Radiation damage occurs in reactor pressure vessel (RPV) steel, causing microstructural changes such as point defect clusters, interstitial loops, vacancy-solute clusters, and precipitates, that cause material embrittlement. Radiation damage is a crucial concern in the nuclear industry since many nuclear plants throughout the US are entering the first period of life extension and older plants are currently undergoing assessment of technical basis to operate beyond 60 years. The result of extended operation is that the RPV and other components will be exposed to higher levels of neutron radiation than they were originally designed to withstand. There is currently no nondestructive evaluation technique that can unambiguously assess the amount of radiation damage in RPV steels. Nonlinear ultrasound (NLU) is a nondestructive evaluation technique that is sensitive to microstructural features such as dislocations, precipitates, and their interactions in metallic materials. The physical effect monitored by NLU is the generation of higher harmonic frequencies in an initially monochromatic ultrasonic wave, arising from the interaction of the ultrasonic wave with microstructural features. This effect is quantified with the measurable acoustic nonlinearity parameter, beta. In this work, nonlinear ultrasound is used to characterize radiation damage in reactor pressure vessel steels over a range of fluence levels, irradiation temperatures, and material composition. Experimental results are presented and interpreted with newly developed analytical models that combine different irradiation-induced microstructural contributions to the acoustic nonlinearity parameter.

Le développement des lasers de puissance engendre un intérêt pour la recherche de matériaux présentant des propriétés optiques non linéaires (ONL). Les matériaux vitreux sont de très bons candidats puisqu’ils peuvent être transparents et élaborés en grandes dimensions. La précipitation de particules non centro-symétrique dans un verre permet d’engendrer cette propriété en volume, et d’ingérer facilement ce matériau dans les dispositifs lasers. Dans ce contexte, cette thèse présente les résultats obtenus sur la précipitation de la phase LiNO3 dans la matrice vitreuse 35 Li2O- 25 Nb2O5- 40 SiO2. Le mécanisme de cristallisation de cette phase est étudié par analyse thermique, imagerie optique et électronique ainsi que par une analyse in-situ. Ces analyses mettent en évidence une cristallisation sphérolitique du niobate de lithium dans ce verre, conduisant à l’obtention de vitrocéramiques. Les propriétés optiques non linéaires d’ordre deux sont mesurés sur ces matériaux. Un signal original et isotrope de Génération de Second Harmonique a été mesuré. Une analyse multi-échelle permet une meilleure compréhension et une corrélation entre la structure des sphérolites et l’origine de la génération d’un tel signal. Le modèle développé suite à ces analyses permet d’entrevoir le développement de nouveaux matériaux micro-composites à propriétés ONL isotropes. / The high power laser development required the need of materials with nonlinear properties. Glass materials can be considered as ideal materials as they can be transparent and elaborated in very large dimension. Precipitation of non-centro symmetric crystalline particles in bulk glass leads to a material with bulk nonlinear properties. This glass-ceramic should be then easily integrated in such laser facilities. In this thesis, the results concerning the precipitation of the LiNO3 phase in the glassy-matrix 35 Li2O- 25 Nb2O5- 40 SiO2 are detailed. The crystallization mechanism of this phase is studied through thermal analysis, optical and electronic microscopy as well as in-situ analyses. These studies reveal glass-ceramics are obtained through a precipitation of the lithium niobate crystalline phase in spherulite shape. The nonlinear optical properties are investigated on this materials and an original, isotropic Second Harmonic Generation signal (SHG) is registered in the bulk glass-ceramic. A complete study using a multi-scale approach allows the correlation between the spherulite structure and the nonlinear optical properties. A mechanism at the origin of the SHG signal is proposed. This leads to a new approach for transparent inorganic materials development for isotropic SHG conversion.

