The existence of singly, doubly, and triply charged diatomic molecular ions was observed by using an Accelerator Mass Spectrometry (AMS) technique. The mean lifetimes of 3 MeV boron diatomic molecular ions were measured. No isotopic effects on the mean lifetimes of boron diatomic molecules were observed for charge state 3+. Also, the mean lifetime of SiF^3+ was measured.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

The aim to this work was to develop methods for the determination of 2 aminobiphenyl (2-AB), 3 aminobiphenyl (3-AB), and 4-aminobiphenyl (4-AB) in model mixtures. Concretely, the direct determination of the mixture of studied analytes has been tested using spectrophotometry and differential pulse voltammetry (DPV). Furthermore, separation and detection of 2-AB, 3-AB, and 4-AB have been performed using high performance liquid chromatography with electrochemical detection (HPLC-ED) with boron-doped diamond film thin electrode (BDDFE) in ,,wall-jet" configuration and using high performance liquid chromatography with UV detection (HPLC-UVD). It was found out that the spectrophotometric determination of 2-AB, 3-AB, and 4-AB is impossible in their mixture because of nearby values of local absorption maxima wavelengths of all three analytes studied. Upon the determination of 2-AB, 3-AB, and 4-AB in their mixture using DPV in BR buffer pH 2.0, the difference in peak potentials of 2-AB and 3-AB is too low for their determination in mixture. Upon the determination of mixture containing 2-AB and 4-AB in BR buffer pH 12.0, the limits of determination (LDs) were obtained in the concentration order of 10-6 mol.l-1 for 2-AB and 10-7 mol.l-1 for 4-AB. LDs for the mixture containing 3-AB and 4-AB were obtained in the...

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / The exceptional radiation resistance, high melting point, and wide energy bandgap (3.2 eV) of icosahedral boron arsenide, B[subscript]12As[subscript]2, make it an attractive candidate for applications in radiation intense environments, for example, in radioisotope batteries. These devices have potential lifetimes of decades rather than days or weeks that are typical of conventional chemical power cells. Solid state neutron detectors are another potential application of this semiconductor, as the boron-10 isotope has a high thermal neutron capture cross-section, orders of magnitude higher than most elements. To produce high quality crystalline B[subscript]12As[subscript]2 for these applications, this research focused on the epitaxy and electrical properties of B[subscript]12As[subscript]2 thin films. The major findings include the following. Twin-free heteroepitaxial B[subscript]12As[subscript]2 layers were obtained on m-plane 15R-SiC and c-plane 4H-SiC inclined 4° and 7° off-axis in the [1-100] direction. These substrates exposed asymmetric step-terrace surface structures that force B[subscript]12As[subscript]2 layers to adopt a single orientation, thus, twins were eliminated. Consequently, the crystal quality was greatly improved over films on on-axis c-plane 6H-SiC, yielding a maximum hole mobility of 80 cm[superscript]2V[superscript]-1s[superscript]-1, nearly 100 times higher than previously reported values. B[subscript]12As[subscript]2 epilayers grown at 1300°C had the lowest defect densities, smallest residual strains, highest mobility and highest deposition rate. Excess AsH[subscript]3 concentration was advantageous to prevent the loss of arsenic from the epilayer. Undoped B[subscript]12As[subscript]2 exhibited a variable-range-hopping conduction, indicating it was a highly disordered system. All films were p-type with a room temperature hole concentration on the order of 10[superscript]12~10[superscript]15cm[superscript]-3. The thermal activation energy of acceptors varied from 0.15 eV to 0.33 eV. The Hall mobility was dominated by impurity scattering at low temperatures and by polar phonon scattering at high temperatures. H, C, O and Si were the major impurities present in the undoped B[subscript]12As[subscript]2 films with concentrations on the order of 10[superscript]18~10[superscript]19 cm[superscript]-3. Si doping and annealing decreased the resistivity by up to two orders of magnitude. The density of localized states was small in the undoped B[subscript]12As[subscript]2 as the intrinsic acceptor levels (IALs) were compensated by the boron interstitials. However, in Si-doped B[subscript]12As[subscript]2, Si may prevent the interstitial boron atoms from compensating the IALs, yielding a decreased density of localized states. The Hall mobility of B[subscript]12As[subscript]2 epilayer was significantly reduced with increasing silicon concentration.

