By an improved understanding of Mg-doped GaN through an exhaustive review of current limitations, increased control over the material was achieved by addressing several of these issues. To address the issues of the memory effect, low sticking coefficient and high vapor pressure of Mg, a new Mg dopant source was implemented, characterized and modeled for p-type doping of GaN. The device enhanced the sticking coefficient of Mg by energizing the outgoing Mg flux, and also allowed the first reported demonstration of an abrupt junction between two non-zero Mg concentrations and a graded Mg-doped GaN film. The significant compensation of Mg acceptors at high dopant concentrations was used advantageously to develop a new ex situ resistivity analysis technique using the energy distributions of SIMS to characterize doping of buried layers. The new technique was used to identify the barrier between conductive and resistive Mg doping for increased Mg concentration, which was then used to optimize Mg-doped GaN. Because Mg doping exhibits a dependence upon the growth regime, a new growth and regime characterization technique was developed using specific RHEED intensity responses to repeat growth conditions. During the development of this technique, a new surface kinetics growth model for III-nitrides was discovered based on DMS observations, which suggests preferential buildup of the metal bilayer before growth begins with an unfamiliar cation-anion exchange process initially upon metal shutter opening. Using the new RHEED growth and regime characterization technique, a new growth technique called metal modulated epitaxy (MME) was developed to increase repeatability, uniformity and smoothness. The MME technique was enhanced with a closed-loop control using real-time feedback from RHEED transients to control shutter transitions. This enhancement, called smart shuttering, led to improved growth rate and further improvement of surface roughness and grain size, which were repeatable within low percentages. Effects of smart-shuttering MME were observed with Si, Mg and In during GaN growths. Repeatable Mg-doped GaN was achieved with a variation of less than 8%, and a peak hole carrier concentration of 4.7E18 cm^-3.

In der vorliegenden Arbeit wurde das Wachstum der planaren aromatischen Moleküle Perylen-3,4,9,10-tetracarbonsäure-3,4,9,10-dianhydrid (PTCDA) und Peri-Hexabenzocoronen (HBC) auf verschiedenen einkristallinen Oberflächen von Gold und Graphit untersucht. Zur Abscheidung der Moleküle und zur Herstellung dünner hochgeordnerter organischer Schichten wurde eine Molekularstrahlepitaxieanlage mit mehreren Kammern aufgebaut. Bei den Untersuchungen des Wachstums von PTCDA auf der Au(111)- und Au(100)-Fläche wurden drei Klassen von Strukturen gefunden: Eine Fischgrätenstruktur, deren Gitterparameter und molekulare Anordnung der (102)-Ebene des PTCDA-Kristalls entsprechen, eine quadratische Struktur, sowie eine Stabstruktur, die der (010)-Ebene des PTCDA-Kristalls zugeordnet werden kann. Während die Stabstruktur auf Au(100) ein inkommensurables Wachstum zeigt, konnten alle anderen PTCDA-Strukturen sowohl auf Au(111) als auch auf Au(100) als point-on-line epitaktisch klassifiziert werden. Die HBC-Schichten auf Au(111), Au(100)hex und Graphit zeigen abweichend von der Kristallstruktur eine hexagonale Symmetrie. Auf Graphit wächst HBC in einer kommensurablen Struktur. Auf den beiden Au-Oberflächen existieren mehrere Strukturen, die sich in ihrer Orientierung und ihren Gitterkonstanten unterscheiden. Neben einer dominierenden HBC-Struktur lassen sich auf den Au-Flächen weitere Strukturen beobachten, deren Auftreten durch den Bedeckungsgrad und die Substratmorphologie, d.h. die Stufenzahl und Terrassengröße des Substrates bestimmt wird. Alle diese HBC-Strukturen konnten als kommensurabel klassifiziert werden. Die Anordnung der HBC-Moleküle in Multilagen wurde für das System HBC auf Au(100)hex mit Hilfe molekularmechanischer Berechnungen modelliert. Die HBC-Moleküle sind in der zweiten Lage gegenüber denen der ersten Lage so verschoben, dass die C-Atome der Moleküle eine graphitähnliche Anordnung zeigen. Wie die STM Untersuchung der organischen Heteroschichten aus HBC und PTCDA zeigen, ist es möglich, epitaktische organische Heteroschichten auch von Molekülen herzustellen, die sich in ihren Gitterkonstanten und in der Symmetrie unterscheiden. Erstmals ließen sich derartige Schichten mittels Rastertunnelmikroskopie direkt und durch LEED auch im reziproken Raum abbilden. Aus dem in den STM Bildern sichtbaren Moirékontrast wurde die Orientierung der beiden organischen Gitter bestimmt. PTCDA wächst bezüglich des HBC-Gitters weder kommensurabel noch point-on-line koinzident, zeigt jedoch eine feste Winkelorientierung. Es handelt sich in diesem Fall um eine inkommensurable Struktur bezüglich des HBC-Gitters, die jedoch bezüglich des zugrundeliegenden Graphitgitters point-on-line Koinzidenz zeigt. Das Versagen der einfachen geometrischen Epitaxiemodelle kann in diesem Fall auf die Existenz mehrerer, energetisch nahezu gleichwertiger Adsorptionsplätze innerhalb der Einheitszelle des Substrates zurückgeführt werden.