L’Optique non linéaire est un outil très puissant pour étudier les propriétés des matériaux. Dans cette thèse, nous avons utilisé deux techniques d’optique non linéaire pour l’étude des non linéarités moléculaires: la génération de seconde harmonique induite sous champ électrique (EFISH) et la diffusion harmonique de la lumière (DHL). Tout d'abord, nous avons mis en évidence la conjugaison des groupements donneurs pi- dans les complexes d’iridium cyclométallés. Nous avons également exploré une série de molécules trinucléaires organométalliques (triaryle-1, 3, 5-triazinane-2, 4, 6-triones) fonctionnalisées par des acétylures métalliques avec des complexes des métaux de transition à leur périphérie- l’hyperpolarisabilité est beaucoup plus élevée que celles des dérivés purement organiques équivalents. D'autre part une série de complexes métalliques dipolaires et octupolaires contenant des ligands 2, 2-bipyridine photochromes à base de dithiényléthène (DTE) ont été synthétisés et caractérisés. L'étude révèle une forte augmentation de Les hyperpolarisabilités après irradiation UV correspondant à la fermeture de cycle associée au DTE. Cette forte exaltation reflète bien la délocalisation du système d’électrons pi- et la formation de chromophores push-pull dans les formes fermées. Troisièmement, nous avons étudié les propriétés optiques non linéaires de complexes de bis (phtalocyaninato) lanthanide (III) en sandwich, avec 2 phthalocyanines substituées en ABAB (alternance de donneurs d'électrons et d’accepteurs d'électrons), AB3 (3 groupes de donneurs), A4 (4 groupes d’accepteurs) et B4 (aucun groupe de donneur). L’hyperpolarisabilité du 1er ordre beta- mesurées sont les plus élevées jamais enregistrées pour des molécules octupolaires. La contribution directe d’électrons f dans les ions lanthanides complexés est également observée sur l'activité non linéaire du second ordre. Enfin, des nanosphères (AuNSs) et des nanotubes d'or (AuNRs) avec différents rapports d'aspect (AR) allant de 1,7 à 3,2 nm ont été synthétisés par la méthode de radiolyse. Le signal de deuxième harmonique émis par des AuNRs est nettement supérieur à celui des nanosphères et révèle leur dépendance à l'AR. Nous avons également mélangé un dérivé du chromophore 4-diméthylamino-N-méthyl-4-stilbazolium tosylate (DAST) avec les AuNRs et observé une influence des AuNRs sur l'amélioration des propriétés ONL du DAST. Une nette augmentation de l’hyperpolarisabilité (par un facteur 8) du derive de DAST en est la preuve. / Nonlinear optics is well known to be a highly powerful tool to investigate the properties of the materials. In this thesis we used two important nonlinear optical techniques known as Electric Field Induced Second Harmonic Generation (EFISH) and Harmonic Light Scattering (HLS) to study the first hyperpolarizability of various molecular objects. Firstly, we evidenced the pi donor conjugation in cyclometallated Ir complexes. We have also explored the series of trinuclear organometallic triaryl-1, 3, 5-triazinane-2, 4, 6-triones functionalized by d6-transition metal acetylides complexes at their periphery- large hyperpolarizabilities, far higher than those of related purely organic derivatives are reported. Secondly, a series of dipolar and octupolar dithienylethene (DTE)-containing 2, 2-bipyridine ligands with different metal ions featuring two, four and six photochromic dithienylethene units have been synthesized and fully characterized. The study reveals a large increase in the hyperpolarizability after UV irradiation and subsequent formation of ring-closed isomers. This efficient enhancement clearly reflects the delocalization of the pi-electron system and the formation of strong push&pull chromophores in the closed forms. Thirdly, we have investigated NLO properties of bis (phthalocyaninato) lanthanide-(III) double-decker complexes with crosswise ABAB (phthalocyanine bearing alternating electron-donor and electron-acceptor groups), AB3 (3 donor groups), A4 (4 donor groups) and B4 (no donor groups) ligands. First-order hyperpolarizability is measured and displays the highest quadratic hyperpolarizability ever reported for an octupolar molecule. The direct contribution of f-electrons in coordinated lanthanides ions is also observed on second order nonlinear activity. Finally, gold nanospheres (AuNSs) and gold nanorods (AuNRs) with different aspect ratios (AR) ranging from 1.7 to 3.2 nm have been synthesized by Radiolysis method. Second harmonic intensity collected from AuNRs is clearly higher than that of the nanospheres and reveals their dependence on the AR. We have also mixed the chromophore 4-dimethylamino-N-methyl-4-stilbazolium tosylate (DAST) derivative with AuNRs and observed the enhancement of DAST NLO properties in the presence of AuNRs. A clear increase in the hyperpolarizability (by a factor of 8) of DAST derivatives has been evidence.

