The quantum confined Stark effect (QCSE) and ultrafast absorption dynamics near the bandedge have been investigated in p-i-n waveguides comprising quantum confined heterostructures grown on GaAs substrates, for emission at 1.3um. The materials are; isolated InAs/InGaAs dot-in-a-well (DWELL) quantum dots (QD), bilayer InAs quantum dots and GaInNAs multiple quantum wells (MQW). The focus was to investigate these dynamics in a planar waveguide geometry, for the purpose of large scale integration in optical systems. Initial measurements of the QCSE using photocurrent measurements showed a small shift for isolated QDs whilst a significant shift of 40nm (at 1340nm) was demonstrated for bilayer dots, comparable to that of GaInNAs MWQ (30nm at 1300nm). These are comparable to InP based quaternary multiple quantum wells used in modulator devices. With the use of a broadband continuum source the isolated quantum dots exhibit both a small QCSE (15nm at 1280nm) and minimal broadening which is desirable for saturable absorbers used in monolithic modelocked semiconductor lasers (MMSL). A robust experimental set-up was developed for characterising waveguide modulators whilst the electroabsorption and electro-refraction was calculated (dn=1.5x10⠻³) using the Kramers-Kronig dispersion relation. Pump probe measurements were performed at room temperature using 250fs pulses from an optical parametric oscillator (OPO) on the three waveguide samples. For the isolated QDs ultrafast absorption recovery was recorded from 62ps (0V) to 700fs (-10V and the shortest times shown to be due to tunneling. Additionally we have shown good agreement of the temperature dependence of these dots and the pulse width durations from a modelocked semiconductor laser using the same material. Bilayer QDs are shown to exhibit ultrafast absorption recovery from 119ps (0V) to 5ps (-10V) offering potential for applications as modelocking elements. The GaInNAs multiple quantum wells show absorption recovery of 55ps (0V), however under applied reverse bias they exhibit long lived field screening transients. These results are explained qualitatively by the spatial separation of electrons and holes at heterobarrier interfaces.

This thesis presents ultrafast photophysical measurements on a number of phosphorescent iridium complexes and establishes relationships between the relaxation rates and the vibrational properties of the material. When ultrafast luminescence is measured on the peak of the phosphorescence spectrum and on its red-side, 230 fs and 3 ps decay time constants were observed in all materials studied, and this was attributed to population redistribution amongst the three electronic substates of the lowest triplet metal-ligand charge transfer (MLCT) state. The observation of luminescence at higher values of energy embodied ultrafast dissipation of excess energy by intramolecular vibrational redistribution (IVR) and it was found that the dissipation channels and rate of IVR could be modified by chemical modification of the emitting molecule. This was tested in two ways. Firstly by adding electronically inactive dendrons to the core, an increase in the preference for dissipation of excess energy by IVR rather than by picosecond cooling to the solvent molecules was found, but this did not change the rate of IVR. The second method of testing was by fusing a phenyl moiety directly onto the ligand, this both increased the rate of IVR and also the preference for dissipation by it rather than by picosecond cooling. Fluorescence was recorded in an iridium complex for the first time and a decay time constant of 65 fs was found, thus allowing a direct observation of intersystem crossing (ISC) to be made. In a deep red emitting iridium complex internal conversion (IC) and ISC were observed and the factors controlling their time constants deduced. IC was found to occur by dissipation of excess energy by IVR. The rate of IC was found to be dependent on the amount of vibrational energy stored in the molecule, with IC fast (< 45 fs) when < 0.6 eV of energy is stored and slower (~ 70 fs) when the value is > 0.6 eV. The rate of ISC agreed with these findings, indicating that the very process of ISC may be thought of as closely analogous to that of IC given the strongly spin-mixed nature of the singlet and triplet MLCT states.

The work of this dissertation has been to prove that the coherence of multiphoton excitation can be studied by an appropriately phased and time delayed sequence of pulses. An application of this fundamental study of coherence has been made for the enhancement of third harmonic generation. The coherent recovery of the energy lost to the two photon absorption process enalled a larger propagation distance for the fundamental than in an interaction which is incoherent or coherent, but not using a 90 degree phase shifted pulse pair. Phase matching over this longer propagation distance gave an enhancement of third harmonic generation.

