Des silicates de calcium hydratés (C-S-H) forment le liant des matériaux cimentaires et sont responsables de sa cohésion. Mais la structure du C-S-H est encore mal décrite. Nous proposons une description de la porosité basée sur une caractérisation par la relaxation RMN des protons contenus dans les pâtes de C3S. Des courbes de relaxation longitudinale sont extraites des distributions de cinq temps de relaxation (T1). La spectroscopie RMN puis la relaxométrie permettent l'interprétation de ces T1 : le dernier correspond à la portlandite, chacun des quatre premiers correspond à une taille de pore, allant de l'interfeuillet à la plus grande dimension de l'empilement. Dans chacun de ces cas, la relaxation est due à l'association de deux mécanismes impliquant des interactions avec des impuretés paramagnétiques à la surface des C-S-H, ces surfaces comportant des groupements SiOH, CaOH et HOH. La texturation d'une pâte comporte trois étapes. Après une période de latence, l'hydratation s'accélère. La formation des C-S-H implique le développement de la surface associée : ce phénomène est lié à la décroissance progressive de la valeur du T1. Ensuite se dissocient quatre grandes familles de porosité dont trois sont extra-lamellaires. Alors que la réaction d'hydratation est terminée, ces trois familles évoluent vers la formation d'une distribution en loi de puissance. La modification des paramètres de cure influence essentiellement les proportions des deux plus grandes échelles de porosité. La perte de l'organisation en loi d'échelle ou du moins la diminution de son coefficient sont associées à une diminution des modules d'élasticité. C'est le cas lorsque le rapport e/c est supérieur à 0,4 ou quand la température de cure dépasse 50°C. L'ajout de fumée de silice ou l'augmentation de la température de cure, entre 20 et 50°C, accélère la cinétique de texturation. La présence de fumée de silice fait également apparaître une famille de pores supplémentaire aux échelles supérieures.

Cette thèse présente une étude théorique des interactions électron-phonon dans les boîtes quantiques InAs/GaAs, où le régime de couplage fort entre les porteurs confinés dans les boîtes et les phonons optiques a pour conséquence la formation d'états intriqués appelés polarons.<br />Nous prenons tout d'abord en compte le couplage fort entre excitons et phonons optiques afin de calculer l'absorption interbande sous champ magnétique.<br />Nous calculons ensuite le temps de vie des états polarons, dont l'instabilité est due à leur composante phonon. Nous démontrons la nécessité de prendre en compte de manière détaillée les différents processus anharmoniques, dont l'efficacité dépend fortement de l'énergie du polaron. Ces calculs permettent d'expliquer les variations non monotones du temps de vie mesuré des polarons avec leur énergie.<br />Nous étudions ensuite la dynamique de relaxation dans les boîtes doublement chargées, où l'interaction spin-orbite, associée aux couplages électron-phonon, entraîne des processus de retournement du spin entre états singulets et triplets.<br />Finalement, nous étudions la cohérence optique de la transition intrabande fondamentale, dont l'élargissement avec la température est dû aux transitions réelles et virtuelles vers le deuxième état excité.

L'objet de cette thèse est l'étude de l'interaction d'un laser femtoseconde avec un support photosensible particulier : un verre phosphate dopé à l'argent appelé verre photo-luminescent (PL). Une nouvelle approche permettant de réaliser en trois dimensions dans un verre PL des nanostructures d'argent aux dimensions bien inférieures à la limite de diffraction est tout d'abord présentée. La mesure des propriétés optiques et structurales pour différentes échelles (spatiales et temporelles) a permis de proposer un mécanisme de formation des structures photo-induites qui est basé sur un jeu subtil entre les phénomènes d'absorption non-linéaire et de thermo-diffusion. La deuxième partie de cette thèse sera rientée sur les propriétés optiques (linéaires et non-linéaires) et les applications des ces nanostructures d'argent. En particulier, l'exaltation des propriétés non-linéaires des agrégats d'argent sera exploitée pour stocker optiquement de l'information en trois dimensions.

