Ce travail de thèse se concentre sur l'évaluation de la fiabilité des transistors à haute mobilité électronique (HEMT) AlGaN / GaN à grille ultra-courte sur substrat silicium dédiés aux applications de puissance à une fréquence supérieure à 40GHz. Il a été réalisé au sein des laboratoires IMS Bordeaux et IEMN Lille.Ce travail compare initialement les HEMT AlGaN / GaN réalisés par croissance MOCVD avec ceux obtenus par croissance MBE. En particulier, l'analyse électrique statique a permis d'étudier l'influence de la géométrie des dispositifs sur les performances des composants.Des tests de vieillissement accéléré ont été effectués pour évaluer la robustesse des transistors HEMTs en AlGaN/GaN à grille ultra-courte sur Si. Une méthodologie basée sur une séquence d'essais de vieillissement a été définie pour établir le diagnostic in-situ d’une dégradation statique et permanente et d’une dégradation qui se traduit par un transitoire de courant de drain au cours du chaque palier de la séquence de vieillissement. La valeur de la tension critique de dégradation à partir de laquelle le courant de drain commence à diminuer de façon significative dépend des conditions de polarisation du vieillissement, de la distance grille-drain et de la longueur de grille. De plus, l’aire de sécurité de fonctionnement de cette technologie a été déterminée. / This Ph.D. work focuses on the reliability assessment of ultra-short gate AlGaN/GaN high electron mobility transistor (HEMT) on silicon substrate dedicated to power applications at frequency above 40GHz. It was carried out within IMS Bordeaux and IEMN Lille laboratories.This work initially compares AlGaN/GaN HEMTs grown by MOCVD with those grown using MBE, through electrical characterization.In particular, the device geometry impact on the device performances has been studies by static electrical characterization.Step-stress experiments are performed to investigate reliability assessment of ultra-short gate AlGaN/GaN high electron mobility transistor (HEMT) on Si substrate. A methodology based on a sequence of step stress tests has been defined for in-situ diagnosis of a permanent degradation and of a degradation which is identified by a drain current transient occurring during each step of the ageing sequence . The same stress conditions were applied on HEMTs with different geometries. It is found no evolution of the drain current during non stressful steps. The value of the critical degradation voltage beyond which the stress drain current starts to decrease significantly is also found dependent on the stress bias conditions, the gate-drain distance and the gate length. Moreover, the safe operating area of this technology has been determined.

Contemporary laser research involves the development of spectroscopic techniques to understand the microscopic structural aspects of a simple molecular system in chemical and materials to more complex biological systems such as cells. In particular, Raman spectroscopy, which provides bond specific information, has attracted considerable attention. Further with the advent of femtosecond (fs) laser, the recent trend in the field of fs chemistry is to develop nonlinear Raman techniques that allow one to acquire vibrational structural information with both fs temporal resolution as well as good spectral resolution. Among many advanced nonlinear Raman techniques, the development of fs Stimulated Raman scattering (SRS) has gathered momentum in the recent decade due to its ability to (1) provide vibrational structural information of various system including fluorescent molecules with good signal to noise ratio and (2) circumvent the limitation imposed on the spectral resolution by the necessary pulse durations according to the energy-time uncertainty principle where ‘K’ is a constant that depends on the pulse shape) unlike in the case of fs normal resonance Raman spectroscopy. We have developed a technique named “Ultrafast Raman loss spectroscopy (URLS)” that is analogues to SRS, but is more advantageous as compared to SRS and has the potential to be an alternative if not competitive tool as a vibrational structure elucidating technique. The concept and the design of this novel technique, URLS, form the core of the thesis entitled “Ultrafast Raman Loss Spectroscopy (URLS)”. Chapter 1 lays the theoretical groundwork for ultra-short pulses and nonlinear spectroscopy which forms the heart of URLS. It