No / A novel process chain for serial production of polymer-based devices incorporating both micro- and nano-scale features is proposed. The process chain is enabled by the use of Zr-based bulk metallic glasses (BMG) to achieve the necessary level of compatibility and complementarity between its component technologies. It integrates two different technologies, namely laser ablation and focused ion beam (FIB) milling for micro-structuring and sub-micron patterning, respectively, thus to fabricate inserts incorporating different length scale functional features. Two alternative laser sources, namely nano-second (NS) and pico-second (PS) lasers, were considered as potential candidates for the first step in this master-making process chain. The capabilities of the component technologies together with some issues associated with their integration were studied. To validate the replication performance of the produced masters, a Zr-based BMG insert was used to produce a small batch of micro-fluidic devices by micro-injection moulding. Furthermore, an experimental study was also carried out to determine whether it would be possible by NS laser ablation to structure the Zr-based BMG workpieces with a high surface integrity whilst retaining the BMG’s non-crystalline morphology. Collectively, it was demonstrated that the proposed process chain could be a viable fabrication route for mass production of polymer devices incorporating different length scale features.

In the electronics industry, several greenhouse gases (GHGs) are used as process gases in manufacturing processes. The organization RF360 as a Qualcomm Inc. subsidiary is using GHGs as input gases in the manufacturing processes dry etching, Chemical Vapor Deposition (CVD) and trimming in the fabrication plant in Munich.The estimation of GHG emissions from the use of process gases under Scope 1 requires a global and comprehensive approach to determine emission sources. This work provides the basis for the GHG emission estimation from process gas use under consideration of the 2019 Refinement to the 2006 IPCC Guidelines for National Greenhouse Gas Inventories. Dry etching and CVD process GHG emissions arecalculated using the Tier 2c method with process specific default emission factors. The process GHG emissions from trimming are characterized under Tier 3a, by determination of site-specific process emission factors. These emission factors are obtained from FTIR measurements in the inline. The measurement results show the input gas NF3 is largely not converted or destroyed in the trimming process. The total GHG emissions resulting from process gas use in the considered processes are determined by emissions of NF3, CF4 and N2O. The implementation and improvement of the approach requires further measurements of site-specific emission factors in the processes and Destruction Removal Efficiencies of the abatement systems.

This thesis aims to measure the mechanical properties of ceramics on the microscale using microcantilever beams. Focussed Ion Beam milled triangular cross-sectional beams (approximately 3 x 5 x 20µm) were fractured using a nanoindenter to measure the Young’s modulus, fracture strength, and fracture toughness. By developing the technique with a sapphire bicrystal, it was found that the mechanical properties could be successfully ascertained if correction factors were used. Experiments and theoretical work showed that sapphire and polycrystalline alumina beams undergo moisture assisted sub-critical crack growth when tested in air. Whilst corrections for the Young’s modulus have been previously reported, this is the first reported attempt to correct for the notch tip residual stress and the first to consider sub-critical crack growth. Once these factors were characterised using the sapphire bicrystal, the technique was applied to a range of different ceramics, such as polycrystalline α-alumina and silicon nitride. These are the first reported direct measurements the grain boundary toughness of these ceramics using microcantilever beams. The grain boundary toughness was correlated with the macroscopic fracture properties and the characteristics of the ceramic (grain boundary composition, impurities, and fracture mode). Two grades of α-alumina were used and the macro- and micro-scale properties extensively compared. The damage evolution during uniaxial compression of alumina was investigated in depth, and compared to a previous reported microcrack evolution model using the measured grain boundary toughness. Investigation of whether deformation twins formed during loading was undertaken and the phenomenon was shown to not occur.

Ion beam therapy is an innovative radiotherapy technique using mainly carbon ion and proton irradiations. Its aim is to improve the current treatment modalities. Because of the sharpness of the dose distributions, a control of the dose if possible in real time is highly desirable. A possibility is to detect the prompt gamma rays emitted subsequently to the nuclear fragmentations occurring during the treatment of the patient. In a first time two different Compton cameras (double and single scattering) have been optimised by means of Monte Carlo simulations. The response of the camera to a photon point source with a realistic energy spectrum was studied. Then, the response of the camera to the irradiation of a water phantom by a proton beam was simulated. It was first compared with measurement performed with small-size detectors. Then, using the previous measurements, we evaluated the counting rates expected in clinical conditions. In the current set-up of the camera, these counting rates are pretty high. Pile up and random coincidences will be problematic. Finally we demonstrate that the detection system is capable to detect a longitudinal shift in the Bragg peak of +or- 5 mm, even with the current reconstruction algorithm.

