Das reaktiv gesteuerte Ionenstrahlätzen von optischen Aluminiumoberflächen bietet einen vielversprechenden Prozessansatz, um Formfehlerkorrektur, Glättung periodischer Drehstrukturen und die Reduzierung von Rauheitsmerkmalen im Ortsfrequenzbereich der Mikrorauheit in einer Technologie zu kombinieren. Diese Arbeit konzentriert sich auf die experimentelle Analyse der niederenergetischen Ionenbestrahlung von einkorn-diamantgedrehten, technischen Aluminiumlegierungen RSA Al6061 und RSA Al905. Die Ionenstrahlbearbeitung unter Verwendung der Prozessgase Sauerstoff und Stickstoff ermöglicht eine direkte Oberflächenformfehlerkorrektur bis zu 1 µm Bearbeitungstiefe unter Beibehaltung der Ausgangsrauheit. Die sich aus dem vorangegangenen Formgebungsverfahren, dem Einkorn-diamantdrehen, ergebende Drehmarkenstruktur schränkt allerdings häufig die Anwendbarkeit dieser Spiegeloberflächen im kurzwelligen Spektralbereich ein. Daher wurde im Rahmen dieser Arbeit ein zweistufiger Prozessablauf entwickelt, um eine weitere Verbesserung der Oberflächenrauheit zu erreichen. Durch die Ionenstrahl-Planarisierungstechnik unter Verwendung einer Opferschicht werden die im hohen Ortsfrequenzbereich liegenden Drehmarken erfolgreich um insgesamt 82 % reduziert. Eine Kombination mit anschließender, direkter Ionenstrahlglättung zur nachfolgenden Verbesserung der Mikrorauigkeit wird vorgestellt. Um die Prozessführung in einem industrietauglichen Rahmen zu etablieren, wurden die experimentellen Untersuchungen mit einer 13,56 MHz betriebenen Hochfrequenz-Ionenquelle durchgeführt, konnten aber auch erfolgreich auf eine Breitstrahl-Ionenquelle vom Typ Kaufman übertragen werden.:Bibliographische Beschreibung iv Danksagung vi Table of Contents viii 1 Introduction 1 2 Surface engineering with energetic ions 8 2.1 Ion target interactions during ion beam erosion 8 2.2 Ion beam finishing methods 10 2.2.1 Ion beam figuring 11 2.2.2 Ion beam planarization 12 2.2.3 Ion beam smoothing 14 3 Experimental set-up and analytical methods 15 3.1 Experimental set-up 15 3.2 Kaufman-type broad beam ion source 18 3.3 Materials 19 3.3.1 Aluminium alloy materials 19 3.3.2 Photoresist materials as planarization layer 21 3.4 Surface topography error regimes 22 3.5 Analytical Methods 23 3.5.1 Analysis of surface roughness 23 3.5.1.1 White light interferometry (WLI) 23 3.5.1.2 Atomic force microscopy (AFM) 25 3.5.1.3 Power spectral density (PSD) analysis 27 3.5.2 Scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX) 29 3.5.3 X-ray photoelectron spectroscopy (XPS) 31 3.5.4 Time of flight- secondary ion mass spectrometry (ToF-SIMS) 32 3.5.5 Reflectometry 34 3.5.6 Photoresist composition 35 3.5.6.1 Attenuated total reflection infrared spectroscopy (ATR-IR) 35 3.5.6.2 Thermogravimetric analysis (TGA) 36 3.5.6.3 Differential scanning calorimetry (DSC) 38 3.5.6.4 Gas chromatography coupled mass spectrometry (GC-MS) 39 4 Surface engineering by reactive ion beam etching 41 4.1 Reactive ion beam etching with nitrogen 41 4.1.1 Dependence of the aluminium alloy composition 42 4.1.2 Ion beam etching of Al905 44 4.2 Local smoothing by reactive ion beam etching 50 4.2.1 Local surface error slope dependent sputter erosion 51 4.2.2 RIBE O2 direct smoothing 56 4.2.2.1 Oxygen finishing at 1.5 keV 56 4.2.2.2 Oxygen finishing at 0.6 keV 62 4.3 Conclusions 66 5 Technological aspects on photoresist preparation for ion beam planarization 69 5.1 Selection of a suitable photoresist 69 5.2 Photoresist application steps 71 5.2.1 DUV exposure of the photoresist layer 72 5.2.2 Postbake: the influence of the amount of organic solvent 73 5.2.3 Postbake: the influence of the baking temperature 74 5.3 Influence of process gas composition 77 5.3.1 Influence on roughness evolution during ion beam irradiation of the photoresist layer 78 5.3.2 Dependency of the process gas on the selectivity 79 5.4 Influence of the ion energy on the selectivity 80 5.5 Ion beam irradiation of the photoresist layer with nitrogen at different material removal depths 81 5.6 Conclusions 82 6 Ion beam planarization of optical aluminium surfaces RSA Al6061 and RSA Al905 84 6.1 Photoresist application on SPDT aluminium alloys 84 6.2 Ion beam planarization 85 6.2.1 Iterative nitrogen processing of RSA Al905 86 6.2.2 Iterative nitrogen processing of RSA Al6061 90 6.3 Ion beam direct smoothing 93 6.3.1 RIBE O2 smoothing of RSA Al905 93 6.3.2 RIBE O2 smoothing of RSA Al6061 97 6.4 Conclusions 101 7 Process transfer to a Kaufman-type broad beam ion source 103 7.1 RIBE machining investigations on RSA Al905 103 7.2 Ion beam planarization of RSA Al6061 106 7.3 Ion beam incidence angle dependent sputtering 107 7.4 Conclusions 113 8 Summary 115 9 Conclusions and Outlook 123 A List of abbreviations 127 B Selected properties of photoresist materials 129 References 131 / Reactively driven ion beam etching of optical aluminium surfaces provides a promising process route to combine figure error correction, smoothing of periodically turning structures and roughness features situated in the microroughness regime within one technology. This thesis focuses on experimental analysis of low-energy ion beam irradiation on single-point diamond turned technical aluminium alloys RSA Al6061 and RSA Al905. Reactively driven ion beam machining using oxygen and nitrogen process gases enables the direct surface error correction up to 1 µm machining depth while preserving the initial roughness. However, the periodic turning mark structures, which result from preliminary device shaping by single-point diamond turning, often limit the applicability of mirror surfaces in the short-periodic spectral range. Hence, during this work a two-step process route was developed to attain further improvement of the surface roughness. Within the ion beam planarization technique with the aid of