Carbo- and heterocyclic compounds are of great interest to chemists. Intramolecular cyclization strategies of donor-acceptor (D-A) cyclopropanes and alkylidene malonate monoamides have excellent potential for synthesis as they offer easy access to structurally-diverse compounds. The work described in this thesis accesses the scope of the In(OTf)3-catalyzed cyclization reaction of cyclopropanes and alkylidene malonate monoamides. In(OTf)3-catalyzed reactions of alkenyl and heteroaryl cyclopropyl ketones were examined in the synthesis of functionalized cyclohexenone-based derivatives (Chapter 2). Subsequent efforts to utilize a tandem cyclopropane ring-opening/Friedel-Crafts alkylation sequence of methyl 1-(1H-indolecarbonyl)-1-cyclopropanecarboxylates to prepare functionalized hydropyrido[1,2-a]indole-6(7H)-ones is discussed in Chapter 3. The extension of this tandem protocol towards the total synthesis of (±)-deethyleburnamonine is the subject of Chapter 6. Intramolecular Friedel-Crafts alkylation of N-indolyl alkylidene malonate monoamides was also examined. An In(OTf)3-catalyzed cyclization of substituted methyl 2-(1H-indole-1-carbonyl) acrylates afforded a series of 1H-pyrrolo[1,2-a]indole-3(2H)-ones (Chapter 4), whereas substrates with the indole 2-position blocked provided access to substituted 4H-pyrrolo[3,2,1-ij]quinolin-4-ones (Chapter 5).

No description available.

Amorphous oxide semiconductors (AOSs) are of great current interest for thin-film transistor (TFT) channel layer applications. In particular, indium gallium zinc oxide (IGZO) is under intense development for commercial applications because of its demonstrated high performance at low processing temperatures. The objective of the research presented in this thesis is to provide detailed assessments of device stability, temperature dependence, and related phenomena for IGZO-based TFTs processed at temperatures between 200 °C and 300 °C. TFTs tested exhibit an almost rigid shift in log₁₀(I[subscript D]) – V[subscript GS] transfer curves in which the turn-on voltage, V[subscript ON], moves to a more positive gate voltage with increasing stress time during constant-voltage bias-stress testing of IGZO TFTs. TFT stability is improved as the post-deposition annealing temperature increases over the temperature range of 200 – 300 ºC. The turn-on voltage shift induced by constant-voltage bias-stressing is at least partially reversible; V[subscript ON] tends to recover towards its initial value of V[subscript ON] if the TFT is left unbiased in the dark for a prolonged period of time and better recovery is observed for a longer recovery period. V[subscript ON] for a TFT can be set equal to zero after bias-stress testing if the TFT electrodes are grounded and the TFT is maintained in the dark for a prolonged period of time. Attempts to accelerate the recovery process by application of a negative gate bias at elevated temperature (i.e., 100 ºC) were unsuccessful, resulting in severely degraded subthreshold swing. An almost rigid log₁₀(I[subscript D]) – V[subscript GS] transfer curve shift to a lower (more negative) V[subscript ON] with increasing temperature is observed in the range of –50 °C to +50 °C, except for a TFT with an initial V[subscript ON] equal to zero, in which case the log₁₀(ID) – V[subscript GS] transfer curve is temperature-independent. A more detailed temperature-dependence assessment, however, indicates that the log₁₀(I[subscript D]) – V[subscript GS] transfer curve shift is not exactly rigid since the mobility is found to increase slightly with increasing temperature. A noticeable anomaly is observed in certain log₁₀(I[subscript D]) – VGS transfer curves, especially when obtained at elevated temperature (e.g., 30 and 50 ºC), in which I[subscript D] decreases precipitously near zero volts in the positive gate voltage sweep. This anomaly is attributed to a gate-voltage-step-involved detrapping and subsequent retrapping of electrons in the accumulation channel and/or channel/gate insulator interface. In fact, all IGZO TFT stability and temperature-dependence trends are attributed to channel interface and/or channel bulk trapping/detrapping. / Graduation date: 2009

[Formulae and special characters can not be reproduced here. Please see the pdf version of the Abstract for an accurate reproduction.] Indium nitride is an important III-V nitride semiconductor with many potential applications such as in high frequency transistors, laser diodes and photo voltaic cells. The mobility and peak drift velocity of this material are predicted to be extremely high and superior to that of gallium nitride. However, many material properties such as the origin of the n-type conductivity and the electronic band gap are not well understood. Moreover, there is limited information on the stoichiometry and the level of impurity contaminations in the films from different growth techniques. The n-type conductivity observed for as-grown indium nitride films has long been attributed to nitrogen vacancies, implying that the material is nitrogen deficient. A band gap value around 2 eV, as measured by the optical absorption method, is suggested by some authors to be a result of the formation of an InNIn2O3 alloy. Alternatively, the observation of a lower absorption edge, suggesting a band gap around 0.7 