<p>The electronic and geometrical structure of free neutral clusters and liquids have been studied using synchrotron-radiation based photoelectron and Auger electron spectroscopy in combination with lineshape modeling. A novel experimental setup has been developed for studies of liquids, based on the liquid microjet technique. Theoretical lineshapes have been computed using both classical (molecular dynamics) and quantum mechanical (mainly density functional theory) methods.</p><p>Clusters are finite ensembles of atoms or molecules, ranging in size from a few to several thousand atoms. Apart from being fundamentally interesting, clusters are also promising as building blocks for nano-technology. In this thesis results are presented for rare-gas and molecular clusters, ranging from weakly van-deer-Waals bonded to hydrogen bonded. It is shown that the combination of core-level photoelectron spectroscopy (XPS) and lineshape modeling can be used to estimate the sizes of clusters. A model for treating the effect of inter-molecular nuclear relaxation upon ionization is proposed. The structure of single-component molecular clusters are investigated by molecular dynamics simulations, validated against XPS data. Finally, the radial structure of a two-component molecular cluster is investigated by XPS.</p><p>Liquids have been studied for centuries, but still many questions remain regarding the microscopic properties. With the recent development of the liquid microjet technique, new insight into the atomic structure can be obtained. In this thesis we study aqueous solutions using photoelectron and Auger electron spectroscopy (AES). We investigate the structure of surface active molecules by XPS, study the Auger decay after core-level ionization in aqueous potassium chloride (KCl), and follow the changes in molecular structure of glycine as a function of pH.</p>

The continuous high demand on permanent magnets in industries opened new research plateau to develop alternative magnetic material. The current used permanent magnet materials in the market still suffer from high cost and insufficient magnetic or thermal properties. The central focus of this dissertation work is the optimization of cobalt carbide based nanomaterial by means of modifying polyol synthesis assisted by nucleation agent and systematic statistics using JMP software tool. In most existing literatures, producing cobalt carbide (Co2C or Co3C) lack reproducibility and consistency resulting in nonsolid magnetic properties results. The practical requirements for cobalt carbide to be used as permanent magnet are high coercivity (Hc), high magnetization (Ms), resulting in a high-energy product (HcxMs). Previous literatures have shown coercivities of 1.5 to 2.5 kOe for cobalt carbides under aggressive temperatures conditions (300oC) or after aligning the particles under magnetic field. A statistical guided method performed a sequence of experiments toward producing high coercivities using surface response design. Primarily, the statistical study to optimize cobalt carbide was made by analyzing experimental condition to fulfill high magnetic properties with tuned conditions as much as possible. Therefore, having the advantage for superior control on process variable when shifting cobalt carbide for scale up production in flow chemistry set up using microreaction system (MMRS). The optimization is based upon selecting the most important conditions in polyol reaction to produce cobalt carbide (Co2C or Co3C) and feed JMP software model e.g. reaction temperature, reaction time, and or precursor concentration…etc. These factors called (effects) used to design experiments and generate tables to run minimum experiments. Points of each effect (levels) are selected based on previous knowledge and experience with the synthesis. The output called (response) can be any of the magnetic properties of our interest e.g. magnetization (Ms), coercivity (Hc), or energy magnetic product (HcxMs). In the first model fit of cobalt carbide magnetic was studied in a polyol reaction to increase its magnetic energy product and optimize the experimental conditions. The results disclosed increase in magnetic energy product (6.2 MGOe) when validating the prediction model conditions suggested by JMP: shorter reaction time, and lower precursor concentration conditions at maximum reaction temperature. Finally, to my knowledge studying the effect of the nucleating agent to alter cobalt carbide growth have not been studied so far. Therefore, statistical study design using central composite design (CCD) to investigate the nucleating agent effect of silver nitrite on cobalt carbide coercivity was made. The importance of nucleating agent on coercivity is vigorous to attain and control the growth direction of cobalt carbide nanoparticles. This is due to the shape anisotropy contribution to enhance coercivity unlike weak shape anisotropy attributed to agglomeration of nanoparticles demonstrated in previous studies. Enhancement of coercivity reached 3 kOe with aspect ratio control as a function of silver nitrite