Cette thèse en deux parties porte sur le développement de sources lasers nano et picosecondes et leurs applications. La première partie présente l'étude, et la réalisation d'une chaîne amplificatrice laser nanoseconde pour l'allumage de turbomoteurs. Après avoir présenté les performances et l'évolution de cette chaîne seront présentes les résultats des campagnes d'essais réalisées sur une chambre de combustion sur un banc d'essai à l'ONERA dans des conditions de basses températures et de basses pressions. La deuxième partie de cette thèse traite du développement d'un oscillateur paramétrique optique (OPO) nécessaire pour accorder en longueur d'onde dans l'infrarouge un laser impulsionnel picoseconde ou femtoseconde à haute cadence et forte puissance moyenne. Après avoir présenté la cavité de l'OPO ainsi que ses performances, nous détaillerons la capacité de cet OPO à générer des impulsions femtoseconde comprimées à partir d'impulsions pompe présentant un étirement temporel. / This two-part thesis focuses on the development of nano and picosecond laser sources and their applications. The first part presents the study, and the realization of a nanosecond laser amplifier chain for the ignition of turboshaft engines. After the repport of the performances and the evolution of this amplifier chain will be presented the results of the tests carried out on a combustion chamber on a test bench at ONERA under low temperatures and low pressures conditions. The second part of this thesis deals with the development of an optical parametric oscillator (OPO) in order to tune in the infrared the wavelength of a pulsed picosecond or femtosecond laser at high cadency and high average power. After presenting the OPO cavity and its performance, we will detail the ability of this OPO to generate compressed femtosecond pulses from pump chirped pulses.

Le mécanisme de radiolyse de l’eau est bien établi. Sous l’effet des rayonnements ionisants, les produits de la radiolyse de l’eau pure sont les radicaux et les produits moléculaires tels que les électrons solvatés, les atomes hydrogènes, les radicaux hydroxyles, le peroxyde d’hydrogène et les ions hydroniums. Lorsque les solutions concentrées sont irradiées, le résultat de la radiolyse change à cause de la fraction d’énergie absorbée par le soluté, cette fraction est négligeable dans le cas des solutions diluées. Les produits de la radiolyse du solvant peuvent réagir avec les molécules du solvant engendrant des changements dans leurs rendements radiolytiques ainsi qu’un changement dans le mécanisme de radiolyse du solvant. L’effet du rayonnement ionisant sur les solutions concentrées est appelé l’effet direct du rayonnement ionisant. La compréhension de cet effet est fondamentale dans plusieurs domaines tels que l’énergie nucléaire, la radiothérapie et la radiobiologie.L’objectif de ce travail est de comprendre le mécanisme de radiolyse des solutions concentrées ainsi que de quantifier l’effet direct du rayonnement ionisant en étudiant des solutions concentrées d’halogénures tels que les bromures de sodium et les chlorures de sodium, de même qu’une étude préliminaire sur les solutions concentrées d’acide nitrique.Tout d’abord, en effectuant la radiolyse stationnaire des solutions concentrées de bromures de sodium, nous avons quantifié le rendement radiolytique de formation de Br3- qui est l’unique produit stable de ces solutions sous rayonnements sous différentes conditions expérimentales.Ensuite, en effectuant la radiolyse pulsée picoseconde sur l’installation ELYSE des solutions aqueuses de NaCl, NaBr et HNO3, nous avons montré l’ionisation direct du soluté après le passage du faisceau d’electron. Selon les cinétiques obtenues, nous avons montré que la formation Br2•-, Cl2•-, NO3• prend place durant l’impulsion picoseconde d’électron d’électron. La radiolyse pulsée picoseconde nous a permis donc de conclure qu’il existe deux voies pour la formation de Br2•- et Cl2•-. La première voie résulte de l’ionisation directe du soluté. La deuxième résulte du changement dans le mécanisme de radiolyse de l’eau dû à la forte concentration des ions halogénures autour des molécules d’eau ionisées. Nos résultats montrent que la formation du radical hydroxyle HO• dans les solutions concentrées est marginale puisque la molécules d’eau ionisée, le trou H2O+ , réagit très rapidement avec les ions halogénures. / The mechanism of water radiolysis is well established. As a result of the action of ionizing radiation on pure water, radicals and molecular products such as solvated electrons, hydrogen atoms, hydroxyl radicals, hydrogen peroxide and hydronium ions are formed. When highly concentrated solutions are irradiated, the outcome of irradiation is changed due to the important fraction of energy being absorbed by the solute which in the case of diluted solutions is skipped. Products of solvent radiolysis may react with the molecules of the solute leading to the change in their yields and moreover, may cause changes in the mechanism of solvent radiolysis. The action of ionizing radiation on highly concentrated solutions is named direct action of radiation. The understanding of direct effect of ionizing radiation is very important in several aspects, for example in nuclear energy, or radiotherapy or radiobiology. The aim of this work was to understand the mechanism and quantify the direct action of ionizing radiation in model systems such as highly concentrated sodium bromide and sodium chloride solutions. Firstly, by performing gamma radiolysis of highly concentrated solution of sodium bromide we quantify the yield of direct ionization of bromide ions for different experimental conditions.Secondly, by carrying out picosecond pulse radiolysis of aqueous solutions of NaCl, NaBr, and HNO3, we showed the direct ionization of the solute after the passage of electron beam. On the base of recorded kinetics, we showed that the formation of Br2•-, Cl2•-, NO3• takes place during the electron pulse. Picosecond pulse radiolysis allowed us to conclude that two ways of formation of Br2•- and Cl2•- exist. The first results from the direct ionization of the solute. The second results from the change in the mechanism of water radiolysis due to the high concentration of halide ions around the molecules of ionized water. Our results show that the formation of HO• radical in highly concentrated solutions is marginal and only stem from the dissociation of excited water, since the molecules of ionized water react with halide ions instead of hydronium ions leading to the formation of HO• hydroxyl radical.

