Third-harmonic generation (THG) is a fundamental nonlinear optical process that has been used in different applications such as third-order nonlinear materials characterization and nonlinear microscopy. It is widely employed since the third-order nonlinearity is the most important in isotropic materials and THG occurs in all media regardless of symmetry. In the tightly focused laser beam condition THG is observed only at the materials interfaces, where the focal symmetry is broken due to the presence of two media with different refractive index and/or third-order susceptibilities. Measuring slabs of different types of optical glasses, using femtosecond laser pulses, we could explain the asymmetric THG intensity profile observed at the interfaces. The harmonic generated at the exit interface is systematically stronger than the one generated at the entrance and this phenomenon can be understood by taking into account the presence of self-focusing effects. Basically, the self-focusing reduces the beam waist radius at the exit interface, resulting in greater laser irradiance and, consequently, higher THG. This study was then extended to the interfaces of a cuvette filled with organic solvents. Such systems present four interfaces and a mixture of nonlinear processes contributions since the cuvette walls present only electronic nonlinearity and the solvents present both electronic and orientational ones. In this way, the solvents may present an additional self-focusing contribution and, due to the noninstantaneous nature of the orientational process, the self-focusing from the solvent may be influenced by the pulse duration. In this case, the THG, which is an instantaneous electronic phenomenon, can be indirectly affected by pulse duration by means of the self-focusing effect. Usually, the slow orientational contribution is not considered for materials characterization by THG which may lead to incorrect nonlinear coefficient values, that means our study is important from the fundamental physics point of view and also for applications such as materials characterization. Based on the application of THG in nonlinear microscopy, we also present a microscopy technique which makes use of spatial frequency-modulated imaging (SPIFI) with single element detection. The microscope was developed at Colorado School of Mines (CSM) during an internship. The system uses a spatial light modulator (SLM) to provide the spatial frequency modulation and permits enhanced resolution images. THG SPIFI images are shown for the first time and we also report images obtained by other nonlinear optical process. In summary, the studies presented in this PhD work are of great importance for THG fundamental understanding, materials characterization and nonlinear optical microscopy. / Geração de terceiro harmônico (GTH) é um processo óptico não linear fundamental que tem sido usado em diferentes aplicações, como em caracterização óptica não linear de materiais e microscopia não linear. Ele é amplamente empregado uma vez que a não linearidade de terceira ordem é a mais importante em materiais isotrópicos e GTH ocorre em todos os meios independente da simetria. Na condição de feixe fortemente focalizado a GTH é observada apenas nas interfaces do material, onde a simetria focal é quebrada devido à presença de dois meios com diferentes índices de refração e/ou susceptibilidades de terceira ordem. Medindo lâminas de diferentes tipos de vidros ópticos, com pulsos de laser de femtossegundos, nós explicamos o perfil assimétrico de intensidade de GTH observado nas interfaces. O harmônico gerado na interface de saída é sistematicamente mais intenso do que o gerado na entrada e este fenômeno pode ser entendido levando-se em conta a presença do efeito de autofocalização. Basicamente, a autofocalização reduz a cintura do feixe na interface de saída do material, resultando em uma maior irradiância e, consequentemente, maior GTH. Este estudo foi estendido para o caso de interfaces de uma cubeta preenchida com diferentes solventes orgânicos. Tais sistemas apresentam quatro interfaces e uma mistura na contribuição dos processos não lineares, dado que as paredes da cubeta apresentam apenas não linearidade eletrônica e os solventes podem apresentar não linearidades tanto eletrônicas quanto orientacionais. Neste sentido, os solventes podem apresentar uma contribuição adicional de autofocalização e, devido à natureza não instantânea do processo orientacional, a autofocalização proveniente do solvente pode ser influenciada pela duração do pulso. Neste caso, a GTH, que é um fenômeno eletrônico (instantâneo), pode ser indiretamente afetada pela duração do pulso por meio do efeito de autofocalização. Usualmente, a contribuição orientacional não é considerada na caracterização de materiais por GTH, o que pode levar à valores incorretos para os coeficientes não lineares, o que significa que nosso estudo é importante do ponto de vista de física fundamental como também em aplicações como caracterização de materiais. Por conta da aplicação da GTH em microscopia não linear, apresentamos também nesta tese uma técnica de microscopia, que baseia-se em uma modulação em frequência espacial para imageamento (SPIFI) com uso de um detector de elemento único. O microscópio foi desenvolvido na Colorado School of Mines (CSM) durante um período de estágio. O sistema utiliza um modulador espacial de luz (SLM) para produzir a modulação em frequência espacial e permite obtenção de imagens em alta resolução. Imagens por GTH SPIFI são mostradas pela primeira vez e também apresentamos imagens obtidas por outros processos ópticos não lineares. Em resumo, os estudos apresentados neste trabalho de doutorado são de grande importância para o entendimento fundamental do processo de GTH, caracterização de materiais e microscopia óptica não linear.