eV, may be caused by Mie scattering at indium clusters that may form during film growth. Secondary ion mass spectroscopy and x-ray techniques provide only qualitative composition information. The quantitative interpretation of the results relies on calibration samples which are not available for indium nitride. In Rutherford backscattering spectroscopy, while quantitative, the carbon, nitrogen and oxygen signals cannot be separated unless the film is very thin ([tilde]150 nm). However, with heavy ion Elastic Recoil Detection (ERD) analysis all the elements in indium nitride films can be fully separated even for a film thickness of [tilde] 800 nm. In this work, indium nitride films from different growth techniques have been analysed with ERD using 200 MeV 197Au projectiles. The observed nitrogen depletion during the ERD analysis was monitored as a function of projectile fluence using a gas ionisation detector with a large solid angle. Different models have been tested and it has been shown that the bulk molecular recombination model accurately describes the nitrogen depletion so that the original nitrogen-to- indium ratio can be measured with an accuracy of [plus or minus]3 [percent]. The correlation of nitrogen depletion rate and stopping power of the projectile ion has been investigated. The study has shown that the rate of depletion is slower for low-Z projectiles. It has been shown that for a film with good structural properties, no loss of nitrogen occurs during the ERD analysis with low-Z projectiles such as 42 MeV 32S. Thus, the original nitrogen-to-indium ratio can be obtained without any theoretical modelling, and with a precision of better than [plus or minus]1 [percent]. All the indium nitride films studied in this work, for which X-ray diffraction shows no metallic indium, are nitrogen-rich which is contradictory to expectation. Therefore, the common assertion that nitrogen vacancies are the cause of n-type conductivity in as-grown films is diffcult to explain. Instead, the existence of In vacancies, N antisites and interstitial N2 may be speculated. The carbon and oxygen contamination is an issue for films grown by all common growth techniques. However, the suggested correlation of oxygen content in the film with the apparent band gap is not supported by the ERD results. Instead, a correlation between nitrogen-to-indium ratio and the measured band gap has been observed for films grown by RF-sputtering. This work reports the implantation of radioisotope probes using negative ions. The 111In/Cd probe was selected for this work as it is a common Perturbed Angular Correlation (PAC) probe and ideally suited for the study of indium nitride. For the synthesis of the probe 111In/Cd, several possibilities, such as the production of 111In/Cd via nuclear fusion evaporation reactions and from commercially available 111InCl3 solutions, were explored. Different materials, including powders of Al2O3 and In2O3, were investigated as a carrier for the probe in the ion source of the radioisotope implanter. It has been established that combining the 111InCl3 solution as the source and In2O3 powder as the carrier material gives optimum implantation efficiency. The radioisotope implanter facility has been developed to a stage that the radioisotope probe 111In/Cd can be routinely implanted into materials as molecular 111InO?? ions. An implantation rate of 3x10 4[th] Becquerel per hour has been demonstrated. Measurements on different materials (Ag, In, Ni, Si, InP) have shown that condensed matter spectroscopies such as Low Temperature Nuclear Orientation, Nuclear Magnetic Resonance on Oriented Nuclei (NMRON) and Perturbed Angular Correlation can be reliably performed. NMRON measurements on silver indicate a new resonance frequency of 75.08 MHz for 111InAg at 8.0 T. The local lattice environment of indium nitride thin films has been investigated with PAC spectroscopy. Several methods of introducing a radioisotope probe into a host material have been investigated for indium nitride. The thermal diffusion of the radioisotope probe 111In/Cd into indium nitride at a temperature below the dissociation temperature (about 550 [degrees] C) was not possible. The probe was, however, successfully introduced into indium nitride films with ion implantation techniques. Recoil implantation at MeV energies following fusion evaporation reactions and ion implantation at keV energies, both have been investigated for indium nitride films. An interaction frequency of v = 28 MHz has been measured for the 111In/Cd probe in indium nitride. This result is consistent with that obtained for indium nitride bulk grains. The PAC results suggest that all types of indium nitride films have a highly disordered lattice which could only be partially improved by annealing. Furnace annealing in nitrogen atmosphere above 400 [degrees] C resulted in the dissociation of the film. However, such dissociation could be avoided with rapid thermal annealing up to 600 [degrees] C. More detailed defect studies with PAC require the availability of better material. This study has also shown that indium nitride is highly sensitive to ion beam irradiation. Severe depletion of nitrogen during exposure to ions with MeV and KeV energies is an issue for the ion beam characterisation and processing of indium nitride.

