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In this work the two experimental dental implant materials FAT and FAW, made of fluoroapatite particles embedded in polymer matrices, and films of the proteins lysozyme, amylase and bovine serum albumin (BSA), adsorbed to the two dental implant materials, were investigated with time-of-flight secondary ion mass spectrometry (ToF-SIMS) and the multivariate data analysis technique discriminant principal component analysis (DPCA).

Pseudoexfoliation (PEX) syndrome is an age-related condition characterized by the production and accumulation of extracellular fibrillary material in the anterior segment of the eye. PEX predisposes for several pathological conditions, such as glaucoma and complications during and after cataract surgery. The pathogenesis of PEX is not yet fully understood. It is multifactorial with genetics and ageing as contributing factors. We aimed to study the proteome in aqueous humor (AH) in PEX in order to increase the knowledge about its pathophysiology. Therefore, we developed sampling techniques and evaluated separation methods necessary for analyzing small sample volumes. Other objectives were to study the lens capsule in eyes with PEX regarding small molecules, and to investigate the association between PEX and cataract surgery in a population-based 30-year follow-up study. Samples of AH from eyes with PEX and control eyes were collected during cataract surgery. In pooled, and individual samples, various liquid based separation techniques and high resolution mass spectrometry were utilized. For quantitation, various methods for labeling, and label free techniques were applied. Lens capsules were collected from some of the patients, and analysed by imaging mass spectrometry. A cohort of 1,471 elderly individuals underwent a comprehensive ophthalmological examination at baseline. Medical information was obtained by questionnaires, and from medical records. Incident cases of cataract surgery were identified by review of medical records. In the initial study, several techniques were explored for protein detection, and a number of proteins were identified as differentially expressed. In the individually labelled samples, changes in the proteome were observed. Eyes with PEX contained higher levels of proteins involved in inflammation, oxidative stress, and coagulation, suggesting that these mechanisms are involved in the pathogenesis in PEX. The levels of β/γ-crystallins were significantly increased in PEX, which is a novel finding. In the lens capsules from individuals with PEX, changes in the lipid composition was observed with time-of-flight secondary ion mass spectrometry. These changes remain to be elucidated. By multivariate analysis, lens opacities were the first, and PEX the second most important predictor for cataract surgery, the later accounting for a 2.38-fold increased risk for cataract surgery.

Les conditions sévères de fonctionnement des réacteurs du futur, Génération-IV, -haute température et fortes irradiations-nécessitent le développement de matériaux adaptés. Les aciers ODS (Oxide Dispersion Strengthened) sont des candidats très compétitifs pour le gainage du combustible en raison de leurs excellentes propriétés de gonflement et de fluage. Ces atouts majeurs sont induits par la fine dispersion de nanoparticules d’oxydes (Y, O, Ti) obtenue par co-broyage de poudres de la matrice et d’oxyde dont les conditions sont à optimiser pour maitriser la distribution en taille et composition de ces nanoparticules. Dans l’objectif de mieux comprendre le mécanisme de formation de ces nanoparticules à l’échelle atomique, la présente thèse met à profit l’utilisation de la spectroscopie d’annihilation de positons (PAS) et de la spectrométrie de masse d’ions secondaires pour étudier l’interaction des défauts lacunaires avec des solutés Y, O et Ti et évaluer leur rôle dans la formation des nanoparticules. Les irradiations avec des ions He ont été effectuées pour révéler les propriétés des défauts lacunaires et les implantations d’Y, Ti, O ont été réalisées pour étudier les interactions de ces éléments Y, Ti, O avec les lacunes dans la matrice de fer. La distribution des défauts en profondeur indique la présence de défauts lacunaires avec une taille plus petite dans la région où la concentration d’Y, Ti, O est la plus élevée. Cet effet est plus prononcé pour O, Y et Ti respectivement. Il est