presents a detailed discussion on the basis behind the elementary experimental problems associated with the ultra-short laser pulses when they travel through a medium, the characterization of these ultrashort pulses as well as various non-linear phenomena induced within a medium due to the propagation of these pulses. Chapter 2 focuses on the concept of SRS which resulted into the foundation of URLS. It illustrates the theoretical as well as the experimental aspects of SRS and demonstrates the sensitivity of SRS over normal Raman spectroscopy. Chapter 3 introduces the conceptual and the technical basis which ensued into the development of URLS while Chapter 4 demonstrates its application and efficiency over its analogue SRS. URLS involves the interaction of two laser sources, viz. a picosecond (ps) pulse and a fs white light (WL), with a sample leading to the generation of loss signal on the higher energy (blue) side with respect to the wavelength of the ps pulse unlike the gain signal observed on the lower energy (red) side in SRS. These loss signals are at least 1.5 times more intense than SRS signals. Also, the very prerequisite of the experimental protocol for signal detection to be on the higher energy side by design eliminates the interference from fluorescence, which appears on the red side. Thus, the rapid data acquisition, 100% natural fluorescence rejection and experimental ease ascertain “Ultrafast Raman Loss Spectroscopy (URLS)” as a unique valuable structure determining technique. Further, the effect of resonance on the line shape of the URLS signal has been studied which forms the subject of discussion in Chapter 5. The objective of the study is to verify whether the variation of resonance Raman line shapes in URLS could provide an understanding of the mode specific response on ultrafast excitation. It is found that the URLS signal’s line shape is mode dependent and can provide information similar to Raman excitation profile (REP) in the normal Raman studies. This information can have impact on the study of various dynamical process involving vibrational modes like structural dynamics and coherent control. Chapter 6 demonstrates the application of URLS as a structure elucidating technique for monitoring ultrafast structural and reaction dynamics in both chemical and biological systems using α-terthiophene (3T) as the model system. The objective is to understand the mechanism of the molecular structure dependent electronic relaxation of the first singlet excited state, S1, of α-terthiophene using fs URLS. The URLS data along with the ab-initio calculations indicate that the electronic transition is associated with a structural rearrangement from a non-planar to a planar configuration in the singlet manifold along the ring deformation co-ordinate. The experimental findings suggest that the singlet state decays exponentially with a decay time constant ( 1/e) of about 145 ps and this decay could be assigned to the intersystem crossing (ISC) pathway from the relaxed S1 state to the vibrationally hot triplet state, T1*. Lastly, Chapter 7 summarizes the entire thesis and presents some possible future prospects for URLS. Considering the advantages of URLS, it is proposed that URLS can be exploited [1] to determine the structure of any fluorescent/non-florescent condensed materials and biological systems with a very good spectral resolution (10- 40 cm-1); [2] to obtain the vibrational signature of weak Raman scattering molecules and vibrational modes with relatively small Raman cross-section owing to its high detection sensitivity with good signal to noise ratio; [3] for performing fs time-resolved study by introducing an additional fs pulse for photo-excitation of the molecule and using URLS to probe the excited state dynamics with good temporal (fs) and spectral (10-40 cm-1) resolution; and lastly, [4] the high chemical selectivity of URLS and the fact that the signal is generated only within the focal volume of the lasers where all the beams overlap can be utilized for developing this method into a microscopy for labeled-free effective vibrational study of biological samples. Consequently, it is hoped that this technique, “Ultrafast Raman Loss Spectroscopy (URLS)”, would be a suitable alternative to other nonlinear Raman methods like coherent anti-Stokes Raman spectroscopy (CARS) that has made major inroads into biology, medicine and materials.

