L’objectif de ce travail porte sur l’étude et la réalisation de résonateurs optiques à état liquide en microfluidique digitale. Les gouttes sphériques constituent des résonateurs à mode de galerie, dans lesquels la lumière peut être piégée par réflexion totale interne. A l’échelle microscopique, elles exhibent des propriétés optiques remarquables. Leurs facteurs de qualité très élevés en font notamment des objets propices à l’étude de phénomènes optiques non linéaires, tel l’effet laser, et leur confèrent un potentiel certain en spectroscopie. Par ailleurs, la microfluidique digitale, qui a trait aux systèmes multiphasiques dans des microcanaux artificiels, offre une grande liberté de manipulation des microgouttes : génération au kHz, transport, encapsulation, fusion, division, stockage, triage… Aussi, pour les laboratoires-sur-puce, le développement de ces microgouttes en cavités résonantes constitue une opportunité d’intégrer des outils d’analyse optique capables de sonder des échantillons allant du picolitre au nanolitre.Après un exposé des propriétés optiques des résonateurs à modes de galerie, ce mémoire rapporte les travaux réalisés. Une présentation des méthodes de microfabrication et du montage expérimental précède l’étude de la génération de cavités optiques liquides en dynamique. Ces cavités résonantes sont ensuite appliquées aux sources lasers microfluidiques. En particulier, un effet laser a été mis en évidence dans des microgouttes sphériques d’éthylène glycol contenant de la rhodamine 6G. Enfin, une ouverture sur des systèmes couplant microgouttes et cavités Fabry-Perot présente d’autres perspectives telles que l’analyse de gouttes passives en intravité laser ou bien la commutation rapide de la longueur d’onde d’émission de lasers microfluidiques monomodes. / The purpose of this work is to study and realize liquid state optical resonators in digital microfluidics. Spherical droplets may behave as whispering gallery mode resonators, in which light is trapped by total internal reflections. At the microscopic scale, they exhibit outstanding optical properties. Their high quality factors make them attractive for studying non-linear optical phenomena, such as lasing, and for spectroscopy. In another field of research, digital microfluidics, that deals with multiphase fluid systems in artificial microchannels, also involves microdroplets. It offers a high degree of freedom in handling microdroplets: kHz generation, transport, encapsulation, fusion, division, stockpiling, sorting… Therefore, in lab-on-chip systems, turning microdroplets into resonant microcavities constitutes an opportunity for integrating optical analysis tools that can probe picoliter to nanoliter samples.After a review of the optical properties of whispering gallery mode resonators, this thesis reports the experimental results. A presentation of the methods of microfabrication and of the experimental bench top precedes the study of the dynamic generation of liquid optical microcavities. Then, these resonant cavities are applied to microfluidic laser sources. In particular, lasing effect has been demonstrated in spherical microdroplets of ethylene glycol and rhodamine 6G. Finally, an opening towards systems that combine microdroplets and Fabry-Perot cavities presents other perspectives such as the analysis of passive droplets in laser intacavity or the capability of fast switching the output wavelength of single mode microfluidic dye lasers.

The objective of the work presented in this thesis is to implement high-Q silicon capacitive micromechanical resonators operating in the HF, VHF and UHF frequency bands. Several variations of a fully silicon-based bulk micromachining fabrication process referred to as HARPSS have been developed, characterized and optimized to overcome most of the challenges facing application of such devices as manufacturable electronic components. Several micromechanical structures for implementation of high performance capacitive silicon resonators covering various frequency ranges have been developed under this work. Design criteria and electromechanical modeling of such devices is presented. Under this work, HF and VHF resonators with quality factors in the tens of thousands and RF-compatible equivalent electrical impedances have been implemented successfully. Resonance frequencies in the GHz range with quality factors of a few thousands and lowest motional impedances reported for capacitive resonators to date have been achieved. Several resonator coupling techniques for implementation of higher order resonant systems with possibility of extension to highly selective bandpass filters have been investigated and practically demonstrated. Finally, a wafer-level vacuum sealing technique applicable to such resonators has been developed and its reliability and hermeticity is characterized.