a sacrificial layer, the turning marks situated in the high spatial frequency range are successfully reduced by overall 82 %. A combination with subsequently applied direct ion beam smoothing procedure to perform a subsequent improvement of the microroughness is presented. In order to establish the process control in an industrial framework, the experimental investigations were performed using a 13.56 MHz radio frequency ion source, but the developed process routes are also successfully transferred to a broad-beam Kaufman-type ion source.:Bibliographische Beschreibung iv Danksagung vi Table of Contents viii 1 Introduction 1 2 Surface engineering with energetic ions 8 2.1 Ion target interactions during ion beam erosion 8 2.2 Ion beam finishing methods 10 2.2.1 Ion beam figuring 11 2.2.2 Ion beam planarization 12 2.2.3 Ion beam smoothing 14 3 Experimental set-up and analytical methods 15 3.1 Experimental set-up 15 3.2 Kaufman-type broad beam ion source 18 3.3 Materials 19 3.3.1 Aluminium alloy materials 19 3.3.2 Photoresist materials as planarization layer 21 3.4 Surface topography error regimes 22 3.5 Analytical Methods 23 3.5.1 Analysis of surface roughness 23 3.5.1.1 White light interferometry (WLI) 23 3.5.1.2 Atomic force microscopy (AFM) 25 3.5.1.3 Power spectral density (PSD) analysis 27 3.5.2 Scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX) 29 3.5.3 X-ray photoelectron spectroscopy (XPS) 31 3.5.4 Time of flight- secondary ion mass spectrometry (ToF-SIMS) 32 3.5.5 Reflectometry 34 3.5.6 Photoresist composition 35 3.5.6.1 Attenuated total reflection infrared spectroscopy (ATR-IR) 35 3.5.6.2 Thermogravimetric analysis (TGA) 36 3.5.6.3 Differential scanning calorimetry (DSC) 38 3.5.6.4 Gas chromatography coupled mass spectrometry (GC-MS) 39 4 Surface engineering by reactive ion beam etching 41 4.1 Reactive ion beam etching with nitrogen 41 4.1.1 Dependence of the aluminium alloy composition 42 4.1.2 Ion beam etching of Al905 44 4.2 Local smoothing by reactive ion beam etching 50 4.2.1 Local surface error slope dependent sputter erosion 51 4.2.2 RIBE O2 direct smoothing 56 4.2.2.1 Oxygen finishing at 1.5 keV 56 4.2.2.2 Oxygen finishing at 0.6 keV 62 4.3 Conclusions 66 5 Technological aspects on photoresist preparation for ion beam planarization 69 5.1 Selection of a suitable photoresist 69 5.2 Photoresist application steps 71 5.2.1 DUV exposure of the photoresist layer 72 5.2.2 Postbake: the influence of the amount of organic solvent 73 5.2.3 Postbake: the influence of the baking temperature 74 5.3 Influence of process gas composition 77 5.3.1 Influence on roughness evolution during ion beam irradiation of the photoresist layer 78 5.3.2 Dependency of the process gas on the selectivity 79 5.4 Influence of the ion energy on the selectivity 80 5.5 Ion beam irradiation of the photoresist layer with nitrogen at different material removal depths 81 5.6 Conclusions 82 6 Ion beam planarization of optical aluminium surfaces RSA Al6061 and RSA Al905 84 6.1 Photoresist application on SPDT aluminium alloys 84 6.2 Ion beam planarization 85 6.2.1 Iterative nitrogen processing of RSA Al905 86 6.2.2 Iterative nitrogen processing of RSA Al6061 90 6.3 Ion beam direct smoothing 93 6.3.1 RIBE O2 smoothing of RSA Al905 93 6.3.2 RIBE O2 smoothing of RSA Al6061 97 6.4 Conclusions 101 7 Process transfer to a Kaufman-type broad beam ion source 103 7.1 RIBE machining investigations on RSA Al905 103 7.2 Ion beam planarization of RSA Al6061 106 7.3 Ion beam incidence angle dependent sputtering 107 7.4 Conclusions 113 8 Summary 115 9 Conclusions and Outlook 123 A List of abbreviations 127 B Selected properties of photoresist materials 129 References 131

In an electron fluid, both resistive and viscous mechanisms can be present. In systems with perfect translational invariance momentum is a conserved quantity, and as the electrons carry both charge and momentum, the current cannot decay. Predictions from theories at the particle physics-condensed matter physics interface using the `AdS/CFT' correspondence suggest that hydrodynamic charge flow might exist in some exotic metallic states. In the high-Tc cuprates the T-linear resistivity in the strange metal regime is conjectured to be due to hydrodynamic effects. In this dissertation, I start out drawing a theoretical outline of the hydrodynamic theory of electron transport in solids. In the search for a high purity metal that can host such a hydrodynamic electron transport, we looked at the non-magnetic delafossite oxides PdCoO2 and PtCoO2, which have the highest conductivities of any known oxides, and whose key properties I will review. As the signatures of viscosity can only be realised in transport through boundary scattering, the samples had to be taken down to the mesoscopic limit, where the momentum conserving and relaxing scattering mean free paths of the material are comparable to the channel width. I will discuss the focussed ion beam (FIB) micro-structuring technique that I have implemented to fabricate the mesoscopic devices. To interpret the transport in the mesoscopic regime, a comprehensive understanding of the bulk transport is first necessary and I will present my measurements of the magnetoresistance and Hall effect in both materials, which show deviations from the predictions of standard models highlighting some intriguing physics even in the bulk limit. Finally, I will present the data from magnetotransport measurements at the mesoscopic limit. Magnetic field introduces a variable length scale, the cyclotron radius, in the system which can be used to tune through different transport regimes. I will discuss the ballistic and hydrodynamic signatures in the transport that becomes accessible through magnetic field tuning in the mesoscopic samples of the delafossites PdCoO2 and PdCoO2.