expliqué par la formation de V-X (X=O, Y, Ti) complexes qui réduisent la probabilité de la mobilité et d’agglomération des défauts lacunaires. Les recuits des échantillons implantés Y et O révèlent que des complexes O-lacune sont mobiles à température ambiante, et que l’yttrium ne diffuse pas jusqu’à 550°C alors que des complexes Y-lacunes sont encore détectés comme cela est attendu par des résultats théoriques. Un modèle des premières étapes de la nucléation des nanoparticules est proposé en utilisant les résultats obtenus dans cette thèse. / The severe operating conditions of the future nuclear reactor, Generation-IV, -high temperature and high irradiation damage-, require the adapted materials development. Oxide-dispersion strengthened (ODS) alloy is one of the most potential candidates expected to be used for fuel cladding material because of their outstanding swelling and creep properties. Their excellent properties are induced by the fine dispersion of oxide nanoparticles (Y, O, Ti), obtained by mechanical alloying of steel and oxide powders and which has to be better mastered. But the atomic scale clustering mechanism of these nanoparticles is not yet cleared. In this context, the present thesis using positron annihilation spectroscopy (PAS) and secondary ion mass spectrometry (SIMS) sheds light on the interaction of vacancy defects with Y, O and Ti solutes to better understand their roles in the nanoparticles formation. The He irradiations have been performed to reveal the vacancy defects properties and Y, Ti, O implantations realized to study the Y, Ti, O-vacancy interactions in bcc Fe matrix. In all cases, the defects depth distribution shows a lower size of vacancy defects in the region where the concentration of the incident ions Y, Ti and O is the highest. This effect of the ions on the damage formation is more pronounced for respectively O, Y and Ti. It is explained by the formation of V-X (X=O, Y, Ti) complexes which reduce the mobility and agglomeration probability of the vacancy defects. The annealing of the Y and O implanted samples reveals that some O-vacancy complexes are mobile at room temperature and Y doesn’t diffuse up to 550°C whilst Y-vacancy complexes remain as it is expected from theory. A model of the first steps of the ODS nanoparticles nucleation is proposed by using the results obtained in this thesis.

Progress in chemomechanical functionalization was made by investigating the binding of molecules and surface coverage on the silicon surface, demonstrating functionalization of silicon with gases by chemomechanical means, analyzing atomic force microscopy probe tip wear in atomic force microscopy (AFM) chemomechanical nanografting, combining chemomechanical functionalization and nanografting to pattern silicon with an atomic force microscope, and extending chemomechanical nanografting to silicon dioxide. Molecular mechanics of alkenes and alkynes bound to Si(001)-2x1 as a model of chemomechanically functionalized surfaces indicated that complete coverage is energetically favorable and becomes more favorable for longer chain species. Scribing a silicon surface in the presence of ethylene and acetylene demonstrated chemomechanical functionalization with gaseous reagents, which simplifies sample cleanup and adds a range of reagents to those possible for chemomechanical functionalization. Thermal desorption spectroscopy was performed on chemomechanically functionalized samples and demonstrated the similarity in binding of molecules to the scribed silicon surface and to the common Si(001)-2x1 and Si(111)-7x7 surfaces. The wearing of atomic force microscope probe tips during chemomechanical functionalization was investigated by correlating change over time and force with widths of created lines to illustrate the detrimental effect of tip wear on mechanically-driven nanopatterning methods. In order to have a starting surface more stable than hydrogen-terminated silicon, silicon reacted with 1-octene was used as a starting surface for AFM chemomechanical functionalization, producing chemomechanical nanografting. Chemomechanical nanografting was then demonstrated on silicon dioxide using silane molecules; the initial passivating layer reduced the tip friction on the surface to allow only partial nanografting of the silane molecules. These studies broadened the scope and understanding of chemomechanical functionalization and nanografting.