Das Ziel der vorliegenden Arbeit ist es, nanokristalline und laserpuls-strukturierte Elektroden für die alkalische Wasserelektrolyse zu untersuchten und hinsichtlich ihrer elektrokatalytischen Eigenschaft zu bewerten. Dabei besteht die Hauptaufgabe in der Aufklärung der Zusammenhänge zwischen der elektrokatalytischen Aktivität und der Struktur der Elektroden. Es soll der Effekt der nanokristallinen Kristallstruktur auf die Elektrodenaktivität aufgeklärt werden. Zudem stellt die elektrokatalytische Wirkung von Mo in Ni-Elektroden für die Wasserstoffentwicklungsreaktion eine zentrale Untersuchung in der vorliegenden Arbeit dar. Für die Sauerstoffentwicklungsreaktion soll der Einfluss von Fe in nanokristallinen Ni-Materialien näher analysiert und unter industriell relevanten Betriebsbedingungen bewertet werden. Zum anderen richtet sich der Fokus auf die Nutzung eines Ultrakurzpulslasers zur Strukturierung von Ni-Elektrodenoberflächen. Besonderes Augenmerk wird auf die Korrelation zwischen den individuellen Strukturmerkmalen, der erzielten Oberflächenvergrößerung und der elektrokatalytischen Aktivität bezüglich der Wasserstoffentwicklung gelegt. Zudem werden Langzeituntersuchungen bei Stromdichten von bis 1 A/cm² durchgeführt, um die Stabilität zu bewerten und Degradationsmechanismen aufzuklären.

PFAS are anthropogenic substances used in many different industrial operations and products because of their unique properties. Due to their negative impact on human health and environmental bioaccumulative characteristics different authorities have addressed the issue. In Sweden the limit is4 ng/L for four different PFAS in drinking water. Another risk to human health is elevated concentrations of toxic elements, causing Sweden to include them in the drinking water regulations withlimits such as 5 µg/L for arsenic, 25 µg/L for chromium and 5 µg/L for lead.This study is a continuation of an investigation for PFAS remediation in contaminated water by sorption to pine and spruce bark. The earlier study was a laboratory scale and implied that pine and spruce have some sorption capacity for long-chain PFAS. In this study pine and spruce bark were used as sorbent at an industrial site. The analysis was performed by weak-anion exchange extraction followed bysupercritical fluid chromatography coupled with a tandem mass spectrometer (SFC-MS/MS) and liquid chromatography coupled with tandem mass spectrometer (LC-MS/MS) for instrumental analyses of target ultra-short-chain PFAS, short- and long chain PFAS and branched PFOS isomers. An elemental analysis was executed with inductively coupled plasma mass spectrometry. The obtained results indicated removal for certain long-chain PFAS, potential for sorption of a specific ultra-short-chain PFAS and the elemental analysis implied some reduction of the chromium concentrations.

<p dir="ltr">Manganese (Mn) is an essential trace element for humans that functions primarily as a coenzyme in several biological processes such as nerve and brain development, energy metabolism, bone growth and development, as well as cognitive functioning. However, overexposure to environmental Mn via occupational settings or contaminated drinking water can lead to toxic effects on the central nervous systems and cause a Parkinsonian disorder that features symptoms such as fine motor control deficits, dystonia rigidity, speech and mood disturbances, and cognitive deficits summarized under the term “manganism”. Over time, Mn exposure has shifted from acute, high-level instances leading to manganism, to low-level chronic exposure. Considering that Mn exposure is significantly lower than in the past, it is unlikely to expect manganism from chronic Mn exposure under current working conditions. Therefore, there is a need to develop sensitive methods to aid in updating the clinical diagnostic standards for manganism and Mn neurotoxicity as chronic exposure to Mn leads to more subtle symptoms.</p><p><br></p><p dir="ltr">Historically, magnetic resonance imaging (MRI) has been used as a non-invasive tool for detecting excess brain Mn accumulation. Specifically, T1-weighted images show bilateral hyperintensities of the globus pallidus (GP) due to the paramagnetic properties of Mn which increases the MR relaxation rate R1. Although the GP is considered the hallmark of excess brain Mn, this brain area is not necessarily associated with symptoms, exposure, or neuropsychological outcomes. Thus, the focus should not be on the GP only but on the entire brain. With recent advances in quantitative MRI (qMRI), whole brain mapping techniques allow for the direct measurement of relaxation rate changes due to Mn accumulation. The work in this dissertation uses such quantitative techniques and network science to establish novel computational in vivo imaging methods to a) visualize and quantify excess Mn deposition at the group and individual level, and b) characterize the toxicokinetics of excess brain Mn accumulation and the role of different brain regions in the development of neurotoxicity effects.