Master of Science / Department of Chemical Engineering / James H. Edgar / Boron nitride is a purely synthetic material that has been known for over 150 years but only recently has sparked interest as a semiconductor material due to its potential in ultraviolet lasing and neutron detection. Thin-layer hexagonal boron nitride (hBN) is probably most attractive as a complementary material to graphene during its intense research endeavors. But for hBN to be successful in the realm of semiconductor technology, methods for growing large single crystals are critical, and its properties need to be accurately determined. In this study, hBN crystals were grown from metal solvents. The effects of soak temperature, soak time, source materials and their proportions on hBN crystal size and properties were investigated. The largest crystals of hBN measured five millimeters across and about 30 micrometers thick by precipitation from BN powder dissolved in a nickel-chromium solvent at 1700°C. High temperatures promoted outward growth of the crystal along the a-axis, whereas low temperatures promoted growth along the c-axis. Crystal growth at high temperatures also caused bulk hBN to adopt a triangular habit rather than a hexagonal one. A previously unreported method of synthesizing hBN was proven successful by substituting BN powder with elemental boron and a nitrogen ambient. XRD and Raman spectroscopy confirmed hBN from solution growth to be highly crystalline, with an 8.0 cm[superscript]-1 FWHM of the Raman peak being the narrowest reported. Photoluminescence spectra exhibited peaks mid-gap and near the band edge, suggesting impurities and defects in the hBN samples. However, high-purity reactants and post-growth annealing showed promise for synthesizing semiconductor-grade hBN. Several etchants were explored for defect-selective etching of hBN. A molten eutectic mixture of KOH/NaOH was the most effective defect-selective etchant of hBN at temperatures of 430-450°C for about one minute. The two prevalent hexagonal etch pit morphologies observed were deep, pointed-bottom pits and shallow, flat-bottom pits. TEM and SAED confirmed basal plane twists and dislocations in hBN crystals, but due to the highly anisotropic nature of hBN, their existence may be inevitable no matter the growth technique.

Master of Science / Department of Agronomy / Dorivar Ruiz Diaz / The limitation of an essential nutrient for plant growth can affect crop yield. Research has been focused mainly on macronutrients, nevertheless micronutrients are equally important. This thesis is divided into three studies, which had the purpose of assessing frequent questions that producers have about micronutrient fertilizers and their effect on several crops in Kansas. The objective of the first study was to summarize and analyze results from studies since 1962 until 2015 to verify responses to zinc (Zn) and sulfur (S) fertilization in corn (Zea mays), sorghum (Sorghum bicolor (L.) Moench), wheat (Triticum aestivum) and soybean (Glycine max (L.) Merr). The treatments evaluated consisted of fertilizer Zn or S application versus their respective unfertilized treatments. Zinc fertilization significantly increased corn yield; no significant response was found for sorghum, wheat and soybean. Sulfur fertilization did not increase yields on corn and wheat. The objectives of the second study were: (i) to evaluate soybean response to S and micronutrients boron (B), copper (Cu), manganese (Mn), and Zn fertilizer application and to assess soil test and soybean seed and tissue nutrient concentration with fertilization. Treatments consisted of an unfertilized control, micronutrient fertilizer as individual nutrient for B, Cu, Mn, S and Zn applied broadcast pre-plant, in addition to a blend of these nutrients using two different placements (broadcast and band). Secondary and micronutrient fertilization showed no significant effect on soybean yield at any of the ten locations. Zinc fertilization showed significant effects on soybean tissue and seed Zn concentration. The objective of the third study was to evaluate soybean tissue nutrient response to micronutrient fertilizers in field strips with high variability in soil properties in the area evaluated. The study consisted of two strips (with and without fertilizer) and replicated three times. The treatment with fertilizer included a blend of Cu, Mn and Zn at a rate of 11.2 kg ha⁻¹ and B at a rate of 2.8 kg ha⁻¹. Initial soil tests B, Cu, Mn and Zn were not good indicators of soybean tissue response. Within-field variability of soybean Zn and B tissue content were affected by soil pH and organic matter; and these factors may be used to help explain field variability in plant availability. The micronutrient blend treatment showed higher tissue Zn and B values compared to the control. When pH ranged from 5.5 to 7.6, B in soybean tissue was higher on the control than the micronutrient blend treatment. Copper concentration in soybean tissue did not show significant difference between treatments at any location, regardless of pH and organic matter levels.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / The semiconductor boron phosphide (BP) has many outstanding features making it attractive for developing various electronic devices, including neutron detectors. In order to improve the efficiency of these devices, BP must have high crystal quality along with the best possible electrical properties. This research is focused on growing high quality crystalline BP films on a variety of superior substrates like AIN, 4H-SiC, 3C-SiC and ZrB₂ by chemical vapor deposition. In particular, the influence of various parameters such as temperature, reactant flow rates, and substrate type and its crystalline orientation on the properties of BP films were studied in detail. Twin-free BP films were produced by depositing on off-axis 4H-SiC(0001) substrate tilted 4° toward [1-100] and crystal symmetry matched zincblende 3C-SiC. BP crystalline quality improved at higher deposition temperature (1200°C) when deposited on AlN, 4H-SiC, whereas increased strain in 3C-SiC and increased boron segregation in ZrB₂ at higher temperatures limited the best deposition temperature to below 1200°C. In addition, higher flow ratios of PH₃ to B₂H₆ resulted in smoother films and improved quality of BP on all substrates. The FWHM of the Raman peak (6.1 cm⁻¹), XRD BP(111) peak FWHM (0.18°) and peak ratios of BP(111)/(200) = 5157 and BP(111)/(220) = 7226 measured on AlN/sapphire were the best values reported in the literature for BP epitaxial films. The undoped films on AlN/sapphire were n-type with a highest electron mobility of 37.8 cm²/V·s and a lowest carrier concentration of 3.15x1018 cm⁻ᶟ. Raman imaging had lower values of FWHM (4.8 cm⁻¹) and a standard deviation (0.56 cm⁻¹) for BP films on AlN/sapphire compared to 4H-SiC, 3C-SiC substrates. X-ray diffraction and Raman spectroscopy revealed residual tensile strain in BP on 4H-SiC, 3C-SiC, ZrB₂/4H-SiC, bulk AlN substrates while compressive strain was evident on AlN/sapphire and bulk ZrB₂ substrates. Among the substrates studied, AlN/sapphire proved to be the best choice for BP epitaxy, even though it did not eliminate rotational twinning in BP. The substrates investigated in this work were found to be viable for BP epitaxy and show promising potential for further enhancement of BP properties.