In this thesis both an experimental and computational study of selected prospective materials for nonlinear optics is presented. The main focus was put on 2-aminopyrimidinium hydrogen- phosphite (AMPPO3), a salt with high SHG efficiency and Type I. phase matching properties. AMPPO3 had been studied by our research group and its favourable qualities such as easy preparation, colourlessness, great water solubility and good crystallinity motivated further in- terest and the attempts for the growth of bulk single crystals from thermostated aqueous solu- tions as presented here. The products are meant to be probed by laser in a specific direction to determine the maximum SHG efficiency, so far the polarized microscopy study revealing the extreme dispersion effects is provided. AMPPO3 is an example of H-bond stabilized framework with both organic and inorganic building blocks. The computational study was led as to understand the structure which is typical for one of the classes of compounds exhibiting nonlinear optical properties. DFT implemented in parallel CP2K was used and for the comparison three other optically active materials of sim- ilar composition were studied - urea, guanylurea hydrogenphosphite and 2-aminopyrimidine- boric acid 3/2 cocrystal. After the constrained geometry optimization and cell...

Les propriétés optique des nanoparticules ont ouvert de nouvelles voies dans de nombreux domaines, de l'optique fondamental avec la compréhension des interactions dans la matière, la biologie et la compréhension du fonctionnement des milieux cellulaires, en passant par la microscopie en champ proche, qui permet de sonder localement les propriétés physiques de divers nano-systèmes. Au cours de ce travail, nous avons réalisé l'étude de la génération de seconde harmonique (GSH) de nanoparticules de KTP ainsi que de dimères d'or isolés. Des mesures optiques du rayonnement émis par ces nano-objets montrent qu'ils sont parfaitement photostables. Par ailleurs, nous avons aussi étudié de nouvelles particules actives qui permettent d’obtenir un double signal, de luminescence ainsi que de GSH. Ces nanosources bimodales sont constituées des nanoparticules de KTP dopées avec des ions Europium. Dans une seconde partie, nous tentons de fabriquer des sondes optiques pour le champ proche en utilisant les nanocristaux non-linéaires de KTP, ceci dans le but de développer une nouvelle microscopie optique en champ proche capable de sonder localement et vectoriellement un champ électromagnétique. Une pointe de microscopie à force atomique est fonctionnalisée par une particule d'or, puis approchée d'un nanocristal de KTP. Des résultats préliminaires montrent qu'il est possible par cette méthode de sonder le champ électromagnétique présent autour d'une nanoparticule d'or. / The optical properties of nanoparticles have opened new avenues in many areas of optics with the fundamental understanding of the interactions in matter, biology and understanding of the functioning of cell media, through the near-field microscopy, which allows us to probe locally the physical properties of various nano-systems. In this work, the study of second harmonic generation (SHG) has been performed on isolated nanoparticles of KTP and dimers of gold. Optical measurements of radiation emitted by these particles show that nanoparticles are perfectly photostable.Furthermore, we also explored new active particles that deliver a double signal, luminescence and GSH. These nanosources bimodal nanoparticles consist of KTP doped with europium ions. In the second part, we try to manufacture optical probes for near field using nonlinear nanocrystals in this case the probe is KTP nanocrystals. A tip of atomic force microscopy is functionalized by a particle of gold, then approached a nanocrystal of KTP. Preliminary results showed that it was possible to probe the electromagnetic field present around a gold nanoparticle.