Cavity enhanced spectroscopies (CES) are currently amongst the most sensitive spectroscopic techniques available for probing gas-phase samples, however their application to the liquid-phase has been more limited. Sensitive analysis of submicrolitre liquid samples is highly desirable, as miniaturisation allows for the reaction and analysis of scarce or expensive reagents, produces less waste, and can increase the speed of separations and reactions, whilst having a small footprint and high throughput. Absorption spectroscopy is a particularly desirable technique due to its universal, label-free nature, however its application to small volume liquid samples is hampered by the associated short absorption pathlengths, which limit sensitivity. CES improve sensitivity by trapping light within a confined region, increasing the effective pathlength through the sample. Three distinct types of optical cavity were constructed and evaluated for the purposes of making optical absorption measurements on liquid samples. The first incorporated a high optical quality flow cell into a "macrocavity" formed from two dielectric mirrors separated by 51.3 cm. Cavity losses were minimised by positioning the flow cell at Brewster's angle to the optical axis, and the setup was used to perform a single-wavelength cavity ringdown spectroscopy experiment to detect and quantify nitrite within aqueous samples. The detection limit was determined to be 8.83 nM nitrite in an illuminated volume of only 74.6 nL. Scattering and reflective losses from the flow cell surfaces were found to be the largest barrier to increased sensitivity, leading us to focus on the integration of cavity mirrors within a microfluidic flow system in the work that followed. In the second set of experiments, cavity enhanced absorption spectroscopy (CEAS) measurements were performed on Thymol Blue using custom-made microfluidic chips with integrated cavity mirrors. Unfortunately, due to the plane-parallel configuration of the mirrors and the corresponding difficulty in sustaining stable cavity modes, the results were underwhelming, with a maximum cavity enhancement factor (CEF) of only 2.68. At this point, attention was focussed toward a more well-defined cavity geometry: open-access plano-concave microcavities. The microcavities consist of an array of micron-scale concave mirrors opposed by a planar mirror, with a pathlength that is tunable to sub-nanometer precision using piezoelectric actuators. In contrast to the other experimental setups described, themicrocavities allow for optical measurements to be performed in which we monitor the change of wavelength and/or amplitude of a single well-defined cavity mode in response to a liquid sample introduced between the mirrors. In the first microcavity experiment, we used 10 μm diameter mirrors with cavity lengths from 2.238 μm to 10.318 μm to demonstrate refractive index sensing in glucose solutions with a limit of detection of 3.5 x 10^-4 RIU. The total volume of detection in our setup was 54 fL. Thus, at the limit of detection, the setup can detect the change of refractive index that results from the introduction of 900 zeptomoles (500,000 molecules) of glucose into the device. The microcavity sensor was then adapted to enable broadband absorption measurements of methylene blue via CEAS. By recording data simultaneously from multiple cavities of differing lengths, absorption data is obtained at a number of wavelengths. Using 10 μm diameter mirrors with cavity pathlengths from 476 nm to 728 nm, a limit of detection, expressed as minimum detectable absorption per unit pathlength, of 1.71 cm^-1 was achieved within a volume of 580 attolitres, corresponding to less than 2000 molecules within the mode volume of the cavity. Finally, a new prototype was developed with improved cavity finesse, a much more intense and stable light source, and improved flow design. Using a single plano-concave microcavity within the array with a cavity pathlength of 839.7 nm, and 4 μm radius of curvature mirror, absorption measurements were performed on Methylene Blue. Analysis of this data indicated a CEF of around 9270, and a limit of detection based on the measured signal-to-noise ratio of 0.0146 cm^-1. This corresponds to a minimum detectable concentration of 104 nM Methylene Blue, which given the mode volume of 219 aL, suggests a theoretical minimum detectable number of molecules of 14.

