Les nanofils de ZnO à puits quantiques et le dopage p par implantation ionique d'azote sont étudiés pour la fabrication de LED ultra-violettes. Des pyramides de polarité O et des nanofils de polarité Zn sur substrats de saphir et ZnO sont élaborés. La croissance organisée de nanofils sur ZnO de polarité Zn est démontrée. De même, des pyramides ou des nanofils de GaN sont obtenus sur GaN de polarité Ga ou N. Sur saphir, l'élimination des dislocations dans les pyramides sous-jacentes aux nanofils est analysée. Les nanofils sans défauts structuraux permettent l'élaboration de puits quantiques coeur-coquille ZnO/Zn(1-x)MgxO. La relaxation plastique dans les nanofils est étudiée, puis la composition en Mg est optimisée pour l'éviter et atteindre un rendement quantique interne de 54%. Concernant l'implantation, les défauts sont identifiés avant et après recuit. Ils disparaissent en surface, d'où une guérison facilitée des nanofils. Un matériau guéri avec des accepteurs activés n'est pas obtenu. / Quantum well ZnO nanowires and p-type doping by nitrogen ion implantation are studied to make ultraviolet light-emitting diodes. O-polar pyramids and Zn-polar nanowires on sapphire and ZnO substrates are grown. Organized growth of nanowires on a masked Zn-polar ZnO is demonstrated. Similarly, GaN pyramids and nanowires are grown on Ga and N-polar GaN respectively. On sapphire, the dislocation elimination in the underlying pyramids is analyzed. Nanowires with no structural defects allow the growth of ZnO / Zn (1-x) Mg x O core-shell quantum wells. Plastic relaxation is studied, and the Mg composition is optimized to avoid it and attain an internal quantum efficiency as high as 54%. Concerning ion implantation, the defects are identified before and after annealing. They disappear in the near-surface, which lead to an easier recovery of nanowires compared to bulk ZnO. However, a recovered material with activated acceptors is not obtained.

L’arséniure de gallium est un semi-conducteur disposant de propriétés physiques adaptées à laréalisation de dispositifs optoélectroniques et hyperfréquences. Ces dispositifs sonttypiquement réalisés sur des substrats massifs de GaAs, chers et fragiles. Nous proposonsdans cette thèse de les remplacer par un substrat innovant ne comprenant qu’une fine couchede GaAs reportée sur un substrat saphir (GaAsOS) à l’aide de la technologie Smart CutTM.Cette technologie permet de ne prélever qu’une fine couche de GaAs sur un substrat donneuret de le reporter sur un substrat saphir. Elle se base sur l’implantation d’ions légers (H/Hetyp.) dans le substrat GaAs, reporté par la suite sur le substrat saphir par collage direct. Unefracture est induite au niveau de la zone implantée, aboutissant au transfert de la couche deGaAs superficielle sur le substrat saphir. Après des étapes de finition, le substrat GaAsOSprésente des propriétés similaires à celles d’un substrat de GaAs massif. / Gallium arsenide is a compound semiconductor, whose properties are perfectly suited to themanufacturing of optoelectronic and RF devices. These devices are usually realized usingbulk GaAs substrates, which are fragile and expensive. The aim of this PhD is to replace themwith engineered substrates based on a thin single-crystal GaAs layer reported on a sapphire(GaAsOS) substrate by the Smart CutTM technology. This technology allows to only take therequested GaAs thickness from a donor substrate and to transfer it on a sapphire one. It isbased on light (H and/or He) ion implantation into the GaAs donor, which is assembled tosapphire using direct bonding. Fracture is induced on the implanted zone, inducing superficialGaAs layer transfer onto the sapphire substrate. After some finishing steps, the GaAsOSsubstrate properties are similar to the GaAs bulk substrate ones.