Les foldamères de type oligopyridine biscarboxamide constituent une famille d’oligomères synthétiques pouvant adopter une structure hélicoïdale et s’hybrider pour former des hélices doubles. Ce travail a eu pour objectif de synthétiser une nouvelle génération de foldamères π-fonctionnels porteurs de groupements photoactifs ou électroactifs, d’étudier les facteurs gouvernant l’équilibre entre hélice simple et hélice double, d’analyser l’impact de cet équilibre sur les propriétés optiques, et enfin de mettre en place un nouveau type de stimulus permettant de contrôler cet équilibre. Deux foldamères photoactifs dotés d’unités Disperse Red, ont été synthétisés. Leurs structures cristallographiques confirment la formation de structures hélicoïdales. Un choix précis du solvant permet d’orienter sélectivement l’équilibre vers la formation d’une hélice simple ou double.Le contrôle de l’équilibre d’hybridation par dilution permet de moduler l’activité en Génération de Seconde Harmonique du foldamère. En outre, la cavité générée par l'hélice permet la reconnaissance de divers anions. Enfin, les premiers efforts fournis pour induire une hélicité donnée à ces foldamères par voie supramoléculaire sont décrits. Par ailleurs, un foldamère électroactif fonctionnalisé par deux unités tétrathiafulvalène (TTF) a été synthétisé selon une méthodologie originale. La présence des unités TTF permet un contrôle redox inédit de la structuration du foldamère, par dimérisation de cations radicaux. Le concept a été élargi via l’immobilisation d’un foldamère sur surface d’or (SAMs). Enfin, une capsule électroactive capable de complexer l’acide tartrique a également été synthétisée et caractérisée. / Oligopyridine biscarboxamide-based foldamers constitute a family of synthetic oligomers that can fold into helical structures and hybridize to form double helices. This work aims at synthesizing a new generation of π-functionalized foldamers featuring photoactive and electroactive moieties, in order: to study the factors governing the equilibrium between simple and double helices, to analyze the impact of this equilibrium on the optical and recognition properties, and to set up a new type of stimulus to control this equilibrium. Two photoactive foldamers of different lengths and bearing two Disperse Red units were synthesized. Their crystallographic structures confirm the formation of helical structures. A precise choice of the solvent allows to drive the equilibrium towards the single or the double helix selectively.The cavity generated within the helix presents a good affinity for anions. The control over the hybridization equilibrium allows modulating the Second Harmonic Generation activity. Eventually, our first efforts to control the helicity of these foldamers through supramolecular chiral induction are described. On the other hand, an electroactive foldamer featuring two tetrathiafulvalene (TTF) units was synthesized according to an original methodology. The presence of TTF units allows an unprecedented redox control of the structure of foldamer, by dimerization of radical cations. The concept has been extended by immobilizing a foldamère on a gold surface (SAMs). Finally, an electroactive capsule capable of complexing tartaric acid has also been synthesized and characterized.

Univerzita Karlova v Praze Přírodovědecká fakulta Studijní program: Vývojová biologie (P1520) Studijní obor: Vývojová biologie (1501V000) Oleksandr Chernyavskiy Zdokonalené metody pro snímání obrazových dat a analýzu tkání a buněk pomocí konfokální a multifotonové mikroskopie Improved Methods of Image Acquisition and Analysis of Tissues and Cells by Confocal and Multi-Photon Microscopy Abstrakt disertační práce Školitel: RNDr. Lucie Kubínová CSc Praha, 2015 Abstract The aim of this study was to develop methods and approaches for image acquisition with subsequent image analysis of data, obtained by confocal and two- photon excitation microscopy as well as their combination, enabling new possibilities of visualization and assessment of information on biological tissues and cell structures in 3D and their measurement. We focused on methods that exploited advantages of confocal and multi-photon excitation microscopy. Our further aim was to demonstrate the applicability of non-invasive approach for in vivo applications, usefulness and the relevance of these methods in several special biological applications with emphasis on improved image acquisition, analysis and evaluation of real biological specimens. The present work was not oriented on just one specific biological problem, but rather to methodological...

