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Les marchés de la thermoélectricité sont en pleine expansion avec l’intérêt croissant pour la récupération d’énergie thermique ou encore pour la gestion de la température de composants électroniques. En dépit de ses nombreux avantages, le développement de cette technologie est freiné par les performances des matériaux. Une voie d’amélioration identifiée est leur nanostructuration afin d’en diminuer la conductivité thermique de réseau.Dans ce travail de thèse, cette voie est appliquée au tellurure de bismuth, matériau connu pour posséder les meilleures performances autour de la température ambiante. Les matériaux sont obtenus par synthèse de nanoparticules en solution avant d’être mis en forme par pressage à chaud.Une première étude est réalisée sur la recherche d’un optimum de la taille de grain dans le massif. On montre que le contrôle des conditions de synthèse permet le contrôle des dimensions des nanoparticules. Par ailleurs, les analyses structurales et fonctionnelles des massifs après densification montrent que la variation de la taille initiale des particules permet le contrôle de la microstructure et des propriétés detransport des massifs.Une seconde étude porte sur la recherche d’un optimum en composition des matériaux Bi2Te3-xSex. Les analyses morphologiques mettent en évidence une structure complexe et particulière, laissant apparaitre la présence de trois phases dans les massifs.Les matériaux obtenus par cette méthode de synthèse possèdent a priori des propriétés de transport anisotropes. La caractérisation de leurs performances thermoélectriques est donc difficile. Plusieurs techniques de caractérisation sont mises en oeuvre afin de mieux connaitre leurs conductivités thermiques. Celles-ci sont faibles, ce qui montre l’intérêt de l’approche. Toutefois, leur conductivité électrique est plus basse que leurs homologues obtenus par des techniques plus conventionnelles. On montre néanmoins que l’optimisation des conditions de synthèse des particules entrant dans la composition des massifs alliés permet d’améliorer leurs propriétés électriques et donc leurs performances thermoélectriques / The global thermoelectric markets are in expansion with a growing interest for the energy harvesting or the thermal management of electronic components. Despite numerous advantages, this technology development is limited by the materials performances. A way to improve them is to use nanostructures in order to decrease the lattice thermal conductivity.In this work, this approach is applied to bismuth telluride, material well known for its high performance around room temperature. Materials are obtained from solution synthesis of nanoparticles before hot press compaction.A first study focuses on the determination of an optimal grain size in the bulk materials. It is shown that control over the synthesis parameters allows control on the size of nanoparticles.Moreover, structural and physical analyses on the bulks after sintering show that the change of thesynthesis parameters allows control over the microstructure and thermoelectric properties of the bulks.A second study is based on the study of an optimal composition of Bi2Te3-xSex materials. Morphological analysis show a specific and complex structure with three phases in the bulks.It is postulated that these materials should have anisotropic transport properties. Consequently, their characterizations are difficult. Different characterization techniques are used in order to have a better understanding of their thermal conductivities. Thermal conductivity of the bulks is found low which confirm the interest of this approach. However the electrical conductivity is lower than the one of the materials obtained by more conventional methods. We show that the synthesis parameters of the particles can be optimized to increase the thermoelectric performances of the bulk materials.