concentration under lower reaction temperature. The continuous high demand on permanent magnets in industries opened new research plateau to develop alternative magnetic material. The current used permanent magnet materials in the market still suffer from high cost and insufficient magnetic or thermal properties. The central focus of this dissertation work is the optimization of cobalt carbide based nanomaterial by means of modifying polyol synthesis assisted by nucleation agent and systematic statistics using JMP software tool. In most existing literatures, producing cobalt carbide (Co2C or Co3C) lack reproducibility and consistency resulting in nonsolid magnetic properties results. The practical requirements for cobalt carbide to be used as permanent magnet are high coercivity (Hc), high magnetization (Ms), resulting in a high-energy product (HcxMs). Previous literatures have shown coercivities of 1.5 to 2.5 kOe for cobalt carbides under aggressive temperatures conditions (300oC) or after aligning the particles under magnetic field. A statistical guided method performed a sequence of experiments toward producing high coercivities using surface response design. Primarily, the statistical study to optimize cobalt carbide was made by analyzing experimental condition to fulfill high magnetic properties with tuned conditions as much as possible. Therefore, having the advantage for superior control on process variable when shifting cobalt carbide for scale up production in flow chemistry set up using microreaction system (MMRS). The optimization is based upon selecting the most important conditions in polyol reaction to produce cobalt carbide (Co2C or Co3C) and feed JMP software model e.g. reaction temperature, reaction time, and or precursor concentration…etc. These factors called (effects) used to design experiments and generate tables to run minimum experiments. Points of each effect (levels) are selected based on previous knowledge and experience with the synthesis. The output called (response) can be any of the magnetic properties of our interest e.g. magnetization (Ms), coercivity (Hc), or energy magnetic product (HcxMs). In the first model fit of cobalt carbide magnetic was studied in a polyol reaction to increase its magnetic energy product and optimize the experimental conditions. The results disclosed increase in magnetic energy product (6.2 MGOe) when validating the prediction model conditions suggested by JMP: shorter reaction time, and lower precursor concentration conditions at maximum reaction temperature. Finally, to my knowledge studying the effect of the nucleating agent to alter cobalt carbide growth have not been studied so far. Therefore, statistical study design using central composite design (CCD) to investigate the nucleating agent effect of silver nitrite on cobalt carbide coercivity was made. The importance of nucleating agent on coercivity is vigorous to attain and control the growth direction of cobalt carbide nanoparticles. This is due to the shape anisotropy contribution to enhance coercivity unlike weak shape anisotropy attributed to agglomeration of nanoparticles demonstrated in previous studies. Enhancement of coercivity reached 3 kOe with aspect ratio control as a function of silver nitrite concentration under lower reaction temperature.

En 1920, le moteur Diesel marque l'histoire en se faisant une place dans le milieu de l'automobile. Toutefois, malgré la révolution que représente le moteur Diesel notamment en terme de technologie (moteur à combustion interne dont l'allumage n'est pas commandé mais spontané par phénomène d'auto-inflammation (absence de bougie d'allumage)), des inconvénients majeurs subsistent, tout particulièrement au niveau environnemental et sanitaire (émission de gaz à effet de serre, prélèvement accru d'énergie fossile, impact direct sur la santé). Afin de lutter contre ces émissions, l'Union Européen à mit en place les normes EURO (depuis 1993) incitant les constructeurs automobiles à concevoir des procédés d'élimination des particules carbonées et à apporter des évolutions au niveau des motorisations. C'est dans ce contexte qu'a vu le jour la technologie Filtre à Particules initié par Peugeot en 1999 pour évoluer d'années en années jusqu'à être considérées aujourd'hui comme une avancée majeur en terme de traitement des particules Diesel. Encore aujourd'hui les problèmes d'émanations demeurent en raison des imbrûlés générés par le moteur diesel (suies, HC aromatiques polycycliques, d'oxyde de soufre, d'oxyde d'azote…). Les dégagements de particules de suies fines demeurant un problème particulièrement important au niveau de la santé. Cette thèse s'inscrit dans l'optique d'optimisation du procédé FàP en proposant l'élaboration de membrane à base de SiC supportée. Plus généralement, notre étude concerne l'élaboration de céramiques poreuses (membranes supportées et mousses) à base de silicium pour application environnementale et sanitaire (Filtration des particules fines, dépollution et séquestration de CO2).Le Chapitre I traite du contexte général de l'étude. La problématique des