L’objectif principal de ce travail est d’optimise la tomographie par coupe sériée dans un microscope ‘FIB’, en utilisant soit l’imagerie électronique du microscope à balayage (tomographie FIB-MEB), soit la diffraction des électrons rétrodiffusés (tomographie dite EBSD 3D). Dans les 2 cas, des couches successives de l’objet d’étude sont abrasées à l’aide du faisceau ionique, et les images MEB ou EBSD ainsi acquises séquentiellement sont utilisées pour reconstruire le volume du matériau. A cause de différentes sources de perturbation incontrôlées, des dérives sont généralement présentes durant l'acquisition en tomographie FIB-MEB. Nous avons ainsi développé une procédure in situ de correction des dérives afin de garder automatiquement la zone d'intérêt (ROI) dans le champ de vue. Afin de reconstruction le volume exploré, un alignement post-mortem aussi précis que possible est requis. Les méthodes actuelles utilisant la corrélation-croisée, pour robuste que soit cette technique numérique, présente de sévères limitations car il est difficile, sinon parfois impossible de se fier à une référence absolue. Ceci a été démontré par des expériences spécifiques ; nous proposons ainsi 2 méthodes alternatives qui permettent un bon alignement. Concernant la tomographie EBSD 3D, les difficultés techniques liées au pilotage de la sonde ionique pour l'abrasion précise et au repositionnement géométrique correct de l’échantillon entre les positions d'abrasion et d’EBSD conduisent à une limitation importante de la résolution spatiale avec les systèmes commerciaux (environ 50 nm)3. L’EBSD 3D souffre par ailleurs de limites théoriques (grand volume d'interaction électrons-solide et effets d'abrasion. Une nouvelle approche, qui couple l'imagerie MEB de bonne résolution en basse tension, et la cartographie d'orientation cristalline en EBSD avec des tensions élevées de MEB est proposée. Elle a nécessité le développement de scripts informatiques permettant de piloter à la fois les opérations d’abrasion par FIB et l’acquisition des images MEB et des cartes EBSD. L’intérêt et la faisabilité de notre approche est démontrée sur un cas concret (superalliage de nickel). En dernier lieu, s’agissant de cartographie d’orientation cristalline, une méthode alternative à l’EBSD a été testée, qui repose sur l’influence des effets de canalisation (ions ou électrons) sur les contrastes en imagerie d’électrons secondaires. Cette méthode corrèle à des simulations la variation d’intensité de chaque grain dans une série d’images expérimentales obtenues en inclinant et/ou tournant l’échantillon sous le faisceau primaire. Là encore, la méthode est testée sur un cas réel (polycritsal de TiN) et montre, par comparaison avec une cartographie EBSD, une désorientation maximale d'environ 4° pour les angles d’Euler. Les perspectives d’application de cette approche, potentiellement beaucoup plus rapide que l’EBSD, sont évoquées. / The aim of current work is to optimize the serial-sectioning based tomography in a dual-beam focused ion beam (FIB) microscope, either by imaging in scanning electron microscopy (so-called FIB-SEM tomography), or by electron backscatter diffraction (so-called 3D-EBSD tomography). In both two cases, successive layers of studying object are eroded with the help of ion beam, and sequentially acquired SEM or EBSD images are utilized to reconstruct material volume. Because of different uncontrolled disruptions, drifts are generally presented during the acquisition of FIB-SEM tomography. We have developed thus a live drift correction procedure to keep automatically the region of interest (ROI) in the field of view. For the reconstruction of investigated volume, a highly precise post-mortem alignment is desired. Current methods using the cross-correlation, expected to be robust as this digital technique, show severe limitations as it is difficult, even impossible sometimes to trust an absolute reference. This has been demonstrated by specially-prepared experiments; we suggest therefore two alternative methods, which allow good-quality alignment and lie respectively on obtaining the surface topography by a stereoscopic approach, independent of the acquisition of FIB-SEM tomography, and realisation of a crossed ‘hole’ thanks to the ion beam. As for 3D-EBSD tomography, technical problems, linked to the driving the ion beam for accurate machining and correct geometrical repositioning of the sample between milling and EBSD position, lead to an important limitation of spatial resolution in commercial softwares (~ 50 nm)3. Moreover, 3D EBSD suffers from theoretical limits (large electron-solid interaction volume for EBSD and FIB milling effects), and seems so fastidious because of very long time to implement. A new approach, coupling SEM imaging of good resolution (a few nanometres for X and Y directions) at low SEM voltage and crystal orientation mapping with EBSD at high SEM voltage, is proposed. This method requested the development of computer scripts, which allow to drive the milling of FIB, the acquisition of SEM images and EBSD maps. The interest and feasibility of our approaches are demonstrated by a concrete case (nickel super-alloy). Finally, as regards crystal orientation mapping, an alternative way to EBSD has been tested; which works on the influence of channelling effects (ions or electrons) on the imaging contrast of secondary electrons. This new method correlates the simulations with the intensity variation of each grain within an experimental image series obtained by tilting and/or rotating the sample under the primary beam. This routine is applied again on a real case (polycrystal TiN), and shows a max misorientation of about 4° for Euler angles, compared to an EBSD map. The application perspectives of this approach, potentially faster than EBSD, are also evoked.