With the advent of micro and nano electromechanical systems (MEMS/NEMS), there has been rapid development in the design and fabrication of sensitive resonant sensors. Sensitivity of such devices depends on the resonant frequency and the quality factor (Q). The Q of these devices are dependent on process induced prestress in the structural geometry, interaction with the external environment, and the encapsulation method. For high frequency sensors operating in air and under encapsulation condition, the Q is dominated by structural and fluid-structure interaction losses. In this thesis, we set out to study the dominant energy dissipative mechanisms that are constituent of the experimentally observed loss (Q-factor) in two specific test geometries—uncapped and capped circular MEMS drumhead resonators. Considering the importance of various factors, we consider four important problems pertaining to the uncapped as well as capped resonators. In the first problem, the most important factors perhaps are the acoustic radiation losses emanating from the annular plate, and the effect of added mass effect on the natural frequencies of the annular plate. The second problem is to investigate the dominant contribution of squeeze film losses and acoustic radiation losses with respect to various natural frequencies of the annular plate. The third problem is to consider the effect of prestress on the natural frequencies of the annular plate and its associated fluid-structure interaction losses (quality factors due to squeeze film damping and acoustic radiation losses). The fourth problem is to study the dominant fluid-structure interaction losses and structural losses that are constituent of experimentally measured Q-factors of the encapsulated annular plate (conceptual representation of MEMS device under packaged conditions). In the first problem, we study the mode dependent acoustic radiation losses in an uncapped drumhead microresonator which is represented by a annular circular plate fixed at its outer edge, suspended over a fixed substrate. There are two main effects which are associated with such systems due to the fluid-structure interaction. First is the “added mass effect,” which reduces the effective resonance frequency of the structure. The second is the acoustic radiation loss from the top side of the resonator, that affects the quality factor of the vibrating structure. In deriving the analytical solution, we first obtain the exact mode shapes of the structure ignoring any effect of the surrounding fluid (air) on the mode shape. Subsequently, we use these mode shapes to study the effect of the surrounding fluid on the associated natural frequencies and the Q-factor. The effect of “added mass” on the frequencies of the structure is found to be negligible. However, the acoustic radiation losses found to be significant. Additionally, we found that the variation in Qac over the first few modes (< 40 MHz) is marked with a local maximum and a minimum. Beyond this range, Qac increases monotonically over the higher frequency modes. It is also found that such kind of variation can be described using different acoustics parameters. Finally, comparing the acoustics radiation loss based quality factor with the experimental results for the uncapped drumhead resonator, the acoustic damping dominates only at higher modes. Therefore, our second problem forms the basis of finding other fluid-related damping. In the second problem, we explore the fluid losses due to squeeze film damping in the uncapped drumhead micro resonator. In this case, the squeeze film loss is due to the flow of the fluid film between the bottom surface of the annular plate and the fixed substrate. Based on the literature survey, it is found that the squeeze film damping reduces with increase in the air-gap thickness and the operating frequencies respectively. However, the squeeze film effect can not be ignored at lower frequencies. In order to investigate the contribution of squeeze film damping in uncapped resonator, we determine squeeze-film damping based quality factor Qsq corresponding to different modes of the resonators using FEM based software, ANSYS. On comparing Qsq with the experiments, we found that Qsq matches well with the experiments corresponding to the lower modes. Therefore, it is found that Qsq dominates at low frequencies (< 20 MHz) and Qac plays significant role at high frequencies (> 40 MHz). Both types of damping should be considered while modeling the fluid damping in uncapped resonator. In the next study, we discuss the effects of prestress on the resonant frequencies and quality factor. In the third study, we discuss the applicability of thin-plate theory with prestress and membrane theory in computing the frequencies and quality factor due to acoustic and squeeze film losses