The PhD dissertation is organized in two parts. In the first part, we present an experimental study of stimulated Raman scattering in a silicon-on-insulator (SOI) nanowire. We demonstrate that the Raman amplification of a narrow-band Stokes wave experiences a saturation effect for high pump intensities because of self phase modulation of the pump beam. Moreover, an analytical model is presented that describes the experimental results remarkably well. The model furthermore provides an estimation of the Raman gain coefficient γR of silicon. The second part is devoted to the experimental study of stimulated Raman scattering in a doubly resonant planar GaAs microcavity. The nonlinear measurements clearly show some totally unexpected results. We experimentally demonstrate that the relaxation of the electrons in the conduction band of GaAs is significantly modified through the interaction with coherently excited Raman phonons.

La peau est un organe qui enveloppe le corps, elle est une barrière naturelle importante et efficace contre différents envahisseurs. Pour le traitement des maladies dermatologiques ainsi que dans l'industrie cosmétique, les applications topiques sur la peau sont largement utilisées. Ainsi beaucoup d'efforts ont été investis dans la recherche sur la peau visant à comprendre l'absorption moléculaire et les mécanismes rendant efficace la pénétration. Cependant, il reste difficile d'obtenir une visualisation 3D de haute résolution combinée à une information chimique- ment spécifique et quantitative dans la recherche sur la peau. La spectroscopie et la microscopie non-linéaire, incluant la fluorescence excitée à 2-photon (TPEF), la diffusion Raman spontanée, la diffusion Raman cohérente anti-Stokes (CARS) et la diffusion Raman stimulée (SRS), sont introduits dans ce travail pour l'identification sans ambiguïté de la morphologique de la peau et la détection de molécules appliquées de façon topique. Plusieurs méthodes quantitatives basées sur la spectroscopie et la microscopie non-linéaire sont proposées pour l'analyse chimique en3D sur la peau artificielle, ex vivo et in vivo sur la peau humaine. De plus, afin de s'adapter aux applications cliniques à venir, un design endoscopique est étudié pour permettre l'imagerie non-linéaires dans les endoscopes flexibles. / Skin is an organ that envelops the entire body, acts as a pivotal, efficient natural barrier to- wards various invaders. For the treatment of major dermatological diseases and in the cosmetic industry, topical applications on skin are widely used, thus many efforts in skin research have been aimed at understanding detailed molecular absorption and efficient penetration mechanisms. However, it remains difficult to obtain high-resolution visualization in 3D together with chemical selectivity and quantification in skin research. Nonlinear spectroscopy and microscopy, including two-photon excited fluorescence (TPEF), spontaneous Raman scattering, coherent anti-Stokes Raman scattering (CARS) and stimulated Raman scattering (SRS), are introduced in this work for unambiguous skin morphological identification and topical applied molecules detection. Sev- eral quantitative methods based on nonlinear spectroscopy and microscopy are designed for 3D chemical analysis in reconstructed skin, ex vivo and in vivo on human skin. Furthermore, to adapt to forthcoming clinical applications, an endoscopic design is investigated to bring nonlin- ear imaging in flexible endoscopes.