Dehnungssensoren werden zur Überwachung von sicherheitsrelevanten Bauteilen, besonders in Bauteilen aus faserverstärkten Polymermatrixverbundwerkstoffen eingesetzt. Durch deren Integration in das Bauteilinnere werden sie vor schädigenden mechanischen sowie korrosiven Einwirkungen geschützt. Dies gewährleistet eine zuverlässige sowie dauerhafte Funktion. Verschiedene Ansätze zur Weiterentwicklung integrierbarer Dehnungssensoren werden international untersucht. Die Verringerung des Sensordurchmessers auf Abmaße im Bereich des Durchmessers von Verstärkungsfasern ist dabei ein bedeutendes Entwicklungsziel. Insbesondere bei der Integration in Bauteile aus faserverstärkten Kunststoffen sorgen zum Durchmesser von Fasern vergleichbare Sensordurchmesser für eine optimale Sensoranbindung. Die Bildung von Harznestern sowie schwächender Unstetigkeiten kann mittels dünner Sensoren verhindert werden. Dies gewährleistet eine artefaktefreie Dehnungsmessung. Drei verschiedene Ansätze für neuartige Dehnungssensoren mit kleinem Querschnitt wurden in dieser Arbeit untersucht. / Strain sensors are used for structural health monitoring issues, certainly in parts with high safety requirements made of fibre-reinforced plastic composites. The integration of these sensors inside the parts protects them against any mechanical and corrosive impact. The sensor functionality can be enhanced by integration. There is a lot of international research effort to further develop integratable strain sensors. Different approaches are currently pursued. This thesis presents the results of investigations on three different approaches for novel strain sensors. The main goal of these investigations was to minimise the sensor diameter down to the diameter of reinforcing fibres. The small diameter allows for an optimum and artefact free integration of the sensors. The formation of resin nests and notches to the material structure can be prevented by integrating sensor with a smaller diameter. The strain measurement and monitoring is enhanced and more reliable then.

Dehnungssensoren werden zur Überwachung von sicherheitsrelevanten Bauteilen, besonders in Bauteilen aus faserverstärkten Polymermatrixverbundwerkstoffen eingesetzt. Durch deren Integration in das Bauteilinnere werden sie vor schädigenden mechanischen sowie korrosiven Einwirkungen geschützt. Dies gewährleistet eine zuverlässige sowie dauerhafte Funktion. Verschiedene Ansätze zur Weiterentwicklung integrierbarer Dehnungssensoren werden international untersucht. Die Verringerung des Sensordurchmessers auf Abmaße im Bereich des Durchmessers von Verstärkungsfasern ist dabei ein bedeutendes Entwicklungsziel. Insbesondere bei der Integration in Bauteile aus faserverstärkten Kunststoffen sorgen zum Durchmesser von Fasern vergleichbare Sensordurchmesser für eine optimale Sensoranbindung. Die Bildung von Harznestern sowie schwächender Unstetigkeiten kann mittels dünner Sensoren verhindert werden. Dies gewährleistet eine artefaktefreie Dehnungsmessung. Drei verschiedene Ansätze für neuartige Dehnungssensoren mit kleinem Querschnitt wurden in dieser Arbeit untersucht. / Strain sensors are used for structural health monitoring issues, certainly in parts with high safety requirements made of fibre-reinforced plastic composites. The integration of these sensors inside the parts protects them against any mechanical and corrosive impact. The sensor functionality can be enhanced by integration. There is a lot of international research effort to further develop integratable strain sensors. Different approaches are currently pursued. This thesis presents the results of investigations on three different approaches for novel strain sensors. The main goal of these investigations was to minimise the sensor diameter down to the diameter of reinforcing fibres. The small diameter allows for an optimum and artefact free integration of the sensors. The formation of resin nests and notches to the material structure can be prevented by integrating sensor with a smaller diameter. The strain measurement and monitoring is enhanced and more reliable then.