</p><p><br></p><p dir="ltr">First, we developed a novel method for depicting excess Mn accumulation at the group level using high-resolution R1 relaxation maps to identify regional differences using voxel-based quantification (VBQ) and statistical parametric mapping. Second, we departed from a group analysis and developed subject-specific maps of excess brain Mn to gain a better understanding of the relationship between the spatial distribution of Mn and exposure settings. Third, we developed a novel method that combines network science with MRI relaxometry to characterize the storage and propagation of Mn and Fe in the human brain and the role of different brain regions in the development of neurotoxic effects. Lastly, we explore the application of ultra-short echo (UTE) imaging to map Fe content in the brain and compare it against R2* and quantitative susceptibility mapping (QSM).</p><p><br></p><p dir="ltr">Overall, this dissertation is a successful step towards establishing sensitive neuroimaging screening methods to study the effects of occupational Mn exposure. The individual Mn maps offer great potential for evaluating personal risk assessment for Mn neurotoxicity and allow monitoring of temporal changes in an individual, offering valuable information about the toxicokinetics of Mn. The integration of network science provides a holistic analysis to identify subtle changes in the brain’s mediation mechanisms of excess metal depositions and their associations with health outcomes.</p>

Un des problèmes à résoudre lors de la réalisation d'un endoscope non linéaire pour des applications biomédicales concerne la propagation d'impulsions ultra courtes dans une fibre optique. Les processus non linéaires concernés nécessitent de grandes puissances d'excitation, réalisables seulement pour des impulsions de très courte durée qui sont déformés et allongés par la dispersion et les non linéarités des fibres. La plupart des techniques d'illumination fibrées pour la microscopie non linéaire emploient des systèmes de pré-compensation pour neutraliser les effets de ces phénomènes. Dans ce travail, nous explorons les possibilités offertes par la formation de solitons de grande énergie dans une fibre à bandes interdites photoniques à coeur solide. Les solitons optiques ont la propriété de conserver leur forme lors de leur propagation, et leur durée reste proche de la valeur minimum définie par la limite physique imposée par leur largeur spectrale, sans avoir besoin de recourir à un système de pré-compensation. De plus, la longueur d'onde et le retard relatif des solitons peuvent être accordés en changeant la puissance lumineuse en entrée de fibre. Plusieurs sources de lumière ont été conçues et réalisées, pour générer de nombreux contrastes non linéaires. Des images d'échantillons biologiques ont d'abord été réalisées en tirant profit de la courte durée des solitons. Puis, des mesures d'absorption transitoire ont été menées dans une configuration pompe-sonde en contrôlant le retard des solitons dans la fibre. Enfin, un montage de CRS basé sur le principe de focalisation spectrale a été réalisé, et son utilité a été démontrée en suivant un équilibre chimique. / One of the issues that has to be overcome to realize a nonlinear endoscope for biomedical applications is the propagation of ultra-short pulses in an optical fiber. Nonlinear processes require high peak powers in the focal volume in order to generate observable signals, so the pulses should be as short as possible. This makes them sensitive to the dispersion and nonlinearities of the fibers. Most of the existing techniques of ultra-short pulses fiber-delivery rely on complex pre-compensation systems to counteract these effects. In this work, we explore the possibilities offered by the generation of high-energy solitons in a custom-built solid-core photonic bandgap fiber, for nonlinear microscopy and spectroscopy. Optical solitons preserve their shape when they propagate in a fiber, and their duration remains close to the minimum value physically allowed by their bandwidth, without the need of any pre-compensation. Moreover, the wavelength and delay of the soliton can be tuned by changing the power at the input of the fiber. Several soliton-based light sources were designed and realized, generating contrast in the most prevalent nonlinear microscopy modalities. TPEF and SHG images of biological samples were first realized by taking advantage of the short duration of the solitons. By controlling the delay of the soliton, transient absorption measurements were then realized in a pump-probe configuration. Finally, the wavelength tunability of the soliton was used to generate the Stokes beam in a CRS setup based on the spectral focusing technique. The capabilities of this scheme were demonstrated by performing CRS microspectroscopy to monitor a chemical equilibrium.

