it was found that the structural and morphological properties of deposited ZnO strongly depend on growth conditions. Low VI/II ratio and high growth rate favor the growth of ZnO nanostructures (nanowires, nanobelts); while high VI/II ratio and low growth rate favor the growth of ZnO thin films. / The semiconductor ZnO is currently gaining intense interest in the research community because of its prospect in optoelectronic applications, such as blue/ultraviolet emitters and detectors, and high speed electronic devices. However, making reliable and reproducible p-type ZnO is still a bottleneck, which impedes the practical application of ZnO-based devices. The difficulty is mainly due to the self-compensation effect of native defects and the low solubility limit of acceptor dopants. Although substantial research is currently being carried out worldwide towards this goal, the effective p-type dopant and its doping process have not yet been identified. / Wang, Hui. / "Apr 2008." / Adviser: Aaron H. P. Ho. / Source: Dissertation Abstracts International, Volume: 70-03, Section: B, page: 1860. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Metal diketonato complexes are populate in recent ten years, because of diketone compound is easy to get and cheap and also have good volatility to be the precursor of MOCVD, they usually can be the materials of wafer processing by high technology electronics industries. Many scientists are trying to synthesis these diketonato complexes, and find out the better reactivity compounds to be the precursor of MOCVD. In order to knowing the decompose activities of these complexes, we are trying to compare the metal-oxygen bonds of these diketonato complexes in this paper. By the way, these diketonato complexes have difference geometry in cis and trans form, and also have conformation isomers between syn and anti form. We will compare and discuss the structures and controlling factors in these kinds of diketonato complexes in this paper.