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Neste trabalho estudamos uma nova classe de materiais ópticos não-lineares, os cristais orgânicos, que possuem potencial para muitas aplicação em dispositivos. Determinamos diferentes propriedades ópticas lineares e não-lineares de três cristais orgânicos: a l-alanina, a l-treonina e a l-lisina. Esses cristais de aminoácido foram escolhidos por apresentarem propriedades de geração de segundo harmônico (GSH) e por serem materiais nunca estudados sob o ponto de vista da óptica não-linear. Estudamos algumas das propriedades ópticas lineares fundamentais desses cristais biaxiais transparentes, pois deles dependem os fenômenos não-lineares sobre os quais são feitas intensas pesquisas. Determinamos as propriedades lineares como os espectros de absorção, os índices de refração, os eixo ópticos, velocidade de propagação da luz num meio anisotrópico e os limiares de dano por radiação. Posteriormente, determinamos as condições de casamento de fase, a eficiência de GSH, e a auto-modulação de fase. A GSH e a auto-modulação de fase pertencem, respectivamente, a processos não-lineares de segunda e de terceira-ordem. Para o estudo de muitas dessas propriedades foram desenvolvidas novas técnicas experimentais. Uma dessas novas técnicas, a varredura-Z oscilante, teve sensibilidade para determinar, pela primeira vez, o índice de refração não oscilante, vez, o índice de refração não linear desses cristais orgânicos. Além disso, como a todos os processos de caracterização envolveram a preparação de amostras, tivemos a oportunidade de criar procedimentos padrões para manipulação e utilização desses novos materiais. / In this work we studied a new class of nonlinear organic crystals that are potential candidates for devices application. We determined several linear and nonlinear optical properties of three organic crystals: l-alanine, l-threonine and l-lysine. These aminoacid. These aminoacid because their nonlinearities were never studied before. We characterized some of the fundamental linear optical properties of these biaxial transparent crystals, because they have influence on nonlinear phenomena that attracted a lot of research. We determined linear properties like absorption spectra, indices of refraction, optical axes, the light speed propagation in anisotropy media and the optical damage threshold. Subsequently, we determined the phase-matching condition for SHG, efficiency of the SHG and self-phase modulation. The SHG and self-phase modulation belongs, respectively, to the second-order and third-order nonlinear processes. To study several of these properties we had to develop some new experimental techniques. One of them, the oscillatory Z-scan, allows enough sensibility to determine, for the first time, the nonlinear refraction index of these organic crystals. Besides, as all these optical characterization involve the preparation of the samples, we had the opportunity to establishing standard procedures for manipulation of these new materials.

Lasers Raman são dispositivos que proporcionam uma maneira prática de transformar comprimentos de onda fundamentais em novas linhas espectrais via Espalhamento Raman Estimulado (Stimulated Raman Scattering - SRS). Quando combinados com outros processos de conversão não lineares, os lasers Raman fornecem acesso a comprimentos de onda na região do visível no espectro eletromagnético, que de outra maneira seriam de difícil acesso, como o laranja-amarelo, verde-limão e diversas linhas no azul. A grande vantagem dos lasers Raman é a possibilidade de geração de múltiplas frequências a partir de uma mesma combinação de cristais, tornando esse tipo de laser dispositivos baratos e compactos quando comparados a tecnologias como OPO. Neste trabalho um cristal de Nd:YVO4 foi bombeado por diodo, em configuração transversal, sendo o cristal o responsável pela emissão laser e pelo espalhamento Raman. Na primeira parte do trabalho, a cavidade utilizada apresentava alto fator de qualidade para o comprimento de onda fundamental (1064 nm) e foi estudada a operação laser do 1º Stokes (1176 nm) em regimes de operação quase contínua (q-cw) e contínua (cw). Foi explorada a configuração com uma dobra do