Ce manuscrit de thèse présente les recherches et les applications potentielles en tant que plate-forme (bio) capteur des couches minces conformes de ZnO et / ou Al2O3 / ZnO nanolaminates, déposées par dépôt de couche atomique (ALD) sur les différents substrats. Tout d'abord, une étude des propriétés optiques des films minces ZnO (20 et 50 nm) déposés par la technique ALD sur les grandes zones de nanofils de silicium ordonné (SiNW), réalisée en combinant la lithographie à la nanosphère et la gravure chimique à base de métal, a été réalisée. Ces méthodes ont permis la morphologie et le contrôle organisationnel des SiNW sur une grande surface. L'étude détaillée des propriétés structurales et optiques de l'hétérostructure SiNWs / ZnO à noyau-coquille a été réalisée en utilisant respectivement la spectroscopie XRD, SEM, de réflectance et de photoluminescence. L'intégration des tableaux SiNWs en tant que noyau et ZnO comme coque peut avoir un impact important sur le développement d'éléments de détection avec des propriétés améliorées. Dans les recherches ultérieures, des films ZnO formés par ALD en tant que plate-forme de biocapteur optique pour la détection des protéines de type A du virus Grapevine (antigènes GVA) ont été représentés. La détection de l'antigène GVA a été effectuée en utilisant les changements dans le comportement de la bande PL liée à la GVA. La sélectivité du biocapteur a été prouvée. La possibilité de détecter les antigènes GVA sans étiquettes supplémentaires a été démontrée. Ainsi, on a développé un biosensor à base de photoluminescence à base de photoluminescence libre pour les antigènes GVA. Une autre partie de notre étude est un contrôle spécifique de l'ancrage des protéines par le développement d'une surface multifonctionnelle avec une grande gamme de sphères de polystyrène (PSS), produite par la lithographie de nanosphère et bloquant davantage l'adsorption non spécifique des protéines à la surface du PSS par SAM de PEG. La microscopie d'épifluorescence a été utilisée pour confirmer qu'après l'immersion de l'échantillon sur la protéine cible (avidine et anti-avidine), ces dernières sont spécifiquement situées sur une sphère de polystyrène. Ces résultats sont significatifs pour l'exploration de dispositifs basés sur un nanoarray à grande échelle de sphères de PS et peuvent être utilisés pour la détection de protéines cibles ou simplement pour structurer une surface avec des protéines spécifiques. Notre recherche comprend également l'ajustement des propriétés structurelles et l'amélioration des propriétés électroniques et optiques des nanolaminés 1D PAN ZnO / Al2O3 conçus par dépôt de couche atomique (ALD) et électrospinning. Les propriétés structurelles et optiques de Al2O3 / ZnO déterminées à partir des analyses XPS, TEM, FTIR, XRD et PL. L'amélioration des propriétés électroniques et optiques permettrait l'application dans différents domaines de tels capteurs et biosensors. / This thesis manuscript presents the investigations and potential applications as a (bio)sensor platform of the conform thin layers of ZnO and/or Al2O3/ZnO nanolaminates, deposited by atomic layer deposition (ALD) on the various substrates. First, a study of the optical properties of ZnO thin films (20 and 50 nm) deposited by ALD technique on the large areas of ordered silicon nanowires (SiNWs), produced by combining nanosphere lithography and metal-assisted chemical etching, was performed. These methods allowed the morphology and the organization control of SiNWs on a large area. The detailed study of structural and optical properties of core-shell SiNWs/ZnO heterostructure was done by utilizing XRD, SEM, reflectance and photoluminescence spectroscopy, respectively. Integration of SiNWs arrays as core and ZnO as shell can have a strong impact on the development of sensing elements with improved properties. In the further investigations, ZnO films formed by ALD as an optical biosensor platform for the detection of Grapevine virus A-type proteins (GVA-antigens) were represented. The GVA-antigen detection was performed using the changes in the GVA related PL band behavior. The biosensor selectivity has been proved. The possibility to detect GVA-antigens without additional labels has been demonstrated. Thus, label free and sensitive photoluminescence based biosensor for GVA-antigens has been developed. Another part of our study is a specific control of protein anchoring by the development of multifunctional surface with large-scale array of polystyrene spheres (PSS), which produced by nanosphere lithography and further blocking the unspecific adsorption of protein on the surface of the PSS by PEG SAMs. The epifluorescence microscopy was used to confirm that after immersion of sample on target protein (avidin and anti-avidin) solution, the latter are specifically located on polystyrene sphere. These results are meaningful for exploration of devices based on large-scale nanoarray of PS spheres and can be used for detection of target proteins or simply to pattern a surface with specific proteins. Our research also includes the tuning of structural properties and the enhancement of electronic and optical properties of 1D PAN ZnO/Al2O3 nanolaminates designed by atomic layer deposition (ALD) and electrospinning. The structural and optical properties of Al2O3/ ZnO determined from the XPS, TEM, FTIR, XRD and PL analysis. The enhancement of electronic and optical properties would allow application in different fields such sensors and biosensors.