PIXE, Particle Induced X-ray Emission, est une méthode d’analyse multiélémentaire, rapide, non destructive, basée sur la détection des rayons X caractéristiques émis suite à l’interaction de particules chargées avec la matière. Cette méthode est usuellement utilisée avec des protons accélérés à une énergie de l’ordre de quelques MeV dans des domaines d’applications variés, atteignant une limite de détection de l’ordre de quelques μg/g (ppm). Cependant, la profondeur d’analyse est relativement limitée. Grâce au cyclotron ARRONAX, nous pouvons utiliser des protons ou des particules alpha jusqu’à une énergie de 70 MeV pour mettre en œuvre la technique PIXE à haute énergie. Avec de telles énergies, nous excitons préférentiellement les raies X K, plus énergétiques que les raies L utilisées dans la PIXE classique pour l’analyse des éléments lourds. L’analyse d’échantillons épais, en profondeur, est ainsi accessible. Pour l’analyse des éléments légers, nous pouvons utiliser la détection de rayons gamma émis pas les noyaux excités en combinant les méthodes PIGE et PIXE. Nous allons tout d’abord présenter les caractéristiques et les principes d’analyse de la méthode PIXE à haute énergie que nous avons développée à ARRONAX. Nous détaillerons ensuite les performances atteintes, notamment en termes de limite de détection dans différentes conditions expérimentales. Enfin, nous présenterons les résultats obtenus pour l’analyse d’échantillons multicouches et la quantification d’éléments traces dans des échantillons épais. / Particle Induced X-ray Emission (PIXE) is a fast, nondestructive, multi-elemental analysis technique. It is based on the detection of characteristic X-rays due to the interaction of accelerated charged particles with matter. This method is successfully used in various application fields using low energy protons (energies around few MeV), reaching a limit of detection of the order the μg/g (ppm). At this low energy, the depth of analysis is limited. At the ARRONAX cyclotron, protons and alpha particles are delivered with energy up to 70 MeV, allowing the development of the High Energy PIXE technique. Thanks to these beams, we mainly produce KX-rays, more energetic than the LX-rays used with standard PIXE for the heavy elements analysis. Thus, in depth analysis in thick materials is achievable. For light element analysis, the PIGE technique, based on the detection of gamma rays emitted by excited nuclei, may be used in combination with PIXE. First of all, we will introduce the characteristics and principles of high energy PIXE analysis that we have developed at ARRONAX. Then we will detail the performance achieved, particularly in terms of detection limit in various experimental conditions. Finally, we present the results obtained for the analysis of multilayer samples and quantification of trace elements in thick samples.

Cette thèse porte sur l'étude de la production d'une source d'ionsCes travaux de thèse ont consisté à étudier la faisabilité d'une source d'ions césium brillante et de faible dispersion énergétique à partir d'atomes froids dans le but de la coupler à une optique de faisceau d'ions focalisés (FIB).Il s'agit de produire une source ionique continue, de fort courant et de plus faible dispersion en énergie que les sources actuellement utilisées. Un schéma expérimental innovant a donc été imaginé.Un flux continu d'atomes de césium est issu d'un four à recirculation. Les atomes sont ensuite collimatés et compressés en se basant su les techniques de refroidissement d'atomes par laser. Des simulations de la mélasse optique pour la collimation et du MOT-2D pour la compression sont présentées. Issus d'un jet effusif de césium produit par un four à recirculation, la collimation grâce à une mélasse optique et la compression effectuée en en utilisant un MOT-2D des atomes de césium a été étudiée. Le schéma d'ionisation des atomes de césium passe par une excitation vers un état de Rydberg puis par une ionisation par champ électrique. Les propriétés remarquables des atomes pour ces niveaux d'énergie permettent d'obtenir une ionisation des atomes en champ électrique quasi-instantanée qui permet la minimisation de la dispersion énergétique. Nous avons développer une simulation permettant d'étudier les propriétés du champ électrique nécessaire pour l'ionisation afin de choisir le niveau de Rydberg approprié. Des simulations complémentaires ont permis de définir et de concevoir les électrodes nécessaires à la production du champ électrique d'excitation et d'ionisation. Une première étude des effets coulombiens de la source d'ions lors de l'ionisation des atomes de Rydberg est présentée. Enfin, l'étude théorique du couplage de la source obtenue avec une optique de faisceaux d'ions focalisés est réalisée.Un montage expérimental vient compléter ces diverses études et a permis d'obtenir les premiers résultats. / The main goal of this thesis consists on studying the production of a bright ion cesium source with a low energy dispersion. In this work, the technology of cold atoms is used to coupled this source with optical elements of focused ion beams (FIB).A cw ionic source with high current and small energy spread is necessary to complete the performances of others available sources. A new experimenal scheme is presented here.A continuous high flux of cesium atoms is produced by a recirculating oven. The atoms are the collimated and compessed using laser cooling technology. Several simulations concerning the collimation and the compression have been made.A different way of producing ions comes from the excitation in an electric field of Rydberg atoms and then their ionization in an electric field. The remarkable properties of Rydberg atoms show the possibilty to ionize them almost instantanely reducing this way the energy spread. In the work several simulations indicate the way to choose the right Rydberg state for this application and the correct corresponding electric field.Further simulations determinate the electrdes needed for the excitation and the ionization of the Rydberg atoms from the beam. Moreover, a first study of the coulombian effects occuring in this ion source is described. Finally, a theorical study of the ion source and optic FIB coupling is shown.The description of the experimental setup and the first results complete this work.

