Dual-comb spectroscopy (DCS) has widespread applications. It has become a more prominent spectroscopic tool because it has broad spectral coverage with high frequency resolution. We demonstrate the broadband and high resolution of DCS to probe transient events, showing the rst use of DCS of laser-induced plasmas (LIPs). Our measurements span absorption features 7 THz wide, simultaneously detecting Rb D2, K D1 and D2 absorption lines with the ability to resolve the isotope ratios in the Rb D2 line. This technique is more broadband and faster than tunable laser absorption spectroscopy because it eliminates the requirement to scan across transitions. Additionally, DCS makes higher resolution measurements than laser-induced break- down spectroscopy. Our ultimate goal is to use DCS as a technique to ascertain the chemical composition of unknown samples. Our rst demonstration of this technique illustrates that DCS makes broadband, high-resolution measurements with the ability to measure isotope ratios, which is necessary for determining sample composition.

En plus de 40 ans d’existence, la spectroscopie de Fourier, basée sur l’interféromètre de Michelson,a permis des progrès considérables dans notre connaissance de la structure des atomes et des molécules s’imposant peu à peu comme un outil de base pour le diagnostic optique. Aujourd’hui, dépasser ses performances en terme de limite de résolution, rapidité, sensibilité et exactitude permettrait de répondre à de nouveaux enjeux. Cette thèse porte sur le développement expérimental de la spectroscopie de Fourier par peignes de fréquences femtosecondes. Deux peignes de fréquences, lasers composés de centaines de milliers de raies fines dont la position est parfaitement contrôlée, sondent l’échantillon et la transformation de Fourier de leurs interférences temporelles fournit le spectre. Trois dispositifs basés sur des lasers femtosecondes à fibres dopées (à 1 μm et 1.5 μm) ou à solides (à 2.4 μm) illustrent les performances de la méthode. Par comparaison à la spectroscopie de Fourier traditionnelle, les temps de mesure ont été réduits de la seconde à la microseconde, pour des spectres de molécules en phase gazeuse couvrant une centaine de nanomètres à des limites de résolution du GHz. La sensibilité atteint celle des spectromètres par laser accordable les plus performants grâce à des méthodes de détection différentielle ou d’utilisation de cavités multipassages ou résonnantes. Augmenter le temps de mesure et résoudre les raies individuelles du peigne permet une spectroscopie de précision à large bande spectrale, car la fréquence absolue de chaque raie de peigne peut être connue avec l’exactitude d’une horloge atomique. / For four decades, Fourier transform spectroscopy has greatly improved our atomes and molecules structures knowledges, and thus became a widely used tool for optical diagnosis. However, today it is useful to overcome some of its limitations in order to address new challenges. This thesis is about experimental developpement concerning frequency comb fourier transform spectroscopy. Two frequency combs, made of thousands of very narrow frequency lines perfectly known and controlled, are probing an absorbing sample. The fourier transform of their temporal interference pattern provides the optical spectrum. Three devices based on fiber doped lasers (emitting at 1μm and 1.5 μm) and solid lasers (at 2.4 μm) are used to demonstrate the method advantages. Compared to traditional Fourier transform spectroscopy the recording time has shrunk by one million for the acquisition of spectra spreading on a hundred of nanometers at GHz resolution. Using multipass cells of differential detection devices, the sensitivity reached is comparable to that provided by the most efficient laser based methods. Increasing the resolution allows for clear observation of the comb individual tooth which position can be measured with the accuracy of an atomic clock, providing thus a simple and accurate method for auto calibrated spectra.