émissions de particules est abordée d'un point de vue sanitaire et environnemental en précisant les normes en vigueurs pour leur contrôle. La technologie FàP est décrite avant d'introduire le SiC et la voie dite des « polymères précéramiques » (PDCs). L'aspect catalytique est ensuite abordé avant de développer le principe d'élaboration de membrane SiC et leur intérêt pour une application de dépollution automobile.Le Chapitre II traite de l'élaboration de membranes SiC supportées. L'étude concerne l'élaboration d'un procédé optimale pour déposer une membrane au sein de la porosité du FàP qui modifierait les caractéristiques de porosité de ce dernier sans pour autant engendrer des répercussions néfastes sur la filtration. Le polymère précéramique, précurseur de SiC, sera alors décrit et nous étudierons sa mise en forme par la technique dite de « trempage-tirage » (dip-coating) afin d'élaborer, après pyrolyse, une membrane SiC. Cette dernière sera caractérisée par de nombreux outils expérimentaux.Le Chapitre III reprend le procédé d'élaboration des membranes de SiC élaboré dans le Chapitre II mais il proposera d'aller plus loin avec la réalisation et l'étude de catalyseurs pour la combustion des suies, et leur intégration au sein d'une microémulsion de type SiC-MxOy utilisée pour revêtir les FàP.Le Chapitre IV propose une étude sur la préparation de mousses à base de SiC. Ce chapitre d'aspect plus fondamental consistera à développer des mousses cellulaires et à porosité hiérarchisée à base des éléments silicium (Si), bore (B), carbone (C) et azote (N). Cette phase de carbonitrure de silicium et de bore (Si/B/C/N) sera élaborée par couplage de la voie PDCs avec soit des agents sacrificiels soit par réplication. Une étude préliminaire sur la séquestration de CO2 sera alors décrite pour finir. / Since the 90's, Diesel engines are widely used though they are criticized because of the pollution emitted. The constant updates of the Europeans norms (since 1993) concerning the diesel emissions imply a perpetual improvement of filtration techniques. The Diesel Particles Filter (DPF) technology used by the car manufacturer PSA Peugeot Citroën is one of the best ways to fulfill the limitation for diesel emissions. However, particles emission issue is still a problem and future legislations more and stricter, so an improvement of the DPF process is required to respect them. In this context, we have considered the elaboration of two different types of porous membranes on the DPF channels. The first one was in SiC, and had the aim to enhance the filtration efficiency. In this way, the smallest particles matter could be locked in the filter. The second kind of membrane integrates a catalytic phase inside the ceramic matrix, so in addition to the filtration aspect, it could improve soot combustion during the regeneration step of the DPF.The first chapter of my thesis deals with the literature corresponding to the subject, i.e. the DPF technology, non-oxides Si-based ceramics, and in particular those obtained through polymer-derived ceramics route (also called PDCs route). Then, ceramic coatings and catalytic phases are also treated. In the second chapter, we have considered the PDCs route and preceramic polymers to elaborate a SiC coating inside the DPF channels. We employed the dip-coating technique to overlay the channel surface with the AHPCS precursor of SiC (allylhydridopolycarbosilane), then, a pyrolysis under argon allows obtaining a SiC coating, in order to decrease the average pore diameter of the DPF (keeping an efficient filtration while avoiding overpressure) to catch soot nanoparticles evolving from Diesel engine.The third part of my PhD deals with the elaboration of another kind of coating for the DPF channels including a catalytic phase in the ceramic membrane. For this purpose, the microemulsion synthesis has been considered to prepare SiC-MxOy membrane. Further, we incorporated various catalytic phases based on Ce, Fe and Pt as activators of soot combustion. By employing the dip-coating technique, we successfully covered the DPF channels of our monoliths with the aforementioned microemulsion and after a heat treatment under controlled atmosphere; a porous coating consisting of the catalytic phase and the ceramic matrix was obtained. From this film, the porosity has been modified by lowering the diameter of the initial pores, but also by getting an additional porosity due to the polymer conversion and the surfactant decomposition. Catalytic sites in the ceramic have improved the soot combustion by lowering the temperature of the combustion.The fourth chapter introduces the elaboration of porous SiBCN materials through two approaches, replication and warm-pressing with sacrificial template (polymethylmethacrylate, PMMA). The SiBCN ceramic is a promising material due to its high mechanical properties and its stability at high temperature (1700-1800°C). By coupling the PDCs way with those two techniques, we are able to elaborate SiBCN porous materials which features can be tuned according to the technological application envisaged.