Orientador: Fernando Alvarez / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-05T23:16:31Z (GMT). No. of bitstreams: 1 Zagonel_LuizFernando_D.pdf: 13909392 bytes, checksum: 08d9ce72a7691aa00b93b053302e92d1 (MD5) Previous issue date: 2006 / Resumo: O objetivo deste trabalho é estudar processos de tratamento superficial por plasma com especial atenção às peculiaridades da técnica frente às demais práticas de nitretação, buscando compreender o processo a partir dos fenômenos observados na superficie. Dois tipos de tratamento foram realizados e três as técnicas utilizadas: nitretação por feixe de íons e por plasma pulsado e carbonitretação por deposição assistida por feixe de íons. A liga tratada foi o aço AISI-H13. As superficies das amostras foram tratadas em diversas temperaturas, de 260°C a 6000C, diversos tempos de processo, de 75 minutos a 5 horas, diversas densidades de corrente e diversas misturas gasosas, permitindo a observação de diferentes estruturas cristalinas, durezas, microestruturas e concentrações de nitrogênio na camada nitretada. Os diferentes estudos realizados dentro dessas amplas condições experimentais permitiram observar e/ou modelar o processo de tratamento superficial em condições diferenciadas. Estudos de nitretação com diferentes composições de feixe iônico de nitrogênio e hidrogênio mostraram que o hidrogênio tem um importante papel no processo, mesmo na ausência de oxigênio. A presença de hidrogênio levou ao aumento da concentração superficial de nitrogênio e à formação de fases de nitretos de ferro tipo E-Fe2-3N. Um estudo da nitretação em diversas temperaturas indicou que o processo de oferta de nitrogênio não depende da temperatura e que a 260°C nitretos de ferro de alta concentração de nitrogênio podem ser formados. A difusão de nitrogênio no aço utilizado mostrou-se ativada pela temperatura, mas efeitos de difusão por bordas de grão pareceram estar presentes, o que causou um aumento da dureza em altas profundidades. A técnica de deposição assistida por íons foi utilizada nesse estudo para o tratamento de superficie de carbonitretação. Nessa técnica, o carbono foi depositado continuamente sobre a superficie da amostra enquanto esta foi bombardeada com íons de nitrogênio. O estudo mostrou que a técnica apresenta características distintas daquelas da carbonitretação a gás ou a plasma. Em especial, foi observada a restauração da fase ferrita com altas concentrações de carbono e nitrogênio para alta deposição de carbono. Um estudo amplo sobre o papel do fluxo de íons, temperatura e tempo no processo de nitretação também foi realizado, visando clarificar as características do potencial químico na nitretação a plasma. Como demonstrado, esse potencial depende do balanço de massa entre o fluxo de íons e a difusão para o volume / Abstract: The objective of this project is to study processes of plasma surface treatment with special emphasis to the differences these techniques might show in relation to others, looking forward to understand the process from surface phenomena. Two kinds of surface treatment have been studied, including three different techniques: ion beam nitriding, pulsed plasma nitriding and carbonitriding by ion beam assisted deposition. The treated alloy was the steel AISI-H13. The samples surfaces have been treated at several different temperatures, from 260°C to 600°C, several process times, from 75 minutes to 5 hours, several ion current densities e several gas mixtures, allowing the observations of different crystalline structures, surface and profile hardness, microstructures, and nitrogen concentration at the surface and within a profile. The undergone studies over these wide conditions leaded to the observation and modeling of the surface treatments at these different situations. Studies of nitriding with different ion beam compositions of nitrogen and hydrogen showed that hydrogen play a major role even in the absence of oxygen. The hydrogen presence within the surface allowed an enhancement on the nitrogen concentration and the formation of iron nitrides 1ike E-Fe2-3N. A study of nitriding over several different temperatures indicates that the nitrogen offer at the surface is not dependent upon temperature and even at very low temperatures like 260°C, high nitrogen concentration iron nitrides can be formed. The nitrogen diffusion is shown to be activated by temperature, but grain boundary effects seam to be present, what caused a hardness increase at high depths. The ion beam assisted deposition technique was used for carbonitriding. In this set-up, carbon is continuously deposited over the surface while the sample is exposed to nitrogen ions. The study showed that the approach displays distinct characteristics with respect to gas or p1asma carbonitriding. By this new technique, high carbon deposition preserves the formation of E-Fe2-3N phase, without loss of diffusion to bulk. A wide study about the role of the ion flux, temperature and time on ion nitriding process was also performed, looking forward to clarify the behavior of the chemical potential of nitrogen at the surface. As it was understood, this quantity will depend on the mass balance between the ion flux and the diffusion to bulk / Doutorado / Física da Matéria Condensada / Doutor em Ciências