Nonlinear optical microscopy is a collection of very powerful imaging techniques. Linear optical microscopes probe the refractive index and absorption, which both stem from the first-order linear electric susceptibility. Especially in biological tissue, the variation in the refractive index is often small and the tissue is, in many cases, transparant. Nonlinear optical microscopes on the other hand probe the nonlinear higher-order susceptibilities, which can be chemically sensitive, leading to the capability to achieve label-free imaging. Nonlinear optical microscopes have been in development for more than thirty years and they are based on numerous nonlinear optical processes. The ones I will concentrate on in this thesis are second harmonic generation (SHG), coherent anti-Stokes Raman scattering (CARS), and stimulated Raman Scattering (SRS). The first technique is commonly used to image collagen as those molecules have a particularly large second-order nonlinear susceptibility due to their chiral structure. CARS and SRS on the other hand are often used because they resonantly target vibrational resonances in molecules, giving rise to the aforementioned label-free imaging. Deep understanding of the nonlinear imaging process is crucial to the interpretation of the images these techniques produce. Computational tools are exceptionally suited for this task as they allow studying the electromagnetic field anywhere in the sample as well as the far-field, and one can change any of the material properties to study their effect. One such tool is finite-difference time-domain (FDTD) that our group developed for nonlinear optical microscopy simulations. It is a direct discretization of Maxwell's equation. While computationally costly, it does allow any arbitrary shaped sample to be simulated. The sample can have frequency dependent refractive indexes, and also nonlinear media with third-order nonlinearities such as Kerr media and Raman-active media, but also second-order nonlinearities for SHG. The code is designed in such a way that it can run on thousands of CPUs on a wide variety of compute cluster which allows our group to obtain nanoscale resolution. Another computational tool I use is the free-space Green's function solution to the Helmholtz equation, which can be used to calculate the Hertz vector in the frequency domain, both in the near- and far-field, based on the induced nonlinear polarization. The electric field is then calculated from this Hertz vector. This technique is much faster then FDTD and also allows for arbitrary shapes of the nonlinear electric susceptibility in the sample. However, it assumes a homogeneous refractive index throughout the entire spatial domain and requires complete knowledge of the input beam or beams that induce the nonlinear polarization. In this thesis, I use these tools to study the image formation process of various nonlinear optical processes mentioned earlier. For example, I study the effect of an inhomogeneous refractive index on the images produced by these microscopes. In literature the index of refraction is almost always assumed to be homogeneous, because, as mentioned before, the inhomogeneity of the refractive index is often small. However, I show that these small differences in the index of refraction can have a significant effect on the measured far-field intensity signal. For example, in SRS and CARS images, the measured signal can increase by an order of magnitude depending on the index mismatch and structure of the sample. Additionally, significant shifts in perceived position occur. Even nonresonant nonlinear signals can be evoked purely through a mismatch in linear refractive index. Computational modelling can also help reveal additional detail. As SHG is a coherent process, subwavelength information can be inferred through the phase information. Our experimental collaborators built an interferometric SHG (I-SHG) microscope for exactly that purpose. We used this to image collagen fibrils, which are all aligned in a parallel fashion. However, because collagen fibrils have a chiral molecular structure, they can point either ``up'' or ``down''. Using my Green's function simulations of the SHG imaging process of collagen fibrils, I was able to predict the standard deviation in the measured phase and link it to the orientation of collagen fibrils in the focal spot of the probing laser beam, even though the diameters are far below the minimum resolvable capabilities of the microscope. We found that the ``upwards'' fibrils make up 46--53% of the sample. Even with a normal SHG microscope that does not measures phase, additional subresolution information is obtainable. With our collaborators we measured the ratio of the forward SHG intensity signal to that in the backward direction and with my simulations, we are able to link this to the fibril diameters in collagen tissue. Thus we inferred that the fibril diameter increases as a function of tissue depth. Furthermore, a computational technique called ptychography is able to retrieve phase information without an interferometric reference beam. Additionally, it increases resolution to the theoretical limit, independent of the laser focal spot size, and corrects for distortions in the input beam as well. I have developed this technique for use with nonlinear optical microscopy and was able to show it is a viable alternative to I-SHG by imaging simulated rat tail tendon at the diffraction limit while retrieving the orientation of the fibrils through the phase of the SHG signal. I also implemented the algorithm for CARS, where the phase information can be used to greatly increase the signal-to-noise ratio by