An experimental method was further developed to quantify the anisotropy of multi-site fatigue crack initiation behaviors in high strength Al alloys by four-point bend fatigue testing under stress control. In this method, fatigue crack initiation sites (fatigue weak-links, FWLs) were measured on the sample surface at different cyclic stress levels. The FWL density in an alloy could be best described using a three-parameter Weibull function of stress, though other types of sigmoidal functions might also be used to quantify the relationship between FWL density and stress. The strength distribution of the FWLs was derived from the Weibull function determined by fitting the FWLs vs. stress curve experimentally obtained. As materials properties, the FWL density and strength distribution could be used to evaluate the fatigue crack nucleation behaviors of engineering alloys quantitatively and the alloy quality in terms of FWL density and strength distribution. In this work, the effects of environment, types of microstructural heterogeneities and loading direction on FWLs were all studied in detail in AA7075-T651, AA2026-T3511, and A713 Al alloys, etc. It was also found that FWLs should be quantified as a Weibull-type function of strain instead of stress, when the applied maximum cyclic stress exceeded the yield strength of the tested alloys. In this work, four-point bend fatigue tests were conducted on the L-T (Rolling-Transverse), L-S (Rolling-Short transverse) and T-S planes of an AA7075-T651 alloy plate, respectively, at room temperature, 20 Hz, R=0.1, in air. The FWL populations, measured on these surfaces, were a Weibull-type function of the applied maximum cyclic stress, from which FWL density and strength distribution could be determined. The alloy showed a significant anisotropy of FWLs with the weak-link density being 11 mm-2, 15 mm-2 and 4 mm-2 on the L-T, L-S and T-S planes, respectively. Fatigue cracks were predominantly initiated at Fe-containing particles on the L-T and L-S planes, but only at Si-bearing particles on the T-S plane, profoundly demonstrating that the pre-fractured Fe-containing particles were responsible for crack initiation on the L-T and L-S planes, since the pre-fracture of these particles due to extensive deformation in the L direction during the prior rolling operation could only promote crack initiation when the sample was cyclically stressed in the L direction on both the L-T and L-S planes. The fatigue strengths of the L-T, L-S and T-S planes of the AA7075 alloy were measured to be 243.6, 273.0 and 280.6 MPa, respectively. The differences in grain and particle structures between these planes were responsible for the anisotropy of fatigue strength and FWLs on these planes. Three types of fatigue cracks from particles, type-I: the micro-cracks in the particles could not propagate into the matrix, i.e., type-II: the micro-cracks were fully arrested soon after they propagated into the matrix, and type-III: the micro-cracks became long cracks, were observed in the AA7075-T651 alloy after fatigue testing. By cross-sectioning these three-types of particles using Focused Ion Beam (FIB), it was found that the thickness of the particles was the dominant factor controlling fatigue crack initiation at the particles, namely, the thicker a pre-fractured Fe-containing particle, the easier it became a type-III crack on the L-T and L-S planes. On the T-S plane, there were only types-I and III Si-bearing particles at which crack were initiated. The type-I particles were less than 6.5 μm in thickness and type-III particles were thicker than 8.3 μm. Cross-sectioning of these particles using FIB revealed that these particles all contained gas pores which promoted crack initiation at the particles because of higher stress concentration at the pores in connection with the particles. It was also found that fatigue cracks did not always follow the any specific crystallographic planes within each grain, based on the Electron Backscatter Diffraction (EBSD) measurement. Also, the grain orientation did not show a strong influence on crack initiation at particles which were located within the grains. The topography measurements with an Atomic Force Microscope (AFM) revealed that Fe-containing particles were protruded on the mechanically polished surface, while the Si-bearing particles were intruded on the surface, which was consistent with hardness measurements showing that Si-bearing particles were softer (4.030.92 GPa) than Fe-containing ones (8.9 0.87 GPa) in the alloy. To verify the 3-D effects of the pre-fractured particles on fatigue crack initiation in high strength Al alloys, rectangular micro-notches of three different types of dimensions were fabricated using FIB in the selected grains on the T-S planes of both AA2024-T351 and AA7075-T651 Al alloys, to mimic the three types of pre-fractured particles found in these alloys. Fatigue testing on these samples with the micro-notches verified that the wider and deeper the micro-notches, the easier fatigue cracks could be initiated at the notches. In the AA2024-T351 samples, cracks preferred to propagate along the {111} slip plane with the smallest twist angle and relatively large Schmid factor. These experimental data obtained in this work could pave a way to building a 3-D quantitative model for quantification of fatigue crack initiation behaviors by taking into account the driving force and resistance to short crack growth at the particles in the surface of these alloys.