Es ist seit einigen Jahren bekannt, dass Elektronen unter bestimmten Bedingungen in dünne Filme eingeschlossen werden können, selbst wenn diese Filme aus Metall bestehen und auf Metall-Substrat aufgebracht werden. In Photoelektronenspektren zeigen diese Filme charakteristische diskrete Energieniveaus, und es hat sich herausgestellt, dass sie zu großen, technisch nutzbaren Effekten führen können, wie der oszillatorischen magnetischen Kopplung in modernen Festplatten-Leseköpfen. <br><br> In dieser Arbeit wird untersucht, inwieweit die der Quantisierung in zweidimensionalen Filmen zu Grunde liegenden Konzepte auf niedrigere Dimensionalität übertragbar sind. Das bedeutet, dass schrittweise von zweidimensionalen Filmen auf eindimensionale Nanostrukturen übergegangen wird. Diese Nanostrukturen sind zum einen die Terrassen auf atomar gestuften Oberflächen, aber auch Atomketten, die auf diese Terrassen aufgebracht werden, bis hin zu einer vollständigen Bedeckung mit atomar dünnen Nanostreifen. Daneben werden Selbstorganisationseffekte ausgenutzt, um zu perfekt eindimensionalen Atomanordnungen auf Oberflächen zu gelangen. <br><br> Die winkelaufgelöste Photoemission ist als Untersuchungsmethode deshalb so geeignet, weil sie das Verhalten der Elektronen in diesen Nanostrukturen in Abhängigkeit von der Raumrichtung zeigt, und unterscheidet sich darin beispielsweise von der Rastertunnelmikroskopie. Damit ist es möglich, deutliche und manchmal überraschend große Effekte der eindimensionalen Quantisierung bei verschiedenen exemplarischen Systemen zum Teil erstmals nachzuweisen. Die für zweidimensionale Filme wesentliche Rolle von Bandlücken im Substrat wird für Nanostrukturen bestätigt. Hinzu kommt jedoch eine bei zweidimensionalen Filmen nicht vorhandene Ambivalenz zwischen räumlicher Einschränkung der Elektronen in den Nanostrukturen und dem Effekt eines Übergitters aus Nanostrukturen sowie zwischen Effekten des Elektronenverhaltens in der Probe und solchen des Messprozesses. Letztere sind sehr groß und können die Photoemissionsspektren dominieren. <br><br> Abschließend wird der Effekt der verminderten Dimensionalität speziell für die d-Elektronen von Mangan untersucht, die zusätzlich starken Wechselwirkungseffekten unterliegen. Auch hierbei treten überraschende Ergebnisse zu Tage. / It has been known for several years that under certain conditions electrons can be confined within thin layers even if these layers consist of metal and are supported by a metal substrate. In photoelectron spectra, these layers show characteristic discrete energy levels and it has turned out that these lead to large effects like the oscillatory magnetic coupling technically exploited in modern hard disk reading heads. <br><br> The current work asks in how far the concepts underlying quantization in two-dimensional films can be transferred to lower dimensionality. This problem is approached by a stepwise transition from two-dimensional layers to one-dimensional nanostructures. On the one hand, these nanostructures are represented by terraces on atomically stepped surfaces, on the other hand by atom chains which are deposited onto these terraces up to complete coverage by atomically thin nanostripes. Furthermore, self organization effects are used in order to arrive at perfectly one-dimensional atomic arrangements at surfaces. <br><br> Angle-resolved photoemission is particularly suited as method of investigation because is reveals the behavior of the electrons in these nanostructures in dependence of the spacial direction which distinguishes it from, e. g., scanning tunneling microscopy. With this method intense and at times surprisingly large effects of one-dimensional quantization are observed for various exemplary systems, partly for the first time. The essential role of bandgaps in the substrate known from two-dimensional systems is confirmed for nanostructures. In addition, we reveal an ambiguity without precedent in two-dimensional layers between spacial confinement of electrons on the one side and superlattice effects on the other side as well as between effects caused by the sample and by the measurement process. The latter effects are huge and can dominate the photoelectron spectra. <br><br> Finally, the effects of reduced dimensionality are studied in particular for the d electrons of manganese which are additionally affected by strong correlation effects. Surprising results are also obtained here. <br><br>----------------------------<br> Die Links zur jeweiligen Source der im Appendix beigefügten Veröffentlichungen befinden sich auf Seite 83 des Volltextes.