Silicon carbide is a promising wide bandgap semiconductormaterial for high-temperature, high-power, and high-frequencydevice applications. However, there are still a number offactors that are limiting the device performance. Among them,one of the most important and critical factors is the formationof low resistivity Ohmic contacts and high-temperature stableSchottky diodes on silicon carbide. In this thesis, different metals (TiW, Ti, TiC, Al, and Ni)and different deposition techniques (sputtering andevaporation) were suggested and investigated for this purpose.Both electrical and material characterizations were performedusing various techniques, such as I-V, C-V, RBS, XRD, XPS,LEED, SEM, AFM, and SIMS. For the Schottky contacts to n- and p-type 4H-SiC, sputteredTiW Schottky contacts had excellent rectifying behavior afterannealing at 500 ºC in vacuum with a thermally stableideality factor of 1.06 and 1.08 for n- and p-type,respectively. It was also observed that the SBH for p-type SiC(ΦBp) strongly depends on the choice the metal with alinear relationship ΦBp= 4.51 - 0.58Φm, indicating no strong Fermi-level pinning.Finally, the behavior of Schottky diodes was investigated byincorporation of size-selected Au nano-particles in Ti Schottkycontacts on silicon carbide. The reduction of the SBH isexplained by using a simple dipole layer approach, withenhanced electric field at the interface due to the small sizeof the circular patch (Au nano-particles) and large differenceof the barrier height between two metals (Ti and Au) on both n-and p-SiC. For the Ohmic contacts, titanium carbide (TiC) was used ascontacts to both n- and p-type 4H-SiC epilayers as well as onAl implanted layers. The TiC contacts were epitaxiallydeposited using a co-evaporation method with an e-beam Tisource and a Knudsen cell for C60, in a UHV system at low substrate temperature(500 ºC). In addition, we extensively investigatedsputtered TiW (weight ratio 30:70) as well as evaporated NiOhmic contacts on both n- and p-type epilayers of SiC. The bestOhmic contacts to n-type SiC are annealed Ni (&gt;950ºC)with the specific contact resistance of ≈ 8× 10-6Ω cm2with doping concentration of 1.1 × 10-19cm-3while annealed TiW and TiC contacts are thepreferred contacts to p-type SiC. From long-term reliabilitytests at high temperature (500 ºC or 600 ºC) invacuum and oxidizing (20% O2/N2) ambient, TiW contacts with a platinum cappinglayer (Pt/Ti/TiW) had stable specific contact resistances for&gt;300 hours. <b>Keywords</b>: silicon carbide, Ohmic and Schottky contacts,co-evaporation, current-voltage, capacitance-voltagemeasurement, power devices, nano-particles, Schottky barrierheight lowering, and TLM structures.

The electronic and geometrical structure of free neutral clusters and liquids have been studied using synchrotron-radiation based photoelectron and Auger electron spectroscopy in combination with lineshape modeling. A novel experimental setup has been developed for studies of liquids, based on the liquid microjet technique. Theoretical lineshapes have been computed using both classical (molecular dynamics) and quantum mechanical (mainly density functional theory) methods. Clusters are finite ensembles of atoms or molecules, ranging in size from a few to several thousand atoms. Apart from being fundamentally interesting, clusters are also promising as building blocks for nano-technology. In this thesis results are presented for rare-gas and molecular clusters, ranging from weakly van-deer-Waals bonded to hydrogen bonded. It is shown that the combination of core-level photoelectron spectroscopy (XPS) and lineshape modeling can be used to estimate the sizes of clusters. A model for treating the effect of inter-molecular nuclear relaxation upon ionization is proposed. The structure of single-component molecular clusters are investigated by molecular dynamics simulations, validated against XPS data. Finally, the radial structure of a two-component molecular cluster is investigated by XPS. Liquids have been studied for centuries, but still many questions remain regarding the microscopic properties. With the recent development of the liquid microjet technique, new insight into the atomic structure can be obtained. In this thesis we study aqueous solutions using photoelectron and Auger electron spectroscopy (AES). We investigate the structure of surface active molecules by XPS, study the Auger decay after core-level ionization in aqueous potassium chloride (KCl), and follow the changes in molecular structure of glycine as a function of pH.