O desenvolvimento da Odontologia Restauradora culminou com a era das restaurações estéticas adesivas e da intervenção minimamente invasiva, para as quais técnicas inovadoras e materiais de última geração vêm sendo constantemente introduzidos. As técnicas conservadoras visam não somente a remoção do substrato dental cariado, mas também o preparo das paredes da cavidade para a realização da restauração adesiva. Este estudo visou avaliar a possibilidade de introdução dos lasers de pulsos ultracurtos na Odontologia Restauradora, com o intuito de suprir os requisitos básicos para a realização de uma restauração conservadora adequada. A intenção foi de manter os benefícios já conhecidos relacionados à remoção seletiva de cárie com os lasers de alta potência, bem como superar as desvantagens relacionadas às fontes lasers atualmente disponíveis para este fim, como aumento excessivo de temperatura e adesão prejudicada da superfície irradiada à resina composta. Para a melhor avaliação da interação entre os lasers de pulsos ultracurtos e o substrato dental, os experimentos foram realizados em três fases. A Fase 1 visou avaliar o efeito de diferentes comprimentos de onda (355 nm, 532 nm, 1045 nm e 1064 nm), durações de pulso (pico e femtossegundos) e protocolos de irradiação (velocidade de escaneamento da superfície, espessura do espécime, método de refrigeração e taxa de repetição de pulso) em esmalte e dentina. Para a Fase 2, os parâmetros de irradiação que apresentaram resultados mais favoráveis na Fase 1 foram analisados para relacionar o aumento de temperatura com a taxa de ablação e a eficiência de ablação para cada parâmetro. A Fase 3 teve como objetivo analisar a interface adesiva e os valores de microtração da dentina irradiada com os parâmetros selecionados e estudados na Fase 2, utilizando sistemas adesivos do tipo condicione e lave e autocondicionante com diferentes protocolos de adesão (Clearfil SE Bond com e sem Primer, Adper Single Bond com e sem condicionamento ácido). Os resultados obtidos na Fase 1 indicam que a dentina e o esmalte irradiados com lasers de femtossegundos de 1045 nm e picossegundos de 1064 nm apresentam superfície rugosa livre de carbonização. Os protocolos de irradiação selecionados mostram que a irradiação deve ser conduzida com maior velocidade de escaneamento da superfície, e não há necessidade de refrigeração durante a irradiação. Todos os parâmetros utilizados promoveram ablação seletiva do substrato dental, e apresentaram maior taxa de ablação para dentina que para esmalte. A Fase 2 permitiu observar que todos os parâmetros de irradiação selecionados não provocaram aumento de temperatura maior que 6,1 ºC para esmalte e 4,6 ºC para dentina, quando o aumento de temperatura foi aferido no lado oposto ao irradiado, em espécimes de 1 mm de espessura e sem refrigeração. Exceção foi observada para a maior potência do laser de picossegundos, para a qual a temperatura aumentou até 12 ºC em esmalte e 15 ºC em dentina. Os valores obtidos no ensaio de microtração variaram de acordo com os parâmetros de irradiação e o sistema adesivo. A adesão à dentina irradiada com lasers de pulsos ultracurtos apresentou valores de resistência adesiva semelhantes ou significantemente maiores que os obtidos nos grupos controle, para todos os parâmetros de irradiação selecionados. Os resultados obtidos neste estudo indicam que os lasers de pulsos ultracurtos apresentaram resultados favoráveis para o preparo cavitário em esmalte e dentina em relação à morfologia produzida na superfície e ao aumento de temperatura provocado durante a irradiação. A resistência adesiva à dentina irradiada foi semelhante, ou mesmo significantemente maior que a obtida nos grupos controle. Portanto, os lasers de pulsos ultracurtos são considerados uma técnica promissora para a realização de intervenção minimamente invasiva com lasers de alta potência. / The development of restorative dentistry has reached the era of esthetic adhesive restorations and minimally invasive approach, for which innovative techniques and advanced materials are constantly introduced. Conservative techniques aim not only to remove carious dental substrate, but also to prepare cavity surfaces for adhesive restoration. The main objective of this study was to evaluate the possibility of introducing ultra-short pulsed lasers in Restorative Dentistry, in attempt to fulfill the basic requirements of adequate conservative restoration, by maintaining the well-known benefits of lasers for caries removal, but also overcoming disadvantages related to current laser sources available for this purpose, such as temperature increase and damaged adhesion