The most promising applications for targeted alpha-therapy with astatine-211 (At-211) include treatments of disseminated microscopic disease, the major medical problem for cancer treatment. The primary advantages of targeted alpha-therapy with At-211 are that the alpha-particle radiation is densely ionizing, translating to high relative biological effectiveness (RBE), and short-range, minimizing damage to surrounding healthy tissues. In addition, theranostic imaging with I-123 surrogates has shown promise for developing new therapies with At-211 and translating them to the clinic. Currently, Canada does not have a way of producing At-211 by conventional methods because it lacks alpha-particle accelerators with necessary beam energy and intensity. The work presented here was aimed at studying the Rn-211/At-211 generator system as an alternative production strategy by leveraging TRIUMF's ability to produce rare isotopes. Recognizing that TRIUMF provided production opportunities for a variety of astatine isotopes, this work also originally hypothesized and evaluated the use of At-209 as a novel isotope for preclinical Single Photon Emission Computed Tomography (SPECT) with applications to At-211 therapy research. At TRIUMF's Isotope Separator and Accelerator (ISAC) facility, mass separated ion beams of short­-lived francium isotopes were implanted into NaCl targets where Rn-211 or At-209 were produced by radioactive decay, in situ. This effort required methodological developments for safely relocating the implanted radioactivity to the radiochemistry laboratory for recovery in solution. For multiple production runs, Rn-211 was quantitatively transferred from solid NaCl to solution (dodecane) from which At-211 was efficiently extracted and evaluated for clinical applicability. This validated the use of dodecane for capturing Rn-211 as an elegant approach to storing and shipping Rn-211/At-211 in the future. Po-207 contamination (also produced by Rn-211 decay) was removed using a granular tellurium (Te) column before proceeding with biomolecule labelling. Although the produced quantities were small, the pure At-211 samples demonstrated these efforts to have a clear path of translation to animal studies. For the first time in history, SPECT/CT was evaluated for measuring At-209 radioactivity distributions using high energy collimation. The spectrum detected for At-209 by the SPECT camera presented several photopeaks (energy windows) for reconstruction. The 77-90 Po X­-ray photopeak reconstructions were found to provide the best images overall, in terms of resolution/contrast and uniformity. Collectively, these experiments helped establish guidelines for determining the optimal injected radioactivity, depending on scan parameters. Moreover, At-209-based SPECT demonstrated potential for pursuing image-­based dosimetry in mouse tumour models, in the future. Simultaneous SPECT imaging with At-209 and I-123 was demonstrated to be feasible, supporting the future evaluation of At-209 for studying/validating I-123 surrogates for clinical image-based At-211 dosimetry. This work also pursued a novel strategy for labelling cancer targeting peptides with At-211, using octreotate (TATE, a somatostatin analogue for targeting tumour cells, mostly neuroendocrine tumours) prepared with or without N-terminus PEGylation (PEG2), followed by conjugation with a closo-decaborate linking moiety (B10) for attaching At-211. Binding affinity and in vivo biodistributions for the modified peptides were determined using iodine surrogates. The results indicated that B10-PEG2-TATE retained target binding affinity but that the labelling reaction with iodine degraded this binding affinity significantly, and although having high in vivo stability, no I-123-B10-PEG2-TATE tumour uptake was observed by SPECT in a mouse tumour model positive for the somatostatin receptor (sstr2a). This suggested that further improvements are required for labelling. A new method for producing At-211 at TRIUMF is established, and At-209-­based SPECT imaging is now demonstrated as a new preclinical technology to measure astatine biodistributions in vivo for developing new radiopharmaceuticals with At-211. Combined with the theranostic peptide labelling efforts with iodine, these efforts provide a foundation for future endeavours with At-211-­based alpha-therapy at TRIUMF. All procedures were performed safely and rapidly, suitable for preclinical evaluations. All animal studies received institutional ethics approval from the University of British Columbia (UBC). / Graduate

Les faisceaux d’électrons et d’ions sont au cœur de nombreuses techniques instrumentales servant à explorer, analyser et agir sur des matériaux à l’échelle du micromètre au nanomètre (Microscopie électronique, spectrométrie d’électrons, techniques de « FIB »). Les limites de résolution spatiale et énergétique de ces techniques dépendent en grande partie des propriétés des sources qu’elles utilisent et en particulier de leur température de fonctionnement. De fait, depuis plus de 10 ans, le potentiel des atomes froids ionisés comme nouveau type de source d’électrons ou d’ions est intensivement exploré.Le projet expérimental réalisé au LAC et décrit dans cette thèse utilise un jet d’atomes de césium issu d’un piège magnéto-optique à deux dimensions. La température transverse du jet est de l’ordre de 100 µK. Malgré cela, le jet est encore trop divergent après la sortie de la zone de refroidissement pour notre expérience. Afin guider le jet d’atomes jusqu’à la zone d’ionisation, nous avons étudié une méthode particulière de guidage dipolaire. L’utilisation d’un seul laser convenablement réglé nous a permis de guider et pousser les atomes du jet en même temps tout en limitant le chauffage. Nous avons ainsi pu compresser avec ce laser pousseur-guideur le jet d’atomes sur un diamètre de 400 µm à 60 cm de la zone de refroidissement du PMO-2D.Le jet est ensuite ionisé par la méthode d’ionisation en champ électrique statique d’atomes de Rydberg. Les atomes sont tout d’abord excités par laser sur un état de Rydberg (n~30) en présence d’un champ électrique uniforme et homogène. Les atomes du jet ainsi excités voyagent vers une zone présentant un fort gradient de champ où ils vont alors s’ioniser autour de la même valeur de potentiel, réduisant ainsi la taille de la zone d’ionisation et donc de la dispersion en énergie potentielle initiale du faisceau d’électron. La probabilité d’ionisation des atomes dans le champ dépend grandement de l’état de Rydberg préalablement excité. Le choix de l’état de Rydberg optimal, i.e. qui a une probabilité d’ionisation la plus grande possible, nécessite une étude de l’ionisation des états de Rydberg du césium. Un modèle à deux niveaux est présenté dans cette thèse qui permet de retrouver le comportement d’ionisation d’état de Rydberg observé expérimentalement. Ce modèle simple nous a permis de comprendre quel type d’état nous devions exciter. Enfin une étude expérimentale est également présentée. / Electron and Ion beams are at the base of many instrumental techniques used to explore, to analyse and to modify materials from the micrometer to the manometer scale (Electronic Microscopy, Electron Spectrometry, Focused Ion beams techniques…). Spatial and Energetic resolutions of these techniques are strongly dependent on its source‘s properties and particularly their working temperature. In fact, for more than ten years, the potential of ionised cold atoms have been intensively studied. Our experiment at LAC, described in this thesis, uses a 2 dimensional magneto-optical trap (2D-MOT) to create a caesium atomic beam. The transverse temperature of the beam is around 100 µK. Despite this, the beam is still too divergent after exiting the cooling area. To guide the atomic beam up to the ionisation area, we have studied and implemented a particular method of dipolar guiding. The use of a unique laser properly set allowed us to push and guide altogether the atoms of the beam while limiting the heating effect. Thus, we have managed to compress the atomic beam’s size to 400 µm at 60 cm from the output of the MOT.Afterward, the atomic beam is ionised by the method of Rydberg (static) field ionisation. The atoms are firstly excited by laser on a Rydberg state (n~30) as a static homogeneous and uniform electric field is applied. The excited atoms of beam travel therefore to a high-gradient field area where they ionise around the same electric potential value, therefore reducing the ionisation area’s size and the initial potential energy spread of the electron beam. The ionisation probability of the atoms in the field depends greatly on the excited Rydberg state. The choice of an optimal Rydberg state , i.e. with the highest probability of ionisation, needs better knowledge of the ionisation of cesium Rydberg states. A two levels model us to describe the ionisation behaviour of some Ryberg. This simple models helps to understand what kind of states we want to excite in order to optimise the ionisation area‘s size. An experimental study of cesium Rydberg states is also presented.