Boron carbide nano-powders, singly-doped over a range of compositions, were pressurelessly-sintered at identical temperature and atmospheric conditions in a dif- ferential dilatometer to investigate sintering behavior. Samples that achieved relative densities greater than 93% of theoretical density were post-HIPed. Post-HIPing re- sulted in an increase in relative density as well as an increase in Vicker's hardness. To optimize the sintering behavior, nano-powders with multiple dopants were prepared based on the results of single dopant experiments. These powders were studied using the same heating schedule as the single dopant samples. The powder with optimized composition was selected, and 44.45 mm diameter disks were pressed to determine the effects of sample size. Powder composition #166 with Al, Ti, W and Mg additions was processed using di¢çerent methods in order to create defect-free green bodies after uniaxial press- ing. The 44.45 mm diameter compacts were heat-treated to remove organics and B₂O₃coatings on particles and then encapsulated in an evacuated fused silica am- pule. Encapsulated samples were HIPed at temperatures below the coarsening region observed in the dilatometric traces of multiply-doped nano-powders. The E-HIPed sample showed a relative density of 96% with a limited extent of nano-sized grain microstructure.

<p>Silicon carbide is a promising wide bandgap semiconductormaterial for high-temperature, high-power, and high-frequencydevice applications. However, there are still a number offactors that are limiting the device performance. Among them,one of the most important and critical factors is the formationof low resistivity Ohmic contacts and high-temperature stableSchottky diodes on silicon carbide.</p><p>In this thesis, different metals (TiW, Ti, TiC, Al, and Ni)and different deposition techniques (sputtering andevaporation) were suggested and investigated for this purpose.Both electrical and material characterizations were performedusing various techniques, such as I-V, C-V, RBS, XRD, XPS,LEED, SEM, AFM, and SIMS.</p><p>For the Schottky contacts to n- and p-type 4H-SiC, sputteredTiW Schottky contacts had excellent rectifying behavior afterannealing at 500 ºC in vacuum with a thermally stableideality factor of 1.06 and 1.08 for n- and p-type,respectively. It was also observed that the SBH for p-type SiC(Φ_Bp) strongly depends on the choice the metal with alinear relationship Φ_Bp= 4.51 - 0.58Φ_m, indicating no strong Fermi-level pinning.Finally, the behavior of Schottky diodes was investigated byincorporation of size-selected Au nano-particles in Ti Schottkycontacts on silicon carbide. The reduction of the SBH isexplained by using a simple dipole layer approach, withenhanced electric field at the interface due to the small sizeof the circular patch (Au nano-particles) and large differenceof the barrier height between two metals (Ti and Au) on both n-and p-SiC.</p><p>For the Ohmic contacts, titanium carbide (TiC) was used ascontacts to both n- and p-type 4H-SiC epilayers as well as onAl implanted layers. The TiC contacts were epitaxiallydeposited using a co-evaporation method with an e-beam Tisource and a Knudsen cell for C₆₀, in a UHV system at low substrate temperature(500 ºC). In addition, we extensively investigatedsputtered TiW (weight ratio 30:70) as well as evaporated NiOhmic contacts on both n- and p-type epilayers of SiC. The bestOhmic contacts to n-type SiC are annealed Ni (>950ºC)with the specific contact resistance of ≈ 8× 10^-6Ω cm²with doping concentration of 1.1 × 10^-19cm^-3while annealed TiW and TiC contacts are thepreferred contacts to p-type SiC. From long-term reliabilitytests at high temperature (500 ºC or 600 ºC) invacuum and oxidizing (20% O₂/N₂) ambient, TiW contacts with a platinum cappinglayer (Pt/Ti/TiW) had stable specific contact resistances for>300 hours.</p><p><b>Keywords</b>: silicon carbide, Ohmic and Schottky contacts,co-evaporation, current-voltage, capacitance-voltagemeasurement, power devices, nano-particles, Schottky barrierheight lowering, and TLM structures.</p>