[pt] Filmes de carbono amorfo hidrogenados, (a - C: H) e nitrogenados,) ( a - C: H(N) - depositados pela técnica Plasma Enhanced Chemical Vapor Deposition (PECVD) em atmosferas de metano e metano-nitrogênio foram submetidos a tratamento em plasmas de N2. A influência de vários parâmetros foi investigada: a pressão da câmara, tensão de autopolarização e tempo de exposição. A taxa de erosão determinada por perfilometria. A taxa aumenta com a tensão e tende a saturar-se para altas pressões. A incorporação de nitrogênio foi medida por reação nuclear. O resultado indica um decréscimo no conteúdo de N com o aumento da tensão de autopolarização e pode ser explicado pelo aumento da erosão química e física. As ligações químicas foram analisadas por XPS e dois ambiente podem ser identificados: um com átomos de N rodeado por átomos de C e o outro com átomos N ligado ao H. A modificação da rugosidade da superfície e coeficiente de atrito foi caracterizada por Microscopia de Força Atômica (AFM). A rugosidade da superfície é independente do valores de autopolarização, quando o coeficiente de atrito decresce com o aumento da tensão de autopolarização. / [en] Amorphous Hydrogenated carbon films (a - C: H) and nitrogenated films ) (a - C: H(N) - deposited by plasma enhanced chemical vapor deposition in 4 CH and CH4-N2 atmospheres were submitted to nitrogen r.f.- plasma treatment. The influence of several parameters was investigated: the chamber pressure, the self-bias voltage and the exposure time. The erosion rate was determined by profilometry. It increases as the self-bias increases and tends to saturate for higher pressures. The nitrogen incorporated in the films was measured by nuclear reation analysis. The results indicate a decrease in the N content a the self-bias increase that can be atributted toen increase of the sputtering yield. The chemical bonds were probed by XPS and two chemical environments can be identified, one with N atoms surrounded by C atoms and the other one with N atoms binding to H. Surface roughness and friction coefficient modifications were followed by atomic force and lateral force microscopies. The surface roughness is independent on the value of the self-bias voltage, while the friction coefficient slightly decreases.

The progress in device performance of modern microelectronic technology is mainly driven by down-scaling. In the near future, this road will probably reach a point where physical limits make even more down-scaling impossible. The substitution of single components materialwise over the last decades, like high-k dielectrics or metal gates, has been a suitable approach to foster performance improvements. In this scheme, the integration of high-mobility III-V compound semiconductors as channel materials into Si technology is a promising route to follow for the next one or two device generations. III-V integration, today, is conventionally performed by using techniques like molecular beam epitaxy or wafer bonding which utilize solid phase crystallization but suffer to strain due to the lattice mismatch between III-V compounds and Si. An alternative approach using sequential ion beam implantation in combination with a subsequent flash lamp annealing is presented in this work. Using this technique, nanocrystals from various III-V compounds have been successfully integrated into bulk Si and Ge as well as into thin Si layers which used either SOI substrates or were grown by plasma-enhanced chemical vapour deposition. The III-V compounds which have been fabricated are GaP, GaAs, GaSb, InP, InAs, GaSb and InxGa1-xAs with variable composition. The structural properties of these nanocrystals have been investigated by Rutherford backscattering, scanning electron microscopy and transmission electron microscopy, including bright-field, dark-field, high-resolution, high-angle annular dark-field and scanning mode imaging, electron-dispersive x-ray spectroscopy and energy-filtered element mapping. Furthermore, Raman