<p>III-V nanowire (NW) ensemble devices were fabricated using novel approaches to address key NW optoelectronic issues concerning electrical contacts, doping, surface effects and underlying electrostatics physics.</p> <p>NWs were first embedded in a filling medium, thus achieving low sheet resistance front contacts while preventing shunts. Various filling materials were assessed for porosity, surface roughness and thermal stability, giving Cyclotene as an ideal filing material. Sonication was also introduced as a novel method to achieve perfect planarization.</p> <p>The presence of the Cyclotene also enabled the NWs to be characterized precisely and easily by secondary ion mass spectrometry (SIMS) to give the NW dopant concentration with excellent spatial resolution. Additionally, SIMS characterization demonstrated the ability to characterize the height uniformity of individual segments in a heterostructure NW ensemble.</p> <p>The focus of the work shifted towards surface effects on NW device performance. Therefore, Poisson's equation was solved to provide a comprehensive model of NW surface depletion as a function of interface state density, NW radius and doping density. Underlying physics was examined where surface depletion was found to significantly reduce the conductivity of thin NWs, leading to carrier inversion for some.</p> <p>This model was then applied in conjunction with a transport model to fit current-voltage curves of an AlInP-passivated GaAs NW ensemble device. A 55% decrease in surface state density was achieved upon passivation, corresponding to an impressive four order of magnitude increase in the effective carrier concentration. Additionally, conventional and time-resolved photoluminescence measurements showed intensity and carrier lifetime improvement greater than 20x upon passivation.</p> <p>Finally, the model was extended to describe radial pn junction NWs with surface depletion to give radial energy band profiles for any arbitrary set of NW parameters. Specific cases were analyzed to extract pertinent underlying physics, while the built-in potential was optimized for the design for an optimal device.</p> / Doctor of Philosophy (PhD)

Neste trabalho, estudamos e aplicamos técnicas analíticas com feixes iônicos para a identificação e quantificação do elemento químico Boro em amostras de Boro depositado sobre Níquel 11B/Ni, sobre Silício B/Si e em amostras de Silício Grau Metalúrgico - SiGM. Estas últimas foram fornecidas pelo grupo de metalurgia do Instituto de Pesquisas Tecnológicas (IPT). Especificamente, as seguintes técnicas analíticas foram utilizadas: Nuclear Reaction Analysis - NRA, Elastic Recoil Detection Analysis - ERDA e Secondary Ion Mass Spectrometry - SIMS. Nas amostras de B/Ni e B/Si, as concentrações foram obtidas com medidas de NRA, ERDA e SIMS. Também foi abordado quais dentre essas três técnicas apresentam menor limite de deteção e menor incerteza para a quantificação de Boro. Usando a reação nuclear 11B(p,a0)8Be, foi possível calcular a sua seção de choque diferencial para ângulo de espalhamento theta=170, cujo resultado, para este ângulo específico, é inédito na literatura. As amostras de SiGM foram analisadas com a técnica SIMS e comparadas com medidas de Inductively Coupled Plasma - ICP realizadas pelo grupo do IPT. Uma vez que técnicas nucleares podem ser consideradas absolutas, concluímos que as medidas de ICP apresentaram dados compatíveis com as medidas SIMS, e que o grupo de metalurgia do IPT está medindo as concentrações de Boro em suas amostras de SiGM corretamente por meio de ICP. Uma reta de calibração entre medidas SIMSxICP foi construída, que poderá servir como um guia para futuras quantificações de Boro com ICP feitas pelo grupo de metalurgia do IPT. / In this work we investigated the use of analytical techniques based on ion beams in the quantification of Boron in many kinds of samples. Specifically, we applied techniques such Nuclear Reaction Analysis (NRA), Elastic Recoil Detection Analysis (ERDA) and Secondary Ion Mass Spectrometry (SIMS) to 11B/Ni and B/Si samples to measure the boron concentration. We also discuss and show what technique has a better detection limit and lower uncertainty. For the first time in the literature, we obtained the cross section for the $^{11}B(p,\\alpha_0){^8}Be$ nuclear reaction in the energy range from 1.6 up to 2.0 MeV in theta = 170 scattering angle. The SIMS technique was applied to analise samples of metallurgical grade silicon (SiGM) from Metallurgy Group of Instituto de Pesquisas Tecnologicas (IPT) to check the Inductively Coupled Plasma (ICP) measurements carried out by the IPT. Moreover, it was possible to build a calibration curve between SIMS and ICP measurements, that can be used to help of Metallurgy Group with futures ICP\'s measurements.