Photonic crystals (PhCs) are periodic dielectric structures that exhibit a photonic band gap; a range of wavelengths for which light propagation is forbidden. 2D PhCs exhibit most of the properties as their three dimension counterparts with a compatibility with standard semiconductor processing techniques such as epitaxial growth, electron beam lithography, Plasma deposition/etching and electromechanical lapping/polishing. Indium Phosphide (InP) is the material of choice for photonic devices especially when it comes to realization of coherent light source at 1.55 μm wavelength. Precise engineering of the nanostructures in the PhC lattice offers novel ways to confine, guide and control light in phonic integrated circuits (PICs). Strong confinement of light in PhCs offer novel opportunities in many areas of physics and engineering. Dry etching, a necessary process step in PhC device manufacturing, is known to introduce damage in the etched material. Process induced damage and its impact on the electrical and optical properties of PhCs depends on the etched material, the etching technique and process parameters. We have demonstrated a novel post-etch process based on so-called mass-transport (MT) technology for the first time on InP-based PhCs that has significantly improved side-wall verticality of etched PhC holes. A statistical analysis performed on several devices fabricated by MT process technology shows a great deal of improvement in the reliability of optical transmission characteristics which is very promising for achieving high optical quality in PhC components. Several PhC devices were manufactured using MT technology. Broad enough PhC waveguides that operate in the mono/multi-mode regime are interesting for coarse wavelength de-multiplexing. The fundamental mode and higher order mode interaction creates mini-stop band (MSB) in the dispersion diagram where the higher order mode has a lower group velocity which can be considered as slow light regime. In this thesis work, the phenomena of MSBs and its impact on transmission properties have been evaluated. We have proposed and demonstrated a method that enables spectral tuning with sub-nanometer accuracy which is based on the transmission MSB. Along the same lines most of the thesis work relates to broad enough PhC guides that operated in the multimode regime. Temperature tuning experiments on these waveguides reveals a clear red-shift with a gradient of dλ/dT=0.1 nm/˚C. MSBs in these waveguides have been studied by varying the width in incremental amounts. Analogous to semiconductors heterostructures, photonic heterostructures are composed of two photonic crystals with different band-gaps obtained either by changing the air-fill factor or by the lattice constant. Juxtaposing two PhC and the use of heterostructures in waveguide geometry has been experimentally investigated in this thesis work. In particular, in multimode line defect waveguides the “internal” MSB effect brings a new dimension in single junction-type photonic crystal waveguide (JPCW) and heterostructure W3 (HW3) for fundamental physics and applications. We have also fabricated an ultra-compact polarization beam splitter (PBS) realized by combining a multimode waveguide with internal PhC. MSBs in heterostructure waveguides have shown interesting applications such as designable band-pass flat-top filters, and resonance-like filters with high transmission. In the course of this work, InGaAsP suspended membrane technology was developed. An H2 cavity with a linewidth of ~0.4 nm, corresponding to a Q value of ~3675 has been shown. InGaAsP PhC membrane is an ideal platform to study coupled quantum well/dot-nanocavity system. / <p>QC 20120831</p>

In this study, the OMCVD method is demonstrated as a powerful, fast, economic and environmental friendly method to produce a set of PGMelectrocatalysts with different supports, metal content and metal alloys in one step and without the multiple processing stages of impregnation, washing, drying, calcinationsand activation.

<p>In this study, the OMCVD method is demonstrated as a powerful, fast, economic and environmental friendly method to produce a set of PGMelectrocatalysts with different supports, metal content and metal alloys in one step and without the multiple processing stages of impregnation, washing, drying, calcinationsand activation.</p>

Diatoms possess characteristics such as abundance, diversity, and high reproductivity, which make their nano-structured frustules (diatom frustules) attractive for a wide range of applications. To overcome the limitation of their silica based frustule composition, diatom frustules have been converted into a variety of materials including silicon, silicon carbide, silver, gold, palladium and carbon in the present study. The compositions and the extent of shape preservation of the replicas are examined and evaluated with different characterization methods such as X-ray diffraction, SEM, TEM and FTIR analyses. These replicas still retained the complex 3D structures and nano-scaled features of the starting diatom frustules. Some properties and possible applications of converted materials are explored and the kinetics and thermodynamics related to the successful replications (conversions) are also studied and discussed.