reducing the nonresonant background radiation that results from competing nonlinear optical processes. I showed an example of this by imaging a simulated fibroblast cell where the CARS process was tuned to the lipid droplets inside of the cell. I am currently in talk with experimentalists to apply this theoretical technique to experiments as that would further demonstrate the impact of my work. Finally, keeping in theme with the collagen fibrils, I show that the ratio of the forward SHG signal to the backward signal, the F/B ratio, is affected by a mismatch in the refractive index for fibrils larger than 100nm. This measure is an indicator of fibril diameter and thus important for making qualitative predictions. Single fibrils are generally too small to be significantly affected by near-field effects, but the bigger fibrils can be. Fibrils in rat tail tendon have a distribution of fibrils diameters and the large fibrils occur infrequent. However, I found that the large fibrils are largely responsible for the forward as well as backward signal, thus refractive index mismatches still affect the F/B ratio significantly despite their infrequency. The F/B ratio for a collection of fibrils placed in a n=1.47 medium was found to be 31.8±0.7% higher than for those in a n=1.33 medium. Our experimental colleagues have done preliminary measurements on mouse tail tendon where they found an increase of 40±20%, in line with the value of 28.1±0.6% that I found for simulations with mouse tail tendon. In conclusion, the theoretical tools I have used in my thesis have provided me with the ability to study nonlinear optical image formation processes with a level of detail that would be near-impossible to do experimentally. I have used this ability to show how refractive index mismatches, such as those found in biological tissue, can significantly distort the far-field intensity signals. I have shown this for SRS and CARS where the far-field intensity signal appeared an order-of-magnitude larger compared to the same sample without a refractive index mismatch with the background medium. Additionally, shifts in the perceived position of the object under investigation were observed and I showed the presence of a nonresonant background signal in AM-SRS. Likewise I showed that in the SHG imaging of collagen fibrils significant changes in the F/B ratio can occur. All of these effects have important implications as these types of images as biomedical researches rely on the correct interpretation of nonlinear optical microscopy images for both research and diagnostics. Apart from showing the effect of a refractive index mismatch, I have also shown that computation modelling can be used to infer subwavelength features in SHG imaging experiments of collagen fibril such as fibril orientation and fibril diameter. These methods have the potential to aid medical researchers as changes in the structure of collagen are often an early indicator of diseases such as osteoarthritis. Finally, I showed that the ptychography algorithm I developed for nonlinear optical microscopy is able to retrieve phase information of the nonlinear electric susceptibility in SHG and CARS imaging while also enhancing the resolution and correcting for distortions in the input beams. I can also use much larger laser spot sizes than in conventional experiments without compromising the obtained resolution, thus fewer measurements are required. The technique is not limited to SHG and CARS either; it will work for other nonlinear optical processes as well. Experimental verification of nonlinear ptychography will be done soon. This technique has to potential to significantly improve current imaging techniques since access to the phase information allows one to observe additional information about the sample as we showed with the I-SHG microscope.

De part ses nombreuses applications scientifiques et sociétales comme la radiographie protonique ou encore la protonthérapie, l’accélération d’ions par laser suscite un grand intérêt. Cette thèse s’inscrit dans ce cadre et présente une étude de l’interaction d’une impulsion laser d’intensité relativiste avec un plasma de densité modérée. Dans ce régime, le plasma est transparent à l’onde laser et les électrons oscillent à des vitesses relativistes dans le champ de l’onde incidente. Ces conditions sont favorables à un transfert efficace de l’énergie laser vers le plasma, et donc sont intéressantes pour l’accélération d’ions par laser. Ce régime permet également la création de solitons électromagnétiques et acoustiques dont les mécanismes de formation et les propriétés nécessitent une meilleur compréhension. Nous réalisons une étude détaillée de simulations Particle-In-Cell (réalisées avec le code OCEAN) de l’interaction d’une impulsion laser intense avec un plasma sous dense. Nous montrons que la diffusion Raman stimulée (SRS) dans le régime relativiste est le principal processus responsable de l’absorption de l’énergie laser par le plasma et qu’il est, en outre, très efficace puisqu’il permet de transférer près de 70 % de l’énergie de l’impulsion laser aux électrons. Cette instabilité apparaît dans des plasmas dont la densité est nettement supérieure à la densité quart-critique du fait de la diminution de la fréquence plasma électronique et se développe sur des temps très courts. Il permet ainsi un chauffage homogène des électrons tout le long de la propagation de l’impulsion laser à travers le plasma. Ces électrons participent à la détente du plasma, et créent sur ses bords raids un champ électrostatique permettant l’accélération des ions. Ces derniers gagnent 30 % de l’énergie laser initiale. Nous avons aussi développé