Neste trabalho, estudamos e aplicamos técnicas analíticas com feixes iônicos para a identificação e quantificação do elemento químico Boro em amostras de Boro depositado sobre Níquel 11B/Ni, sobre Silício B/Si e em amostras de Silício Grau Metalúrgico - SiGM. Estas últimas foram fornecidas pelo grupo de metalurgia do Instituto de Pesquisas Tecnológicas (IPT). Especificamente, as seguintes técnicas analíticas foram utilizadas: Nuclear Reaction Analysis - NRA, Elastic Recoil Detection Analysis - ERDA e Secondary Ion Mass Spectrometry - SIMS. Nas amostras de B/Ni e B/Si, as concentrações foram obtidas com medidas de NRA, ERDA e SIMS. Também foi abordado quais dentre essas três técnicas apresentam menor limite de deteção e menor incerteza para a quantificação de Boro. Usando a reação nuclear 11B(p,a0)8Be, foi possível calcular a sua seção de choque diferencial para ângulo de espalhamento theta=170, cujo resultado, para este ângulo específico, é inédito na literatura. As amostras de SiGM foram analisadas com a técnica SIMS e comparadas com medidas de Inductively Coupled Plasma - ICP realizadas pelo grupo do IPT. Uma vez que técnicas nucleares podem ser consideradas absolutas, concluímos que as medidas de ICP apresentaram dados compatíveis com as medidas SIMS, e que o grupo de metalurgia do IPT está medindo as concentrações de Boro em suas amostras de SiGM corretamente por meio de ICP. Uma reta de calibração entre medidas SIMSxICP foi construída, que poderá servir como um guia para futuras quantificações de Boro com ICP feitas pelo grupo de metalurgia do IPT. / In this work we investigated the use of analytical techniques based on ion beams in the quantification of Boron in many kinds of samples. Specifically, we applied techniques such Nuclear Reaction Analysis (NRA), Elastic Recoil Detection Analysis (ERDA) and Secondary Ion Mass Spectrometry (SIMS) to 11B/Ni and B/Si samples to measure the boron concentration. We also discuss and show what technique has a better detection limit and lower uncertainty. For the first time in the literature, we obtained the cross section for the $^{11}B(p,\\alpha_0){^8}Be$ nuclear reaction in the energy range from 1.6 up to 2.0 MeV in theta = 170 scattering angle. The SIMS technique was applied to analise samples of metallurgical grade silicon (SiGM) from Metallurgy Group of Instituto de Pesquisas Tecnologicas (IPT) to check the Inductively Coupled Plasma (ICP) measurements carried out by the IPT. Moreover, it was possible to build a calibration curve between SIMS and ICP measurements, that can be used to help of Metallurgy Group with futures ICP\'s measurements.

L’industrie microélectronique est régie depuis plusieurs années par la loi de miniaturisation. En particulier, en technologie CMOS, les procédés de fabrication de l’oxyde permettant l’isolation électrique entre les transistors nécessitent sans cesse d’être améliorés pour répondre aux défis de cette loi. Ainsi, on est passé du procédé d’isolation par oxydation localisée de silicium (LOCOS) au procédé d’isolation par tranchées (STI). Cependant, ce dernier a montré pour les technologies en développement des limitations liées au remplissage non parfait par la silice de tranchées de moins en moins larges (Voiding) et au ‘‘surpolissage’’ des zones les plus larges (Dishing). Le procédé FIPOS (full isolation by porous oxidation of silicon) a été donc proposé comme solution alternative. Il est basé sur la formation sélective et localisée du silicium poreux qui est transformé ensuite en silice par un recuit oxydant. Cette piste prometteuse a constitué le point de départ de ce travail. Dans ce contexte, la thèse s’est focalisée sur deux axes principaux qui concernaient d’une part la maîtrise du procédé d’anodisation électrochimique pour la formation du silicium poreux et d’autre part l’optimisation du procédé d’oxydation. Dans une première partie de notre travail, l’analyse des caractéristiques courant-tension I-V menée sur le silicium durant son anodisation électrochimique a permis de montrer que la formation du silicium poreux dépend fortement de la concentration en dopants. Cette propriété nous a permis de développer une technique simple d’extraction du profil de dopage dans le silicium de type p par voie électrochimique. On a montré que la résolution en profondeur de cette technique est liée au niveau du dopage et s’approche de celle du SIMS (spectroscopie de masse d'ions secondaires) pour les fortes concentrations avec une valeur estimée à 60 nm/décade. Dans une deuxième partie, nous avons mis en évidence la formation localisée du silicium poreux oxydé. En effet, un choix judicieux du potentiel d’anodisation permet de rendre poreux sélectivement des régions fortement dopées implantées sur un substrat de silicium faiblement dopé. Ces régions sont ensuite transformées en oxyde par un recuit oxydant. Par ailleurs, les conditions optimales des processus d’oxydation et d’anodisation permettant d’obtenir un oxyde final de bonne qualité diélectrique sont analysées. / The microelectronic industry is still ruled up to now by the law of miniaturization or scaling. In particular, in CMOS (complementary metal-oxide semiconductor) technology, the oxide allowing electric isolation between p- and n-MOS transistors has also been scaled down and has then exhibited different technological processes going from LOCOS (local oxidation of silicon) to STI (shallow trench isolation) and arriving to FIPOS (full isolation by porous oxidation of silicon). The latter seems to be the most promising alternative solution that can overcome actual limitations of voiding and dishing encountered in the STI process. The approach, which is based on selective formation of porous silicon and its easy transformation to silicon dioxide, has aroused our motivation to be well studied. In this context, the PhD project has first focused on the understanding of electrochemical porous silicon formation, and then on the study of porous silicon oxidation. In a first part of our work, we emphasize the dependence of porous silicon formation with the silicon doping concentration through the investigation of current-voltage I-V characteristics measured on p- and n-type silicon electrodes during electrochemical anodization. Taking advantage of this dependence, we have developed a very simple electrochemical method allowing an accurate determination of doping profiles in p-type silicon. It has been shown that the depth resolution of the technique is readily linked to the doping level and it approaches that of the secondary ion mass spectroscopy (SIMS) analysis for high doping concentrations with an estimated value of 60 nm/decade. In a second step, we highlight the selective formation of oxidized porous silicon. In fact, with a correct choice of the applied potential during anodization, only highly doped regions implanted on a lightly doped silicon wafer are preferentially turned into porous silicon and subsequently oxidized. Furthermore, we give the optimum conditions for oxidation and anodization processes which result in an insulating oxide of reliable dielectric properties.