Higher frequencies in the MHz and GHz range and the increasing miniaturization lead to a higher load of the SAW (surface acoustic wave) metallizations. This higher SAW load and the intrinsic stresses result in a stress induced material transport, called acoustomigration. These microstructural changes can destroy the characteristic of the SAW device. Different Al based material combinations were investigated by different authors to improve the reliability of the metallizations and to delay the cost-intensive change to Cu based metallizations. The Cu based metallizations with TaSiN diffusion barriers were also investigated in this work. The barrier layers are necessary to impede the oxygen diffusion into the Cu layer and the Cu diffusion into the piezoelectric substrate. Also in this work the analytical TEM were used as a tool to investigate these microstructural changes in the SAW electrodes. Chemical changes in the metallizations were analysed by EDXS and EELS. The locally high resolved stress measurement in metallizations is a challenge for the future. The CBED (convergent beam electron diffraction) technique has shown the best resolution, however, it can only be applied to TEM lamellas. The aim of this work was to measure the stress within the SAW metallizations by using the CBED method. With it, we could correlate the microstructural changes with the causing stresses within the metallizations. To qualify the CBED method the thermal expansion of Al and Cu single crystals was measured by using a new model for thin TEM lamallas.

Structural characterization is essential for the understanding of the magnetic properties of thin films and multilayers. In this thesis, both crystalline and amorphous thin films and multilayers were analyzed utilizing transmission electron microscopy (TEM). High resolution TEM and electron diffraction studies emphasize on the growth of amorphous Fe91Zr9 and Co68Fe24Zr8 on both Al2O3 and Al70Zr30 in multilayer structures by magnetron sputtering. The properties of the growth surfaces were found to strongly influence the formation of nano-crystallites of the magnetic material at interfaces. Field induced uniaxial magnetic anisotropy was found to be possible to imprint into both fully amorphous and partially crystallized Co68Fe24Zr8 layers, yielding similar magnetic characteristics regardless of the structure. These findings are important for the understanding of both growth and magnetic properties of these amorphous thin films. As magnetic systems become smaller, new analysis techniques need to be developed. One such important step was the realization of electron energy-loss magnetic circular dichroism (EMCD) in the TEM, where information about the ratio of the orbital to spin magnetic moment (mL/mS) of a sample can be obtained. EMCD makes use of angular dependent inelastic scattering, which is characterized using electron energy-loss spectroscopy. The work of this thesis contributes to the development of EMCD by performing quantitative measurements of the mL/mS ratio. Especially, methods for obtaining energy filtered diffraction patterns in the TEM together with analysis tools of the data were developed. It was found that plural inelastic scattering events modify the determination of the mL/mS ratio, wherefore a procedure to compensate for it was derived. Additionally, utilizing special settings of the electron gun it was shown that EMCD measurements becomes feasible on the nanometer level through real space maps of the EMCD signal.