spectroscopy and X-ray diffraction have been performed to characterise the nanocrystals optically. In Raman spectroscopy, the characteristic transversal and longitudinal optical phonon modes of the different III-V compounds have been observed. These signals proof that the nanocrystals have formed by the combination of ion implantation and flash lamp annealing. Additionally, the appearance of the typical phonon modes of the respective substrate materials verifies recrystallization of the substrate by the flash lamp after amorphisation during implantation. In the bulk Si samples, the nanocrystals have a circular or rectangular lateral shape and they are randomly distributed at the surface. Their cross-section has either a hemispherical or triangular shape. In bulk Ge, there are two types of precipitates: one at the surface with arbitrary shape and another one buried with circular shape. For the thin film samples, the lateral shape of the nanocrystals is more or less arbitrary and they feature a block-like cross-section which is limited in height by the Si layer thickness. Regarding crystalline quality, the nanocrystals in all samples are mainly single-crystalline with only a few number of stacking faults. However, the crystalline quality in the bulk samples is slightly better than in the thin films. The X-ray diffraction measurements display the (111), (220) and (311) Bragg peaks for InAs and GaAs as well as for the InxGa1-xAs where the peaks shift with increasing In content from GaAs towards InAs. The underlying formation mechanism is identified as liquid phase epitaxy. Hereby, the ion implantation leads to an amorphisation of the substrate material which is then molten by the subsequent flash lamp annealing. This yields a homogeneous distribution of the implanted elements within the melt due to their strongly increased diffusivity in the liquid phase. Afterwards, the substrate material starts to recrystallize at first and an enrichment of the melt with group-III and group-V elements takes place due to segregation. When the temperature is low enough, the III-V compound semiconductor starts to crystallize using the recrystallized substrate material as a template for epitaxial growth. In order to gain control over the lateral nanocrystal distribution, an implantation mask of either aluminium or nickel is introduced. Using this mask, only small areas of the samples are implanted. After flash lamp treatment, nanocrystals form only in these small areas, which allows precise positioning of them. An optimal implantation window size with an edge length of around 300nm has been determined to obtain one nanocrystal per implanted area. During an additional experiment, the preparation of Si nanowires using electron beam lithography and reactive ion etching has been conducted. Hereby, two different processes have been investigated; one using a ZEP resist, a lift-off step and a Ni hard mask and another one using a hydrogen silsesquioxane resist which is used directly as a mask for etching. The HSQ-based process turned out to yield Si nanowires of better quality. Combining both, the masked implantation and the Si nanowire fabrication, it might be possible to integrate a single III-V nanocrystal into a Si nanowire to produce a III-V-in-Si-nanowire structure for electrical testing. / Der Fortschritt in der Leistungsfähigkeit der Bauelemente moderner Mikroelektroniktechnologie wird hauptsächlich durch das Skalieren vorangetrieben. In naher Zukunft wird dieser Weg wahrscheinlich einen Punkt erreichen, an dem physikalische Grenzen weiteres Herunterskalieren unmöglich machen. Der Austausch einzelner Teile auf Materialebene, wie Hoch-Epsilon-Dielektrika oder Metall-Gate-Elektroden, war während der letzten Jahrzehnte ein geeigneter Ansatz, um die Leistungsverbesserung voranzubringen. Nach diesem Schema ist die Integration von III-V-Verbindungshalbleiter mit hoher Mobilität ein vielversprechender Weg, dem man für die nächsten ein oder zwei Bauelementgenerationen folgen kann. Heutzutage erfolgt die III-V-Integration konventionell mit Verfahren wie der Molekularstrahlepitaxie oder dem Waferbonden, welche die Festphasenkristallisation nutzen, die aber aufgrund der Gitterfehlanpassung zwischen III-V-Verbindungen und Silizium an Verspannungen leiden. In dieser Arbeit wird ein alternativer Ansatz präsentiert, welcher die sequenzielle Ionenstrahlimplantation in Verbindung mit einer darauffolgenden Blitzlampentemperung ausnutzt. Mit Hilfe dieses Verfahrens wurden Nanokristalle verschiedener III-V-Verbindungshalbleiter erfolgreich in Bulksilizium- und -germaniumsubstrate sowie in dünne Siliziumschichten integriert. Für