Au début du XXIème siècle, la Microscopie Electronique à Transmission en mode Environnemental (ETEM) est devenue l’une des techniques les plus fiables de caractérisation de nanomatériaux dans des conditions simulant leur vie réelle. L’ETEM est maintenant en mesure de suivre l’évolution dynamique des nanomatériaux dans des conditions variables comme l’exposition à des températures élevées, l’observation en milieux liquide ou gazeux à diverses pressions. Parmi différents domaines de recherche et développement concernés, la catalyse peut bénéficier de manière significative des avancées permises par la microscopie électronique environnementale. Cette thèse, dédiée au développement de l’ETEM au laboratoire MATEIS, a commencé avec l’étude du système catalytique Pd-alumine. Les nanoparticules de Pd déposées sur alpha -Al2O3 et delta-Al2O3 sont très utilisées en physicochimie avec un impact environnemental important : en particulier dans le domaine de l’hydrogénation sélective, pour la synthèse de polymères ou l’hydrogénation de CO2 pour la production de méthane. Nous avons tout d’abord effectué des analyses 2D aux différentes étapes du processus de synthèse du catalyseur : imprégnation du précurseur, séchage et chauffage pour la calcination dans l’air à la pression atmosphérique. La motivation de cette approche a été de comparer des analyses post mortem avec des traitements en ETEM où l’évolution des nanoparticules peut être mesurée in situ et pas seulement « avant » et « après ». De manière générale, les études faites en ETEM en 2D donnent un aperçu limité sur la morphologie des objets et la distribution spatiale des nanoparticules supportées. Nous avons développé une nouvelle approche d’acquisition rapide pour collecter dans des temps très courts des séries d’images sous différents angles de vue pour la tomographie électronique, la rapidité de cette acquisition étant un prérequis pour appréhender correctement la morphologie d’un nano-système au cours de son évolution dynamique in situ. La technique a ensuite été utilisée pour l’étude de plusieurs systèmes où une acquisition tridimensionnelle rapide est indispensable, notamment sur un sujet concernant un enjeu sociétal important, la dépollution des moteurs diesel : l’oxydation de la suie a été étudiée in situ sur des supports à base de zircone entre 400 et 600°C et une pression de 2 mbar d’oxygène à différents degrés de combustion, ce qui a permis d’extraire des données cinétiques telle que l’énergie d’activation du processus. La tomographie électronique rapide a été également appliquée à des matériaux sensibles au faisceau électronique, comme des nanocomposites polymères et des objets biologiques, montrant le large spectre d’applications possibles pour cette technique, qui constitue un pas important vers la caractérisation operando 3D de nanomatériaux en temps réel. / In the beginning of the XXIst century, Environmental Transmission Electron Microscopy has become one of the reliable characterization techniques of nanomaterials in conditions mimicking their real life. ETEM is now able to follow the dynamic evolution of nanomaterials under various conditions like high temperature, liquid or various gas pressures. Among various fields of research, catalysis can benefit significantly from Environmental Microscopy. This contribution starts with the study of the Palladium-Alumina catalytic system. Pd nanoparticles supported by α-Al2O3 and δ-Al2O3 are of an important physicochemical and environmental interest, particularly in the field of selective hydrogenation in petrochemistry, for the synthesis of polymers or CO2 hydrogenation for methane production. We first performed 2D analyses at different steps of the synthesis process, then the same synthesis steps were performed under in situ conditions. The motivation of this approach was to compare post mortem treatments with ETEM observations. In general, 2D data provide limited insights on, for example, the morphology and position of supported nanoparticles. We have then developed a new fast acquisition approach to collect tomographic tilt series in very short times, enabling to reconstruct nano-systems in 3D during their dynamical evolution. Taking advantage of this approach, we have determined the activation energy for soot combustion on YSZ oxidation catalysts for diesel motors from volumetric data extracted from in situ experiments. Fast electron tomography was also applied to electron beam sensitive materials, like polymer nanocomposites and biological materials, showing the wide spectrum of possible applications for rapid 3D characterization of nanomaterials.