Uranium-zirconium (U-Zr) alloys comprise a class of metallic nuclear fuel that is regularly considered for application in fast nuclear energy systems. The U-10wt%Zr alloy has been demonstrated to very high burnup without cladding breach in the Experimental Breeder Reactor-II (EBR-II). This was accomplished by successfully accommodating gaseous fission products with low smear density fuel and an enlarged cladding plenum. Fission gas swelling behavior of the fuel has been experimentally revealed to be significantly affected by the temperature gradient within a fuel pin and the multiple phase morphologies that exist across the fuel pin. However, the phase effects on swelling behavior have not been yet fully accounted for in existing fuel performance models which tend to assume the fuel exists as a homogeneous single phase medium across the entire fuel pin. Phase effects on gas bubble nucleation and growth in the alloy were investigated using transmission electron microscopy (TEM). To achieve this end, a comprehensive examination of the alloy system was carried out. This included the fabrication of uranium alloys containing 0.1, 2, 5, 10, 20, 30, 40, and 50 wt% zirconium by melt-casting. These alloys were characterized using electron probe micro-analysis (EPMA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Once the alloys were satisfactorily characterized, selected U-Zr alloys were irradiated with 140 keV He^(+) ions at fluences ranging from 1 × 10^(14) to 5 × 10^(16) ions/cm^(2). Metallographic and micro-chemical analysis of the alloys indicated that annealing at 600 °C equilibrates the alloys within 168 h to have stable α-U and δ-UZr_(2) phase morphologies. This was in contrast to some reported data that showed kinetically sluggish δ-UZr_(2) phase formation. Phase transformation temperatures and enthalpies were measured using DSC-TGA for each of the alloys. Measured temperatures from different time annealed alloys have shown consistent matches with most of the features in the current U-Zr phase diagram which further augmented the EPMA observed microstructural equilibrium. Nevertheless, quantitative transformation enthalpy analysis also suggests potential errors in the existing U-Zr binary phase diagram. More specifically, the (β-U, γ2) phase region does not appear to be present in Zr-rich (> 15 wt%) U-Zr alloys and so further investigation may be required. To prepare TEM specimens, characterized U-Zr alloys were mechanically thinned to a thickness of ~150 μm, and then electropolished using a 5% perchloric acid/95% methanol electrolyte. Uranium-rich phase was preferentially thinned in two phase alloys, giving saw-tooth shaped perforated boundaries; the alloy images were very clear and alloy characterization was accomplished. During in-situ heating U-10Zr and U-20Zr alloys up to 810 °C, selected area diffraction (SAD) patterns were observed as the structure evolved up to ~690 °C and the expected α-U → β-U phase transformation at 662 °C was never observed. For the temperature range of the (α-U, γ2) phase region, phase transformation driven diffusion was observed as uranium moved into Zr-rich phase matrix in U-20Zr alloy; this was noted as nonuniform bridging of adjacent phase lamellae in the alloy. From the irradiation tests, nano-scale voids were discovered to be evenly distributed over several micrometers in U-40Zr alloys. For the alloys irradiated at the fluences of 1 × 10^(16) and 5 × 10^(16) ions/cm^(2), estimated void densities were proportional to the irradiation doses, (250 ± 40) and (1460 ± 30) /μm^(2), while void sizes were fairly constant, (6.0 ± 1.5) and (5.2 ± 1.2) nm, respectively. Measured data could be foundational inputs to the further development of a semi-empirical metal fuel performance model.

No description available.

Novel open-framework germanates and vanadoborates, which are constructed from typical types of clusters, have been synthesized based on different strategies. The crystal structures are solved by using single crystal X-ray diffraction (SXRD) technique or by combined techniques. Additionally, the structures of two open-framework materials, PKU-3 and PKU-16, are determined from nano-sized crystals by rotation electron diffraction (RED) combined with powder X-ray diffraction (PXRD). This thesis serves as an introduction to synthesis of open-framework germanates and vanadoborates based on different design strategies. Two germanates are obtained; SU-74 is achieved by employing a novel structure directing agent (SDA), SUT-8 is achieved by assembling the novel structure building units (SBUs) of Co@Ge14 with the introduction of cobalt ions in the synthesis. Four strategies are successfully used in construction of open-framework vanadoborates: using metal-oxo polyhedra as the linkages in SUT-6; applying the scale chemistry approach in SUT-7; employing metal-organic complexes as the linkages in SUT-12, SUT-13, SUT-14; and introducing covalent bond organic linkages into SUT-10 and SUT-11. Single crystal X-ray diffraction is used to conduct the structure determination in combination with other techniques. Furthermore, the structures of two open-framework materials, an aluminoborate PKU-3 and a germanosilicate PKU-16, are solved from nano-sized crystals using RED data. The structures are further confirmed by Rietveld refinement against PXRD data. The advantages of the RED techniques are demonstrated in two aspects. In PKU-3, the presence of seriously preferred orientation and light elements in the structure makes it difficult for structure determination by PXRD, but it is easier by RED. In PKU-16, the RED technique is used to determine its structure from the as-synthesized multi-phasic sample containing nano-sized crystals. After the structure of PKU-16 has been solved, the synthesis of this interesting phase can be optimized and pure PKU-16 can be obtained. Keywords: Open-framework, germanates, vanadoborates, aluminoborates, germanosilicates, crystal structure, hydrothermal synthesis, single crystal X-ray diffraction, rotation electron diffraction, powder X-ray diffraction