Contexte: La cardiopathie ischémique (IHD) reste une cause majeure de mortalité en Amérique du Nord. La thérapie cellulaire cardiaque (CCT) a émergé comme une thérapie prometteuse pour aider à guérir certaines malades cardiaques. Parmi les cellulaires avec propriétés pluripotentes, les cellules stromales mésenchymateuses (MSC) sont prometteuses. Cependant, plusieurs questions demeurent non résolues et certaines défis empêchent l'application clinique de la CCT se dans l'IHD, tels que le faible taux de rétention cellulaire in situ, le suivi des cellules in vivo post-implantation et post-acheminements et l`apoptose. Ici, le traitement préliminaire des MSC avec des facteurs de croissance et leur couplage avec des nanoparticules (NP) seront étudiés comme des méthodes pour optimiser MSC. Méthodes: Des MSCs provenant du rat (rMSC) et du cochon (pMSC) ont été isolés à partir de moelle osseuse. Les rMSC ont été préconditionnées avec SDF-1a, TSG-6 et PDGF-BB, et ensuite soumises à une hypoxie, une privation de sérum et a un stress oxydatif. Des études de cicatrisation ont également été effectués avec rMSCs préconditionnées. En parallèle, de nouvelles NP ferromagnétiques liées aux silicones ont été synthétisées. Les NPs ont été couplées aux pMSCs suivant leur fonctionnalisation avec l`anticorps, CD44, un antigène de surface du MSC bien connu. Par la suite, les études de biocompatibilité ont été réalisées sur pMSC-NP et en incluant des tests des processus cellulaires tels que la migration, l'adhésion, la prolifération et les propriétés de la différenciation. Résultats: Parmi toutes les cytokines testées, PDGF-BB a démontré la plus grande capacité à améliorer la survie de MSC dans des conditions d'hypoxie, de privation de sérum et en reponse au stress oxydatif. La conjugaison de NP a atténué la migration et la prolifération des pMSCs, mais n`a pas changé leur capacité de différenciation. Enfin, la complexe du MSC-NP est détectable par IRM. Conclusion: Nos données suggèrent que de nouvelles stratégies, telles que traitement préliminaire de PDGF-BB et le couplage des nanoparticules ferromagnétiques, peuvent être considérés comme des avenues prometteuse pour optimiser les MSCs pour la CCT. / Background: Ischemic heart disease (IHD) remains a leading cause of mortality in North America. Cardiac cell therapy (CCT) has emerged as a promising therapy to help heal the damaged heart. Among the various candidates for stem-progenitor cells, Mesenchymal Multipotential Stromal/Stem Cells (MSC) is of great promise. However, there remain unresolved issues and challenges that prevent clinical application of MSC-based CCT in IHD. Among the latter, low cellular retention rate, in vivo cell tracking and post-delivery apoptosis. Here in, growth factor preconditioning and MSC coupling to nanoparticles are investigated as methods to optimize MSC. Methods：Lewis Rat MSC (rMSC) and pig MSC (pMSC) were isolated from bone marrow. Rat MSCs were preconditioned with SDF-1a, TSG-6 and PDGF-BB, and then subjected to hypoxia, serum deprivation and oxidative stress. Wound healing assays were also done with preconditioned rat MSCs. In parallel, novel ferromagnetic silicone core-shell nanoparticles (NP) were synthesized. Pig MSCs were coupled to NPs following functionalization of the NPs with an antibody to a well-recognized MSC surface antigen, CD44. Subsequently, biocompatibility studies were performed on the pMSC-NP complex and included testing of key cellular processes such as migration, adhesion, proliferation and differentiation properties. Results: Of all cytokines used, PDGF-BB showed greatest capacity to improve MSC survival under conditions of hypoxia, serum deprivation and oxidative stress. NP conjugation has mitigated effect on the migration and proliferation of pig MSC, but do not change the differentiation capacity of MSC. Finally, the MSC-NP complex was detectable by MRI. Conclusion: Our data suggest that novel strategies, such as PDGF-BB preconditioning and ferromagnetic nanoparticle coupling, can be considered as promising avenues to optimize MSCs for CCT.