Indium phosphide (InP) is an important III-V compound, with a variety of applications, for example, in light emitting diodes (LED), InP based photonic crystals and in semiconductor lasers, heterojunction bipolar transistors in integrated circuit applications and in transistors for microwave and millimeter-wave systems. The optical and electrical properties of this compound can be further tailored by ion implantation or prospectively by swift heavy ion beams. ¶ Thus knowledge of ion-induced disorder in this material is of important fundamental and practical interest. However, the disorder produced during heavy ion irradiation and the subsequent damage accumulation and recovery in InP is far from being completely understood. In terms of the damage accumulation mechanisms, the conclusions drawn in the numerous studies performed have often been in conflict with one another. A factor contributing to the uncertainties associated with these conflicting results is a lack of information and direct observation of the “building blocks” leading to the ultimate damage created at high ion fluences as an amorphous layer. These building blocks formed at lower fluence regimes by single ion impacts can be directly observed as isolated disordered zones and ion tracks for low energy and swift heavy ion irradiation, respectively. ¶ The primary aim of this work has thus been to obtain a better understanding of the disorder in this material through direct observations and investigation of disorder produced by individual heavy ions in both energy regimes (i.e. elastic and inelastic energy deposition regimes) especially with low ion fluence irradiations. In this thesis the heavy ion induced disorder introduced by low energy Au ions (100 keV Au+) and high energy Au (200 MeV Au+16) ion irradiation in InP were investigated using Transmission Electron Microscopy (TEM), Rutherford Backscattering Spectrometry (RBS/C) and Atomic Force Microscopy (AFM). ¶ The accumulation of damage due to disordered zones and ion tracks is described and discussed for both low energy and swift ion irradiation respectively. ¶ The in-situ TEM annealing of disordered zones created by 100 keV Au+ ion irradiation shows that these zones are sensitive to electron beam irradiation and anneal under electron energies not sufficient to elastically displace lattice atoms, i.e. subthreshold energies for both constituent atoms In and P. ¶ Ion tracks due to swift heavy ion irradiation were observed in this material and the interesting track morphology was described and discussed. The surface nanotopographical changes due to increasing fluence of swift heavy ions were observed by AFM where the onset of large increase in surface roughness for fluences sufficient to cause complete surface amorphization was observed. ¶ In addition to InP, the principle material of this project, a limited amount of TEM observation work has been performed on several other important compounds (apatite and monazite) irradiated by 200 MeV Au+ ions for comparative purposes. Again the observed segmental morphology of ion tracks were shown and possible track formation scenario and structure were discussed and similarities were drawn to the previously observed C60 cluster ion tracks in CaF2 as more knowledge and data base exist about defect dynamics and formation in that material.

Materials in smaller scales exhibit promising properties that are useful for wide variety of applications. Semiconductor quantum wells and quantum dots are two main examples of low-dimensional systems, where the quantum wells act as two-dimensional systems and the quantum dots act as zero-dimensional systems. Alternatively, semiconductor nanowires act as one-dimensional materials, and they exhibit promising and device applicable properties. These nanowires are relatively new class of materials compared to the quantum wells and the quantum dots. The semiconductor nanowires are expected to be the building blocks for future nanoelectronic and nano-optoelectronic device technology. Vapor-liquid-solid (VLS) mechanism is a widely used mechanism for the growth of semiconductor nanowires, where metal nanoparticles are used as the catalysts for the nanowires growth. This growth mechanism offers a flexibility to control the size, morphology and location of the semiconductor nanowires. In the VLS growth, changing the chemical composition of vapor constituents produce consequent compositional modulation in each nanowire. The compositional modulation along the nanowire axis produces axial nanowire heterostructures and in radial direction