Thesis (M.S. in Physics)--Naval Postgraduate School, January 1965. / Thesis Advisor(s): Handle, Harry E. "January 1965." Description based on title screen as viewed on June 2, 2010 DTIC Descriptor(s): (Neutron Cross Sections, Thermal Neutrons), (Research Reactors, Reactor Feasibility Studies), Fast Neutrons, Gold, Radioactive Isotopes, Measurement, Perturbation Theory, Neutron Capture, Indium, Standards, Errors, Materials, Neutron Flux, Mathematical Analysis, Cadmium, Reactor Shielding Materials, Computer Programming, Foils (Materials), Reactor Control, Reactor Kinetics, Reactor Start Up Sources. DTIC Identifier(s): AGN-201 Reactors Includes bibliographical references (p. 32). Also available in print.

Made available in DSpace on 2014-10-09T12:51:12Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:53Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Transparent electrodes (TEs) have become important components of displays, touch screens, and solar photovoltaic (PV) energy conversion devices. As electrodes, they must be electrically conductive while being transparent. Transparent materials are normally poor conductors and materials with high electrical conductivity, such as metals, are typically not transparent. From the few candidate materials, indium tin oxide (ITO) is currently the best available, but indium is an expensive material and ITO cost has risen with increasing demand. Therefore, alternative materials or methods are sought to encourage production needs of applications and help in reducing their price. This thesis presents and discusses results of experimental work for a method, field-directed chaining, to produce a TE device which is nanowire-based, with a figure of merit FoM= 2.39 x10E-4 Ohm E-1, comparable to ITO but with potential for far lower cost. Using electric field-directed chaining, multiple parallel long chains of metal nanowires are assembled on inexpensive transparent materials such as glass by field directed nanowire chaining, using methods first demonstrated in our laboratory. In this work, we have improved the fraction of functional chains, by tuning the field/voltage, a key step in increasing the FoM and lowering the cost. The effect of operating parameters on TE optical and electrical properties has been studied and identified as well. From experiments with twenty seven substrates, each with a range of electric field and nanowire concentration, the highest light transmission achieved is 78% and the lowest sheet resistance achieved is 100 Ohm/sq. Among all the operating parameters, the electric field has the most significant influence on the fraction of nanowire chains that are functional. In the operating range of electric field strength available to us, we observed a monotonic increase in the fraction of functional nanowire chains. We found a counter-intuitive change in TE properties in a sub-range of nanowire concentration, associated with a change in the structure of chained patterns. / Graduate

This thesis describes the synthesis and characterisation of novel mono and dinuclear homogenous [Zn(II)] and [In(III)] metal complexes. Their applications as catalysts for CO₂/epoxide or epoxide/anhydride ring opening copolymerisation and lactide ring opening polymerisation to generate polycarbonates and polyesters, respectively, are also reported. Chapter 3 reports the first indium phosphasalen catalysts for CO₂/cyclohexene oxide ring opening copolymerization. The catalysts are active at 1 bar pressure of CO₂ and are most effective without any co-catalyst. It is also possible to use the complexes to isolate and characterise the key intermediates in the catalytic cycle. Kinetic and spectroscopic analyses show that polymerisation proceeds via a rare cis-mononuclear coordination- insertion mechanism. Chapter 4 describes a series of mono and dinuclear zinc macrocycle catalysts with very high activities for the racemic lactide ring opening polymerisation. In most cases, the dinuclear zinc catalysts significantly out-perform the mono-zinc homologue. In addition, kinetic and spectroscopic investigations suggest a role for the ligand conformation in mediating rate. The catalysts perform very well under immortal conditions and operate at low catalyst loading, whilst conserving high activities. Chapter 5 presents four dinuclear zinc acetate salen catalysts for the ring opening copolymerisation of CO₂/cyclohexene oxide and phthalic anhydride/cyclohexene oxide. The catalysts show moderate activities for CO₂/epoxide copolymerisation but are highly active for epoxide/anhydride copolymerisation. Structure/activity relationship studies reveal that the more flexible and electron donating ligand displays the highest activity. Poly(ester-b-carbonate)s are also afforded using the most active catalyst in terpolymerisations of anhydride/epoxide/CO₂.