M.Sc. / The origin of a wine plays a key role in establishing the quality and the price the consumer is prepared to pay. Fingerprinting techniques based on multi-element data combined with multivariate statistical analysis as well as isotope ratio data for certain elements such as boron (11B/10B) and strontium (87Sr/86Sr) are being developed and have been used for provenance determination of wine with varying degrees of success. The aim of this study was to develop a method to determine boron isotope ratios (11B/10B) with the required precision using ICP-MS (inductively coupled plasma mass spectrometry) in soil and wine samples and applying this method to establish the origin of South African wines. Analytical difficulties such as the boron memory effect, dead time, mass bias drift and matrix effects were investigated. Although the memory effect, dead time and mass bias drift were satisfactorily resolved, it was not possible to determine what the cause of all the observed matrix effects was during this study. The method was used to categorise wines from the Robertson, Swartland and Stellenbosch regions and an attempt was made to link the measured boron isotope ratios with that obtained from the corresponding provenance soils. The 11B/10B isotope ratios for the wine samples (Robertson: 4.202 ± 0.014, Swartland: 4.173 ± 0.013 and Stellenbosch: 4.174 ± 0.028) were, however, higher than the ratios obtained for the soil samples (Robertson: 4.108 ± 0.020, Swartland: 4.070 ± 0.023 and Stellenbosch: 4.124 ± 0.039). It was possible to distinguish, using the boron isotope ratios (wine and soil samples), between the Robertson area (Breede River region) and the Swartland area (Coastal region). The wine and soil 11B/10B isotope ratios obtained for the Stellenbosch area (Coastal region) overlapped with the 11B/10B isotope ratios of the Robertson and Swartland regions making it impossible to differentiate it from these two regions.