produces radial nanowire heterostructures. Such compositional modulation within an individual nanowire enables the designing of band structure of a nanowire and thereby allows the fabrication of single nanowire devices. These nanowire heterostructures show many potential properties and consequent applications. Although the semiconductor nanowire heterostructures are promising semiconductor nanostructures, the fundamental growth mechanisms of axial and radial nanowire heterostructures have not been explored sufficiently due to their complex nature of the growth. In this regard, this PhD thesis addresses the fundamental issues associated with axial and radial nanowire heterostructures. For such fundamental investigations, this PhD work chooses InAs/GaAs nanowire heterostructure system due to its potential applications. In fact, InAs/GaAs nanowire heterostructures are the first reported axial nanowire heterostructure system. However, no detailed investigations were reported on this system so far. The detailed nucleation and growth mechanisms associated with InAs/GaAs nanowire heterostructure system are explored in this thesis using electron microscopy investigations. This objective is achieved in the following steps. • InAs/GaAs nanowire heterostructures are grown using Au nanoparticles and metal-organic chemical vapor deposition (MOCVD) method. To determine the axial and radial growth evolution of InAs on GaAs nanowires, different InAs/GaAs nanowire heterostructures are produced by depositing InAs for different durations on GaAs nanowires. The GaAs nanowires are initially grown for 30 min and then the InAs is deposited on these nanowires for 1, 3, 5 and 30 min. • These InAs/GaAs nanowire heterostructures are subjected to scanning electron microscopy (SEM) and transmission electron microscopy (TEM) investigations. These investigations determine that, in the initial stages of the InAs axial growth (1 min), the Au particles move sidewards and subsequently downwards by maintaining an interface with the GaAs nanowire. Such a movement of Au catalysts is attributed to lower Au/GaAs interfacial energy than Au/InAs. The detailed TEM investigations show that this Au movement depends upon the crystallographic nature of the GaAs nanowire. The Au particle is always tend to move towards {112}B sidewall of the GaAs nanowire rather than its {112}A sidewalls. Increase in InAs growth duration shows that InAs branches evolve from GaAs-InAs core-shell structures. Such evolution is observed in following steps: (1) the movement of Au particle terminates when it encounters the radially grown InAs on GaAs nanowires; (2) further growth of InAs leads to the InAs nanowire growth from those terminated Au nanoparticles in the form of branches. • The TEM observations of InAs/GaAs nanowire heterostructures show that, in the initial stages of InAs radial growth on GaAs nanowires, InAs nucleates preferentially in the concave regions of the non-planar sidewalls of the GaAs nanowire. The further growth of InAs leads to the preferential formation of InAs shell structure at the regions of concave regions. Such heterogeneous formation of shell structure resembles InAs nanoring structures around GaAs nanowire cores. InAs growth on the planar {112} sidewalls of GaAs nanowires with hexagonal cross sections shows different growth phenomena to the above described InAs nanorings formation. In this case, InAs preferentially nucleates on {112}A sidewalls of the GaAs nanowires and with further deposition of InAs, the complete shell structure of InAs form with {110} sidewalls on the GaAs nanowire cores. • In addition to the above mentioned investigations, to observe the growth evolution of GaAs on InAs nanowires, GaAs is grown for 3 and 30 min on InAs nanowires. The TEM investigations of these nanostructures show that the axial GaAs/InAs hetero-interface contains an InGaAs transition segment in contrast to the sharp InAs/GaAs (InAs on GaAs) hetero-interface. The different nature of hetero-interfaces is attributed to the different affinities between Au catalysts and Ga or In. The radial growth of GaAs on InAs nanowires show that the GaAs shell has grown in wurtzite structure around the wurtzite structured InAs nanowire cores. Overall, through the extensive SEM and TEM investigations, this PhD thesis addresses the fundamental issues related to the growth of axial and radial nanowire heterostructures. Such fundamental investigations are expected to advance the processing and application prospective of the semiconductor nanowires and their associated heterostructures.