die dünnen Schichten wurden hierbei entweder SOI-Substrate verwendet oder sie wurden mittels plasmagestützer chemischer Gasphasenabscheidung gewachsen. Die hergestellten III-V-Verbindungen umfassen GaP, GaAs, GaSb, InP, InAs, InSb und InxGa1-xAs mit veränderbarer Zusammensetzung. Die strukturellen Eigenschaften dieser Nanokristalle wurden mit Rutherford-Rückstreu-Spektroskopie, Rasterelektronenmikroskopie und Transmissionselektronenmikroskopie untersucht. Bei der Transmissionelektronenmikroskopie wurden die Hellfeld-, Dunkelfeld-, hochauflösenden, “high-angle annular dark-field” und Rasteraufnahmemodi sowie die energiedispersive Röntgenspektroskopie und die energiegefilterte Elementabbildung eingesetzt. Darüber hinaus wurden Ramanspektroskopie- und Röntgenbeugungsmessungen durchgeführt, um die Nanokristalle optisch zu charakterisieren. Mittels Ramanspektroskopie wurden die charakteristischen transversal- und longitudinal-optischen Phononenmoden der verschiedenen III-V-Verbindungen beobachtet. Diese Signale beweisen, dass sich unter Verwendung der Kombination von Ionenstrahlimplantation und Blitzlampentemperung Nanokristalle bilden. Weiterhin zeigt das Vorhandensein der typischen Phononenmoden der jeweiligen Substratmaterialien, dass die Substrate aufgrund der Blitzlampentemperung rekristallisiert sind, nachdem sie durch Ionenimplantation amorphisiert wurden. In den Bulksiliziumproben besitzen die Nanokristalle eine kreisförmige oder rechteckige Kontur und sind in zufälliger Anordnung an der Oberfläche verteilt. Ihr Querschnitt zeigt entweder eine Halbkugel- oder dreieckige Form. Im Bulkgermanium gibt es zwei Arten von Ausscheidungen: eine mit willkürlicher Form an der Oberfläche und eine andere, vergrabene mit sphärischer Form. Betrachtet man die Proben mit den dünnen Schichten, ist die laterale Form der Nanokristalle mehr oder weniger willkürlich und sie zeigen einen blockähnlichen Querschnitt, welcher in der Höhe durch die Siliziumschichtdicke begrenzt ist. Bezüglich der Kristallqualität sind die Nanokristalle in allen Proben mehrheitlich einkristallin und weisen nur eine geringe Anzahl an Stapelfehlern auf. Jedoch ist die Kristallqualität in den Bulkmaterialien ein wenig besser als in den dünnen Schichten. Die Röntgenbeugungsmessungen zeigen die (111), (220) und (311) Bragg-Reflexe des InAs und GaAs sowie des InxGa1-xAs, wobei sich hier die Signalpositionen mit steigendem Gehalt an Indium von GaAs zu InAs verschieben. Als zugrundeliegender Bildungsmechanismus wurde die Flüssigphasenepitaxie identifiziert. Hierbei führt die Ionenstrahlimplantation zu einer Amorphisierung des Substratmaterials, welches dann durch die anschließende Blitzlampentemperung aufgeschmolzen wird. Daraus resultiert eine homogene Verteilung der implantierten Elemente in der Schmelze, da diese eine stark erhöhte Diffusivität in der flüssigen Phase aufweisen. Danach beginnt zuerst das Substratmaterial zu rekristallisieren und es kommt aufgrund von Segregationseffekten zu einer Anreicherung der Schmelze mit den Gruppe-III- und Gruppe-V-Elementen. Wenn die Temperatur niedrig genug ist, beginnt auch der III-V-Verbindungshalbleiter zu kristallisieren, wobei er das rekristallisierte Substratmaterial als Grundlage für ein epitaktisches Wachstum nutzt. In der Absicht Kontrolle über die laterale Verteilung der Nanokristalle zu erhalten, wurde eine Implantationsmaske aus Aluminium beziehungsweise Nickel eingeführt. Durch die Benutzung einer solchen Maske wurden nur kleine Bereiche der Proben implantiert. Nach der Blitzlampentemperung werden nur in diesen kleinen Bereichen Nanokristalle gebildet, was eine genaue Positionierung dieser erlaubt. Es wurde eine optimale Implantationsfenstergröße mit einer Kantenlänge von ungefähr 300 nm ermittelt, damit sich nur ein Nanokristall pro implantierten Bereich bildet. Während eines zusätzlichen Experiments wurde die Präparation von Siliziumnanodrähten mit Hilfe von Elektronenstrahllithografie und reaktivem Ionenätzen durchgeführt. Hierbei wurden zwei verschiedene Prozesse getestet: einer, welcher einen ZEP-Lack, einen Lift-off-Schritt und eine Nickelhartmaske nutzt, und ein anderer, welcher einen HSQ-Lack verwendet, der wiederum direkt als Maske für die Ätzung dient. Es stellte sich heraus, dass der HSQ-basierte Prozess Siliziumnanodrähte von höherer Qualität liefert. Kombiniert man beides, die maskierte Implantation und die Siliziumnanodrahtherstellung, miteinander, sollte es möglich sein, einzelne III-V-Nanokristalle in einen Siliziumnanodraht zu integrieren, um eine III-V-in-Siliziumnanodrahtstruktur zu fertigen, welche für elektrische Messungen geeignet ist.