un modèle simple qui permet de prédire et donc d’optimiser le taux de rétro-diffusion du plasma du fait du développement de l’instabilité SRS. Nous nous intéressons également à la séquence des processus permettant la formation des cavités électromagnétiques. Cette analyse souligne le rôle joué par l’instabilité modulationnelle ou de Benjamin-Feir sur le front de l’impulsion laser qui est divisée en un train de plusieurs solitons électromagnétiques. À l’aide d’une étude détaillée, nous montrons que ces solitons excitent des ondes plasmas dans leur sillage en se propageant dans le plasma, perdent de l’énergie et finissent par être piégés. Ils forment également des dépressions (cavités) des densités électroniques et ioniques du plasma. Ces cavités sont des pièges pour les champs électromagnétiques rayonnés par le plasma (par exemple du fait de l’instabilité SRS) et survivent grâce à un équilibre entre la pression de radiation des champs piégés et les pressions cinétiques électroniques à leurs bords. Ces cavités absorbent une part importante de l’énergie laser mais elles n’en conservent qu’une partie sous forme d’énergie électromagnétique piégée. Le reste de l’énergie permet l’expansion de la cavité, la génération de solitons acoustiques supersoniques et l’accélération de particules. / The laser-accelerated ions draw an increasing interest due to their potential applications and to their unique properties. This manuscript presents a study of the interaction between a relativistic intense laser pulse and a low density plasma. In this regime, the plasma is transparent to the laser pulse and electrons oscillate with relativistic velocities in the field of the incident wave. These conditions make the transfer of the laser pulse energy to the plasma efficient, and therefore are interesting for the ion acceleration. This regime generates also electromagnetic and acoustic solitons whose formation mechanisms and properties need to be better understood. We carry out a detailed analysis of Particle-In-Cell simulations (performed with the code OCEAN) of interaction of an intense laser pulse with a low density plasma.We show that the stimulated Raman scattering (SRS) is the main mechanism responsible for the absorption of laser energy in plasma. This process is very efficient : it leads to the transfer of 70 % of the laser pulse energy to electrons. This instability occurs in plasmas with a density larger than the quarter critical one due to the decrease of the electron plasma frequency and develops in a very short time scale. It leads to an homogeneous electron heating all along the distance of propagation of the laser pulse through the plasma. The ions are efficiently accelerated at the plasma edges and can get nearly 30%of the initial laser energy. This study is accompanied by a simple analytical model which is able to predict and so optimize the laser backscattering fraction due to the development of the SRS instability. We also present a sequence of stages which lead to the formation of electromagnetic cavities. This analysis highlights the role of the modulationnal or Benjamin-Feir instability in the front of the laser pulse, which is split in a train of electromagnetic solitons. Our detailed study shows that these solitons excite plasmas waves in their wake, lose energy and are finally trapped in the plasma. They lead to the formation of density depressions (cavities) which may trap the electromagnetic fields produced in the plasma (by the SRS instability, for example). These structures may survive for a long time thanks to an equilibrium of the trapped field radiation pressure and the electronic kinetic pressure at their borders. These cavities absorb an significant part of the laser energy but only a part of it is trapped inside. The remaining part is invested in the cavity expansion, generation of acoustic solitons and acceleration of charged particles.

Die vorliegende Dissertation befasst sich mit der Anwendung und Weiterentwicklung der CARS -Mikroskopie (CARS, (Coherent anti-Stokes Raman scattering)) zur Lokalisierung von Wirkstoffen in Zellen. Aufgrund einer C-Deuterierung dieser Wirkstoffe werden diese intrinsisch markiert und lassen sich nicht-invasiv mit Hilfe Raman-basierter Mikrospektroskopietechniken von Zellbestandteilen unterscheiden. Diese Arbeit widmet sich der für biomedizinische Anwendungen zu geringen Sensitivität und zu hohen Komplexität des experimentellen Aufbaus für CARS-Mikroskopie. Auf der Anwendungsseite wurdenzunächst mittels quantitativer Raman- und CARS- Mikroskopie die Detektionsgrenzen C-deuterierter Stoffe bestimmt. Anhand von mit deuterierter Fettsäure inkubierter Makrophagen wurde chemischer Kontrast in Zellen qualitativ gezeigt. Die Weiterentwicklung des experimentellen Aufbaus erfolgte durch den Einsatz von Impulsformern. Diese können das Anregungslicht in Amplitude und Phase formen und somit den Schwingungskontrast optimieren und den experimentellen Aufbau vereinfachen. Verwendet wurden dabei sowohl ein spatial light modulator (SLM) als auch ein akustooptischer Modulator (AOM), die in dieser Arbeit miteinander verglichen werden. Mit Hilfe einer photonischen Kristallfaser als spektral breite Lichtquelle und des AOM als spektraler Filter konnte der Aufbau vereinfacht und ein Schema zur Implementierung von Quasi-Multiplex CARS-Mikroskopie aufgebaut werden, welches ein schnelles Schalten zwischen verschiedenen bildgebenden Raman-Banden erlaubt. Die automatisierte Optimierung des Schwingungskontrasts erfolgte schließlich durch den Einsatz des SLM, der mit Hilfe eines selbstlernenden Algorithmus den Schwingungskontrast von CARS-Bildern um bis zu 160 % verbessern konnte.