The present thesis reports on the transmission electron microscopy structure characterization of semiconducting thin films of higher manganese silicides (HMS or MnSi1.7) grown on (001)Si by different UHV deposition methods (the template method, reactive deposition and surfactant mediated reactive deposition). In this work electron diffraction technique was applied for the fist time to reveal the HMS phase growing in thin MnSi1.7 films. The obtained results suggest the presence of the shortest in c-axis length HMS phase, namely Mn4Si7, within our experiments. It has been shown that growth of epitaxial Mn4Si7 grains can be achieved by the template technique. In particular, the influence of the template thickness on the silicide layer quality has been investigated. It has been found that deposition of a thin Mn layer of 0.8 nm nominal thickness at room temperature prior to the Mn/Si codeposition at 550°C causes the formation of a silicide template that leads to the preferred epitaxial Mn4Si7 growth with (110)[4-41]Mn4Si7 || (001)[110]Si. Silicide crystallites of two additional orientation relations, (3-38)[-443]Mn4Si7 || (001)[110]Si and (001)[110] Mn4Si7 || (001)[110]Si, were present at the same template thickness to a lesser extent. Due to the crystal symmetry of Mn4Si7 and Si the epitaxial Mn4Si7 growth on (001)Si leads to the formation of a number of Mn4Si7 domains for each observed orientation. Additional experiments were carried out using the reactive deposition process. It has been shown that the deposition of Mn onto (001)Si at substrate temperatures higher then 600°C leads to the formation of large silicide islands growing with the major part of their elongated grains parallel to <110>Si. XRD investigations show the observed silicide grains to exhibit the following texture: (110)Mn4Si7 || (001)Si. The found island morphology of Mn4Si7 films can be modified by the deposition of about one monolayer of Sb (surfactant) onto (001)Si prior to the Mn-deposition. This process results in an increase of the silicide island density by about two orders of magnitude and decrease of the silicide grain dimensions to nanometer range. Furthermore, in the presence of Sb the silicide layers grow with the preferential orientation: (100)[010]Mn4Si7 || (001)[100]Si. The observed changes in the morphology and orientation of the Mn4Si7 layers can be explained by the reduced diffusion of Mn and Si atoms in the presence of the Sb overlayer. / In der vorliegenden Arbeit wird die Struktur von dünnen MnSi1.7-Schichten, die mit verschiedenen UHV-Herstellungsmethoden (template-Verfahren, reaktive Abscheidung und surfactant gesteuerte Abscheidung) auf (001)Si hergestellt wurden, mittels Elektronenmikroskopie charakterisiert. Die Ergebnisse der Elektronenbeugung an dünnen Mangansilicid-Schichten können vollständig interpretiert werden, wenn von den bekannten höheren Mangansiliciden (HMS) das Mn4Si7 als einzige vorliegende Phase angenommen wird. Der Hauptteil der Arbeit beschäftigt sich mit den mittels template-Verfahren abgeschiedenen Mn4Si7-Schichten. In diesen Experimenten wurde der Einfluss der template-Dicke auf die Morphologie und Orientierung der hergestellten Schichten untersucht. Es wird gezeigt, dass bei der Abscheidung von einer dünnen Mn-Schicht mit einer nominalen Dicke von 0,8 nm bei Raumtemperatur und weiterer Mn/Si-Koabscheidung bei einer Substrattemperatur von 550°C nahezu geschlossene Silicidschichten mit der bevorzugten Orientierungsbeziehung (110)[4-41]Mn4Si7 || (001)[110]Si entstehen. Weiterhin wachsen bei dieser template-Dicke Mn4Si7-Kristallite mit den Orientierungsbeziehungen: (3-38)[-443]Mn4Si7 || (001)[110]Si und (001)[110] Mn4Si7 || (001)[110]Si. Bei jeder gefundenen Orientierungsbeziehung treten beim Wachstum von Mn4Si7 auf (001)Si mehrere Domäne auf. Zusätzliche Experimente wurden unter Verwendung der reaktiven Schichtabscheidung durchgeführt. Sie verdeutlichen, dass bei reaktiver Abscheidung von Mn auf (001)Si ab einer Substrattemperatur von 600°C ein Wachstum von Mn4Si7-Inseln entlang den [110]-Richtungen des Siliciums erfolgt. XRD-Untersuchungen zeigen, dass diese Inseln die folgende Textur haben: (110)Mn4Si7 || (001)Si. Durch eine Modifizierung der Si-Oberfläche mit einer bis zu einer Monolage dicken Sb-Schicht (surfactant) kann das Mn4Si7-Inselwachstum beeinflusst werden. Die dabei gefundene Erhöhung der Mn4Si7-Inseldichte wird hier auf die reduzierte Mn- und Si-Diffusion zurükgeführt. Weiterhin wurde gefunden, dass dieser Abscheidungsprozess Mn4Si7-Kristallite der bevorzugten Orientierung (100)[010]Mn4Si7 || (001)[110]Si liefert.