in the uncapped drumhead resonator. In the first two studies, although the quality factor due to acoustic losses and the squeeze film captures the correct trend of the experimental results, there is a mismatch between the experimental and theoretical frequencies computed with added mass effect. In order to improve the computation of frequencies corresponding to measured modes, we first used membrane theory to predict the frequencies, and finally we quantify that there exists discrepancy between computed and the corresponding experimental frequencies with error of about 8–55%. Since, both the membrane as well as thin plate theory without prestress do not correctly model the frequencies, we used the thin plate theory with prestress. For a prestress level of 96 MPa, we found the match between the computed frequencies and the corresponding quality factors with the measured values. However, we also found that there exists strong dependence of prestress on the acoustic radiation loss, with decrease in the acoustic loss based quality factors with increase in the prestress level. In the subsequent problem, we focus on the computation of losses in capped drumhead resonator which leads to a design possibility of improving the quality factor by containing the acoustic radiation losses. In the fourth problem, we study the structural and fluid-structure interaction losses which are dominant constituent of net Q-factor observed in experiments due to encapsulation of uncapped drumhead resonator. Essentially, the geometry of the capped resonator constitutes upper and lower cavities subjected to fluid-structure interaction losses on both sides of the annular plate. The dominant fluid-structure interaction loss is found to be due to squeezing action acting simultaneously in the upper and lower cavities. However, as we go to the higher modes, squeeze film damping become very small and the damping due to structure related losses such as clamping and thermoelastic losses becomes significant. We found the thermoelastic damping to be the dominant source of structural damping at higher resonant modes, whereas, the clamping losses are found to be relatively smaller. Finally, on comparing the net quality factor with the experimental results, we observed that the squeeze film losses are dominant at lower frequencies, and thermoelastic losses dominate at the higher frequencies. However, there remains some discrepancy between theoretical and experimental Q-factors particularly over higher frequency range. Such discrepancy may be due to some unaccounted factors which may be explored to improve the modeling of damping in capped resonators. The emphasis of this work has been towards developing a comprehensive understanding of different dominant dissipative mechanisms, classified into the fluid-structure interaction and the structural losses, that are constituent of the Q-factor at various resonant modes of uncapped and capped drumhead resonators.

The objective of this research is to apply micromachined silicon-based resonant gravimetric sensors to the detection of gas-phase volatile organic compounds (VOCs). This is done in two primary tasks: 1) the optimization and application of silicon disk resonators to the detection of gas-phase VOCs, and 2) the development and application of a novel gravimetric-capacitive multisensor platform for the detection of gas-phase VOCs. In the rst task, the design and fabrication of a silicon-based disk resonator structure utilizing an in-plane resonance mode is undertaken. The resonance characteristics of the disk resonator are characterized and optimized. The optimized characteristics include the resonator Q-factor as a function of geometric parameters, and the dynamic displacement of the in-plane resonance mode. The Q-factors of the disk resonators range from 2600 to 4360 at atmosphere for disk silicon thicknesses from 7 µm to 18 µm, respectively. The resonance frequency of the in-plane resonance mode ranges from 260 kHz up to 750 kHz. The disk resonators are applied to the sensing of gas-phase VOCs using (poly)isobutylene as a sensitive layer. Limits of detection for benzene, toluene and m-xylene vapors of 5.3 ppm, 1.2 ppm, and 0.6 ppm are respectively obtained. Finally, models for the limits of detection and chemical sensitivity of the resonator structures are developed for the case of the polymer layers used. In the second task, a silicon-based resonator is combined with a capacitive structure to produce a multisensor structure for the sensing of gas-phase VOCs. Fabrication of the multisensor structure is undertaken, and the sensor is theoretically modeled. The baseline capacitance of the capacitor component of the multisensor is estimated to be 170 fF. Finally, initial VOC detection results for the capacitive aspect of the sensor are obtained.