to resin composite. In order to better evaluate the interaction between ultra-short pulsed lasers and dental substrates, experimental procedures were divided in three phases. Phase 1 aimed to evaluate the effect of different wavelengths (355 nm, 532 nm, 1,045 nm, and 1,064 nm), pulse durations (pico and femtoseconds) and irradiation protocols (surface scanning speed, sample thickness, cooling method, pulse repetition rate) on enamel and dentin. For Phase 2, laser parameters with most favorable results in Phase 1 were evaluated to relate temperature increase to ablation rate or ablation efficiency. Phase 3 aimed to analyze adhesive interface and microtensile bond strength to dentin irradiated with the selected parameters by using etch-and-rinse and self-etch adhesive systems with different bonding protocols (Clearfil SE Bond with and without Primer, Adper Single Bond with and without acid etching). The results of Phase 1 indicate that dentin and enamel irradiated with 1,045-nm fs-laser and 1,064-nm ps-laser present a rough surface without carbonization. Irradiation should be conducted with higher scanning speed, and no additional cooling during irradiation was necessary. All parameters provided selective tissue ablation, with higher ablations rate for dentin than enamel. Phase 2 indicated that all parameters tested provoked temperature increase of up to 6.1 ºC for enamel and 4.6 ºC for dentin, when temperature increase was measured at the back side of 1-mm thick samples without cooling during irradiation, except for higher power for ps-laser, for which temperature increased up to 12 ºC for enamel and 15 ºC for dentin. Microtensile bond strength values varied according to laser parameters and adhesive systems used. Adhesion to dentin irradiated with ultra-short pulsed lasers resulted in similar or significantly higher bond strength values than control groups, for all laser parameters analyzed. Based on the results of this study, ultra-short pulsed lasers presented favorable results for cavity preparation in dentin and enamel regarding surface morphology and temperature increase. Adhesion to irradiated dentin was either similar or superior to traditional techniques. Thus, ultra-short pulsed lasers are considered a promising technique for the promotion of laser-supported minimally invasive approach.

O desenvolvimento da Odontologia Restauradora culminou com a era das restaurações estéticas adesivas e da intervenção minimamente invasiva, para as quais técnicas inovadoras e materiais de última geração vêm sendo constantemente introduzidos. As técnicas conservadoras visam não somente a remoção do substrato dental cariado, mas também o preparo das paredes da cavidade para a realização da restauração adesiva. Este estudo visou avaliar a possibilidade de introdução dos lasers de pulsos ultracurtos na Odontologia Restauradora, com o intuito de suprir os requisitos básicos para a realização de uma restauração conservadora adequada. A intenção foi de manter os benefícios já conhecidos relacionados à remoção seletiva de cárie com os lasers de alta potência, bem como superar as desvantagens relacionadas às fontes lasers atualmente disponíveis para este fim, como aumento excessivo de temperatura e adesão prejudicada da superfície irradiada à resina composta. Para a melhor avaliação da interação entre os lasers de pulsos ultracurtos e o substrato dental, os experimentos foram realizados em três fases. A Fase 1 visou avaliar o efeito de diferentes comprimentos de onda (355 nm, 532 nm, 1045 nm e 1064 nm), durações de pulso (pico e femtossegundos) e protocolos de irradiação (velocidade de escaneamento da superfície, espessura do espécime, método de refrigeração e taxa de repetição de pulso) em esmalte e dentina. Para a Fase 2, os parâmetros de irradiação que apresentaram resultados mais favoráveis na Fase 1 foram analisados para relacionar o aumento de temperatura com a taxa de ablação e a eficiência de ablação para cada parâmetro. A Fase 3 teve como objetivo analisar a interface adesiva e os valores de microtração da dentina irradiada com os parâmetros selecionados e estudados na Fase 2, utilizando sistemas adesivos do tipo condicione e lave e autocondicionante com diferentes protocolos de adesão (Clearfil SE Bond com e sem Primer, Adper Single Bond com e sem condicionamento ácido). Os resultados obtidos na Fase 1 indicam que a dentina e o esmalte irradiados com lasers de femtossegundos de 1045 nm e picossegundos de 1064 nm apresentam superfície rugosa livre de carbonização. Os protocolos de irradiação selecionados mostram que a irradiação deve ser conduzida com maior velocidade de escaneamento da superfície, e