Noise-immune cavity-enhanced optical heterodyne molecular spectro-metry (NICE-OHMS) is one of the most sensitive laser-based absorption techniques. The high sensitivity of NICE-OHMS is obtained by a unique combination of cavity enhancement (for increased interaction length with a sample) with frequency modulation spectrometry (for reduction of noise). Moreover, sub-Doppler detection is possible due to the presence of high intensity counter-propagating waves inside an external resonator, which provides an excellent spectral selectivity. The high sensitivity and selectivity make NICE-OHMS particularly suitable for trace gas detection. Despite this, the technique has so far not been often used for practical applications due to its technical complexity, originating primarily from the requirement of an active stabilization of the laser frequency to a cavity mode. The main aim of the work presented in this thesis has been to develop a simpler and more robust NICE-OHMS instrumentation without compro-mising the high sensitivity and selectivity of the technique. A compact NICE-OHMS setup based on a fiber laser and a fiber-coupled electro-optic modulator has been constructed. The main advantage of the fiber laser is its narrow free-running linewidth, which significantly simplifies the frequency stabilization procedure. It has been demonstrated, using acetylene and carbon dioxide as pilot species, that the system is capable of detecting relative absorption down to 3 × 10-9 on a Doppler-broadened transition, and sub-Doppler optical phase shift down to 1.6 × 10-10, the latter corresponding to a detection limit of 1 × 10-12 atm of C2H2. Moreover, the potential of dual frequency modulation dispersion spectrometry (DFM-DS), an integral part of NICE-OHMS, for concentration measurements has been assessed. This thesis contributes also to the theoretical description of Doppler-broadened and sub-Doppler NICE-OHMS signals, as well as DFM-DS signals. It has been shown that the concentration of an analyte can be deduced from a Doppler-broadened NICE-OHMS signal detected at an arbitrary and unknown detection phase, provided that a fit of the theoretical lineshape to the experimental data is performed. The influence of optical saturation on Doppler-broadened NICE-OHMS signals has been described theoretically and demonstrated experimentally. In particular, it has been shown that the Doppler-broadened dispersion signal is unaffected by optical saturation in the Doppler limit. An expression for the sub-Doppler optical phase shift, valid for high degrees of saturation, has been derived and verified experimentally up to degrees of saturation of 100.

Cette thèse contribue à la compréhension fondamentale du phénomène de couplage fort de la lumière avec des molécules organiques en mettant en œuvre de nouveaux systèmes et de nouvelles techniques, afin d'étudier les modifications de propriétés de molécules couplées à des résonances photoniques. Nous présentons des techniques de nanofabrication avancées pour la création de grands réseaux de trous sur des métaux et de cavités de Fabry-Pérot (FP) nanofluidiques. Ces systèmes sont ensuite utilisés pour étudier, sous régime de couplage fort, les modifications des propriétés de surface et de volume de molécules organiques en phase solide et liquide. En particulier les transitions électroniques de molécules du colorant cyanine en solution liquide ont été couplées à des modes photoniques résonants de cavités FP nanofluidiques spécialement conçues. Leur couplage fort a conduit à une amélioration du rendement quantique d'émission, mettant en évidence la nature radiative des états polaritoniques. / This thesis contributes to the fundamental understanding of the phenomenon of strong coupling of light with organic molecules by implementing new systems and techniques in order to investigate property modifications of molecules coupled with photonic resonances. State-of-the-art nanofabrication techniques for the formation of large hole-array gratings in metals and nanofluidic Fabry-Perot (FP) cavities are presented. These systems were then invested to study, under strong coupling, surface and bulk properties modifications of organic molecules in the solid and liquid phase. In particular, electronic transitions of cyanine dye molecules in liquid solutions were coupled to resonant photonic modes of specially designed nanofluidic FP cavities. Their strong coupling has led to an enhancement of the emission quantum yield, highlighting the radiative nature of the associated polaritonic states.