Cette thèse présente le développement de tests immunologiques innovants, rapides et sensibles combinant des nanoparticules superparamagnétiques (SPN) fonctionnalisées et des micro-aimants : nos immuno-essais magnétiques exploitent les forts gradients de champ magnétique de ces micro-aimants pour capturer les complexes immunologiques liés aux SPN. L’attraction magnétique est souvent utilisée en biotechnologies car elle peut générér des forces capables de capturer des molécules d’intérêt. Les immuno-essais sur billes utilisent habituellement des aimants centi- et millimétriques pour capturer des micro-particules. Réduire la taille des particules magnétiques est très intéressant pour réduire les cinétiques de réactions, tout en diminuant les phénomènes de sédimentation et d’agrégation. Cette réduction d’échelle des particules permet aussi d’augmenter la surface de réaction et ainsi d’augmenter la sensibilité des tests. Cependant les aimants millimétriques génèrent des gradients faibles qui capturent difficilement les SPN, trop mobiles. Les micro-aimants de l’Institut Néel génèrent des forts gradients locaux et ainsi des forces magnétiques importantes. Ces technologies innovantes sont utilisées dans cette thèse pour développer des immuno-essais rapides tirant profit de la réduction d’échelle des particules et des aimants, par rapport aux technologies commerciales.Dans un premier temps, nous avons développé un test immunologique magnétique (MagIA) colorimétrique, comme approche innovante du test ELISA. Nous avons réalisé une preuve de concept pour la détection d’anticorps dirigé contre l’ovalbumine et comparé les résultats avec ceux de tests ELISA. Le test MagIA optimisé présente une limite de détection et une zone dynamique similaires au test ELISA développé avec les mêmes réactifs biologiques. Les micro-aimants fabriqués selon la méthode de micro-magnetic imprinting sont intégrés à bas coût dans les micro-puits des plaques multi-puits ELISA, et permettent la capture efficace des complexes immunologiques couplés aux SPN. La méthode est générique est permet de réaliser des tests ELISA en 30 minutes avec le même équipement.Nous avons ensuite développé un test magnétique immunologique avec une détection fluorescente locale tirant profit des propriétés de capture locale des SPN sur les micro-aimants. Ce test permet la quantification de la molécule d’intérêt en à peine 15 minutes sans étape de lavage. Une preuve de concept réalisée sur la détection de l’anticorps anti-ovalbumine a été réalisée, avec des anticorps de détection fluorescents et des micro-aimants fabriqués selon la méthode de thermo-magnetic patterning. La mesure différentielle entre le signal fluorescent provenant des complexes immunologiques couplés aux SPN localisées sur les micro-aimants, et le signal non spécifique (à l’extérieur des micro-aimants) permet la quantification d’une molécule. Ce test MLFIA (magnetically localized FIA) possède des performances jusqu’à 100 fois meilleures que les tests ELISA standard, pour la détection d’anticorps anti-ovalbumine en PBS. Le test MLFIA a ensuite été transféré à la détection de paramètres cliniques tels que la protéine C réactive, l'ostéopontine, et les sérologies de la toxoplasmose (IgG et IgM). La comparaison des résultats avec des méthodes automatisées a montré d’excellentes corrélations. Le test MLFIA présente plusieurs avantages : il est versatile, compatible avec les milieux biologiques, utilise de faibles volumes et requiert peu d’énergie. Ces résultats ouvrent la voie à une nouvelle génération de tests immunologiques sensibles et nous développons désormais un lecteur miniature pour le diagnostic portable. / This thesis reports the development of innovative, sensitive and fast immunoassays combining functionalized superparamagnetic nanoparticles (SPN) and micro-magnets. Our magnetic immunoassays exploit high gradients generated by micro-magnets to capture immune-complexes captured on SPN. Magnetic attraction is widely used in biotechnology, because it provides long-range forces able to capture molecules of interest. Bead-based immunoassays use common centimetre-scale magnets to attract micro-particles. Those magnets generate low magnetic gradients and struggle to capture superparamagnetic nano-particles, which are too small and mobile to be efficiently trapped. Down-scaling the size of magnetic particles is very interesting since it allows diffusion-based transport to perform faster reactions, while avoiding particle sedimentation and aggregation. Furthermore, it increases the reaction surface, which improves the sensitivity of immunoassays. Thanks to the scaling law effects micro-magnets from Institut Néel generate high local gradients and therefore large