O objetivo desse trabalho foi estudar a viabilidade de adaptação do Implantador Iônico da Universidade de São Paulo para a técnica de Accelerator Mass Spectrometry (AMS), tendo em vista as baixas energias utilizadas por este acelerador de partículas. A técnica de AMS, amplamente utilizada para a análise de Carbono-14 no estudo de datação de fósseis, requer que algum componente do acelerador garanta a quebra de moléculas de massa 14, contaminantes no processo de medição dos átomos de carbono com massa 14. Com a utilização de energias da ordem de dezenas de keV no acelerador, o estudo do processo de quebra de moléculas para estas energias foi realizado através do projeto, construção e caracterização de um stripper gasoso. Para caracterizar o stripper implementado foram realizadas medidas de seção de choque para troca de carga do feixe e quebra molecular em função da pressão de gás injetado no stripper. Também investigou-se a influência do átomo utilizado como gás, através de três diferentes gases injetados no stripper: Hélio, Argônio e Xenônio. Alguns feixes posivos foram produzidos no Implantador para o estudo destas seções de choques: Ar+, Ar(2+), CO+, CO2(+) e O2(+). O projeto do stripper foi idealizado para minimizar a variação de pressão no interior do implantador, visando preservar as condições da fonte de íons. Curvas de perfil de pressão de gás dentro do tubo do stripper foram calculadas segundo as teorias da Tecnologia do Vácuo que permitiram tanto a estimativa desta variação quanto a quantidade de gás no interior do stripper. Também foram realizados estudos do perfil de pressão em stripper com outras geometrias (cônicas abertas e fechadas), buscando estimar a otimização da espessura do stripper em função da injeção de gás em sua base. Baseando-se nos resultados, foram apontadas mudanças necessárias no atual estágio de adaptação desse acelerador de partículas para que se torne possível a concepção de um sistema AMS em sua linha de pesquisa. / The present work aimed on studying the feasibility of adapting the Ion Implanter of University of Sao Paulo to the Accelerator Mass Spectrometry technique, taking into account the low energies employed by this type of particle accelerator. The AMS technique, largely applied to the Carbon-14 analysis for fossil dating, requires the breaking of molecules with mass 14 by some component in the accelerator, since these lead to interference on the Carbon-14 counting process. By employing energies on the level of keV in the accelerator, the study of the breaking process of the molecules for this energy was accomplished by means desiring, building and characterization of a gaseous stripper. In order to characterize the installed stripper, measurements were taken of the charge state exchange and molecular break up process as a function of the pressure of the gas injection into the stripper. The influence of the atom employed as gas was also investigated. The experiments were realized with the following different gases: Helium, Argon and Xenon. Some positive beams were produced on the implanter: Ar+, \\Ar(2+), CO+, CO2(+) and O2(+). The designed stripper was idealized to minimize the pressure variation on the inside of the implanter in order to preserve the conditions of the ion source. Pressure profiles of the gas inside the stripper were calculated according to the Vacuum Technology theory, which allowed estimating the quantity of gas inside the stripper. Studies on the pressure profile for different stripper geometries (open and closed conic forms) were also carried out to estimate the optimization of the stripper thickness as a function of the gas injection on its base. Based on the results, specifications for further work and changes on the current system were listed to make it possible to implement the AMS system.