Depuis leur avènement, les fibres à cristal photonique à cœur creux ont prouvé leur capacité à convertir des fréquences avec une haute efficacité, notamment en jouant sur le phénomène de diffusion Raman stimulée. Dans le cadre d’un contrat CIFRE entre la société GLOphotonics et l’institut de recherche Xlim, ce projet de thèse a consisté à développer ces fibres afin d’améliorer leurs performances optiques pour cibler deux voies d’applications: une industrielle pour proposer un laser compact multi-ligne dans le visible et dans l’UV et une seconde plus fondamentale pour réaliser un synthétiseur d’onde optique. L’amélioration de ces performances repose sur l’exacerbation de l’inhibition du couplage entre le mode du coeur d’air et les modes de silice de la gaine. Pour cela deux types de micro-structures ont été explorées à savoir une maille Kagomé et une maille tubulaire. Plusieurs fibres ont été alors fabriquées démontrant des performances records sur toute une gamme de longueurs d’onde (8,5 dB/km à 1 µm, 7,7 dB/km à 750 nm, 13,8 dB/ km à 549 nm, et autour de 70 dB/km à 355 nm). Concernant la fonctionnalisation de ces fibres, des micro-capsules photoniques ont été conçues et réalisées permettant à la fois de palier au problème de la perméabilité de la silice au gaz (stabilité de la conversion dépassant 12 mois) et de démontrer une conversion de 26 lignes dans le visible. Un produit industriel nommé CombLas a alors été produit puis appliqué à une étude de cytométrie en flux pour étudier l’influence du taux de répétition du laser de pompe. Ce produit a également été étendu à la gamme spectrale de l’UV avec la génération de 24 lignes entre 225-400 nm. Enfin, des travaux plus fondamentaux ont été réalisés consistant à développer un synthétiseur d’onde optique à base de génération Raman dans ces fibres creuses. Une nouvelle dynamique a été observée démontrant le piégeage de molécules d’hydrogène par un réseau optique auto-assemblé de puits de potentiel ultra-profonds et nanométriques. Cela permis de générer un régime Lamb-Dicke de la diffusion Raman stimulée. Des signatures sub-Doppler usuellement vues dans les atomes froids ont été mesurées avec des largeurs de bandes plus étroites de plus de 5 ordres de grandeurs par rapport à ce qui est prédit dans la littérature. Finalement, cette largeur de bande a été optimisée d’un ordre de grandeur en jouant sur la longueur de la fibre et la pression de l’hydrogène. / Since their advent, hollow-core photonic crystal fibers have proved to be highly efficient for frequency conversion, especially via by playing with stimulated Raman scattering. Within the frame work of a CIFRE contract between the firm GLOphotonics and the Xlim research institute, this thesis project has consisted in developing these fibers to enhance their optical performances, in order to target two different field of applications: an industrial one to offer a a compact multi-line laser in the visible and UV and a second more fundamental one to realize a optical wave synthesizer. The amelioration of these performances relies on the exacerbation of the inhibition of the coupling between the air core mode and the silica cladding modes. Two types of micro-structures have been explored, a Kagomé and a tubular lattice. Several fibers have been fabricated demonstrating record performances on all a wavelength range (8.5 dB/km at 1 µm, 7.7 dB/km at 750 nm, 13.8 dB/km at 549 nm, and around 70 dB/km at 355 nm). Concerning the functionalization of the fibers, photonic micro-cells have been designed and realized enabling to overcome the problem the permeability of silica to gas (conversion stability over 12 months) and demonstrate a conversion to 26 lines in the visible. An industrial product coined CombLas has been made and used for flow cytometry in order to study the influence of the repetition rate of the pump laser. This product has also been extended to the UV range with 24 lines generated between 225-400 nm. Also, more fundamental research has been realized consisting in developing an optical wave synthesizer based on Raman generation in hollow core fibres where a new dynamic has been observed demonstrating the trapping of hydrogen molecules by an auto-assembled optical lattice of ultra-deep and nano-metric potential wells. This configuration has enabled to generate a Lamb-Dicke regime of stimulated Raman scattering. Sub-Doppler signatures usually found in cold atoms have been measured with linewidths narrower than 5 orders of magnitude than what is predicted in the literature. Finally, this linewidth has been optmised of an order of magnitude by plaing on the length of the fiber and the pressure of hydrogen.