Cette thèse a pour objectif d’apporter des informations quantitatives sur la mobilité de l’hélium dans des céramiques nucléaires avancées comme TiC, TiN et ZrC, soumises à des traitements thermiques ou bien en présence de dommages d’irradiation. L’approche expérimentale développée au cours de ce travail est basée sur l’implantation ionique d’ions d’hélium-3 de 3 MeV en profondeur dans les trois matériaux précédemment cités et sur la mesure du profil de concentration en profondeur de l’isotope 3He au moyen d’une réaction nucléaire spécifique induite par des deutérons, 3He(d, p0)4He. La microscopie électronique à transmission et la spectrométrie Raman sont couplées à l’analyse par réaction nucléaire.Parmi les principaux résultats obtenus :- aucun relâchement d’hélium n’est observé à température ambiante pour les trois composés. Les valeurs d’énergie d’activation associée au relâchement d’hélium après un recuit thermique dans l’intervalle 1100 – 1600°C sont comprises entre 0,77 et 1,2 eV et semblent étroitement liées à la microstructure initiale du composé (stoéchiométrie et taille de grains). La capacité de rétention de l’hélium-3 dans des carbures ou nitrures de métaux de transition soumis à des traitements thermiques en conditions contrôlées croît dans l’ordre ZrC < TiC < TiN.- la formation de blisters n’et observée qu’à la surface de ZrC.- les profils d’implantation d’hélium présentent deux composantes pour les trois matériaux, l’une située au voisinage de la fin de parcours des ions et la seconde plus proche de la surface. Cette dernière résulte probablement du piégeage d’atomes d’hélium par les lacunes natives présentes.- les valeurs obtenues pour le coefficient apparent de diffusion de l’hélium varient dans l’intervalle 3,58E-19 – 5,296E-18 m^2s^-1 pour TiN et 4,20E-18 – 2,59E-17 m^2s^-1 pour TiC.Les valeurs correspondantes obtenues pour l’énergie d’activation sont respectivement de 2,50 eV pour TiC et de 1,05 eV pour TiN. Le mécanisme impliqué repose sur une dissociation des amas atomes d’hélium – lacunes au voisinage de la fin de parcours des ions. Plus en surface, la diffusion est plutôt du type substitutionnel.- l’observation au MET de sections transverses de TiN préparées par la technique FIB révèlent la présence de bulles d’hélium dès recuit à 1100°C et montrent la croissance des bulles avec la température. L’énergie d’activation de croissance des bulles a été estimée à 0,38 eV. A partir de 1400°C, cette croissance résulte vraisemblablement de l’absorption de lacunes par les amas.- la pression interne des bulles a été calculée à l’aide du modèle de Trinkaus, et nous avons montré qu’à partir de 1500°C, cette pression tendait à s’approcher de la valeur du module de cisaillement de TiN (240 GPa) et qu’elle atteignait la pression d’équilibre de 2 GPa à 1600°C.- à 1100°C, il semble que la densité des bulles présentes dans TiN varie linéairement avec la fluence d’implantation. A 1500°C, la taille des bulles est d’autant plus grande que la fluence est faible.- pour ZrC, l’effet de la fluence sur la mobilité de l’hélium est comparable à celui observé pour TiN. A la plus basse fluence, le relâchement d’hélium est très faible. Il croît avec la température de recuit et avec la fluence d’implantation.- la pré-Irradiation des trois composés par des auto-Ions avant implantation d’hélium provoque une augmentation de la dureté au moins =jusqu’à une dose de 27 dpa. Une très faible augmentation du paramètre de maille est alors détectée (≤ 0.5%).- dans le cas de ces matériaux non amorphisables sous irradiation aux ions, le recuit par perte d’énergie électronique ou bien le pré-Endommagement balistique ne jouent a priori aucun rôle sur la mobilité de l’hélium, étudiée sous l’angle d’une activation thermique. / While the current second and third generation nuclear plant designs provides an economically, technically, and publicly acceptable electricity supply in many markets, further advances in nuclear energy system design can broaden the opportunities for the use of nuclear energy. The fourth generation of nuclear reactors is under development. These new reactors are designed with the following objective in mind: sustainability, safety and reliability, economics, proliferation resistance. Out of six Generation IV systems namely, Gas-Cooled Fast Reactor (GFR), Lead-Cooled fast reactor (LFR), Molten Salt Reactor (MSR), Sodium-Cooled Fast Reactor (SFR), Supercritical-Water-Cooled Reactor (SCWR), Very-High-Temperature Reactor (VHTR), this work is dedicated to identify specific fuel type that is compatible with gas-Cooled fast reactor (GFR) in-Core service conditions and could be extended to diagnose potential cladding material for SFR. The French strategy is mainly oriented towards the development of sodium-Cooled fast reactors (SFR) and very slightly focused on GFR. This dissertation is focused on the study of transition metal ceramics which are candidates for fuel coatings in GFR and have been considered as potential cladding materials for SFR. The specific fuel type in GFR should consists of spherical fuel particle made up of UC or UN, surrounded by a ceramic coating which provides structural integrity and containment of fission products. The most promising candidates for ceramic coatings are ZrN, ZrC, TiN, TiC & SiC due to a combination of neutronic performance, thermal properties, chemical behavior, crystal structure, and physical properties. It is obvious that these ceramics would be exposed to energetic fission products from fuel such as heavy ions and neutrons. These high-Energy neutron will knock the atoms in the surrounding materials and can induce (n, α) reactions, thus producing