Les détecteurs de radiations nucléaires sont des outils importants dans de nombreux domaines tels que dans les réacteurs nucléaires, la sécurité nationale, mais ils sont également primordiaux dans des applications médicales. Les progrès récents dans la technologie des semi-conducteurs permettent la réalisation de détecteurs très efficaces et quasi-insonores qui permettent la détection de différents types de radiations nucléaires. Le carbure de silicium (SiC) est une bande semi-conductrice large, grâce à sa conductivité thermique élevée et à une résistance élevée aux rayonnements, il est adapté pour les environnements difficiles où peuvent exister des flux élevés de température et de rayonnement. Le but du projet européen (I_SMART) est ainsi de prouver la fiabilité de nouvelles méthodes de réalisation de détecteurs de radiations nucléaires et d'étudier leur performance dans différents types d'irradiation (neutrons rapides et thermiques) et à différentes températures. Différentes méthodes ont été utilisées pour réaliser les détecteurs de rayonnement SiC. Par exemple l'implantation d'ions de bore a été utilisé pour créer la couche de conversion de neutrons soit dans le contact métallique ou directement en SiC. Les détecteurs fabriqués ont été testés dans le réacteur nucléaire BR1, mettant en lumière la présence de neutrons thermiques. En outre, ces détecteurs détectent des neutrons rapides sous n’importe quelle température. En outre, les détecteurs utilisés montrent leur stabilité sous différents flux de neutrons qui indiquent la fiabilité de ces nouveaux modes de réalisation de détecteurs de rayonnement qui pourraient remplacer ceux utilisés actuellement. / Nuclear radiation detectors are important tools in many fields such as in nuclear reactors, homeland security and medical applications. Recent advances in semiconductor technology allow construction of highly efficient low noise detectors for different nuclear radiations. Silicon carbide (SiC) is a wide band gap semiconductor with a high thermal conductivity and high radiation resistance. It is suitable for a harsh environment where high temperatures and radiation fluxes may exist. In the framework of the European project (I_SMART) the purpose of this work is to demonstrate the reliability of new methods of realizing nuclear radiation detectors and to study their performance under different types of irradiation (fast and thermal neutrons) and at elevated temperatures. Different methods have been used to realize SiC based-radiation detectors. For instance boron ion implantation has been used to create the neutron converter layer either in the metallic contact or directly in the SiC. The fabricated detectors have been tested in the BR1 nuclear reactor revealing the thermal neutron detection and the feasibility of gamma discrimination from thermal neutrons using one single detector. Such detectors are sensitive to fast neutrons with a stable response under elevated temperatures (up to 150 °C). Furthermore, the studied detectors show stability under different neutron fluxes, indicating a reliability of such new methods of realizing radiation detectors which could replace those of the current state of the art.

Orientador: Fernando Alvarez / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-08T01:14:15Z (GMT). No. of bitstreams: 1 OchoaBecerra_ErikaAbigail_M.pdf: 6414208 bytes, checksum: be25f7cebf36f2d96cfd208deecb449a (MD5) Previous issue date: 2003 / Resumo: Apresente tese trata sobre a implantação de nitrogênio em sistemas baseados em ferro. Duas técnicas de nitretação são utilizadas, plasma pulsado e feixe iônico por canhão de íons. Os parâmetros de nitretação são otimizados com a finalidade de obter um melhoramento na dureza superficial destes sistemas, isto é, em algumas dezenas de mícron. Tal melhoramento é relacionado com a concentração de nitrogênio em profundidade correspondente a uma sucessão de nitretos formados. A estabilidade destas fases é observada qualitativamente pela dependência com os processos de nitretação. A formação de camadas de nitretos é estudada a partir de um modelo de difusão e determinadas através de caracterização por raios-X, microscopia eletrônica de varredura (MEV) e espectroscopia de fotoelétrons de raios-X (XPS). A dureza em profundidade, de amostras submetidas a diferentes processos de implante de nitrogênio, foi determinada mediante nanoindentação. Amostras portadoras de um alto grau de dureza foram empregadas: aço AISI 4140. O polimento destas amostras, para caracterização em diferentes profundidades, foi processado mediante iesputteringl, com íons de argônio. Os efeitos da erosão foram estudados com auxilio de um perfilômetro. Coeficientes de difusão de nitrogênio em diferentes tipos de nitretos foram determinados e a uma correlação entre a dureza e concentração de nitrogênio em profundidade foi verificada explicitamente / Abstract: This thesis deals about the nitrogen implantation in iron - based