La spectroscopie par transformation de Fourier par peignes de fréquences femtosecondes tire parti d’un interféromètre sans partie mobile. Il mesure les interférences entre deux peignes de fréquences, sources lasers à large bande spectrale constituée de raies fines et équidistantes. Il améliore significativement le temps de mesure et la limite de résolution spectrale des spectromètres de Fourier. Néanmoins, les conditions sur la stabilité à court terme des peignes ne peuvent pas être remplies par les techniques d’asservissement classique. Jusqu’à présent, aucun spectre de qualité n’a pu être mesuré avec un très faible temps d’acquisition. Cette thèse présente le développement d’une méthode de correction en temps réel capable de compenser les fluctuations résiduelles des peignes et de restituer des spectres sans artefacts. La méthode, analogique, ne nécessite aucun asservissement ou traitement informatique a posteriori. Ses performances sont démontrées dans le proche infrarouge (1,5 µm) et le visible (520 nm), à l’aide d’oscillateurs femtosecondes fibrés. Des spectres moléculaires couvrant 12 THz sont mesurés en 500 µs à limite de résolution Doppler. Ils sont en excellent accord avec les données de la littérature. Pour la première fois, le plein potentiel de la spectroscopie de Fourier par peignes de fréquences est démontré. Le domaine de l’infrarouge moyen est la région de prédilection de la spectroscopie moléculaire car la plupart des molécules y présentent des absorptions fortes et caractéristiques. Étendre la spectroscopie par peignes de fréquences à cette région est donc l’objectif suivant à atteindre. Dans cette optique, un peigne émettant autour de 3 µm est caractérisé. Il est basé sur la conversion non-linéaire par différence de fréquences d’un oscillateur à erbium élargi spectralement par une fibre fortement non-linéaire. / Dual-comb Fourier-transform spectroscopy takes advantage of an interferometer without moving parts. Interferences pattern between two femtosecond frequency combs, broadband laser sources whose spectra consist of evenly-spaced narrow lines, is measured. The measurement time and the spectral resolution are significantly improved compared to traditional Fourier spectrometers. However, the required short-term stability of the combs cannot be achieved by classic locking methods. Until now, no high-quality spectra could be recorded within a very short acquisition time. This thesis reports on the development of a real-time correction method able to compensate for the combs’ residual fluctuations and to restore non-distorted spectra. This analog technique does not require any locking system or a posteriori calculation. Its performance is demonstrated in the near-infrared (1.5 µm) and in the visible (520 nm) with fiber-based femtosecond lasers. Doppler-limited molecular spectra spanning 12 THz are measured within 500 µs. They are in excellent agreement with databases. For the first time, the full potential of dual-comb spectroscopy is demonstrated. The mid-infrared region is an attractive spectral range for molecular spectroscopy due to the molecules’ strong and characteristic absorptions. Therefore, extending dual-comb spectroscopy to this region is the next goal to achieve. Toward this goal, a comb emitting around 3 µm is characterized. It is based on the non-linear difference frequency generation from an erbium oscillator spectrally broadened with a highly non-linear fiber.

<p dir="ltr">The beautiful complexity of our world is manifested in how macro- and even planetary-scale processes are essentially completely determined and regulated by chemical and physical transformations happening at the micro- and nanoscale. The introduction and subsequent development of optical microscopy methods have provided us with a unique opportunity to visualize, probe, and sometimes even control these processes that are too small to be seen by the human eye by their nature.</p><p dir="ltr">Among the great variety of truly impressive advances in microscopy instrumentation, two techniques stand out in their widespread and usefulness. First of them, fluorescence imaging has completely revolutionized the study of biological specimens and living systems due to its unprecedented single-molecule sensitivity and resolution combined with video-rate imaging capability. On the other hand, chemical imaging in the mid-infrared region provides an unmatched amount of chemical information enabling label-free mapping of the spatial distribution of various classes of biological molecules. However, each of these techniques falls short where the other excels. For example, despite its high resolution and sensitivity, fluorescence imaging does not carry direct chemical information and relies on labeling specificity, while infrared microscopy is diffraction-limited at the resolution of several micrometers and suffers from low penetration depth in aqueous solutions.</p><p dir="ltr">This dissertation introduces a novel imaging method designed to combine the advantages of fluorescence imaging and infrared spectroscopy. Fluorescence-detected photothermal mid-IR (F-PTIR) microscopy is presented in <b>chapter 1</b> as a technique enabling sub-diffraction chemically-specific microscopy by detecting local temperature-induced fluctuations in fluorescence intensity to inform on localized mid-infrared absorption. F-PTIR applications in targeted biological microspectroscopy (<b>chapter 1</b>) and pharmaceutical materials (<b>chapters 2 and 3</b>) analysis are demonstrated to highlight the potential of this new method. Furthermore, instrumentation developments relying on modern radiation sources such as dual-comb quantum cascade laser and synchrotron infrared radiation are shown to improve spectral acquisition speed (<b>chapter 4</b>) and spectral coverage (<b>chapter 5</b>), respectively, to extend the application range of F-PTIR.</p>