<p>The development of finely dispersed powders and superfine-grained materials intended for application in various areas of science and engineering is one of the challenges facing modern nanotechnology. Thus, specific fundamental and applied research was required in order to consolidate advancement made in preparing nano- and submicron crystalline composite materials.</p> <p><br /> Useful templates for electrochemical deposition of nanowires include porous alumina films formed by anodic oxidation of aluminium, nuclear track-etched porous membranes, nanochannel array-glass and mesoporous channel hosts. The properties of the nanowires are directly related to the properties of the nanoporous templates such as, the relative pore orientations in the assembly, the pore size distribution, and the surface roughness of the pores. The template synthesis method, based on the use of porous polymeric and inorganic matrixes, is now actively used for synthesis of such composite materials. The method allows the chemical and/or electrochemical synthesis of nano- and microstructured tubes and wires consisting of conducting polymers, metals and semiconductors.</p> <p><br /> In this study various technological challenges relating to template synthesis and development of nickel nano- and microstructures on adequately strong and durable substrates were investigated. The two methods used were the electrochemical and chemical deposition. &ldquo / Hard nickel&rdquo / bath solution was used for optimal nickel deposition. This optimization included investigating variables such as the template structure, type of electrolyte and form of electrolytic deposition. Scanning Electron Microscopy was used to investigate the structures of template matrixes and the resultant materials. The cyclic voltammetry method was applied for the analysis of electrochemical properties and hydrogen evaluation reaction of nano- and microstructured nickel based electrodes. The activity of composite nano- and microstructured materials in various configurations resulting from pore filling of template matrices by nickel was explored. Studies of the physical structure and chemical properties of the nanostructured materials included investigating the necessary parameters of template matrices. The optimum conditions of synthesis, which allowed development of materials with the highest catalytic activity, were determined.&nbsp / The effect of the template structure on microcrystallinity of the catalyst particles was established using the XRD method. Different new types of non-commercial asymmetric ion track membranes has been tested for nanostructure preparation. The catalytic activity of the new developed nanomaterials is higher as compared to materials using commercial templates. The procedures to modify the newly developed nickel catalyst with Pt, Pd and Pt-Pd alloy have been developed. The Pt and Pt-Pd alloy containing catalyst showed the best performance in water electrolysis. In this work, the promising role for specific application of the new materials in hydrogen economy has been demonstrated.</p>

The aim of this project was to investigate methods for purification and modification of Single Wall and Multi Wall Carbon Nanotubes. Covalent and noncovalent approaches to functionalization were studied. The dispersibility, structure and electronic properties of modified tubes were characterized by Raman, UV-vis-NIR and XPS. Fluorescence, NMR and TEM were further employed to characterize the interaction between nanotubes and non-covalent modifiers. The effects of five different purification methods on the dispersibility, and degree of carboxylic acid functionality of SWCNTs, along with the level of defects on the tube side walls, and the resulting electronic properties of SWCNTs have been investigated. It was found that all oxidation treatments successfully removed metallic oxides and amorphous carbon impurities, while different oxidation treatments introduced different levels of oxidized sites on the SWCNTs. Heat treatment after oxidation eliminated some of the carboxylic groups introduced by oxidation. SWCNTs covalently functionalized by aromatic diazonium salts containing nitro, carboxylate and fluoro groups on the aromatic ring were prepared. Heating of these tubes in vacuum at 350_C for 5 h partially reversed the effects of functionalization. However, due to the low degree of functionalization achieved in the preliminary studies, the dispersibility/solubility of functionalized tubes did not greatly improve. The interaction in stable suspensions of CNTs with positively or negatively charged pyrene derivatives via noncovalent functionalization, was extensively studied. 1-pyrene methylamine hydrochloride gave most stable dispersions. 1H and 2H NMR spectroscopy of MWCNTs/1-pyrene methylamine hydrochloride dispersion in DMF-d7 showed that the broadened signals are associated with weakly or unbound pyrene, while strongly bound pyrene is not observable in solution-state NMR. The strong pyrene attachment on MWCNTs by π-π stacking can be reversed by dialysis and/or extensive washing. Biological molecules such as polypeptides and amino acids also dispersed MWCNTs into solvents by noncovalent modification. It is found that polytryptophan demonstrated the greatest ability to disperse MWCNTs. Digestion with chymotrypsin enabled polytryptophan binding to be reversed. A combination of tube cutting and non-covalent functionalization by pyrenes or peptides enables tubes to be suspended/dissolved in solvents such as DMF and ethanol, and significantly allows tubes to be manipulated for practical device applications.