Elektronentomographie erlaubt die dreidimensionale (3D) Charakterisierung von Kristalldefekten auf der Nanometerskala. Die Anwendung in der Forschung an epitaktischen Halbleiterheterostrukturen ist bisher nicht durchgesetzt worden, obwohl kleiner werdende Bauteile mit zunehmend dreidimensionaler Struktur entsprechende Untersuchungen verlangen, um die Beziehung von Struktur und physikalischen Eigenschaften in entsprechenden Materialsystemen zu verstehen. Die vorliegende Arbeit demonstriert die konsequente Anwendung der Elektronentomographie auf eine III-Sb basierte Laser- und eine 3D (In,Ga)N/GaN Nanosäulenheterostruktur. Die unerlässliche Zielpräparation von Proben mittels FIB-SEM-Zweistrahlmikroskops wird herausgestellt. Die kontrollierte Orientierung der Probe während der Präparation und die sorfältige Auswahl eines Abbildungsverfahrens im STEM werden detailliert beschrieben. Die umfassende räumliche Mikrostrukturanalyse einer antimonidbasierten Schichtstruktur folgt der Dimensionalität von Kristalldefekten. Die Facettierung und Lage einer Pore (3D Defekt), deren Auftreten in der MBE gewachsenen GaSb-Schicht untypisch ist, werden bestimmt. Das Zusammenspiel von anfänglich abgeschiedenen AlSb-Inseln auf dem Si-Substrat, der Ausbildung eines Fehlversetzungsnetzwerkes an der Grenzfläche der Heterostruktur (2D Defekt) und dem Auftreten von Durchstoßversetzungen wird mit Hilfe der Kombination tomographischer und komplementärer TEM-/STEM-Ergebnisse untersucht. Die räumliche Anordnung von Versetzungen (1D Defekte), die das ganze Schichtsystem durchziehen, wird mit Elektronentomographie offenbart. Die Wechselwirkung dieser Versetzungen mit Antiphasengrenzen und anderen Liniendefekten sind ein einzigartiges Ergebnis der Elektronentomographie. Abschließend sind Unterschiede im Indiumgehalt und in der Schichtdicke von (In,Ga)N-Einschlüssen auf verschiedenen Facetten schief aufgewachsener GaN-Nanosäulen einmalig per Elektronentomographie herausgearbeitet worden. / Electron tomography exhibits a very poor spread in the research field of epitaxial semiconductor heterostructures in spite of the ongoing miniaturization and increasing three-dimensional (3D) character of nano-structured devices. This necessitates a tomographic approach at the nanometre scale in order to characterize and understand the relation between structure and physical properties of respective material systems. The present work demonstrates the rigorous application of electron tomography to an III-Sb based laser and to an (In,Ga)N/GaN nanocolumn heterostructure. A specific target preparation using a versatile FIB-SEM dual-beam microscope is emphasized as indispensable. The purposeful orientation of the specimen during preparation and the careful selection of an imaging mode in the scanning-/transmission electron microscope (S/TEM) are regarded in great detail. The comprehensive spatial microstructure characterization of the antimonide based heterostructure follows the dimensionality of crystal defects. The facetting and position of a pore (3D defect) which is unexpected in the MBE grown GaSb layer, is determined. The interplay of the initially grown AlSb islands on Si, the formation of a misfit dislocation network at the heterostructure interface (2D defect) and the presence of threading dislocations is investigated by the correlation of tomographic and complementary S/TEM results. The spatial arrangement of dislocations (1D defects) penetrating the whole stack of antimonide layers is revealed by electron tomography. The interaction of these line defects with anti-phase boundaries and with other dislocations is exclusively observed in the 3D result. The insertion of (In,Ga)N into oblique GaN nanocolumns is uniquely accessed by electron tomography. The amount of incorporated indium and the (In,Ga)N layer thickness is shown to vary on the different facets of the GaN core.