magnetic volume forces: we use this innovative technology to develop fast immuno-assays that take advantage of a radical size reduction, compared to commercial technology.We first developed a colorimetric magnetic immunoassay (MagIA) as a new approach to standard ELISA. A proof-of-concept based on colorimetric quantification of anti-ovalbumin antibody in buffer was performed and compared with conventional ELISAs. After optimization, MagIA exhibits a limit of detection and dynamic range similar to ELISAs developed using the same biochemical tools. Micromagnets made by the micro-magnetic imprinting method can be fully integrated in multi-well plates at low cost, allowing the efficient capture of immuno-complexes carried by SPNs. The method is generic and performs magnetic ELISA in 30 min.We then developed a magnetically localized fluorescent immunoassay (MLFIA) exploiting the local capture of SPN on micro-magnets. The differential measurement of fluorescence localized on and besides micro-magnet arrays allows the detection and quantification of a molecule in only 15 minutes without fluid handling. We present a proof of concept based on the detection of monoclonal antibody anti-ovalbumin. Functionalized nanoparticles are incubated with fluorescent detection antibody and the sample containing the molecule to be detected. After a single incubation step, the nanoparticles are captured on micro-magnets made by thermo-magnetic patterning. Fluorescence is then read under a microscope. Differential measurement between the signal from the immunological complex localised on the micro-magnets and the non-specific signal localised besides micro-magnets allows the quantification of mAb anti-OVA. The performance of MLFIA was compared with conventional ELISA and exhibits a limit of detection up to 100 times better for anti-OVA mAb in PBS. For further validation, MLFIA was used to measure clinical parameters: we developed a sandwich assay to detect C-reactive protein, and a serology for Toxoplasma gondii immunoglobulin G and M or osteopontin in human samples. Comparisons with data obtained with routine clinical automatized methods show excellent correlation. Our MLFIA technology presents several key advantages: it is compatible with biological media (serum, plasma), uses small volumes and requires little energy. It also is versatile and thus can be used to detect any antigen or antibody in complex media. We are currently developing a portable prototype for point-of-care diagnostics. The results will open the way to a new generation of sensitive immunological lab-on-chip.

Cette thèse présente les travaux effectués au CELIA sur la luminescence ultraviolette et les dynamiques excitoniques dans l’oxyde de zinc (ZnO) sous forme massive et nano-structurée. Les mesures ont été effectuées en conditions expérimentales contrôlées (température, fluence d’excitation), pour différentes énergies de photon excitateur. Nous avons mesuré les spectres d’émission sous excitation à un photon UV (4,66 eV), ainsi que à 3 photons IR (1,55 eV), et proposé un schéma séquentiel de formation des excitons (avec simulations), en particulier pour les excitons DX. Nous avons obtenu une durée de vie nanoseconde de DX dans les deux cas, en désaccord avec la majorité des études publiées dans la littérature. / This thesis presents the work carried out at CELIA about ultraviolet luminescence and exciton dynamics in massive and nano-structured zinc oxide (ZnO). Measurements were carried out under controlled experimental conditions (temperature, excitation fluence), according to different excitation photon energies.We measured emission spectra under UV photon excitation (4.66 eV), and 3 IR photons (1.55 eV), and suggested a sequential exciton formation mechanism (with simulations), especially for DX excitons. We found a nanosecond lifetime for DX in both cases, in disagreement with most of the studies published in the literature. Relaxation dynamics of free and bound excitons are linked by the FX trapping process on donor defect and the DX thermal detrapping.Under VUV excitation (20-50 eV), surface effects and strong local excitation density greatly accelerate the relaxation of excitons. Under X excitation (1 keV), good conditions for the formation of DX seems to be close under excitation at 1.55 and 950 eV.The presence of core 2p band of zinc modifies the relaxation dynamics of excitons by the multiplication of local high density excitations zones and the change of the elementary excitations distribution. We have also conducted measurements on nano-particles. The significant surface effects induced by the small size of these system lead to a sharp acceleration of kinetics, masking the intrinsic exciton relaxation process.