The subject of this thesis is the design and development of a unified set up for femtosecond transient absorption and ultrafast Raman loss spectroscopy and demonstrate its potential in capturing the ultrafast photophysical and photochemical processes with excellent time and frequency resolution. Ultrafast spectroscopy has been serving as a powerful tool for understanding the structural dynamical properties of molecules in the condensed and gas phase. The advent of ultrashort pulses with their high peak power enables the laser spectroscopic community to study molecular reaction dynamics and photophysics that happen at extremely short timescales, ranging from picosecond to femtosecond. These processes can be measured with extremely high time resolution, which helps to resolve the under-lying molecular process. But in order to understand the global mechanism of the underlying molecular processes, we have to resolve the nuclear dynamics with the proper frequency resolution. However, achieving both, time and frequency resolutions simultaneously is not possible according to the Heisenberg uncertainty principle. Later, this limitation was overcome by femtosecond stimulated Raman spectroscopy (FSRS), a third order non-linear Raman spectroscopy. In this thesis we introduced the ultrafast Raman loss spectroscopic (URLS) technique which is analogous to FSRS, offering the modern ultrafast community to resolve molecular processes with better signal-to-noise ratio along with proper time and frequency resolution. We demonstrate the experimental procedure including the single shot detection scheme to measure whitelight background, ground state Ra-man, transient absorption and transient Raman in shot-to-shot detection fashion. URLS has been applied to understand the excited state planarization dynamics of 1,4-bis(phenylethynyl)benzene (BPEB) in different solvents. In addition, excitation wavelength dependent conformational reorganization dynamics of different sub-sets of thermally activated ground state population of BPEB are also discussed. Using the same techniques along with femtosecond transient absorption, we demonstrate the ultrafast vibrational energy transfer and the role of coherent oscillations of low frequency vibrations on the solution phase photo-isomerization of trans-stilbene from an optically excited state. The effects of solvents on the coherent nuclear motion are also discussed in the context of reaction rates. 2

Raman spectroscopy involves change in the polarizability of the molecular system on excitation and is based on scattering process. Spontaneous Raman scattering is a two photon process, in which the input light initiates the excitation, which then leads to an emission of another photon due to scattering. It is extensively used to understand molecular properties. As spontaneous Raman scattering is a weak process, the detection of these weak Raman photons are rather difficult. Alternatively, resonance Raman (RR) scattering is another technique where the excitation wavelength is chosen according to the material under study. The excitation wavelength is chosen to be within the absorption spectrum of the material under study. RR spectroscopy not only provides considerable improvement in the intensity of the Raman signal, but also provides mode specific information i.e. the modes which are Franck-Condon active in that transition can be observed. There are reports on RR studies of many systems using pulsed light as an excitation source. It is necessary to use at least two pulsed laser sources for carrying out the time resolved RR spectroscopy. A single pulse source for excitation would lead to compromise either with temporal or spectral resolution which is due to the uncertainty principle. If an excitation pulse has pulse width of ~100 femtoseconds then the spectral resolution will be ~ 150 cm-1. It is clear now that for improving the temporal and spectral resolution simultaneously, usage of single pulse for Raman experiments (spontaneous scattering) is not adequate. The usage of multiple laser pulses may provide the way out to improve the resolutions. Nonlinear spectroscopy in a broad view helps in understanding the structural and dynamical properties of the molecular systems in a deeper manner. There are a number of techniques as a part of nonlinear spectroscopy that have emerged in due course to meet different requirements and to overcome some difficulties while understanding the molecular properties. Stimulated Raman (SRS) gain, coherent anti-Stokes Raman scattering (CARS) and the inverse Raman spectroscopy are a few to mention as third order nonlinear spectroscopic techniques which give the similar kind of information about the molecular systems. Stimulated Raman scattering is a more general process