The objectives of the work presented were to 1) fabricate reproducible nanorod array SERS substrates, 2) detection of bacteria using nanorod substrates, 3) detection of DNA hybridization using nanorod substrates and 4) critically evaluate the sensing method. Important findings from this work are as follows. A novel method for batch fabrication of substrates for surface enhanced Raman scattering (SERS) has been developed using a modified platen machined to fit in a commercial electron beam evaporator. The use of this holder enables simultaneous deposition of silver nanorod (AgNR) arrays onto six microscope slide substrates utilizing glancing angle deposition. In addition to multiple substrate fabrication, patterning of the AgNR substrates with 36 wells allows for physical isolation of low volume samples. The well-to-well, slide-to-slide, and batch-to-batch variability in both physical characteristics and SERS response of substrates prepared via this method was nominal. A critical issue in the continued development of AgNR substrates is their stability over time, and the potential impact on the SERS response. The thermal stability of the arrays was investigated and changes in surface morphology were evaluated using scanning electron microscopy and x-ray diffraction and correlated with changes in SERS enhancement. The findings suggest that the shelf-life of AgNR arrays is limited by migration of silver on the surface. Continued characterization of the AgNR arrays was carried out using fluorescent polystyrene microspheres of two different sizes. Theory suggests that enhancement between nanorods would be significantly greater than at the tops due to contributing electromagnetic fields from each nanostructure. In contrast to the theory, SERS response of microspheres confined to the tops of the AgNR array was significantly greater than that for beads located within the array. The location of the microspheres was established using optical fluorescence and scanning electron microscopy. The application of SERS to characterizing pathogens such as bacteria and viruses is an active area of investigation. AgNR array-based SERS substrates have enabled detection of pathogens present in biofluids. Specifically, several publications have focused on determining the spectral bands characteristic of bacteria from different species and cell lines. Studies were carried out on three strains of bacteria as well as the medium in which the bacteria were grown. The spectra of the bacteria and medium were surprisingly similar, so additional spectra were acquired for commonly used bacterial growth media. In many instances, these spectra were similar to published spectra purportedly characteristic of specific bacterial species. In addition to bacterial samples, nucleic acid hybridization assays were investigated. Oligonucleotide pairs specifically designed to detect respiratory syncytial virus (RSV) in nasal fluids were prepared and evaluated. SERS spectra acquired on oligos, alone or in combination, contain the known spectral signatures of the nucleosides that comprise the oligo. However, spectra acquired on an oligo with a 5'- or 3' thiol were distinctly different from that acquired on the identical oligo without a thiol pendant group suggesting some control over the orientation of the oligo on the nanorod surface. The signal enhancement in SERS depends markedly upon the location of the probe relative to the substrate surface. By systematic placement of nucleotide markers along the oligo chain, the point at which the nucleotide disappears from the spectrum was identified. The overall findings for AgNR SERS substrates suggest that the applicability of SERS for detecting nucleic acid hybridization is limited. The strong distance dependence coupled with the lack of substrate stability at temperatures required for annealing oligos during hybridization suggest that AgNRs are not the platform to use for hybridization assays.

Dans ce travail théorique, nous présentons une étude de la dynamique vibrationnelle multi-quanta des réseaux quantiques non linéaires. Ces réseaux présentent une distribution périodique de modes de vibration haute fréquence dont la dynamique est le fruit de la compétition entre les phénomènes suivants:<br />Les couplages dipolaires favorisent la délocalisation des vibrations donnant naissance à la propagation d'excitons vibrationnels : les vibrons.<br />L'anharmonicité intramoléculaire favorise une interaction attractive entre les vibrons et entraîne l'apparition d'états liés. Caractérisés par une localisation de l'interdistance vibronique, les états liés sont l'équivalent quantique d'objets non linéaires tels que les solitons.<br />L'interaction vibron-phonon modifie la nature des états à travers le mécanisme d'habillage qui traduit la création de polarons qui sont des vibrons habillés par une déformation du réseau. Ce mécanisme diminue la capacité de délocalisation des polarons et correspond à une seconde source de non linéarité.<br /><br />Notre formalisme, appliqué aux hélices-alpha et aux nanostructures moléculaires, révèle les points suivants:<br />A température biologique, une hélice-alpha, bien représentée par un modèle 1D, est le siège de deux états liés dont la présence a été observée expérimentalement. A basse température, la nature des états polaroniques reflète le caractère 3D des hélices.<br />Dans un nanofil de taille finie, la singularité du mécanisme d'habillage entraîne l'apparition d'états localisés.<br />Les non linéarités locale et non locale permettent un transport énergétique cohérent véhiculé par des états liés liés spécifiques.