The work presented in this thesis focuses on the investigation and improvement of the window stack of layers for thin film CdTe solar cells fabricated in the Center for Renewable Energy Systems Technology (CREST) laboratories. In particular the aim was to change the standard structure including TCO, high resistive transparent (HRT)layer and CdS which is limited by the low transparency of the CdS layer, to a better performing one. The first result chapter of the thesis describes the study of ZnO HRT layers. ZnO thin films were deposited by radio frequency (RF) magnetron sputtering with different structural, optical and electrical properties which were characterized by X-ray diffraction, electron microscopy, spectrophotometry, Hall Effect method and 4-point probe. ZnO films were then incorporated in CdTe solar cells with the structure: FTO/ZnO/CdS/CdTe/Au back contact and the performance of these devices were compared with the film properties to single out trends and identify optimal film characteristics. By varying the deposition pressure of ZnO films, it was possible to increase their transparency and significantly increase their resistivity. While better transparency positively affected the solar cell current density output and efficiency, the resistivity of ZnO films did not show any clear impact on device efficiency. By increasing the deposition temperature the ZnO film grain size was increased. Increased FF was observed in devices incorporating ZnO layers with bigger grains, although this gain was partially counterbalanced by the Voc degradation, leading to a limited efficiency improvement. Finally the addition of oxygen had the main effect of increasing the resistivity of ZnO films, similarly to what happened with the increase of the sputtering pressure. In this case however, an improvement of FF, Jsc and efficiency was observed, especially at an O2/Ar ratio of 1%. By simulating the solar cells behavior with SCAPS-1D, it was found that these performance change can be explained by the variation of interface properties, precisely the amount of interface defects, rather than by bulk properties. The study presented in the second result chapter focuses on magnesium-doped zinc oxide (MZO) and the variation of its energy band structure. MZO was initially used as the HRT layer within a solar cell structure: FTO/MZO/CdS/CdTe/Au back contact. Sputtering MZO films with a target containing MgO 11 weight% and ZnO 89 weight% allowed for and increased band gap from 3.3 eV of intrinsic ZnO to 3.65 eV for MZO deposited at room temperature. Increasing the superstrate deposition temperature allowed for a further band gap increase up to 3.95 eV at 400 °C due mainly to an conduction band minimum upward shift. It was highlighted the importance to create a positive conduction band offset with the MZO layer conduction band slightly above the CdS conduction band, with an optimum found in this case to be 0.3 eV (efficiency 10.6 %). By creating a positive conduction band offset all the performance parameters (Voc, FF, Jsc, efficiency) significantly increased. One of the reasons for this improvement was found to be a diminished interface recombination due to a more ideal MZO/CdS band alignment. In the second part of this investigation the MZO was used as a replacement for the CdS in a simplified structure: FTO/MZO/CdTe/Au back contact. The concepts used to optimise the performance of these devices also involved tuning the conduction band alignment between MZO/CdTe and efficiencies of 12.5 % were achieved with a at conduction band offset. The efficiency increase was achieved mainly thanks to a better transparency of the MZO layer and a higher Jsc output, compared to devices using a CdS buffer layer. The MZO buffers have been tested in combination with different TCOs. Results are presented in the third result chapter and showed that AZO is a good alternative to FTO working effectively in combination with MZO. AZO/MZO efficiency thin film CdTe solar cells (12.6%, compared to 12.5% with FTO). It was found that increasing the IR transparency of the TCOs leads to a potentially higher Jsc. Achieving a better transparency was obtained by using TCOs with high mobility and lower carrier concentration (AZO and ITiO) and also by using a boro-aluminosilicate glass with low iron content. ITiO yielded the best opto-electrical properties among all the TCO materials. Devices incorporating ITiO however, showed lower performance then those using FTO and AZO. ITO/MZO windows also yielded poor performance. In addition, the ITO films deposited had a high carrier concentration leading to a high NIR absorption by plasma resonance and resulted not ideal for application in thin film CdTe PV.