β-lactam antibiotics have long been a reliable course of treatment for bacterial infections. However, with recent increases in resistance and rising populations of immunocompromised patients new β-lactams have been synthesized and tested. The Turos laboratory has recently discovered novel β-lactams that have a mode of action distinct from penicillin and other β-lactam antibiotics as cell lysis is not observed. In the current investigations, these compounds are shown to also have antifungal properties. The rising incidence and prevalence of invasive fungal infections has become an increasing concern. The most common fungal pathogens involved in these infections are species in the genus Candida. In this study antifungal activity is observed for a wide range of N-methylthio β-lactams against C. albicans, C. tropicalis, C. keyfr, C. glabrata, C. lusitinae, C. utilis, and C. parapsilosis. The structure-activity relationship based on studies of β−lactam derivatives leaving different substituents at various positions on the lactam ring are investigated, and the minimum inhibitory concentration values determined using standard methods. In studies towards understanding the mode of action, the products of the interaction between the drug and fungal cells in a suspension were investigated using nuclear magnetic resonance spectroscopy and transmission electron microscopy. The mode of action of these new lactams seems to be similar to that observed in bacteria, involving transfer of the methylthio group to a cellular thiol.

Mesozooplankton are of critical importance to marine food webs by transferring energy from the microbial food web to higher trophic levels and depositing energy to the deeper ocean layers through fecal deposition. While decades of research have shown that viruses have significant impacts in the oceans, and infect a wide range of organisms from bacteria to whales, there is still little known about the impacts of viruses on the mesozooplankton community. As copepods are the most abundant mesozooplankton group, this study sought to characterize the viruses present in natural populations of the calanoid copepods Acartia tonsa and Labidocera aestiva in Tampa Bay, Florida. Viral metagenomics revealed two virus genomes, named Acartia tonsa copepod circovirus (AcCopCV) and Labidocera aestiva copepod circovirus (LaCopCV), which were discovered in their respective copepod species. Both viruses show amino-acid similarities to known circoviruses, and phylogenetic and genomic analyses suggest they may be divergent members of the Circoviridae family. LaCopCV was found to be extremely prevalent in the L. aestiva population, with up to 100% of individuals infected. High viral loads for LaCopCV were observed by quantitative PCR, with an average viral load of 1.3x105 copies per individual. In addition, transcription of the LaCopCV replication gene was detected in L. aestiva, demonstrating active viral replication. AcCopCV could be detected sporadically in A. tonsa populations throughout the year. The circoviruses were specific to their respective hosts, and were not detected in the other copepod species or surrounding seawater. Virus-like particles were observed in A. tonsa and L. aestiva under transmission electron microscopy, demonstrating that viruses were actively proliferating in copepod connective tissue, as opposed to gut tissue, parasites, or symbionts. Preliminary results from in-situ hybridization show that the AcCopCV genome can be detected in A. tonsa tissue, linking the discovered genomes to virus propagation in copepod tissue. This is the first study describing viruses in copepods, as well as the first discovery of circoviruses infecting marine organisms. These results suggest that viruses impact marine copepod populations, necessitating further studies to determine the ecological impacts of viruses on the mesozooplankton community.