systems. Two techniques to nitriding were used, either pulsed plasma or ionic beam by use of a cannon. The nitriding parameters were optimized with the purpose to get an improvement in the superficial hardness of these systems; this is, in a few dozen of micrometers. Such improvement is related with the in-depth nitrogen concentration corresponding to a set of layered phases. The stability of these phases is observed qualitatively because the dependece with the processes of nitriding. The layered phases containing nitrides is studied from a difusion model and determined through X-ray, scanning electron microscopy (SEM) and photoelectron spectroscopy (XPS). The hardness in depth, of samples subjected to different processes of nitrogen implantation, was determined by means of nano-indentation. Samples showing a high degree of hardness were used: steel AISI 4140. The polishment of these samples, for characterization in different depths, was processed by means of sputtering with argon ions. The effect of erosion had been studied by means of a perfilometer. Difusion coefficients of nitrogen in the different types of layered nitrides had been determined and a correlation between hardness and nitrogen concentration in depth was verified explicitly / Mestrado / Física da Matéria Condensada / Mestre em Física

Au cours des procédés de mise en forme du verre creux, les outillages de verrerie sont soumis à des conditions extrêmes avec des températures pouvant dépasser largement 650 °C. De plus, ces derniers sont exposés à des phénomènes d'abrasion sévères et à des réactions physico-chimiques complexes avec le verre fondu. Ceci est particulièrement accentué par les cycles thermiques dus aux contacts répétés avec le verre. L'objectif de ce travail de thèse est de proposer des solutions innovantes de dépôts de superalliages et/ou traitements de surface destinés à augmenter la durée de vie des outillages. Trois axes d'innovation sont présentés dans ce mémoire. Le premier concerne l'étude du dépôt de poudre composite Co/NiB par soudure PTA (Plasma Transfered Arc) sur des moules en alliage cuivreux. Le second est dédié à l'étude de la faisabilité technique d'un dépôt PVD (Physical Vapor Deposition) multicouche à gradient fonctionnel, présentant des caractéristiques intéressantes pour des applications verrières en termes de dureté et de stabilité thermique, sur des poinçons en acier AISI 431. Enfin, le troisième axe de recherche fait l'objet d'une analyse plus approfondie et concerne l'étude de la nitruration par implantation d'ions azotes multichargés, également sur un acier AISI 431. On observe après implantation une augmentation significative de la dureté (+ 240 %). Une approche multi-expérimentale et multi-échelle est alors proposée afin d'étudier la microstructure du matériau implanté ainsi que son évolution après un recuit de 1h à 650 °C de manière à anticiper le comportement du matériau en production, et de corréler ceci aux propriétés de dureté / Glass moulds have to withstand very high temperatures which can far exceed 650 °C during the glass forming process. They are exposed to very tough conditions such as abrasive wear and physico-chemical reactions, accentuated by thermal shocks due to high speed contact with hot glass melt. The aim of this work is to find innovative solutions for superalloy coating or surface treatments in order to increase the service life of glass tools. Three innovation projects are presented in this report. The first one is dedicated to PTA (Plasma Transferred Arc) welded coating of composite Co/NiB powder on copper alloy moulds. The second one is about technical feasibility of a multilayer PVD (Physical Vapor Deposition) coating with properties congruent to glass production in term of hardness and thermal stability, on AISI 431 plunger stainless steel. Last but not least, the third innovative project is about nitriding by ion implantation with multicharged nitrogen ions on AISI 431 stainless steel. We notice after ion implantation a significant hardness increase (+ 240 %). A multi-experimental and multi-scale approach was carried out in order to study the implanted material microstructure and its evolution after annealing at 650 °C during 1h to predict the material behavior during production and correlate it to hardness properties