La thèse porte sur l’étude de la cinétique de Smart Cut™ dans du silicium après implantation hydrogène, pour des températures de recuit comprises entre 500°C et 1300°C. Ainsi, la cinétique de séparation de couches (splitting) est caractérisée en considérant des recuits dans un four à moufle ainsi que des recuits laser. Sur la base de cette caractérisation, un modèle physique, basé sur le comportement de l’hydrogène implanté durant le recuit, est proposé. Le modèle s’appuie sur des caractérisations SIMS de l’évolution de la concentration d’hydrogène durant le recuit, ainsi que sur des simulations numériques. Le modèle propose une explication aux propriétés des films obtenus en fonction des conditions de recuit et mesurées par microscopie optique, AFM ainsi que par des mesures des énergies d’interfaces. Sur la base du modèle de splitting obtenu, deux procédés de fabrication de films de silicium sont proposés pour l’élaboration de matériaux de silicium sur saphir et verre par recuit laser ainsi que pour l’élaboration de feuilles de silicium monocristallin par épitaxie en phase liquide sur substrat silicium implanté. L’étude de premier procédé prouve pour la première fois la possibilité d’appliquer le procédé Smart Cut™ sur des substrats de silicium implanté. Les films ainsi obtenus présentent des grandes surfaces de transfert (wafer de 200 mm), ce qui présente un grand intérêt industriel. L’étude propose différentes caractérisations des films obtenus (AFM, profilométrie optique, mesure 4 pointe). Le deuxième procédé est démontré en utilisant des bancs d’épitaxie en phase liquide de silicium (température supérieure à 1410°C) afin d’effectuer des dépôts sur des substrats de silicium implantés. Les films obtenus montrent un grand degré de croissance épitaxiale (jusqu’à 90% du film déposé mesuré par EBSD) et présentent une épaisseur aussi faible que 100 µm. D’autre part, le détachement par Smart Cut™ des films ainsi déposés est démontré. / At first, the thesis studies the kinetics of Smart Cut™ in silicon implanted with hydrogen ions for annealing temperature in the range 500°C-1300°C. The kinetics is characterized by using a specially-dedicated furnace and by considering laser annealing. Based on the related characterization and observations, a physical model is established based on the behavior of implanted hydrogen during annealing. The model is strengthened by SIMS characterization focused on the evolution of hydrogen during annealing and on numerical calculations. Additionally, the model proposes an explanation for the properties of the obtained films as a function of the annealing conditions, based on optical microscope and AFM observations and bonding energy characterization. Based on this splitting model, two innovative processes for fabrication of silicon films are proposed. The first process allows to produce films of silicon on sapphire and films of silicon on glass by considering a laser annealing. The second produces foils of monocrystalline silicon by liquid phase epitaxial growth on implanted silicon substrate. The study of the first process proves for the first time the possibility to apply the Smart Cut™ for substrates of implanted silicon. The resulting films present large surface of transferred films (up to 200 mm wafers), which is very interesting in an industrial perspective. The study proposes different characterization of the films obtained by this process (AFM, optical profilometry and 4 probe measurement). The second process is demonstrated by using a chamber of liquid phase epitaxial growth of silicon (deposition temperature superior to 1410°C) in order to deposit liquid silicon on implanted silicon substrates. The obtained films show a high degree of epitaxial growth (up to 90% of the film as characterized by EBSD) and show a thickness as low as 100µm. Additionally the detachment by Smart Cut of the deposited films is demonstrated.