não há necessidade de refrigeração durante a irradiação. Todos os parâmetros utilizados promoveram ablação seletiva do substrato dental, e apresentaram maior taxa de ablação para dentina que para esmalte. A Fase 2 permitiu observar que todos os parâmetros de irradiação selecionados não provocaram aumento de temperatura maior que 6,1 ºC para esmalte e 4,6 ºC para dentina, quando o aumento de temperatura foi aferido no lado oposto ao irradiado, em espécimes de 1 mm de espessura e sem refrigeração. Exceção foi observada para a maior potência do laser de picossegundos, para a qual a temperatura aumentou até 12 ºC em esmalte e 15 ºC em dentina. Os valores obtidos no ensaio de microtração variaram de acordo com os parâmetros de irradiação e o sistema adesivo. A adesão à dentina irradiada com lasers de pulsos ultracurtos apresentou valores de resistência adesiva semelhantes ou significantemente maiores que os obtidos nos grupos controle, para todos os parâmetros de irradiação selecionados. Os resultados obtidos neste estudo indicam que os lasers de pulsos ultracurtos apresentaram resultados favoráveis para o preparo cavitário em esmalte e dentina em relação à morfologia produzida na superfície e ao aumento de temperatura provocado durante a irradiação. A resistência adesiva à dentina irradiada foi semelhante, ou mesmo significantemente maior que a obtida nos grupos controle. Portanto, os lasers de pulsos ultracurtos são considerados uma técnica promissora para a realização de intervenção minimamente invasiva com lasers de alta potência. / The development of restorative dentistry has reached the era of esthetic adhesive restorations and minimally invasive approach, for which innovative techniques and advanced materials are constantly introduced. Conservative techniques aim not only to remove carious dental substrate, but also to prepare cavity surfaces for adhesive restoration. The main objective of this study was to evaluate the possibility of introducing ultra-short pulsed lasers in Restorative Dentistry, in attempt to fulfill the basic requirements of adequate conservative restoration, by maintaining the well-known benefits of lasers for caries removal, but also overcoming disadvantages related to current laser sources available for this purpose, such as temperature increase and damaged adhesion to resin composite. In order to better evaluate the interaction between ultra-short pulsed lasers and dental substrates, experimental procedures were divided in three phases. Phase 1 aimed to evaluate the effect of different wavelengths (355 nm, 532 nm, 1,045 nm, and 1,064 nm), pulse durations (pico and femtoseconds) and irradiation protocols (surface scanning speed, sample thickness, cooling method, pulse repetition rate) on enamel and dentin. For Phase 2, laser parameters with most favorable results in Phase 1 were evaluated to relate temperature increase to ablation rate or ablation efficiency. Phase 3 aimed to analyze adhesive interface and microtensile bond strength to dentin irradiated with the selected parameters by using etch-and-rinse and self-etch adhesive systems with different bonding protocols (Clearfil SE Bond with and without Primer, Adper Single Bond with and without acid etching). The results of Phase 1 indicate that dentin and enamel irradiated with 1,045-nm fs-laser and 1,064-nm ps-laser present a rough surface without carbonization. Irradiation should be conducted with higher scanning speed, and no additional cooling during irradiation was necessary. All parameters provided selective tissue ablation, with higher ablations rate for dentin than enamel. Phase 2 indicated that all parameters tested provoked temperature increase of up to 6.1 ºC for enamel and 4.6 ºC for dentin, when temperature increase was measured at the back side of 1-mm thick samples without cooling during irradiation, except for higher power for ps-laser, for which temperature increased up to 12 ºC for enamel and 15 ºC for dentin. Microtensile bond strength values varied according to laser parameters and adhesive systems used. Adhesion to dentin irradiated with ultra-short pulsed lasers resulted in similar or significantly higher bond strength values than control groups, for all laser parameters analyzed. Based on the results of this study, ultra-short pulsed lasers presented favorable results for cavity preparation in dentin and enamel regarding surface morphology and temperature increase. Adhesion to irradiated dentin was either similar or superior to traditional techniques. Thus, ultra-short pulsed lasers are considered a promising technique for the promotion of laser-supported minimally invasive approach.

