In several fields, such as biology, chemistry, combustion and environmental science, laser absorption spectroscopy represents an invaluable tool for the detection and identification of a variety of molecular species in the gas phase. For this detection to be quantitative, it is of paramount importance to rely on accurate spectroscopic parameters for the involved absorption lines in terms of line strength, line center frequency, pressure broadening, and pressure shift coefficients. The mid-infrared region offers the most favorable conditions for sensitive and chemically selective detection. The sensitivity derives from the presence of intense fundamental ro-vibrational transitions of molecules, whereas chemical selectivity relates to the unique absorption spectrum that molecules possess in the mid-IR region, thereby known as the fingerprint region. In this thesis, we combine the accelerating technology of optical frequency combs (OFC), which are powerful tools for accurate optical frequency measurements, with the wide tunability and single line emission in the mid-IR of extended cavity quantum cascade lasers (EC-QCL), to perform highly resolved, accurate and sensitive measurements in the fingerprint region, from 7.25 to 8 μm. Specifically, we have been able to lock for the first time the optical frequency of an EC-QCL to an OFC by utilizing nonlinear optics in the form of sum frequency generation (SFG) (Lamperti, AlSaif et al., 2018) and have exploited this comb-locked EC-QCL for an accurate survey of the entire ν1 ro-vibrational band of one of the most important greenhouse gases, nitrous oxide (N2O). The developed spectrometer is able to operate over a wide region of ~ 100 cm-1, in a fully automated fashion, while affording a 63 kHz uncertainty on the retrieved line center frequencies. The measurement allowed us to determine very accurately rotational constants of both ground and excited states of the ν1 band of N2O through the measurements of tens of lines of the P and R branches (AlSaif et al., JQSRT 2018). The spectrometer was then upgraded with a more recent and narrower linewidth EC-QCL to perform sub-Doppler saturated spectroscopy on the same N2O sample at a spectral resolution below 1 MHz, the sharpest ever observed with this type of laser. Finally, we worked at adding high sensitivity to the apparatus by introducing the gas in a high-finesse passive resonator and by developing a system to measure the intra-cavity absorption with cavity ring-down spectroscopy (CRDS) together with comb calibration.

La mise au point de capteurs optiques moyen infrarouge (MIR) pour la surveillance des polluants organiques dans l'environnement aquatique est actuellement un défi de grande importance. Les capteurs MIR basés sur la spectroscopie à ondes évanescentes sont des outils d'analyse prometteurs pour la détection et la quantification simultanées d'une variété de polluants tels que les composés hydrocarbonés. Les verres de chalcogénure sont particulièrement bien adaptés aux applications de détection en raison de leur large domaine de transparence (jusqu'à 10-16 µm en fonction de leur composition). Ainsi, des films minces de chalcogénure pour le développement de plates-formes optiques intégrées ont été synthétisés. Leur fonctionnalisation par des polymères afin d'augmenter la sensibilité des capteurs a également été réalisée. Parmi les compositions de verre (GeSe2)100-x(Sb2Se3)x, deux cibles en verre séléniure ont été choisies pour leurs propriétés optiques et physiques. Grâce à la spectroscopie de réflexion totale atténuée, des mesures ont été effectuées dans l'eau pour détecter les hydrocarbures aromatiques (benzène, toluène et les trois isomères du xylène) dans des concentrations comprises entre 250 ppb et 40 ppm. Des mesures de détection ont également été effectuées à l'aide d'eau de mer et d'eau souterraine. Pour augmenter leur sensibilité, l'utilisation de nanoparticules métalliques est l'une des solutions prometteuses basées sur l'absorption infrarouge améliorée en surface (SEIRA). Ainsi, des structures hybrides combinant nanoparticules d'or déposées sur des verres de chalcogénure ont été fabriquées et caractérisées. / The development of middle-infrared (MIR) sensors for organic pollutants monitoring in the aquatic environment is currently a challenge of great importance. The mid-infrared sensor based on evanescent wave spectroscopy is a promising analytical tool for simultaneous detection and quantification of a variety of pollutants such as hydrocarbon compounds. Chalcogenide glasses are particularly well adapted for sensing applications due to their wide domain of transparence (up to 10-16 µm depending on their composition). The aims of this study are to synthetize chalcogenide thin films for developing mid-infrared optical integrated platforms and perform their functionalization with polymers in order to increase the sensor sensitivity. Among (GeSe2)100-x(Sb2Se3)x glass compositions, two selenide glass targets were chosen for their optical and physical properties. Thanks to attenuated total reflection spectroscopy, measurements were performed in water to detect aromatic hydrocarbons (benzene, toluene and the three xylene isomers) in the concentrations range of 25 ppb to 10 ppm. Detection measurements have also been fulfilled using seawater and ground-water. To increase their sensitivity, the use of metallic nanoparticles is one of the promising solutions based on Surface Enhanced Infrared Absorption (SEIRA). Thus, hybrid structures combining gold nanoparticles/chalcogenide glass and waveguides were fabricated and characterized.