L’acylation de Friedel-Crafts est parmi les réactions les plus fondamentales et les plus utiles pour former des cétones aromatiques. Bien que la mise en oeuvre de ces réactions soit habituellement pénalisante en termes de sous produits formés, de rendement atomique et de quantité de catalyseur utilisée, cette voie est encore largement utilisée dans l’industrie de la chimie fine. Ces dernières années, la prise de conscience de l’impact des activités industrielles sur l’environnement a mené les chimistes à travailler sur de nouvelles voies, moins dangereuses et plus respectueuses de l’environnement.Nous avons considéré ici l’acylation d’un dérivé du benzofurane par un chlorure d’acyle, correspondant à une étape intermédiaire pour la fabrication d’un principe actif pharmaceutique. Dans cette étude, la première proposition a consisté à remplacer les catalyseurs classiques (FeCl3 ou AlCl3) par des catalyseurs solides réutilisables. Dans ce travail, plusieurs catalyseurs (zéolites, résines échangeuses d’ions...) ont d’abord été testés dans des conditions « conventionnelles » , c’est-à-dire en utilisant un solvant organique, afin de déterminer le plus performant, en termes de réactivité, de durée de vie et de réutilisabilité. Une zéolite Y s’est avéré la plus adaptée. Cependant, l’utilisation d’un solvant organique (ici le 1,2-dichlorobenzène) reste discutable et l’utilisation du CO2 supercritique comme solvant a donc été envisagée. Pour cela, nous avons imaginé et dimensionné un réacteur tubulaire à lit fixe de catalyseur fonctionnant sous pression et en continu. Les résultats présentés montrent la faisabilité d’un tel procédé et pose les jalons pour arriver à une ou des solutions pour une meilleure mise en oeuvre industrielle des réactions de Friedel-Crafts. / Friedel-Crafts acylation is among the most fundamental and useful reactions to yield aromatic ketones, but it is one of the less acceptable in terms of unwanted polluting by-products or atom economy because of overconsumption of catalyst which is used in stoichiometric quantities in the conventional process. This route is nevertheless still widely used in the fine chemicals industry. In recent years, awareness of the impact of industrial activities on the environment has lead chemists to work on new chemical routes, less dangerous and more environmentally friendly. We considered here the acylation of a benzofurane derivative by an acid chloride, as an intermediary step for a pharmaceutical product. In this study, one of the first alternative was to replace conventional catalysts (FeCl3 or AlCl3), by reusable solid catalysts. In this work, different catalysts (zeolites, ion-exchange resins...) were first tested in "conventional" conditions, i.e., using an organic solvent (1,2-dichlorobenzene in our case), to determine the best one, in terms of reactivity, lifetime and reusability. The zeolite Y was found the most appropriate. However, the use of an organic solvent still remains questionable and the use of supercritical carbon dioxide as the solvent was also considered. Its inherent properties include non-flammability, mild critical conditions, tuneable solubility near to the critical point and very low environmental impact. The reaction was operated using a specifically designed continuous high pressure fixed bed and results concerning yield and selectivity are presented. These results demonstrate the feasibility of such an approach, which would ultimately yield to better industrial operation of Friedel-Crafts reactions.