A precise understanding of the fundamental correlation between synthesis, microstructure and physical properties is of vital importance towards rational design of improved functional epitaxial thin films. With the presence of heterogeneous interface and associated inhomogeneous lattice strain, film microstructure becomes sensitive to subtle interfacial perturbations and hence may exhibit intriguing physical properties. Control of the epitaxial film functionality requires accurate knowledge of the actual film chemistry, interfacial defects and associated strain field. This dissertation reports in-depth microstructural characterization of the intrinsic chemical inhomogeneity in selected epitaxial thin films including superconducting Fe1+yTe1-xSex/SrTiO3(STO) heterogeneous systems, the flux-pinning defects at both of conversional YBa2Cu3O7-δ (YBCO)/substrate lateral interfaces and vertical interfaces of YBCO&BaSnO3(BSO) nanocomposite films, and the misfit dislocation core configurations of STO/MgO and MgO/STO heterostructures pair, using the state-of-the-art aberration-corrected scanning transmission electron microscopy (CS-corrected STEM) in combination with geometric phase analysis (GPA). For the first time, the local atomic arrangement of Te and Se as well as interstitial Fe(2) has been clearly revealed in superconducting Fe1+yTe1-xSex/STO epitaxial films. We found that the film growth atmosphere can greatly affect the film stoichiometry, the homogeneity of Se/Te ordering and thus the overall film superconductivity. YBCO/substrate interface mismatch and YBCO&BSO vertical interface contact have been explored through substrate selection and doping-concentration variation. We observed a diverse nature of intrinsic defects in different YBCO/substrate heterosystems; thermal stable defects capable of maintaining individual strain field have been found effective in flux-pinning. Along the vertical heterointerface of YBCO/BSO, misfit dislocations were found throughout the film thickness. It adds another dimension to the flux-pinning landscape design. Four basic misfit dislocation core configurations of a STO/MgO heterosystem have been identified, and found strongly dependent on the actual interface disordering such as substrate atomic-height steps and interdiffussion. To precisely quantify the heterointerface lattice strain, we first conducted systematic investigations on the accuracy of STEM-based GPA. Follow our protocol, 1 pm accuracy has been proven in the STEM fast-scan direction with a spatial resolution less than 1 nm. The effectiveness and reliability of this optimized GPA strain profile were demonstrated in both applications of a relaxed STO/MgO and a partially strained LaAlO3/STO heterointerfaces, respectively.

No description available.

No description available.

Martensite-to-Beta transformation temperatures of CuAlNiMn and CuAlNi shape memory alloys has been determined by differential scanning calorimetry (DSC). In CuAlNiMn alloys, each new betatizing treatment has resulted in randomly varying transformation temperatures on the same specimen and an anomalously diffuse and serrated Martensite-to-Beta transformation peaks in the first cycle. Therefore, as quenched alloy samples were thermally cycled for three times in DSC prior to ageing to obtain thermally stable and reproducible transformation temperatures and to eliminate the anomalous effect of betatizing on the transformation temperatures. CuAlNiMn alloys were aged in martensitic condition at temperatures in the range 80&amp / #61616 / C to 150&amp / #61616 / C for 24 hours to 312 hours ageing periods. Both A_s and A_f temperatures have increased with ageing temperature and time while M_s and M_f temperatures have not changed during martensite ageing. Transformation temperatures of CuAlNi alloys, on the other hand, have not changed during martensite ageing. In this respect, CuAlNiMn alloys were found to be more prone to martensite stabilization than the CuAlNi alloys. Through Transmission Electron Microscope investigation in the Cu-12.6wt%Al-5.9wt%Ni-1.8wt%Mn alloy aged at 150&amp / #61616 / C for 312 hours has revealed no sign of precipitate formation and it has been concluded that the &amp / #65533 / precipitates pinning martensite boundaries&amp / #65533 / mechanism could not be responsible of martensite stabilization. Beta phase ageing of CuAlNiMn alloys at temperatures 200&amp / #61616 / C, 230&amp / #61616 / C, 250&amp / #61616 / C and 270&amp / #61616 / C, have drastically shortened the periods for stabilization to the extent that &amp / #946 / -to-M transformation completely ceases. With regard to the Manganese content, highest Manganese bearing alloy was the one stabilized first and the lowest manganese containing one was the longest lasting alloy during beta phase ageing. Beta stabilization was not observed in any of the four CuAlNi alloys at the end of 96 hours ageing at 200&amp / #61616 / C while beta stabilization was realized after 26, 38 and 11 hours ageing at the same temperature in the three Mn containing alloys studied. In conclusion, on the basis of ageing studies at 200&amp / #61616 / C, with regard to beta stabilization, CuAlNi alloys were found to be more resistant to high temperature ageing than CuAlNiMn alloys. Equilibrium &amp / #947 / _2 and &amp / #945 / phases were observed with coupled-grown lamellar morphologies in Cu-13.6%Al-3.0%Ni alloy aged above 400&amp / #61616 / C.