Le développement de capteurs optiques fonctionnant dans le moyen infrarouge est un enjeu majeur pour détecter les (bio-) molécules. En effet, le moyen infrarouge (4000 - 400 cm-1) contient une grande majorité des absorptions dues aux vibrations des molécules organiques. L'objectif de ces travaux de recherche est d'élaborer des capteurs plus sélectifs, plus sensibles et plus compacts. Les travaux de recherche présentés dans ce manuscrit concernent donc le développement de guides d'ondes optiques à base de verre de chalcogénure sensibles aux molécules cibles via l'absorption de la partie évanescente de la lumière guidée se propageant à la surface du guide. La synthèse des matériaux infrarouges est l'une des étapes clés. Les verres de chalcogénures sont des matériaux particulièrement appropriés pour cette application de détection de polluants. Ces verres présentent un large domaine de transparence dans l'infrarouge (2 - 15 µm pour les verres à base de sélénium) et des indices de réfraction élevés (entre 2 et 3). L'élaboration du guide d'onde nécessite la fabrication de couches minces de verre de chalcogénure par pulvérisation cathodique RF magnétron. Afin de maîtriser le développement du micro-capteur infrarouge, un plan d'expériences a été élaboré pour étudier l'influence des paramètres de dépôt sur les caractéristiques des couches minces. L'architecture du guide a été définie et réalisée par gravure RIE-ICP (gravure ionique réactive couplée au procédé de gravure plasma à couplage inductif) et les mesures de pertes optiques et d'injection dans le MIR (6,3 µm et 7,8 µm) ont été réalisées. Il s'agit des tous premiers guides fonctionnant aussi loin dans le moyen infrarouge. L'ultime étape consiste à fonctionnaliser la surface du guide augmenter sa sélectivité. Des premiers tests ont été réalisés sur un cristal ATR en ZnSe par un polymère hydrophobe. Ils ont permis la détection de molécules polluantes absorbant à 13,8 µm, présentes en très faible concentration (25 ppb) dans des solutions d'hydrocarbures (BTX) ou des eaux plus complexes (eaux de station d'épuration et eaux souterraines). / Development of mid-IR optical sensors is a challenge of great importance for detection of biochemical molecules. Mid-infrared range (4000-400 cm-1) contains the absorptions related to the vibrations of organic molecules. The aim of this work is the elaboration of sensors more selective, sensitive and compact. The work reported in this thesis concerns the development of optical waveguides based on chalcogenide glasses. The evanescent field is used for the detection of pollutant molecules diffusing to the surface of optical waveguide. One of the main step of this research is the synthesis of infrared material. Chalcogenide glasses are appropriate for sensing applications. Indeed, they are used for their wide transparency in the infrared range (2 – 15 µm for selenide glasses) and their high refractive index (between 2 and 3). Elaboration of optical waveguide requires fabrication of chalcogenide thin films by RF magnetron sputtering. In order to control the development of infrared micro-sensor, an experimental design was established to study the influence of sputtering parameters on thin films characteristics. Design of the optical waveguide was defined and etched by RIE-ICP (reactive ion etching-inductively coupled plasma). Measurement of optical losses and injection in mid-infrared (7,8 µm) were realized. This is the first optical waveguides working as far in the mid-infrared. The last step concerns the functionalization of surface waveguides in order to increase their selectivity. First tests were realized on ZnSe ATR prism with a hydrophobic polymer. Thus, detection of pollutant molecules absorbing at 13,8 µm, with very low concentrations (25 ppb), in hydrocarbons solutions (BTX) or in complex water (water purification plant and groundwater) was performed.