involved in nonlinear Raman processes. SRS involves at least two laser pulses and the difference in their frequencies should match with the vibrational frequency of the molecule. The polarization has to be matched between the Raman pump and the Raman probe pulses. We have developed a new nonlinear Raman technique in our laboratory named as ultrafast Raman loss spectroscopy (URLS) using the principles of nonlinear Raman scattering. It involves the Raman pump (~ 1 picosecond (ps) or ~ 15 cm-1spectral resolution) and Raman probe as a white light continuum (100 fs) whose frequency components ranges from 400-900 nm. The laser system consists of Tsunami which is pumped by a Millennia laser and Spitfire-Pro, a regenerative amplifier which is pumped by an Empower laser. Tsunami provides a 100 fs, 780 nm centered, 80 MHz and ~6 nJ energy laser pulses. The Tsunami output is fed into Spitfire to amplify its energy and change the repetition rate to 1 KHz. The pulse length of the input pulse is preserved in amplification. The output of amplifier is split into two equal parts; one part is used to pump the Optical Parametric Amplifier (OPA) in order to generate wavelengths in the range 480-800 nm. The output of the OPA is utilized to generate Raman pump which has to be in ps in order to get the best spectral resolution. A small portion of the other part of amplifier output is utilized to generate white light source for the Raman probe. The remaining part of the amplifier output is used to pump TOPAS to generate wavelengths in the ultraviolet region. URLS has been applied to many molecular systems which range from non-fluorescent to highly fluorescent. URLS has been demonstrated to be very sensitive and useful while dealing with highly fluorescent systems. URLS is a unique technique due to its high sensitivity and the Raman loss signal intensity is at least 1.5-2 times higher as compared to the Raman gain signal intensities. Cresyl violet perchlorate (CVP) is a highly fluorescent system. URLS has been applied to study CVP even at resonance excitation. Rhodamine B has also been studied using URLS. Spontaneous Raman scattering is very difficult to observe experimentally in such high quantum yield fluorescent systems. The variation in the lineshapes of the Raman bands for different RP excitation wavelengths in URLS spectra shows the mode dependent behavior of the absorption spectrum. The experimental observation of variation in the lineshape has been accounted using theoretical formalism. The thesis is focused on discussing the development of the new nonlinear Raman spectroscopic technique URLS in detail and its applicability to molecular systems for better understanding. A theoretical formalism for accounting the uniqueness of URLS among the other nonlinear Raman techniques is developed and discussed in various pictorial representations i.e. ladder, Feynman and closed loop diagrams. A brief overview of nonlinear spectroscopy and nonlinear Raman spectroscopy is presented for demonstrating the difference between the URLS and the other nonlinear Raman techniques.

Initialement poussées par le marché résidentiel, les évolutions du réseau d’accès optique sont aujourd’hui également stimulées par l’expansion du réseau mobile. Comme le montre le premier chapitre de ce document, l’introduction d’un multiplexage en longueur d’onde dense constitue l’une des solutions privilégiées pour permettre la montée en débit dans les réseaux d’accès optique. Dans cette thèse, l’impact de l’introduction du multiplexage en longueur d’onde dense est étudié sous trois axes :• Une prochaine étape de l’évolution des technologies pour les réseaux d’accès passerait par une hybridation entre d’une part, un multiplexage temporel (hérité des précédentes générations), et d’autre part, un multiplexage en longueur d’onde dense. Cette technologie, appelée NGPON2-TWDM, permet aujourd’hui d’envisager des débits de 40Gb/s à 80Gb/s grâce à 4 ou 8 canaux. Les difficultés liées à la stabilité de la longueur d’onde lors de l’émission de données en mode paquet dans le sens montant du lien, ainsi que les solutions associées, sont étudiées dans le second chapitre.• L’importance du marché que représente le réseau d’accès optique (aussi bien pour les clients résidentiels que pour les réseaux mobiles), induit la nécessité pour les différentes générations de technologies de coexister au sein d’une même infrastructure. Du fait des fortes puissances optiques en jeu et des plages spectrales allouées à chaque technologie, cette coexistence peut induire des interactions entre technologies par émission Raman stimulée, dont le principe et les impacts sont décrits dans le troisième chapitre.