<p>Materials prepared on the nanoscale often exhibit many different properties compared to the same materials in their bulk-state. Interest in nanostructured materials has increased because of these properties in fields such as microelectronics, catalysis, optics and sensors. This increased interest in nanostructured materials calls for new and more precise fabrication techniques.</p><p>This thesis describes how to use the porous anodic aluminium oxide as a template for the fabrication of a variety of nanostructured materials. Palladium and copper nanoparticles were deposited along the pore walls in anodic aluminum oxide using electroless deposition and atomic layer deposition. In both cases, it was possible to control the size of the nanoparticles by carefully monitoring the deposition parameters. The thesis also describes how Prussian blue nanoparticles and nanotubes can be fabricated using the anodic aluminium oxide as a template. The deposition of Prussian blue was performed by a sequential wet-chemical method. By using atomic layer deposition, it was also possible to deposit thin films of amorphous Nb2O5 on the pore walls. When the template was removed by etching, freestanding nanotubes were obtained. The anodic aluminium oxide membrane was also used as a mask for high energy (MeV) ion irradiation of an underlying substrate. The tracks produced were etched away with hydrogen fluoride. In this way, it was possible to transfer the highly ordered porous pattern from the mask onto other oxides such as SiO2 and TiO2.</p><p>All fabricated structures were characterized using a variety of analysis techniques: scanning electron microscopy for evaluating sample morphology; transmission electron microscopy for better resolved investigations of the morphology; X-ray diffraction to assess crystallinity; energy dispersive spectroscopy and X-ray fluorescence spectroscopy to determine the elemental composition and identify possible contaminants.</p><p>The general aim of the work described in this thesis has been to create a set of tools for use in the fabrication of a variety of nanostructured materials, whose dimensions composition can be tailored by selecting appropriate fabrication methods and parameters.</p>

Print quality demands for coated papers are steadily growing, and achieving coating uniformity is crucial for high image sharpness, colour fidelity, and print uniformity. Coating uniformity may be divided into two scales: coating thickness uniformity and coating microstructure uniformity, the latter of which includes pigment, pore and binder distributions within the coating layer. This thesis concerns the investigation of both types of coating uniformity by using an approach of quantitative microscopy.First, coating thickness uniformity was analysed by using scanning electron microscope (SEM) images of paper cross sections, and the relationships between local coating thickness variations and the variations of underlying base sheet structures were determined. Special attention was given to the effect of length scales on the coating thickness vs. base sheet structure relationships.The experimental results showed that coating thickness had a strong correlation with surface height (profile) of base sheet at a small length scale. However, at a large length scale, it was mass density of base sheet (formation) that had the strongest correlation with coating thickness. This result explains well the discrepancies found in the literature for the relationship between coating thickness variation and base sheet structure variations. The total variance of coating thickness, however, was dominated by the surface height variation in the small scale, which explained around 50% of the variation. Autocorrelation analyses were further performed for the same data set. The autocorrelation functions showed a close resemblance of the one for a random shot process with a correlation length in the order of fibre width. All these results suggest that coating thickness variations are the result of random deposition of particles with the correlation length determined by the base sheet surface textures, such as fibre width.In order to obtain fundamental understandings of the random deposition processes on a rough surface, such as in paper, a generic particle deposition model was developed, and systematic analyses were performed for the effects of particle size, coat weight (average number of particles), levelling, and system size on coating thickness variation. The results showed that coating thickness variation3grows with coat weight, but beyond a certain coat weight, it reaches a plateau value. A scaling analysis yielded a universal relationship between coating thickness variation and the above mentioned variables. The correlation length of coating thickness was found to be determined by average coat weight and the state of underlying surfaces. For a rough surface at relatively low coat weight, the correlation length was typically in the range of fibre width, as was also observed experimentally.Non-uniformities within the coating layer, such as porosity variations and binder distributions, are investigated by using a newly developed method: field emission scanning electron microscopy (FESEM) in combination with argon ion beam milling technique. The combination of these two techniques produced extremely high quality images with very few artefacts, which are particularly suited for quantitative analyses of coating structures. A new evaluation method was also developed by using marker-controlled watershed segmentation (MCWS) of the secondary electron images (SEI).The high resolution imaging revealed that binder enrichment, a long disputed subject in the area, is present in a thin layer of a 500 nm thickness both at the coating surface and at the base sheet/coating interface. It was also found that the binders almost exclusively fill up the small pores, whereas the larger pores are mainly empty or depleted of binder.