This thesis discusses a new scheme for generating radiation in the mid infrared spectral region, especially the 3.5-5 µm range. The scheme uses established Nd3+-lasers at 1.06 µm and down conversion in nonlinear optical crystals. The down conversion is made by two optical parametric oscillators (OPO) in series. The second OPO is a classical OPO using a zink germanium phosphide (ZGP) crystal. ZGP is the best nonlinear material available for the 4-8 µm spectral range, but it is absorbing below 2 µm. The new development presented in this thesis is the OPO used to convert the 1.06 µm laser radiation to a suitable OPO pump near 2 µm. The OPO uses a type I quasi phase-matched crystal, which accesses high nonlinearities and avoids walk-off. The problem with type I OPOs close to degeneracy is the broad bandwidth of the generated radiation, which reduces the efficiency of a second OPO. This has been solved with a spectrally selective cavity using a volume Bragg grating output coupler. Unlike other bandwidth limiting schemes this introduces no intracavity losses and thus efficient OPO operation is achievable. Narrow linewidth (~0.5 nm) OPO operation has been achieved with periodically poled LiNbO3 (PPLN) and periodically poled KTiOPO4 (PPKTP) while locking the signal wavelength at 2008 nm and simultaneously generating an idler at 2264 nm. A high average power PPLN OPO with 36 % conversion efficiency and 47 % slope efficiency is reported. Operation very close to degeneracy at 2128 nm with the narrowband signal and idler peaks separated by 0.6 nm was demonstrated in a PPKTP OPO. Both the signal at 2008 nm and the combined signal and idler around 2128 nm from the PPKTP OPOs have been used to show efficient pumping of a ZGP OPO. The maximum conversion efficiency from 1 µm to the mid-IR demonstrated is 7 % with a slope efficiency of 10 %. This is not quite as high as what has been presented by other authors, but the experiments reported here have not shown the optimum efficiency of the new scheme. Relatively simple improvements are expected to give a significant increase in conversion efficiency. / QC 20101108

Silicon photonics has been a rapidly growing subfield of integrated optics and optoelectronic in the last decade and is currently considered a mature technology. The main thrust behind the growth is its compatibility with the mature and low-cost microelectronic integrated circuits fabrication process. In recent years, several active and passive photonic devices and circuits have been demonstrated on silicon. Optical delay lines are among important silicon photonic devices, which are essential for a variety of photonic system applications including optical beam-forming for controlling phased-array antennas, optical communication and networking systems and optical coherence tomography. In this thesis, several types of delay lines based on apodized grating waveguides are proposed and demonstrated. Simulation and experimental results suggest that these novel devices can provide high optical delay and tunability at very high bit rate. While most of silicon photonics research has focused in the near-infrared wavelengths, extending the operating wavelength range of the technology into in the 3–5 µm, or the mid-wave infrared regime, is a more recent field of research. A key challenge has been that the standard silicon-on-insulator waveguides are not suitable for the midinfrared, since the material loss of the buried oxide layer becomes substantially high. Here, the silicon-on-sapphire waveguide technology, which can extend silicon’s operating wavelength range up to 4.4 µm, is investigated. Furthermore, silicon-on-nitride waveguides, boasting a wide transparent range of 1.2–6.7 μm, are demonstrated and iv characterized for the first time at both mid-infrared (3.39 μm) and near-infrared (1.55 μm) wavelengths.