<p dir="ltr">Optical frequency combs have revolutionized metrology and advanced other fields such as RF photonics and astronomy. While powerful, they can be bulky, expensive, and difficult to manufacture. This tends to limit uses in real-world scenarios. Within the last decade or so, coherent frequency combs have begun to be generated in millimeter-scale, CMOS fabrication-compatible nonlinear crystals. These so-called “microcombs” have led to hopes of overcoming deployability constraints of more traditional bulk combs.</p><p dir="ltr">One of the first applications for \textit{bulk} frequency combs after their explosion in 2000 was the optical atomic clock. It promised extreme long-term time stability better than that of the Cesium clock that currently defines the SI second. More recently, interest in a fully portable optical atomic clock has grown. Such a device could reliably keep time even without the aid of GPS references, and potentially with greater accuracy than current GPS synchronization can provide.</p><p dir="ltr">Frequency combs have also been used to sample electrical signals more rapidly than traditional electronics can accomplish. This has been used to achieve dramatically increased effective frequency bandwidths for signal detection architectures. One can imagine how this capability would be beneficial in a portable (microcomb-driven) form: a lightweight, comb-enhanced receiver able to capture a broadband snapshot of its surrounding electromagnetic environment could be a powerful tool.</p><p dir="ltr">Timekeeping and RF photonics are the primary applications of microcombs focused upon here. I will attempt to roughly summarize important concepts and highlight relevant work in both subjects in the Introduction. Then I will move a step closer to the hands-on lab work that has largely kept me preoccupied over the last several years and describe important or commonly-employed Methods for experiments. A collection of three journal manuscripts (two published, and the third recently submitted) will follow in the Publications chapter, highlighting some experimental results. Finally, I will conclude with a brief Outlook.</p>

Die vorliegende Arbeit behandelt die Dispersion von Exziton-Polaritonen in ZnO-basierten Mikroresonatoren, welche zum einen theoretisch bezüglich der Eigenschaften der reinen Kavitätsmoden und zum anderen experimentell mittels Photolumineszenz-Spektroskopie und Reflektionsmessungen untersucht wurden. Dabei wird besonders auf die Rolle der linearen Polarisation sowie auf die Besetzung der Exziton-Polaritonen-Zustände eingegangen. Dies ist von Interesse, da diese Mikroresonatoren vielversprechende Kandidaten für die Realisierung eines Exziton-Polariton Kondensates sind, welches ähnliche Eigenschaften wie das klassische Bose-Einstein Kondensat besitzt. Die Eigenschaften der Exzitonen-Polaritonen werden durch die der beteiligten ungekoppelten Exzitonen und Photonen bestimmt. Im Falle der Photonen hängen diese stark von der linearen Polarisation ab, da es sich bei der ZnO-Kavität um ein optisch anisotropes Material handelt. Mittels einer entwickelten Näherung für die Berechnung der Kavitätsmoden, welche die optische Anisotropie der Kavität sowie die endliche Ausdehnung der Spiegel berücksichtigt, konnte gezeigt werden, dass im Falle der hier verwendeten ZnO-Kavität die optische Anisotropie zu einer Reduktion der Energieaufspaltung zw. der s- und p-polarisierten Mode im sichtbaren Spektralbereich führt. Der allgemeine Fall einer optisch anisotropen Kavität wird ebenfalls diskutiert. In den untersuchten ZnO-basierten Mikroresonatoren konnte eine starke Wechselwirkung zwischen Exzitonen und Photonen bis zu einer Temperatur von T = 410 K beobachten werden. Dabei wurde eine maximale Kopplungsstärke von 55 meV bei T = 10 K ermittelt. Anhand des beobachteten Verlaufs der Dispersion der Exziton-Polaritonen konnten in einem Mikroresonator Hinweise für eine zusätzliche Kopplung zwischen gebundenen Exzitonen und Photonen gefunden werden. Des Weiteren zeigte die Dispersion der Exziton-Polaritonen eine starke Polarisationsabhängigkeit. Eine maximale Energieaufspaltung des unteren Zweiges für die beiden linearen Polarisationen von 6 meV bei einem starken negativen Detuning von -70 meV wurde beobachtet. Es wird gezeigt, dass diese hohe Energieaufspaltung einen großen Einfluss auf die Besetzung der Zustände der Exziton-Polaritonzweige hat. Unter Verwendung verschiedener Anregungsleistungen und einer keilartigen Kavität wurde der Einfluss des Detunings systematisch auf die Besetzung der Exziton-Polaritonzustände untersucht und diskutiert. Es konnte eine Voraussage für den optimalen Detuning – Temperaturbereich für eine mögliche Kondensation getroffen werden. Erste Beobachtungen eines Kondensates in einem der Resonatoren bestätigen die Ergebnisse der vorliegenden Arbeit.