Polymer materials are commonly reinforced with organic or inorganic fillers to improve their mechanical properties and to reduce the cost. Such reinforcement strongly depends on the characteristics of fillers (e.g. size, shape, aspect ratio and surface feature) and their dispersion in polymer matrix. The use of inorganic fillers exploits the synergistic effect of high mechanical strength and heat durability of fillers and processing ease of polymers. However, it often causes interfacial incompatibility and an increase in density and a loss of tenacity and opacity. Because layered clays possess rich intercalation chemistry and can be delaminated into disk-like nanopartciles, we investigate the possibility of developing polymer nanocomposites from montmorillonite (MMT). As a result, two nanomaterials, intercalated polyaniline (PANI) nanocomposites and exfoliated PS nanocomposites, have been fabricated via in situ polymerization. Morevoer, experimental work shows that the surface modification of clays and the dispersion of organically modified clays (i.e. organoclays) are crucial to the success of fabricating polymer nanocomposites. Therefore, molecular dynamics (MD) simulations are used to investigate such fundamental aspects on the structure and dynamics of organoclays and the interfacial interactions and structure of diblock copolymer (i.e. PU) nanocomposites. The simulated results are in good agreement with the available experimental data. For organoclays, the results indicate that the alkyl chains exhibit strong layered structures in the interlayer space of clays. Such layering behaviors strongly depend on the chain length and layer charge. More importantly, a pseudo-quadrilayer structure is observed for organoclays modified with dioctadecyldimethyl ammoniums in which the alkyl chains do not lie flat within a single layer but interlace and spread into the adjacent layers. Finally, different orientaion of chain segments is found in the middle and end segments, and within and out of the layer structure. For polyurethane (PU) nanocomposites, van der Waals interaction between apolar alkyl chains and PU soft segments dominates the interactions between organoclay and PU. In addition, hydrogen bonding can form between the siloxane oxygen of clay surface and nitrogen (hard segment) or oxygen (soft segments) of PU. Furthermore, there is no distinct phase-separated structure for PU in the nanocomposites, which is attributed to the results of competitive interactions among PU, alkyl ammonium and clay surface.

In this study, we prepare the zinc oxide nanotip with aqueous solution deposited on ZnO nucleation layer. The directions of nanotip are formed with different ZnO nucleation layer time. The thermal annealing with N2 ambiance at 300 ¢J for 1 hr increase the UV emission and decrease the defects. We use ZnO nanotip as an anti-reflection layer because of surface roughness and optical interference. ZnO nanotip with rough surface decreases reflection and enhance the transmission, so we use ZnO nanotip as an anti-reflection layer, after growin ZnO nanotip on solar cell the efficiency of solar cell was enhancement.

Both zinc oxide rods and zinc hydroxide slices grown on gallium arsenide in the aqueous solution of zinc nitrate and hexamethylenetetramine were studied. Zinc hydroxide is responsible for the growth of slices. Hexamethylenetetramine-zinc nitrate organometallic complex acts as the nucleus for zinc oxide rods formation. Incorporating with appropriate concentration of nitric acid in the aqueous solution, zinc oxide rods can dominate the growth at a lower temperature.

In this study, we prepare the zinc oxide one-dimensional nanostructures with aqueous solution on GaN substrate. The morphologies of nanotip, nanorod and nanotube are formed with different modulation and chemical solutions. The thermal annealing with N2O ambiance at 300 ¢XC for 1 hr increase the UV emission and decrease the defects. The limit of choosing the substrate to grow ZnO nanostructures is lattice mismatch between ZnO and substrate. The buffer layer is sputtered on substrate to remove the limit. The pattern of buffer layer also can be used for selective area growth. Nanotip structure with rough surface shows the obvious lotus effect and nanotube structure with more active site and more surface area shows the better photocatalysis efficiency than nanotip structure.