Femtosecond laser has been an essential tool for nonlinear optics and materials processing at micrometer scale, in which chalcogenide and heavy metal oxide glasses have received special attention not only for their high third-order optical nonlinearities but also due to their transparency up to the infrared regions. Although metallic nanoparticles are expected to improve the optical properties of glasses, there are no enough experimental researches about their influence on the nonlinear refractive index (n2) and nonlinear absorption coefficient (&#946), moreover at femtosecond regime. Based on the scientific and technological interests on highly nonlinear glasses, the goal of this thesis was to apply femtosecond laser pulses in two main domains: (i) at the basis of fundamental science, to study the effect of metallic nanoparticles in the third-order nonlinear optical properties of glasses; and (ii) at the field of applied science, aiming the development of photonic devices, performed by the fabrication of 3D optical waveguides containing metallic nanoparticles. This aim was achieved through the techniques of z-scan and femtosecond laser micromachining, which provided the nonlinear optical characterization and waveguides development, respectively. First, we analyzed the third-order nonlinear optical properties of the GeO2-Bi2O3 glass containing gold nanoparticles, which promoted saturation of the absorption in the region of the surface plasmon resonance band. On the other hand, these gold nanoparticles did not affect the n2 that kept constant in the wavelength range of 480 - 1500 nm. The same features were investigated for a Pb2P2O7-WO3 matrix doped with copper nanoparticles. In contrast to the gold doped ones, these samples showed a slight enhancement of the nonlinear refractive index when the energy of the excitation approaches the surface plasmon band. We also found out that the Pb2P2O7-WO3 matrix is a good host to grow silver nanoparticles by fs-laser micromachining. Similarly, copper nanoparticles were produced in a borosilicate glass using single-step laser processing. The explanation for metallic nanoparticle formation is addressed in this thesis, as well as, its application in waveguides. Thus, we demonstrated the functionality of optical waveguides containing Cu0 or Ag0 nanoparticles. Still based on the technological interests on glasses doped with nanoparticles, we showed a single-step synthesis of silver sulfide nanoparticles in chalcogenide glass, which was carried in partnership with researches at Princeton University. The materials investigated in this PhD work are of great importance for photonics, in which the synthesis of nanoparticles, fabrication of waveguides and nonlinear optical characterization have been performed. / O laser de femtossegundos tem sido uma ferramenta essencial tanto para a óptica não-linear quanto para o processamento de materiais na escala micrométrica, na qual os vidros calcogenetos e óxidos de metais pesados têm recebido atenção especial, não apenas pelas suas elevadas não-linearidades ópticas de terceira ordem, mas também devido à sua transparência até o infravermelho. Embora seja esperado que nanopartículas metálicas melhorem as propriedades ópticas dos vidros, não existe investigações experimentais suficientes sobre a sua influência no índice de refração não linear (n2) e no coeficiente de absorção linear (&#946), sobretudo no regime de femtossegundos. Com base nos interesses científicos e tecnológicos de vidros altamente não-lineares, o objetivo deste trabalho foi aplicar pulsos laser de femtossegundos em dois domínios principais: (i) na campo da ciência fundamental, para estudar o efeito de nanopartículas metálicas nas propriedades ópticas não lineares de terceira ordem destes materiais; e (ii) no domínio da ciência aplicada, visando o desenvolvimento de dispositivos fotônicos, realizado pelo fabricação de guias de onda tridimensionais contendo nanopartículas metálicas. Este objetivo foi alcançado através das técnicas de varredura-z e microfabricação com laser de femtossegundos, que proporcionaram a caracterização óptica não-linear e o desenvolvimento de guias de onda, respectivamente. Primeiramente, foram investigadas as propriedades ópticas não-lineares de terceira ordem do vidro GeO2-Bi2O3 contendo nanopartículas de ouro, as quais promoveram saturação da absorção na região da banda de ressonância de plásmon. Por outro lado, essas nanopartículas não afetaram o n2, que se manteve constante no intervalo de comprimento de onda 480 - 1500 nm. As mesmas características foram investigadas para uma matriz Pb2P2O7-WO3 dopada com nanopartículas de cobre. Em contraste com os vidros dopados com ouro, estas amostras apresentaram um ligeiro aumento do índice de refração não linear quando a energia de excitação está próxima da banda de ressonância de plásmon. Observou-se ainda que a matriz Pb2P2O7-WO3 é ideal para a obtenção de nanopartículas de prata através da