Die vorliegende Arbeit behandelt die Dispersion von Exziton-Polaritonen in ZnO-basierten Mikroresonatoren, welche zum einen theoretisch bezüglich der Eigenschaften der reinen Kavitätsmoden und zum anderen experimentell mittels Photolumineszenz-Spektroskopie und Reflektionsmessungen untersucht wurden. Dabei wird besonders auf die Rolle der linearen Polarisation sowie auf die Besetzung der Exziton-Polaritonen-Zustände eingegangen. Dies ist von Interesse, da diese Mikroresonatoren vielversprechende Kandidaten für die Realisierung eines Exziton-Polariton Kondensates sind, welches ähnliche Eigenschaften wie das klassische Bose-Einstein Kondensat besitzt. Die Eigenschaften der Exzitonen-Polaritonen werden durch die der beteiligten ungekoppelten Exzitonen und Photonen bestimmt. Im Falle der Photonen hängen diese stark von der linearen Polarisation ab, da es sich bei der ZnO-Kavität um ein optisch anisotropes Material handelt. Mittels einer entwickelten Näherung für die Berechnung der Kavitätsmoden, welche die optische Anisotropie der Kavität sowie die endliche Ausdehnung der Spiegel berücksichtigt, konnte gezeigt werden, dass im Falle der hier verwendeten ZnO-Kavität die optische Anisotropie zu einer Reduktion der Energieaufspaltung zw. der s- und p-polarisierten Mode im sichtbaren Spektralbereich führt. Der allgemeine Fall einer optisch anisotropen Kavität wird ebenfalls diskutiert. In den untersuchten ZnO-basierten Mikroresonatoren konnte eine starke Wechselwirkung zwischen Exzitonen und Photonen bis zu einer Temperatur von T = 410 K beobachten werden. Dabei wurde eine maximale Kopplungsstärke von 55 meV bei T = 10 K ermittelt. Anhand des beobachteten Verlaufs der Dispersion der Exziton-Polaritonen konnten in einem Mikroresonator Hinweise für eine zusätzliche Kopplung zwischen gebundenen Exzitonen und Photonen gefunden werden. Des Weiteren zeigte die Dispersion der Exziton-Polaritonen eine starke Polarisationsabhängigkeit. Eine maximale Energieaufspaltung des unteren Zweiges für die beiden linearen Polarisationen von 6 meV bei einem starken negativen Detuning von -70 meV wurde beobachtet. Es wird gezeigt, dass diese hohe Energieaufspaltung einen großen Einfluss auf die Besetzung der Zustände der Exziton-Polaritonzweige hat. Unter Verwendung verschiedener Anregungsleistungen und einer keilartigen Kavität wurde der Einfluss des Detunings systematisch auf die Besetzung der Exziton-Polaritonzustände untersucht und diskutiert. Es konnte eine Voraussage für den optimalen Detuning – Temperaturbereich für eine mögliche Kondensation getroffen werden. Erste Beobachtungen eines Kondensates in einem der Resonatoren bestätigen die Ergebnisse der vorliegenden Arbeit.