Les aciers ODS (Oxide Dispersed Strengthened Steels), renforcés par des dispersions de nano-oxydes métalliques (à base d'éléments Y, Ti et O), sont des matériaux prometteurs pour les réacteurs nucléaires de génération IV. La compréhension fine des mécanismes mis en jeu lors de la précipitation de ces nano-oxydes permettrait d'améliorer la fabrication et les propriétés mécaniques de ces aciers ODS, avec un fort impact économique en vue de leur industrialisation. Pour étudier expérimentalement ces mécanismes, une approche analytique par implantation ionique est utilisée dans cette étude, permettant de contrôler différents paramètres de synthèse de ces précipités comme la température et leur concentration. Ce projet a permis de démontrer la faisabilité de cette méthode et d'étudier le comportement d'alliages modèles (à base d'oxyde d'aluminium) sous recuit thermique. Des alliages Fe-10Cr de haute pureté ont été implantés avec des ions Al et O à température ambiante. Les observations de microscopie électronique en transmission ont montré que des nano-oxydes apparaissent dans la matrice de Fe-10Cr dès l'implantation à température ambiante, sans recuit subséquent. Les défauts créés lors de l'implantation ionique sont à l'origine de la mobilité des éléments introduits, permettant la nucléation de ces nanoparticules, de quelques nm de diamètre. Ces nanoparticules sont composées d'aluminium et d'oxygène, et également de chrome. Les examens en haute résolution montrent que leur structure cristallographique correspond à celle d'un composé hors équilibre de l'oxyde d'aluminium (de type γ-Al₂O₃). Les traitements thermiques effectués après implantation induisent une croissance de la taille de ces nano-oxydes, et un changement de phase qui tend vers la structure d'équilibre (de type α-Al₂O₃). Ces résultats sur des alliages modèles s'appliquent entièrement aux matériaux industriels : en effet l'implantation ionique reproduit les conditions du broyage, et les traitements thermiques sont à des températures équivalentes à celles des traitements d'élaboration thermo-mécaniques. Un mécanisme de la précipitation de nano-oxydes dispersés dans des alliages ODS est proposé dans ce manuscrit. / ODS (Oxide Dispersed Strengthened) steels, which are reinforced with metal dispersions of nano-oxides (based on Y, Ti and O elements), are promising materials for future nuclear reactors. The detailed understanding of the mechanisms involved in the precipitation of these nano-oxides would improve manufacturing and mechanical properties of these ODS steels, with a strong economic impact for their industrialization. To experimentally study these mechanisms, an analytical approach by ion implantation is used, to control various parameters of synthesis of these precipitates as the temperature and concentration. This study demonstrated the feasibility of this method and concerned the behaviour of alloys models (based on aluminium oxide) under thermal annealing. High purity Fe-10Cr alloys were implanted with Al and O ions at room temperature. Transmission electron microscopy observations showed that the nano-oxides appear in the Fe-10Cr matrix upon ion implantation at room temperature without subsequent annealing. The mobility of implanted elements is caused by the defects created during ion implantation, allowing the nucleation of these nanoparticles, of a few nm in diameter. These nanoparticles are composed of aluminium and oxygen, and also chromium. The high-resolution experiments show that their crystallographic structure is that of a non-equilibrium compound of aluminium oxide (cubic γ-Al₂O₃ type). The heat treatment performed after implantation induces the growth of the nano-sized oxides, and a phase change that tends to balance to the equilibrium structure (hexagonal α-Al₂O₃ type). These results on model alloys are fully applicable to industrial materials: indeed ion implantation reproduces the conditions of milling and heat treatments are at equivalent temperatures to those of thermo-mechanical treatments. A mechanism involving the precipitation of nano-oxide dispersed in ODS alloys is proposed in this manuscript based on the obtained experimental results, and the existing literature.

Image charge detection is presented as a possible candidate to realise deterministic ion implantation. The deterministic placement of single impurities in solid substrates will enable a variety of novel applications, using their quantum mechanical properties for sensors or qubit registers. In this work, experimental techniques are used together with theoretical calculations to develop, characterise and optimise the detection of charged objects in a single pass through an image charge detector. In the main experimental part, ion bunches are employed as a model system for highly charged ions in proof-of-principle measurements with detector prototypes built in our labs. Image charge signals are characterised in the time and frequency domain. Using a statistical measurement and data analysis protocol, the noise and signal probability density functions are determined to calculate error and detection rates. It was found that even at an extremely low signal-to-noise ratio of 2, error rates can be suppressed effectively for high fidelity implantation. Aiming to improve the sensitivity, the maximum possible signal-to-noise ratio is calculated and discussed in dependence on the design parameters of an optimised image charge detector and the kinetic ion parameters. Lastly, a new ion implantation set-up combining focused ion beam technology with a source able to produce highly charged ions is introduced.