A thesis submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Doctor of Philosophy.‘ Johannesburg, August 2017 / Fe-B-C composites were produced, from boron carbide and iron powders, using spark plasma sintering. This provided information on the effects of rapid sintering on densification, composition and the microstructure of the materials produced. The composition range included a selection high Fe contents (69.3, 78 and 80.9 vol. % Fe-B4C) and high B4C concentrations (1, 3, 5 vol. % Fe-B4C). The properties of the materials were investigated to determine the potential for using relatively cheap Fe and B4C powders to produce hard, wear resistant materials. High Fe-B4C composites were sintered at 900, 1000 and 1100°C at 60 MPa. Densification increased with increasing temperature and at 1100° each composition achieved ≥ 97 % densification. The materials reacted during sintering with the main phases observed being Fe2B and Fe3(B,C) whilst additional phases formed were FeB, C and Fe23(B,C)6.Comparing the phases that were produced to Fe-B-C phase diagrams showed deviations from expected compositions, indicating the non-equilibrium nature of producing the composites using SPS. Although the composites were not at equilibrium, all the B4C reacted and could not be maintained, even with fast heating and cooling rates. The properties of the materials were dependent on both densification and the phases that were present after sintering. Materials containing higher amounts of the Fe2B phase showed higher hardness and fracture toughness results, up to 13.7 GPa and 3.5 MPa.m0.5 respectively for the 69.3 vol. % Fe-B4C. The materials were sensitive to grain and pore growth which negatively affected properties at 1100°C. The transverse rupture strength of 388.3 MPa for 80.9 vol. % Fe-B4C composite was the greatest, and showed evidence of both intergranular and transgranular fracture. The strength was affected by a fine dispersion of porosity at the grain boundaries, throughout the material, and free carbon in the structure was detrimental to the strength of the 69.3 % Fe-B4C. The wear rates were lower using Si3N4 wear balls compared to stainless steel balls, where 69.3 vol. % Fe-B4C showed the best wear rates, 8.9×10-6 mm3/Nm (stainless steel ball) and 1.77×10-6 mm3/Nm (Si3N4 ball), due to the higher Fe2B composition and free carbon acting as a lubricant during sliding. 1, 3 and 5 vol. % Fe-B4C composites were sintered to densities above 97 % of theoretical at 2000°C and 30 MPa. The formation of a transient FeB liquid phase assisted densification. 1 % Fe-B4C attained hardness and fracture toughness up to 33.1 GPa and 5.3 MPa.m0.5 with a strength of 370.5 MPa. Thermal mismatch between the FeB phase and B4C caused high residual stresses at the interface which led to cracking and pull-out of the FeB phase. Residual carbon at the grain boundary interface exacerbated the pull-out effect. Increasing Fe and the subsequent FeB phase had an embrittling effect. The materials suffered severe wear of up to 36.92×10-6 mm3/Nm as a result of the pull-out with the remaining porosity acting as a stress raiser. 20 vol. % of the Fe in each system was substituted with Ti to reduce the presence of residual carbon. Although in some case the properties of the respective compositions improved, residual carbon was still present in the composites. / MT2018

L’objectif principal de ce travail de thèse a été l’optimisation des conditions de croissance du diamant dans un réacteur MPACVD afin d’une part, obtenir des films de diamant monocristallin à faible densité de dislocations, condition sine qua none pour une utilisation dans le domaine de l’électronique de puissance et, d’autre part, synthétiser des films épais (>100 μm) de diamant monocristallin intrinsèque et fortement dopés au bore sur substrats orientés (111), orientation cristalline connue pour favoriser la formation de macles. Dans une première partie, nous avons développé un procédé d’infléchissement et de confinement desdislocations en utilisant des substrats en forme de pyramide orientés (100) et en déterminant des conditions de croissance bien particulières. Cette étude innovante et originale a permis de lever plusieurs verrous scientifiques et technologiques qui ouvrent la voie à la réalisation de films de diamant monocristallin à faible densité de défauts. Dans une deuxième partie, l’effetdes différents paramètres de croissance a été étudié, afin d’optimiser notre procédé de croissance sur orientation (111). Il a ainsi été mis en évidence l’existence d’une fenêtre de couple pression/puissance micro-onde, température et concentration en méthane qui permettent d’assurer un bon compromis entre qualité cristalline et vitesse de croissance, permettant la synthèse de films épais de diamant fortement dopé au bore sur cette orientation ouvrant ainsi la possibilité de combiner l’efficacité de dopage de type n et la réalisation de composants bipolaires verticaux pour des applications en électronique haute tension-hautetempérature. / The main objective of this PhD thesis is the optimization of diamond growth conditions in a MPACVD reactor in order to one hand, synthesize single crystal diamond films with low dislocation density, prerequisite to their use in the field of power electronics and on the other hand, synthesize thick intrinsic and boron doped monocrystalline diamond films (>100 microns) on (111)-oriented substrates, crystallographic orientation which is well known to promote twinning. In a first part, a process of inflection and confinement of the dislocations has been developed using (100) pyramidal shape substrates coupled with specific growth conditions. This innovative and original study open the way for the fabrication of single crystal diamond films with low defect density. In a second part, the effect of different growth parameters has been studied to optimize our growth process for (111) orientation. It was thus demonstrated the existence of a narrow window of growth parameters pressure, microwavepower, temperature and methane concentration which ensures a good trade-off between crystalline quality and growth rate, allowing the synthesis of heavily boron-doped diamond thick films on this specific orientation, thus opening the possibility of combining the n-type doping efficiency and achieving vertical bipolar components for applications in hightemperaturehigh-voltage electronics.