feixe laser em ângulo rasante na superfície de bombeamento, bem como a configuração com duas dobras nesta mesma superfície (double beam mode controlling - DBMC). Na segunda parte do trabalho, um cristal LBO foi utilizado para a geração do segundo harmônico (SHG) em 588 nm, o que corresponde a um laser laranja-amarelo. Foi utilizada a configuração com uma dobra e operação cw,com a qual a cavidade apresentava alto fator de qualidade tanto para o 1064 nm quanto 1176 nm. Com a configuração de uma dobra, foi demonstrado que o laser Raman opera em multimodo, com uma variedade de modos de Hermite-Gauss que puderam ser selecionados através apenas do alinhamento da cavidade, incluindo o modo TEM00. Com configuração DBMC, o laser apresentou operação estável oscilando o modo TEM00. Em 1176 nm em regime q-cw, foi obtida a potência máxima de 8,2 W por pulso (multimodo) e 11,7% de eficiência óptica de conversão (diodo para o 1º Stokes), e operando em modo TEM00 a potência máxima de 3,7 W por pulso e eficiência de 5,4% foi obtida com a configuração de duas dobras, de maneira que a tecnologia DBMC se mostrou eficiente para geração de um laser robusto e estável operando com o modo TEM00. Em regime cw o melhor resultado em termos de potência e eficiência foi obtido com a configuração de uma dobra, correspondendo a 1,8 W e 7,3% de eficiência com o laser operando em multimodo. Com o laser laranja, foi demonstrada a operação do modo TEM00 para potências de bombeamento abaixo de 14,5 W. A potência máxima obtida em multimodo foi 820 mW correspondendo a 4% de eficiência óptica de conversão. / Raman lasers are devices that provide practical means to shift fundamental laser wavelengths into new spectral lines via Stimulated Raman Scattering (SRS). When combined with other nonlinear conversion processes, Raman lasers permit access to hard-to-reach regions of the visible electromagnetic spectrum, for example, orange-yellow, lime-green and several blue lines. The great advantage of Raman lasers is the possibility of generating multiple wavelengths using the same set of crystals, which make these devices compact and practical when compared to other technologies as OPOs. In this work, the Nd:YVO4 crystal was laterally pumped by a diode laser and this crystal was responsible for laser generation as well as SRS. In the first part of this work, the laser cavity presented a high Q factor for the fundamental laser wavelength (1064 nm) and the laser operation at the first Stokes (1176 nm) was characterized under quasi-continuous wave operation (q-cw) and in continuous wave (cw) operation. The grazing incidence geometry of the cavity with a single bounce of the laser beam at the pumped facet of the crystal was exploited, as well as with the double bounce (double beam mode controlling - DBMC) of the laser beam at this same crystal facet. In the second part of this work, a LBO crystal was utilized for the second harmonic generation (SHG) at 588 nm, which corresponds to an orange-yellow laser. The single bounce cavity configuration was utilized under cw operation, which presented high Q factor at 1176 nm and at 1064 nm. With the single bounce configuration, the laser operated in a variety of Hermite- Gaussian transversal modes that could be selected simply by cavity alignment, including the TEM00 mode. With the DBMC technology, the laser presented stable operation of the TEM00 mode. At 1176 nm, under q-cw regime, the maximum output peak power of 8.2 W (multimode) was achieved, corresponding to an optical conversion efficiency (diode to 1st Stokes) of 11.7%, and operation of the TEM00 mode yielded a maximum output peak power of 3.7 W and 5.4% efficiency with the double bounce configuration, hence the DBMC technology showed to be an efficient method for the generation of a stable and robust laser operating with TEM00 mode. Under cw regime, the best result in terms of power and efficiency was obtained with the single bounce geometry, yielding 1.8 W (multimode) corresponding to 7.3% efficiency. For the orange-yellow laser, operation of the TEM00 laser mode was demonstrated for low pump powers up to 14.5 W. The maximum output power achieved in multimode operation was 820 mW and 4% optical conversion efficiency.