high concentration of helium atoms during and after reactor operation. The helium atoms produced are energetic and can easily penetrate into the surrounding material. Helium atoms are considered to be highly insoluble in previously studied structural nuclear materials. The accumulation of helium into solid matrix, can lead to the formation of bubbles, cavity, swelling, embrittlement etc. Helium can strongly induce grain boundary cavitation that can produce formation of inter-Granular channels, which may serve as pathways for release of radioactive elements to the environment or lead to grain-Boundary weakening and de-Cohesion. Particularly in ceramics, large quantities of helium can also lead to dimensional changes and cracks due to over-Pressurized helium bubbles. Therefore, study of helium behavior in advanced nuclear ceramics under high operating temperatures and extreme radiation conditions predicted for GFRs is viewed as crucial. In this thesis, ion-Implantation technique and material characterization techniques are used to study diffusion of helium in transition metal ceramics under thermal and extreme irradiation environments. Our main aim during this thesis is: 1) To calculate diffusion and migration energies of helium under different experimental conditions by applying theoretical models on experimental data.2) To investigate the role of microstructure such as grain boundaries, native vacancies and porosity on helium accumulation and its evolution after helium accumulation.3) To know the role of helium introduction conditions on helium diffusion. 4) To establish and validate an approach to calculate pressure built by helium gas inside the bubbles and to verify if the pressure approaches mechanical stability limit.

Nos dias atuais, grande parte das intervenções cirúrgicas inclui o implante de materiais. Os grandes obstáculos na implantação de próteses em organismos humanos são a coagulação sanguínea em contato com o material devido ao alto grau de ativação plaquetária e a compatibilidade dos tecidos biológicos ao material implantado. Agregando melhorias de propriedades mecânicas a superfícies biocompatíveis, materiais poliméricos apresentam grandes tendências a serem excelentes candidatos a biomateriais para tais aplicações. O objetivo deste trabalho foi realizar modificações superficiais em polímeros através do método de implantação por feixe iônico a fim de se investigar mudanças induzidas em suas propriedades superficiais e estudar possíveis mudanças em sua biocompatibilidade, em específico, sua hemocompatibilidade. Amostras de policarbonato foram irradiadas com feixes de íons de argônio com energia 23 keV e cinco diferentes doses. As superfícies das amostras foram analisadas com medidas de ângulo de contato, microscopia de força atômica, espectroscopia de massa de íons secundários, espectroscopia de fotoelétrons, espectroscopia de retroespalhamento Rutherford, deteção de recuo elástico, espectroscopia de raios-X induzidos por partículas e testes de adesão plaquetária. Os resultados das diferentes técnicas apontaram de forma consistente a uma série de alterações químicas e físicas induzidas nas superfícies das amostras, dentre elas: a perda significativa de hidrogênio nas amostras irradiadas, aumento do grau de reticulação entre as cadeias poliméricas que levou ao aumento de elétron deslocalizados e mudança de coloração, remoção de aditivos, migração à superfície de átomos de argônio implantados e alteração de hidrofilicidade. Ao confrontar todos os resultados obtidos com os resultados dos testes de adesão plaquetária, constatou-se que os efeitos observados aumentam o caráter trombogênico da superfície do policarbonato e que a remoção de aditivos com grupos sulfato e sulfonato após irradiação com argônio teve grande influência em tal aumento. / In the current days, a big part of the surgical interventions includes the implant of materials. The great obstacles for prosthesis implantation in living organisms are the blood clotting when in contact to the material due to a high level of platelet activation and the biological tissues compatibility to the implanted material. By joining improvements on mechanical properties to biocompatible surfaces, polymer materials present high tendencies to be excellent biomaterials candidates for such applications. The objective of this work was to perform surface modification in polymers through the ion beam implantation method in order to investigate changes induced in their surface properties and study possible biocompatibility changes. Samples of polycarbonate were irradiated with argon ion beam with 23 keV energy and different doses. The surfaces of the samples were analyzed by contact angle measurements, atomic force microscopy, secondary ion mass spectroscopy, x-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy, elastic recoil detection, particle induced x-ray spectroscopy and platelet adhesion tests. The results from the different techniques pointed consistently to a series of chemical and physical changes induced on the samples\' surfaces, such as: significant loss of hydrogen for the irradiated samples, increase of cross-linking between polymer chains which led to the increase of delocalized electrons and color change, removal of additives, migration of argon atoms to the surface and hydrophilicity changes. By comparing all the obtained results to the platelet adhesion tests results, it was found that the observed effects increase the thrombogenic characteristic of the polycarbonate surface and that the removal of additives with sulfate and sulfonate groups after the argon irradiation had great influence on such increase.