Dans cette thèse, nous étudions expérimentalement la génération d'impulsions carrées très énergétiques et accordable à l’échelle nanosecondes et d'impulsions ultracourtes à haute puissance moyenne de sortie dans les lasers à fibre utilisant les nanomatériaux comme absorbant saturable. Tout d'abord, puisque la dynamique des impulsions est dominée par l'interaction de la non linéarité et de la dispersion chromatique cubique de la fibre avec un mécanisme de discrimination d'intensité appelé absorbant saturable, la stabilité d'une distribution harmonique en mode verrouillé est étudiée par injection externe d'une onde continue.Enfin, nous avons utilisés des absorbant saturable à base de nanomatériaux déposés sur des tapers optiques dans les lasers à fibre pour générer des impulsions ultracourtes avec une puissance de sortie moyenne élevée. / In this thesis, we investigate experimentally the generation of high energy nanosecond tunable square pulses and high output power ultrashort pulses in fiber lasers. First, since pulse dynamics are dominated by the interaction of the fiber's cubic Kerr nonlinearity and chromatic dispersion with an intensity-discriminating mechanism referred to as a saturable absorber, the stability of a harmonic mode-locked distribution is studied by external injection of a continuous wave. Finally, we implemented nanomaterial based saturable absorbers in fiber laser configuration to generate ultrashort pulses with high average output power. Different techniques of achieving such components are explicitly detailed: ultrashort pulse generation in ring cavities where graphene and topological insulators are deposited on optical tapers to form a saturable absorber.

Cette thèse traite du contrôle et de la caractérisation de l'alignement et de l'orientation du point de vue théorique et expérimental. L'alignement d'une molécule linéaire consiste à obtenir une probabilité élevée de localisation de l'axe internucléaire symétrique autour de l'axe de polarisation du champ tandis que l'orientation privilégie un sens particulier le long du champ. L'orientation à l'aide d'impulsions bi couleur (2+1) non résonnantes est étudiée en détail et les conditions permettant d'obtenir une orientation efficace sont examinées. Un schéma bi couleur où la deuxième harmonique est en quasi-résonance avec un niveau vibrationnel de la molécule est également étudié. Cette technique présente l'avantage d'offrir un paramètre supplémentaire à savoir l'écart à la résonance qui peut être ajusté de manière à optimiser l'orientation moléculaire. Finalement une nouvelle technique expérimentale de détection de l'alignement moléculaire est présentée. Celle-ci permet une détection monocoup de l'alignement moléculaire sur une étendue temporelle jusqu'alors inégalée. / This thesis is about the control and characterisation of the alignment and orientation of molecules by ultra short laser pulses on a theoretical and experimental approach. Alignment corresponds to a symmetric angular distribution of the molecular axis peaked along the laser field axis, whereas orientation provides an asymmetric distribution favouring one spatial direction. Orientation by sudden two-colour (2+1) pulses is studied extensively for the non resonant case and conditions required for achieving significant orientation are explored. A second two-colour scheme, where the second harmonic is in quasi resonance with a vibrational level of the molecule, is also presented and discussed. The last technique has the advantage to offer the detuning of the laser frequency as an additional free parameter, which can be adjusted to enhance molecular orientation. A new experimental polarization imaging 2D technique for the detection alignment is also developed. Experimental results on single shot detection of molecular alignment achieved over an unprecedented temporal span are presented.