Après la découverte des rayonnements ionisants et leurs effets chimiques, il était important d’étudier et de comprendre les mécanismes de formations des radicaux libres et des produits moléculaires caractérisés par leurs courtes durées de vie. Ceci a encouragé les groupes de recherches à développer leurs outils pour qu’ils puissent réaliser ces études. De nos jours la radiolyse impulsionnelle se manifeste comme un outil fondamental permettant de sonder les effets chimiques ainsi que les mécanismes réactionnels dans le milieu étudié.Le laboratoire de Chimie Physique d’Orsay « LCP » est un laboratoire interdisciplinaire abritant la plateforme « ELYSE » qui est un centre de cinétiques rapides. Grâce au laser femtoseconde et à l’accélérateur d’électrons picoseconde, nous avons eu la possibilité, dans le domaine de la radiolyse, de remonter en temps, en étudiant les effets chimiques dans un milieu réactionnel, jusqu’à ~ 5 ps.Nous nous sommes intéressés par les réactions primaires induites par les rayonnements ionisants en solution et ELYSE représentait l’outil principal pour ces études. Les résultats obtenus concernent :- La détermination directe du rendement radiolytique du radical hydroxyle « HO• » en fonction du temps à l’échelle de la picoseconde ;- Etude de l’effet direct du rayonnement ionisant sur les solutions aqueuses concentrées ainsi que la vérification de la réaction de transfert d’électron ultrarapide entre le soluté et le trou positif « H2O•+ » issu lors de la radiolyse de l’eau ;- Etude à température ambiante de la réaction de transfert d’électron entre un électron solvaté (donneur d’électron) et un soluté organique (accepteur d’électron) en milieu visqueux ;- Etude à température ambiante de la solvatation de l’électron dans l’éthylène glycol et dans le propan-2-ol. / Following the discovery of ionizing radiations and their chemical effects, it was important to study and comprehend the formation mechanisms of short lived free radicals and molecular products. In order to perform such studies, researchers and research groups worked on developing tools allowing both formation and detection of those species at short time scales. Nowadays, pulse radiolysis imposed itself as a fundamental and efficient tool allowing scientists to probe chemical effects as well as reaction mechanisms in studied media.The laboratoire de Chimie Physique d’Orsay “LCP” is an interdisciplinary laboratory hosting the platform of fast kinetics known as “ELYSE”. Due to its femtosecond laser and its picosecond electron accelerator, we have the possibility to study chemical effects of ionizing radiations interaction with media at ultrashort times up to ~5 ps.Knowing that we are interested in primary reactions induced in aqueous media by ionizing radiations, ELYSE represents the essential tool in performing our studies. The obtained results concern:- First direct determination of hydroxyl radical “HO•” radiolytic yield as function of time at picosecond time scale ;- Direct effect of ionizing radiation in highly concentrated aqueous solutions as well as investigation of the ultrafast electron transfer reaction between solute molecules and positive holes “H2O•+” formed upon water radiolysis ;- Study at room temperature of electron transfer reaction between solvated electron (electron donor) and organic solutes (electron acceptors) en viscous medium ;- Study at room temperature of electron’s solvation dynamics in ethylene glycol and 2-propanol.