microfabricação com laser de femtossegundos. Similarmente, nanopartículas de cobre foram produzidas em vidro de borosilicato usando somente uma varredura a laser. A explicação para a formação de nanopartículas metálicas é abordada nesta tese, bem como sua aplicação em guias de onda. Deste modo, demonstrou-se a funcionalidade de guias de onda ópticos compostos por nanopartículas de Cu0 e Ag0. Ainda com base nos interesses tecnológicos em vidros dopados com nanopartículas, demonstrou-se uma síntese de nanopartículas de sulfeto de prata em vidro calcogeneto usando o processamento de única etapa, realizada em parceria com pesquisadores da Universidade de Princeton. Os materiais investigados neste trabalho de doutorado são de grande importância para aplicações em fotônica, em que a síntese de nanopartículas, a fabricação de guias de onda e a caracterização óptica não-linear foram realizadas.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this study, it has been carried out quantum molecular dynamics simulations for the hydrogen abstraction reaction from methane, silane, germane and stannane by H, F, Cl and I atoms and being or not being induced by femtosecond laser pulses with the aim to favor the dissociation of the M-H (M = C, Si, Ge and Sn). All the simulations have been performed using a simulation scheme based on ab initio calculations of molecular dynamics, where the motion of the atomic nuclei is described classically while the electrons are treated quantically by the Density Functional Theory (DFT). The results of the molecular dynamics simulations for the hydrogen abstraction reaction from methane, that is a very inert molecule, show that only the fluorine atom is able to promote the dissociation of the C-H bond. For the simulations performed in the presence of the electromagnetic radiation, it was possible to observe that the femtosecond laser pulse could induce the hydrogen abstraction from methane when the reaction occurs with the hydrogen or fluorine atom. The results of the molecular dynamics simulations for the hydrogen abstraction reaction from silane show that also the fluorine as the hydrogen atoms are able to dissociate effectively the Si-H bond in silane. In the case of the hydrogen abstraction from silane by the chlorine atom, the effective Si-H dissociation does not happen. In the simulations including the pulsed electromagnetic radiation, it is observed that it was possible to favor even more the hydrogen abstraction reaction from silane by the hydrogen and fluorine atoms, moreover, it was possible to turn effective the dissociation of the Si-H bond by the chlorine atom. The GeH4 and SnH4 molecules could be easily dissociated by the hydrogen, fluorine and chlorine atoms. About the iodine atom, it was not able to promote the hydrogen abstraction reaction in germane and stannane, even in the presence of the femtosecond laser pulse. / Neste trabalho foram realizadas simulações de dinâmica molecular quântica para as reações de abstração de hidrogênio nas moléculas de metano, silano, germano e estanano por átomos de H, F, Cl, e I sendo realizadas simulações sem e com o uso do pulso de laser de femtosegundos com o objetivo de favorecer a quebra das ligações M-H (M = C, Si, Ge ou Sn). Todas as simulações foram realizadas utilizando um esquema baseado em cálculos ab initio de dinâmica molecular, onde o movimento dos núcleos atômicos é descrito classicamente, enquanto os elétrons são tratados quanticamente pela Teoria do Funcional de Densidade (DFT). Os resultados das simulações de dinâmica molecular das reações de abstração de hidrogênio no metano mostram que, por esta molécula ser bastante inerte, somente o átomo de flúor é capaz de promover a dissociação da ligação C-H. Para as simulações realizadas na presença da radiação eletromagnética, foi possível observar que o pulso de laser consegue favorecer a abstração de hidrogênio no metano quando a reação acontece com o átomo de hidrogênio ou flúor. Os resultados das simulações de dinâmica molecular para a reação de abstração de hidrogênio no silano mostram que tanto o átomo de flúor quanto o de hidrogênio são capazes de promover a captura do átomo de hidrogênio promovendo a quebra da ligação Si-H. No caso da reação de abstração de hidrogênio na molécula de silano por átomo de cloro, a quebra efetiva da ligação Si-H não acontece. Nas simulações com a radiação eletromagnética pulsada observa-se que foi possível favorecer ainda mais as reações de abstração de hidrogênio no silano por átomos de flúor e hidrogênio, além de tornar efetiva a ruptura da ligação Si-H na reação com o átomo de cloro. As ligações químicas Ge-H e Sn-H nas moléculas de GeH4 e SnH4 conseguiram ser quebradas facilmente nas reações de abstração de hidrogênio por átomos de hidrogênio, flúor e cloro. Quanto ao átomo de iodo, este não foi capaz de promover a reação de abstração de hidrogênio nas moléculas de germano e estanano, mesmo na presença do pulso de laser de femtosegundos.