• Enfin, la quatrième partie de ce document est dédiée à l’étude des limites et potentialités de la technologie self-seeded pour le multiplexage en longueur d’onde dense en bande O, capable de stabiliser automatiquement et passivement la longueur d’onde d’émission de chacun des émetteurs du système. / Initially led by the residential market, today’s optical access network evolutions are stimulated by mobile network expansion. As shown in the first chapter of this document, dense wavelength division multiplexing is one of the favorite solutions in order to increase optical access networks throughput. In this thesis, we propose a study of dense wavelength division multiplexing introduction according to three main topics :• Service providers and equipment suppliers have decided that the next step in residential market evolution will consist in a hybridization between, on one hand, a legacy time division multiplexing, and on the other hand, a dense wavelength division multiplexing. Named NG-PON2, this technology allows today 40Gb/s to 80Gb/s thanks to 4 to 8 channel pairs. Wavelength stability of the upstream emitter under burst mode operation, and related solutions, are studied in the second chapter.• Market importance (for both residential market and mobile networks) requires the different technologies generations to coexist on the same infrastructure. Due to the high optical power and the wavelength spans allocated to each technology, this coexistence can lead to technologies interactions by stimulated Raman scattering, as described in the third chapter.• Finally, the fourth part of this document describes the limits and potentialities of the self-seeded emitter technology for O-band dense wavelength division multiplexing, able to automatically and passively self-stabilize the wavelength of each emitter.

[pt] Neste trabalho é apresentado um estudo sobre a determinação matemática dos valores da dispersão cromática total, do zero de dispersão distribuído e efeitos não lineares em fibras ópticas de dispersão deslocada (DS). Uma metodologia para caracterização das dispersões cromáticas e para os zeros de dispersão local das fibras estudadas é elaborada com a utilização do modelo de fibra degrau equivalente e de aproximações entre as fibras ópticas dos enlaces trabalhados. A relação entre o diâmetro do campo modal e o zero de dispersão cromática distribuído segundo A. Rossaro [6] é discutida e comprovada através da realização de uma série de medidas práticas para a determinação dos efeitos não lineares das fibras de dispersão deslocada dos enlaces da Petrobrás. O objetivo deste trabalho é analisar estes efeitos prejudiciais a transmissão de sinais ópticos de alta velocidade apresentados nos cabos submarinos da Petrobrás entre o Porto de Imbetiba e as plataformas de Pargo I e Pampo I na Bacia de Campos, analisando os resultados obtidos e caracterizando as possibilidades de upgrade destes enlaces. / [en] This work presents a study on the mathematical determination of the total chromatic dispersion, zero dispersion wavelength and nonlinear optical effects in dispersion shifted (DS) fiber optic system. A methodology to determine the chromatic dispersion and zero dispersion wavelength is proposed using the equivalent step index model and the similarity of the total chromatic dispersion measured in fibers of the links under study. The relationship between the mode field diameter and the zero dispersion wavelength according to A. Rossaro [6] is discussed and proven with a series of practical measurements for the determination of the nonlinear effects of the dispersion shifted optical fibers of Petrobras links Imbetiba - Pargo and Imbetiba - Pampo of the Campos Basin. / [es] En este trabajo se presenta un estudio sobre la determinación matemática de los valores de dispersión cromática total, del cero de dispersión distribuido y los efectos no lineales en fibras ópticas de dispersión desplazada (DS). Se elabora una metodología para la caracterización de las dispersiones cromáticas y para los ceros de dispersión local de las fibras estudiadas; utililizando el modelo de fibra escalón equivalente y de aproximaciones entre las fibras ópticas de los enlace. Se discute la relación entre el diámetro del campo modal y el cero de dispersión cromática distribuido según A. Rosaro [6] se comprueba a través de la realización de una serie de medidas prácticas para la determinación de los efectos no lineales de las fibras de dispersión desplazada de los enlaces de la Petrobrás. EL objetivo de este trabajo es analizar los efectos perjudiciales a la transmisión de señales ópticos de alta velocidad que se presentan en los cables submarinos de la Petrobrás entre el Puerto de Imbetiba y las plataformas de Pargo I y Pampo I en la Bacia de Campos, analizando los resultados obtenidos y caracterizando las posibilidades de upgrade de estos enlaces.