Cette thèse présente une étude de la sensibilité à la physique au delà du modèle standard et en particulier aux couplages anormaux entre les photons et les bosons W. Ceci est réalisé en détectant dans ATLAS les protons intacts après interaction et en mesurant leur temps de vol avec une précision de quelques pico-secondes de part et d’autre du détecteur central.Je décrirai également les photo-détecteurs de grande superficie avec une précision de quelques pico-secondes et les algorithmes de reconstruction de temps basés sur l’échantillonnage rapide du signal. Le circuit intégré spécifique SamPic pour une mesure de temps de très haute précision sera enfin présenté ainsi que les premiers résultats de mesure avec ce circuit. Ils montrent en particulier une précision exceptionnelle, meilleure que 5 ps, sur la mesure de temps entre deux impulsions. / In this thesis, we present a study of the sensitivity to Beyond Standard Model physics brought by the design and installation of picosecond time-of-flight detectors in the forward region of the ATLAS experiment at the LHC. The first part of the thesis present a study of the sensitivity to the quartic gauge anomalous coupling between the photon and the W boson, using exclusive WW pair production in ATLAS. The event selection is built considering the semi-leptonic decay of WW pair and the presence of the AFP detector in ATLAS. The second part gives a description of large area picosecond photo-detectors design and time reconstruction algorithms with a special care given to signal sampling and processing for precision timing.The third part presents the design of SamPic: a custom picosecond readout integrated circuit. At the end, its first results are reported, and in particular a world-class 5ps timing precision in measuring the delay between two fast pulses.

Many essential processes and interactions on atomic and molecular scales occur at ultrafast timescales. The ability to measure and manipulate ultrashort pulses hold the key to probing and understanding these key processes that physicists, engineers, chemists and biologists study today. Measuring ultrashort pulses means that we measure both the intensity (which is a function of time) and the phase of the pulse in time. Or alternately we might measure spectrum and spectral phase (in the corresponding Fourier domain). In the early 1990's, the invention of FROG opened up the field of ultrashort measurement with it's ability to measure the complete pulse. Since then, there have been a whole host of pulse measurement techniques that have been invented to measure all sorts of ultrashort pulses. However, no variation of FROG nor any other fs pulse measurement technique, for that matter, has yet been able to completely measure arbitrary ultraweak femtosecond light pulses such as those found in nature. In this thesis, we will explore a couple of highly sensitive methods in a quest to measure ultraweak ultrashort pulses. We explore the use of Spectral Interferometry, a known sensitive technique as one possibility. We find that it has certain drawbacks that make it not necessarily suitable to tackle this problem. But in the course of our quest, we find that this technique is highly suitable for measuring 10s of picosecond-long shaped pulses. We discuss a couple of developments which make SI highly practical to use for such shaped pulse-measurements. We also develop a new technique which is a variation of FROG, based on the non-linearity of Difference Frequency Generation and Optical Parametric Amplification, which can amplify pulses as weak as a few hundred attojoules to be able to spectrally resolve them and measure the full intensity and phase of these pulses. This technique offers great potential to measure generalized ultraweak ultrashort pulses.

The objective of the present dissertation is to advance the science and engineering of metal-dielectric thin-film structures for ultrafast all-optical applications. The research presented consists of three parts: first, the linear and nonlinear optical (NLO) properties of Au and Ag/Au bilayer metallic thin films are comprehensively studied; then the design and properties of a novel nonlinear device structure are presented and finally an ultrafast all-optical shutter is developed and applications are discussed. In the first part, this study describes the linear and NLO properties of bilayer metallic films and shows that they can be tuned by controlling the mass-thickness ratio between Au and Ag. The combined properties of these bilayers are attractive for active plasmonic applications and nonlinear optical filters. Detailed physical models describing the linear and NLO response of Au and Ag/Au bilayers are presented and compared with experiments. In the second part, these models are used to optimize the NLO response of a novel Au-based NLO device. With only four layers, this novel device strongly amplifies the NLO response of the component Au thin film. NLO devices with broad spectral and angular bandwidths in the visible spectral region are demonstrated. The narrow band dependent NLO response of the NLO device is shown to lead to all-optical controls of high peak-power optical signal pulses. Finally, the NLO device technology is integrated into a novel ultrafast all-optical shutter, which allows temporal opening windows (the time shutter remains open) as short as a few ps. Ultrafast all-optical shutter potentially can temporally shape high peak-power nanosecond optical pulses, which could benefit biomedical and micromachining applications. Other possible optical applications such as short electron, X-ray pulse generations, ultrafast photography, and biomedical imaging will also be discussed.

Temporal pulse shaping based on integrated Bragg gratings is investigated in this work to achieve arbitrary output waveforms. The grating structure is simulated based on the sidewall-etching geometry in an AlGaAs platform. The inverse scattering employin the Gel'fan-Levithan-Marchenko theorem and the layer peeling method provides a tool to determine grating structures from a desired spectral reflection response. Simulations of pulse shaping considered flat-top and triangular pulses as well as one-to-one and one-to-many pulse shaping. The suggested grating profiles revealed a compromise between performance and grating length. The integrated grating, a few hundred microns in length, could generate flat-top pulses with pulse durations as short as 500 fs with rise/fall times of 200 fs; the results are comparable to previous work in free-space optics and fiber optics. The theories and the devised algorithms could serve as a design station for advanced grating devices for, but not restricted to, optical pulse shaping.