Die einzigartige (bio)-chemische Spezifität der mittleren Infrarotmikroskopie birgt ein enormes Potential für eine breite Palette biomedizinischer und industrieller Anwendungen. Eine wesentliche Einschränkung ergibt sich jedoch durch die unzureichenden Detektionsmöglichkeiten in diesem Wellenlängenbereich, da derzeitige Mittelinfrarot-Detektoren meist durch geringere Leistungsfähigkeit bei deutlich höheren Anschaffungskosten gekennzeichnet sind. Dementsprechend verlagern neuentwickelte Technologien mitunter die Detektion in den sichtbaren Spektralbereich, in dem eine weitaus bessere, Silizium-basierte Kameratechnologie verfügbar ist. Ein solches Verfahren, das im Mittelpunkt dieser Arbeit steht, ist die Quantenbildgebung mit undetektiereten Photonen, welche sich zunehmend als leistungsfähiges Werkzeug für Infrarot-Bildgebung entwickelt. Der optische Aufbau basiert auf nichtlinearer Interferometrie bei der räumlich verschränkte, nicht-entartete Photonenpaare die Entkopplung der Analyse- und Detektionswellenlängen ermöglicht. Entsprechend wird die Bildgebung im mittleren Infrarotbereich durch die Detektion von Nahinfrarotlicht mit einer handelsüblichen CMOS-Kamera realisiert. In dieser Arbeit wird die beschriebene Methode auf die Mikroskopie übertragen, wodurch Abbildungen biologischer Gewebeproben im mittleren Infrarotbereich mit einer Auflösung von geringer als 10 Mikrometer angefertigt werden können. Darüber hinaus werden zwei Abbildungsregime untersucht, die auf den komplementären Impuls- und Positionskorrelationen der Photonenpaare basieren. Weiterführende Möglichkeiten der Kombination von Quanten-Bildgebung mit unentdeckten Photonen und FTIR-Spektroskopie zum Zwecke der räumlich-spektral kontinuierlichen Datenerfassung werden besprochen. Die vorgestellten Ergebnisse stellen die Entwicklungsfähigkeit der Quantenbildgebung mit unentdeckten Photonen unter Beweis und demonstrieren ihr Potential für praxisnahe Anwendungen in der Biomedizin und der Industrie. / The unique (bio)-chemical specificity of mid-infrared (IR) microscopy holds tremendous promise for a wide range of biomedical and industrial applications. Significant limitation, however, arises from poor detection capabilities in this wavelengths range, with current mid-IR detection technology often marrying inferior technical capabilities with prohibitive costs. Accordingly, emerging approaches shift detection into the visible regime, where vastly superior silicon-based camera technology is available. One such technique, and the one that is in the center of this thesis is quantum imaging with undetected photons (QIUP), which has recently emerged as a new powerful imaging tool. The optical layout is based on nonlinear interferometry, where spatially entangled non-degenerate photon pairs enable the decoupling of the sensing and detection wavelengths, facilitating mid-IR wide-field imaging through the detection of near-IR light with an off-the-shelf CMOS camera. Additionally, the method is expanded towards microscopy, attaining sub-10 μm resolution, demonstrating our technique is fit for purpose, acquiring microscopic images of biological tissue samples in the mid-IR. Additionally, two imaging regimes are explored, based on the complementary momentum and position correlations. A comparison between the two regimes is presented and some limitations of the technique are discussed. Further efforts of combining QIUP with Fourier Transform IR spectroscopy for spatio-spectral continuous data acquisition are reviewed. The presented results demonstrate the achieved progress towards advancing QIUP to enable real-world biomedical as well as industrial imaging applications.

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