Orientador: Flavio Caldas da Cruz / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-09T02:45:38Z (GMT). No. of bitstreams: 1 Nogueira_GiovanaTrevisan_D.pdf: 19393516 bytes, checksum: a3b51900ea17f278fbdc63e608d828d4 (MD5) Previous issue date: 2007 / Resumo: No final da década de 90, pentes de freqüências ópticas baseados em lasers de Ti:safira de modos travados tornaram-se uma importante ferramenta na área de metrologia. Eles têm sido usados, por exemplo, em medidas diretas de freqüências de várias centenas de THz e em relógios atômicos ópticos. Para a implementação de dois sistemas de pentes de freqüências ópticas, desenvolvemos neste trabalho dois lasers de Ti:safira de femtossegundos de alta taxa de repetição, que usam espelhos de varredura (chirped mirros) no lugar de prismas para compensar a dispersão em velocidade de grupo. Um dos lasers tem taxa de repetição em 770 MHz que pode ser facilmente ajustada entre 750 MHz and 1 GHz. A dispersão total da cavidade é de -60 fs2 , produzindo um espectro centrado em 780 nm com largura a meia altura em torno de 10 nm e pulsos de 150 fs. Este laser teve seu espectro alargado por duas fibra de microestrutura, cobrindo um intervalo de 510 à 1100 nm. O outro laser possui cavidade com taxa de repetição sintonizável entre 1 e 2,12 GHz, e um espectro que se estender de de 585 até 1200 nm a -20 dB abaixo do máximo em 986 nm sem o uso de fibra de microestrutura.A cavidade do laser tem dispersão total próxima de zero, porém com oscilações entre -50 a +100 fs2 entre 700 nm e 900 nm, que foi medida por interferometria de luz branca. Nós mostramos que cerca de 17 % (76 %) da potência intracavidade (de saída) é gerada basicamente por efeitos não lineares em passagem única no cristal de Ti:safira, observada na região verde do espectro e entre 960 nm e 1200 nm, fora da banda da cavidade laser e onde o ganho do cristal de Ti:safira é baixo. Ambos os lasers tiveram suas taxas de repetição medidas e estabilizadas em relação a osciladores estáveis, podendo ser sintonizados em um intervalo de 30 kHz através do oscilador de referência. Construímos interferômetros de Michelson e Mach-Zender para a medida do deslocamento entre onda portadora e envelope do pulso do sistema do laser cujo espectro é ampliado pela fibra. O batimento entre freqüências do pente próximas a 520 nm e o segundo harmônico da parte do espectro em 1040 nm é medido em um fotodetector rápido. Estes sistemas serão inicialmente utilizado em um relógio atômico óptico baseado na transição de intercombinação de átomos de cálcio frios e aprisionados. Entretando, além de aplicações em metrologia de tempo e freqüência, os pentes de freqüências ópticas podem ser ferramentas atrativas para uso em espectroscopia atômica e molecular de precisão e estudos de dinâmicas rápidas que exploram a combinação de alta resolução e cobertura espectral larga fornecidas pelo pente de freqüências / Abstract: Optical frequency combs based on femtosecond Ti:sapphire lasers and introduced at the end of the 90s have revolutionized the optical metrology field. They have allowed ultraprecise optical spectroscopy, by direct measurement of frequencies of several hundred THz, and the development of optical atomic clocks . To implement optical frequency combs, we have to stabilize both the repetition rate and the carrier-to-envelope oÿset frequency of the femtosecond laser. We have developed two versions of optical frequency combs based on high-repetition rate femtosecond Ti:sapphire lasers, which use chirped mirrors instead of prisms for compensating the group velocity dispersion. The combs will be initially used in an optical atomic clock based on the intercombination transition of cold and trapped calcium atoms. One of our fsec Ti:sapphire lasers has a repetition rate that can be easily adjusted between 750 MHz and 1 GHz. The total dispersion of the cavity is -60 fs2 . It produces pulses of 150 fs with a spectrum centered at 780 nm, with a width of 10 nm. The spectrum of this laser has been broadened with a microstructure fiber, and covers an optical octave extending from 520 and 1040 nm. The other fsec Ti:sapphire laser has a repetition rate that can be changed from 1 to 2.12 GHz, and a spectrum that extends from 585 nm to 1200 nm, without use of microstructure fibers. These wavelengths are points in the spectrum at -20 dB below the maximum at 986 nm. The laser cavity has total intracavity dispersion near zero, but with oscillations from -50 to +100 fs2 between 700 to 900 nm, that have been measured by white light interferometry. We showed that 17 % (76 %) of the intracavity (output) power is generated by nonlinear effects in a single pass through the crystal, and with a spectral distribution concentrated between 960 nm and 1200 nm, thus outside the laser cavity bandwidth and where the Ti:sapphire gain is lower. Emission in the green has also been observed, which is also outside the laser cavity bandwidth and the emission gain profile of the Ti:sapphire crystal. The repetition rate of both lasers have been phase-locked to stable microwave oscillators, and could also be frequency tuned in a range of 30 kHz with respect to the reference oscillator. We have built f-2f interferometers to measure the carrier-to-envelope oÿset frequency of the laser whose spectrum is broadened by the microstructure fiber. Comb frequencies near 540 nm are heterodyned in a fast photodetector with the second harmonic of the comb light at 1080 nm. In addition to applications in optical time and frequency metrology, the optical frequency combs should be attractive tools for use in precision atomic and molecular spectroscopy, coherent control which exploits the coherent accumulation effect, and studies of fast time dynamics that take advantage of the combination of the ultra high resolution and broadband spectral coverage provided by the comb / Doutorado / Ótica / Doutor em Ciências

L’appauvrissement en lubrifiant d’un contact élasto-hydrodynamique peut menacer la pérennité du film interfacial séparant les surfaces, entraîner l’augmentation des forces de frottement et l’endommagement rapide du tribosystème. Industriellement, la volonté de réduire les quantités de lubrifiant embarquées et de limiter les opérations de maintenance favorisent la sous-alimentation. L’objectif de cette thèse est de contrôler l’alimentation d’un contact EHD sous-alimenté par une texturation de surface multi-échelle, afin d’assurer une lubrification minimale à l’interface. Une démarche scientifique s’appuyant sur la dissociation des échelles spatiales, temporelles ainsi que sur l’analyse des contributions des écoulements dans les différentes zones du contact a été mise en oeuvre. La compréhension de l’interaction laser/matière en irradiation ultra-brève a permis de générer des texturations nanométriques (ripples) et micrométriques (ondulations et réseaux de cavités) à l’aide d’un laser femtoseconde. La contribution de chaque échelle topographique sur la lubrification d’un contact a été étudiée. Lorsque les forces hydrodynamiques sont faibles (contact statique), l’alimentation d’un contact résulte d’une compétition entre une contribution capillaire et une contribution visqueuse. La macro géométrie des solides déformés ainsi que la viscosité pilotent au premier ordre la propagation du lubrifiant à l’extérieur de la zone haute pression. L’imbibition de la zone de Hertz n’est possible qu’avec l’introduction d’une surface nanotexturée et sa cinétique dépend de l’orientation et de l’amplitude des ripples. Pour des nombres capillaires élevés (contact dynamique), un critère de prédiction de l’apparition de la sous-alimentation a été établi. En présence de réseaux de cavités et sous l’action d’un cisaillement interfacial, les surfaces texturées possédant une capacité de rétention élevée réalimentent la zone de haute pression. Le volume piégé envahit alors le contact puis crée une surépaisseur de lubrifiant qui protège les solides de l’endommagement tout en limitant l’augmentation du frottement. Les texturations nanométriques (ripples) et micrométriques, anisotropes et périodiques, modifient l’équilibre entre les débits de réalimentation et les débits de fuite. Une orientation adaptée des motifs peut contenir le drainage du lubrifiant dans le contact et ainsi empêcher ou retarder l’apparition d’un régime de sous-alimentation totale. Au final, chaque échelle topographique contribue à la réalimentation d’un contact sousalimenté, soit en favorisant l’expansion des réservoirs latéraux, soit en apportant localement du lubrifiant, ou en maintenant un film fluide résiduel sur les surfaces. / The lubricant depletion of an elasto-hydrodynamic contact may threaten the sustainability of the interfacial film separating the surfaces, can result in the increase of frictional forces and a rapid damage of the tribosystem. Industrially, the trend to reduce the amount of initial lubricant and to limit maintenance promotes starvation of the lubricated contact. The aim of this work is to control the lubricant feeding of a starved EHL contact by a multi-scale surface texturing, in order to ensure minimal lubrication at the interface. A scientific approach based on the separation of spatial and temporal scales, as well as the analysis of the flow contributions in different zones of the contact has been implemented.The understanding of the laser/matter interaction in ultra-short irradation has helped us to generate both nanoscale texturing (ripples) and microscale texturing such as microwaves and networks of micrometric cavities, using a femtosecond laser. The contribution of each topographic scale on the contact lubrication has been analysed. When the hydrodynamic forces are low (static contact), the feeding of the contact results from a competition between capillary and viscous contributions. The macro geometry of the deformed solids and the lubricant viscosity mainly control the lubricant spread around the high-pressure zone. The imbibition of the Hertz contact area is only possible with the introduction of a nanotextured surface. The imbibition kinetics depends on the orientation and amplitude of the ripples. For high capillary numbers (dynamic contact), a criterion has been established in order to predict the occurrence of starvation. Using a network of micro cavities and the action of an interfacial shear, the high retention capacity textured surfaces brings lubricant to the high-pressure zone. The trapped volume propagates inside the contact and creates a film thickness that protects the solids from damages while limiting the increase in friction. Anisotropic and periodic nanoscale and microscale texturing, like ripples, influences the balance between re-feeding and leakage flow rates. A suitable orientation of the geometries may prevent the lubricant from drainage and thus delay the onset of a starved lubrication regime. In conclusion, each topographic scale contributes to re-feed a starved contact, by promoting lateral reservoir extension, by providing lubricant locally where it is needed, or maintaining a residual fluid film on surfaces.

Les travaux présentés dans cette thèse portent sur le développement de références de fréquence optique, ou lasers ultra-stables. Ceux-ci sont obtenus en asservissant la fréquence d’un laser sur une cavité Fabry-Perot de haute finesse. Un premier laser est asservi sur une cavité commerciale en verre ULE et une stabilité relative de fréquence de 1; 9x 10-15 est obtenue à1 s. Ce signal optique est transféré dans le domaine des fréquences micro-ondes par un laser femto-seconde.Le signal obtenu à10 GHz dispose d’un bruit de phase de -104 dBc=Hz à1 Hz. Dans un second temps, une cavité ultra-compacte de 25 mm est développée. Des simulations par éléments finispoussées ont conduit à la fabrication d’une nouvelle géométrie de cavité, dotée de coefficients de sensibilité accélérométriques simulés inférieurs à10-12=(m=s2) selon toutes les directions. Une enceinte à vide compacte, munie d’un banc optique embarqué, a été réalisée de façon à limiter le volume du système complet à environ 40 L. Enfin, une cavité cryogénique en silicium a été conçue. Régulée à une température de 17 K, elle sera limitée par son bruit thermique à un palier de stabilité relative de fréquence de 3x10-17. Un cryogénérateur à faibles vibrations est utilisé pour atteindre cette température. Des modélisations par éléments finis de la cavité ont permis d’obtenir une sensibilité accélérométrique simulée de 4:5 x10-12=(m=s2). / The work described in this document deals with optical frequency references, or ultrastable lasers. They are obtained from the frequency locking of a laser on a high finesse Fabry-Perot cavity. A first laser is stabilized on a commercial ULE Fabry-Perot cavity and exhibits a 1:9 x10-15 fractional frequency instability at 1 s. A femtosecond laser is phased lock to this ultrastable laser and allows generating an ultra-pure microwave signal. At 10 GHz, the signal exhibits a -104 dBc/Hz phase noise at 1 Hz. In a second project, we design a 25 mm ultra-compact cavity. Extensive finite element modeling led to a new spacer geometry, with simulated acceleration sensitivities below 10-12=(m=s2) in all directions. A compact vacuum chamber with embedded optical set-up has been developed to reduce the size of the system. Finally, a cryogenic silicon cavity has been designed. It will be cooled down to 17 K. At this temperature, its thermal noise would limit its fractional frequency instability to3 x 10-17. A low vibration cryogenerator is used to reach this temperature. Finite element modeling led to 4:5x 10-12=(m=s2) acceleration sensitivity.

Micro/Nanostructuring of polymers by femtosecond pulses is of extreme importance because it drives applications in photonics and biomedicine. A femtosecond pulse, with an intensity of ∼ 10^13 W/cm^2, is capable of causing an optical breakdown and inducing permanent modification in the material. With such high intensity, and considering the fact that polymers possess high band gaps, the interaction nature is completely nonlinear, and the material can be modified locally on the surface and in bulk. The irradiated regions exhibit fluorescence, and they display new wetting properties as a consequence of the optical breakdown of a material. The optical breakdown can be investigated by studying the nonlinear absorption. In this thesis, we discuss the nonlinear absorption of fs-laser pulses inside polymers using transmission measurements. We show a step– function–like behaviour of the transmission, dropping abruptly to ∼ 20% at the optical breakdown threshold with a ∼ 40 % reduction in the band gap. Utilizing spectroscopy, we show that the laser-modified regions contain randomly distributed nanoclusters. The presence of localized nanoclusters is responsible for exhibiting fluorescence, within ∼ 10 µm3 for a single pulse. This feature was exploited to demonstrate high-density data storage in Polymethyl methacrylate (PMMA) without any special material preparation. We demonstrate up to 20 layers of embedded data that can be stored in a standard 120 mm disc. Storage capacity of 0.2 TBytes/disc can be achieved by adjusting read laser parameters. Besides the fluorescence capability induced in the bulk of polymers, the hydrophilicity shown by the fs–laser modified surface is utilized to study selective cell growth on the micro-structured Polydimethylsiloxane (PDMS) surface. We show that the C2C12 cells and rabbit anti-mouse protein attach preferentially to the modified regions when the surface is modified with low pulse energies. However, in the high pulse energy regime, the laser-modified regions exhibit superhydrophobicity inhibiting cell adhesion.

De nos jours, les nanomatériaux inorganiques sont devenus des objets importants pour de nombreuses applications. En même temps la pureté du matériau employé est le facteur clé, et souvent les méthodes de synthèse chimiques ne peuvent assurer l'absence d'une contamination résiduelle. Dans ce contexte, nous avons investigué et développé la synthèse par laser de nanoparticules d'or et de silicium en contrôlant leurs taille et composition. Cette technique se révèle être une approche entièrement physique de la fabrication des nanoparticules pures et exemptes d'agents tensioactifs et de sous-produits toxiques. L'approche engagé comprend deux étapes : 1) la génération de la suspension de micro- et nanoparticules par broyage mécanique, et par ablation préliminaire d'une cible solide ; 2) la fragmentation laser ultra-rapide de colloïdes en suspension qui aboutit à la formation de nanoparticules stables, non agrégées, cristallines et avec une faible dispersion de taille. Ce travail se concentre sur la synthèse de nanoparticules d'or de taille contrôlable entre 7 et 50 nm en absence de ligands. De plus, cette technique nous permet d'obtenir des nano-alliages bimétalliques et d'effectuer un couplage in situ de nanoparticules d'or avec des molécules organiques. Ensuite nous montrons la possibilité d'ajuster la taille moyenne et l'épaisseur de la couche d'oxyde des nanoparticules de Si en variant la concertation des particules initiale, le pH et la quantité d'oxygène dissoutes. Enfin, nous démontrons les propriétés optiques et plasmoniques des nanoparticules obtenues au cours de ce travail et leur potentiel pour les applications catalytiques et biomédicales. / Inorganic nanomaterials are of a major interest for numerous applications, specifically bioimaging, biomedicine, catalysis, and also surface enhanced Raman scattering spectroscopy. In most cases, the purity of the employed material is a key factor. Often the conventional chemical ways of synthesis cannot provide the desirable cleanliness. The aim of this thesis is to investigate and develop a laser-based synthetic concept for the fabrication of Au and Si-based nanoparticles with controlled parameters, free of surfactants and toxic by-products. The engaged approach includes two steps: 1) the generation of a raw suspension of micro- and nanoparticles by either mechanical milling or preliminary ablation of a target; 2) ultrafast laser-induced fragmentation from the suspended colloids leading to the formation of stable, non-aggregated, low-size dispersed and crystalline nanoparticles. In particular, we focus on the technique of the synthesis of bare Au nanoparticles with tunable size between 7 and 50 nm in the absence of any ligands. Moreover, this technique allows performing the in situ coupling of the Au nanoparticles with organic molecules and alloying at the nanoscale. Furthermore, we show the possibility of tuning the mean size and the thickness of the oxide shell of Si nanoparticles by varying the initial concentration of microparticles, the pH and the amount of dissolved oxygen. Finally, we demonstrate the optic and plasmonic properties of the nanoparticles synthesized by the techniques established in our work and their potential for the applications in catalysis and biomedicine.

In this study we applied ultra-short laser pulses on a biological sample (Arabidopsis), in order to cut it precisely in a square pattern and subsequently use it for studying stress generation mechanisms. For this purpose, we utilized femtosecond laser pulses at 100 fs pulse width and 80 MHz repetition rate. We took two processing parameters into consideration such as laser power, laser exposure time which is related to the stage speed. Therefore, we were able to find the laser optimum conditions for ablation of biological tissues. The mutant and wildtype (control) obtained from laser cutting with a size of 500 µm × 500 µm were directly transferred (in-situ with laser cutting) into a microfabricated chamber containing ~500 nanoliters deionized water for measuring ion conductivity. The ion conductivity is a signature of cell-death mechanisms caused by various stresses. A light with intensity of 100 µmol was exposed to the samples for 2 hours and 20 minutes as a source of stress. A quantitative electrical analysis with high accuracy was assured by utilizing a microchamber, which enables a measurement in nanoliter volume. We measured the impedance which is reciprocal of conductivity using a lock-in amplifier and a precise current source at frequency of 130 Hz. Initially high impedance of mutant sample tended to drop within 2 hours and finally approached the constant value which signified that the cell death mechanism was complete. However, the wildtype sample demonstrated approximately constant impedance (conductivity) during the experiment.

Les lasers de haute puissance permettent d'atteindre des intensités très importantes (jusqu'à 10²²W.cm⁻²). Parvenir à ce niveau d'intensité nécessite de concentrer une quantité modérée d'énergie (de l'ordre du joule) dans un temps très court (de l'ordre de la dizaine de femtosecondes) sur une surface réduite (de l'ordre du μm²). Ces faisceaux sont donc ultra-courts et focalisés à l'aide d'une optique à grande ouverture. Ces caractéristiques signifient que leur diamètre avant focalisation est grand et leur largeur spectrale est importante. Pour cette raison, ces faisceaux sont à même de présenter des distorsions spatio-spectrales (ou couplages spatio-temporels). Après focalisation, ces distorsions ont pour effet une diminution drastique de l'intensité pic. Ceci est d'autant plus vrai que le système laser est puissant et donc que son diamètre et sa largeur spectrale sont grands. En dépit de cet effet néfaste, les couplages spatio-temporels présentent aussi un intérêt lorsqu'ils sont maitrisés. On peut en effet introduire des couplages spatio-temporels de faible amplitude à des fins expérimentales. Dans les années 1990 et 2000, un effort important a été fourni pour permettre la caractérisation et l'optimisation du profil temporel des lasers femtoseconde. Dans le même temps, des solutions d'optique adaptative ont été développées pour contrôler le profil spatial des faisceaux ultra-intenses et obtenir la meilleure tache focale possible. Les systèmes laser de haute-puissance actuels sont maintenant caractérisés et optimisés indépendamment par ces deux types de diagnostics. Par essence, cette approche est aveugle aux couplages spatio-temporels. Seule une caractérisation spatio-temporelle permettrait de mesurer ces distorsions. Il existait déjà des méthodes de caractérisation spatio-temporelle avant le début de cette thèse. Aucun de ces dispositifs n'avait cependant été adapté à la mesure de faisceaux ultra-intenses. Lors de cette thèse, nous avons développé une nouvelle technique de caractérisation spatio-temporelle appelée TERMITES. Cette technique est basée sur un schéma de spectroscopie par transformée de Fourier auto-référencée. TERMITES nous a permis d'effectuer la première caractérisation spatio-temporelle totale d'un laser 100 TW (le laser UHI-100 du CEA Saclay). Les distorsions spatio-temporelles détectées à l'aide de ces mesures ont confirmé la nécessité d'une généralisation de la métrologie spatio-temporelle des lasers de haute puissance. / High power laser make it possible to reach very high intensities (up to 10²²W.cm⁻²). In order to get to this level of intensity, a moderate quantity of energy (on the order of the Joule) is concentrated in a very short time (on the order of tens of femtoseconds) onto a small surface (on the order of 1 μm²). These beams are therefore ultra-short and focused with a high aperture optic. These features mean that their diameter prior to focus is large and their spectral width is big. As a result, these beams are subject to spatio-spectral distorsions (of spatio-temporal couplings). After focus, these distorsions induce a dramatic reduction of the peak intensity. This situation is all the more true when the laser is more intense and its diameter and spectral width are therefore bigger. Despite their detrimental effects, spatio-temporal couplings can be of great interest when controlled. One can indeed introduce weak spatio-temporal couplings for experimental purposes. In the 1990s and 2000s, a big effort was put in order to characterize dans optimize the temporal profile of femtosecond lasers. Meanwhile, adaptative optics solutions were developed to control the spatial profil of ultra intense laser beams and provide the best focal spot achievable. By nature, this approach is blind to spatio-temporal couplings. Measuring these distorsions requires a spatio-temporal characterization. Before the start of this Phd thesis, spatio-temporal characterization methods already existed. Although none of these devices were ever adapted to the measurement of ultra-intense laser beams. During this Phd Thesis, we developped a new spatio-temporal characterization technique which we called TERMITES. This technique is based on a self-referenced Fourier transform spectroscopy scheme. TERMITES made it possible for us to perform the first total spatio-temporal characterization of a 100 TW laser (UHI-100 at CEA Saclay, France). The detection of spatio-temporal distorsions with the help of these measurements confirmed the need for a generalization of spatio-temporal characterization of ultra-high power lasers.