No description available.

De par leurs propriétés physico-chimiques spécifiques, les nanomatériaux attirent de plus en plus la communauté scientifique. Dans ce contexte, il est important d'améliorer les techniques de caractérisation à l'échelle nanométrique. Ce travail de thèse est basé sur le développement de techniques de diffraction électronique pour l'étude de matériaux bi-dimensionnels et tri-dimensionnels.La diffraction électronique en faisceau convergent contient de nombreuses informations sur la structure l'échantillon. Ces informations, portées par les lignes de HOLZ, permettent de déterminer l'épaisseur de l'échantillon, le facteur de structure, la direction d'observation, la tension d'accélération des électrons, ainsi que la longueur de caméra. Des ambiguïtés existent dans la détermination de l'état de contraintes car un cliché expérimental est une projection bi-dimensionnelle d'une information tri-dimensionnelle. Il a été possible au cours de cette thèse de réduire ces ambiguïtés et de déterminer ainsi les composantes diagonales du tenseur de déformation à partir d'une seule direction d'observation. En étudiant l'élargissement des lignes de HOLZ, dû à une déformation non uniforme dans le sens de propagation des électrons, il a été possible de remonter au champ de déplacement suivant l'axe du faisceau d'électrons.La seconde partie de cette thèse s'intéresse aux matériaux bi-dimensionnels comme le Graphène, le Nitrure de Bore (BN) et le disulfure de Molybdène (MoS2). L'interprétation du contraste d'une image de microscopie électronique en transmission haute résolution est discutée, notamment sur l'importance de l'orientation de l'échantillon et des aberrations. Une méthode de mesure de l'orientation d'un échantillon bi-dimensionnel basée sur la projection des tâches de diffraction est présentée. Enfin, trois techniques de mesure d'épaisseur sont comparées en les appliquant à quelques couches atomique de MoS2 et BN. / The small dimensions of nanomaterials give them remarkable properties attracting the scientific community. In order to understand and control these properties, it is essential to characterize them at the nanometer scale. This thesis work is based on the development of electron microscopy diffraction techniques for the study of two and three dimensional materials.Convergent Beam Electron Diffraction patterns contain large amount of information on the sample geometry. This information, carried by HOLZ lines, allows to determine the sample thickness, the structure factor, the direction of observation, the electron acceleration voltage and the camera length. Ambiguities in strain measurement arise from the experimental two-dimensional projection of three-dimensional information. During this thesis, it has been possible to reduce these ambiguities and therefore to measure the diagonal components of the deformation gradient tensor from one direction of observation only. By studying the HOLZ lines broadening, due to a non-uniform strain along the electron beam direction, it has been possible to retrieve the displacement field along the beam direction.The second part of this thesis is focused on the study of two-dimensional materials such as Graphene, Boron Nitride (BN) or Molybdenum disulfide (MoS2). The delicate interpretation of the contrast of high-resolution transmission electron microscopy images and especially the importance of aberrations and sample tilt on this contrast is discussed. A method to quantify two-dimensional sample orientation using diffraction spots projection effect is presented. Finally, three thickness measurement techniques are compared by applying them to few-layered MoS2 et BN.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-04-08T12:56:51Z No. of bitstreams: 0 / Made available in DSpace on 2016-04-08T12:56:51Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP