A stimuli-responsive microgel is a three-dimensional polymer network that is able to absorb and expel a solvent (commonly water). These materials are unique in the fact that their sponge-like behavior can be actuated by environmental cues, like temperature, ion concentration, pH, and light. Because of the dynamic properties of these materials they have found applications in drug-delivery systems, micro-assays, selective filtration, artificial muscle, and non-fouling surfaces. The most well-known stimuli-responsive polymer is Poly(N-isopropylacrylamide) or PNIPAAm and it experiences a switchable swelling or deswelling over a critical temperature ( Tc=~32°C). Below the critical temperature, the gel begins mixing with the surrounding solvent and swells; above this temperature, the opposite is true. The unconstrained hydrogel will continue to swell in all directions until equilibrium is established between its propensity for mixing with the surrounding solvent and the elastic restoring forces of the gel matrix. The strength of the elastic restoring forces is dependent on the interconnectedness of the polymer network and is therefore a function of crosslink density. An increase in crosslink density results in a decreased swelling and vice versa. If the hydrogel is mechanically constrained to a surface, it can experience various wrinkling and buckling conformations upon swelling, as the stresses associated with its confinement are relieved. These conformation characteristics are a strong function of geometry (aspect ratio) and extent of swelling (i.e. crosslink density). In order to capitalize on the utility of this material, it is imperative that its volume transition is well characterized and understood. Toward this end, pNIPAAm gels have been created with 1x10-7 to 2x10-³ mol/cm³ crosslink density and characterized. This was done by first examining its bulk, unattached swelling ability and then by evaluating its microscale properties as a surfaceconfined monolithe. The latter was achieved through the use of confocal microscopy and copolymerization with a fluorescent monomer. This method allows for a detail analysis of the deformations experienced (bulk-structural bending and surface undulating) and will ultimately lend itself to the correlation between crosslink density and the onset of mechanical phenomena.

L'impression par transfert, une technique utilisée pour transférer divers matériaux tels que des molécules d'ADN, de la résine photosensible ou des nanofils semi-conducteurs, s'est dernièrement révélée utile pour la réalisation de structures de silicium statiques sous le nom de micro-maçonnerie. L'étude présentée ici explore le potentiel de la technique de micro-maçonnerie pour la fabrication de résonateurs MEMS. Dans ce but, des microplaques de silicium ont été transférées sur des couches d'oxyde avec cavités intégrées à l'aide de timbres de polymère afin de créer des structures de type plaques suspendues. Le comportement dynamique de ces structures passives a été étudié sous pression atmosphérique et sous vide en utilisant une excitation externe par pastille piézo-électrique mais aussi le bruit thermomécanique. Par la suite, des résonateurs MEMS actifs, à actionnement électrostatique et détection capacitive intégrés, ont été fabriqués en utilisant des étapes supplémentaires de fabrication après impression. Ces dispositifs ont été caractérisés sous pression atmosphérique. Les facteurs de qualité intrinsèques des dispositifs fabriqués ont été évalués à 3000, ce qui est suffisant pour les applications de mesure à pression atmosphérique et en milieu liquide. Nous avons démontré que, puisque l'adhérence entre la plaque et l'oxyde est suffisamment forte pour empêcher une diaphonie mécanique entre les différentes cavités d'une même base, plusieurs résonateurs peuvent être facilement réalisés en une seule étape d'impression. Ce travail de thèse montre que la micro-maçonnerie est une technique simple et efficace pour la réalisation de résonateurs MEMS actifs de type plaque à cavité scellée. / Lately, transfer printing, a technique that is used to transfer diverse materials such as DNA molecules, photoresist, or semiconductor nanowires, has been proven useful for the fabrication of various static silicon structures under the name micro-masonry. The present study explores the suitability of the micro-masonry technique to fabricate MEMS resonators. To this aim, silicon microplates were transfer-printed by microtip polymer stamps onto dedicated oxide bases with integrated cavities in order to create suspended plate structures. The dynamic behavior of fabricated passive structures was studied under atmospheric pressure and vacuum using both external piezo-actuation and thermomechanical noise. Then, active MEMS resonators with integrated electrostatic actuation and capacitive sensing were fabricated using additional post-processing steps. These devices were fully characterized under atmospheric pressure. The intrinsic Q factor of fabricated devices is in the range of 3000, which is sufficient for practical sensing applications in atmospheric pressure and liquid. We have demonstrated that since the bonding between the plate and the device is rigid enough to prevent mechanical crosstalk between different cavities in the same base, multiple resonators can be conveniently realized in a single printing step. This thesis work shows that micro-masonry is a powerful technique for the simple fabrication of sealed MEMS plate resonators.

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During the last decades, the continuing need for faster and smaller sensors has indeed triggered the rapid growth of more sophisticated technologies. This has led to the development of new optical-based sensors, able to detect and measure different phenomena using light. Furthermore, material processing technologies and micro fabrication methods have exponentially advanced, allowing engineers and scientists to develop new and more complex sensors on optical fibers platforms; specifically attractive for life science and biomedical research. All these substantial developments have brought biosensors to a point where multifunctionality is needed, this has led to envision the "Lab-on-Fiber" concept. Which promotes the integration of different sensing components into a single platform, an optical fiber. In this work, an integrated system with non-conventional polymer optical fibers and their further surface modification has been developed. With these different approaches, electrodes, hollow channels and plasmonic nanostructures can be incorporated into a single optical fiber-based sensor, allowing for both electrical and optical sensing with the capabilities of tuning and signal enhancement thanks to the metallic nanostructures. Different fiber substrates can be designed and modified in order to satisfy multiple requirements for a wide variety of applications. / MS

The InsulPatch is a novel integrated patch-pump device used to deliver drugs, especially macromolecular drugs that are difficult to deliver through an oral pathway and that require transdermal delivery. The patch-pump is a promising replacement for conventional syringes and battery-powered pumps because it is slim, powerless, painless, and relatively inexpensive. The majority of this thesis focuses on the fabrication and testing of microfluidic devices for the delivery of insulin, which is a model drug that is widely used and needs to be delivered transdermally. In this thesis, we demonstrate the fabrication of the patch-pump, which includes an insect-mimetic microfluidic pump fabricated using photolithography and replica molding, and a microneedle array fabricated using 3D printing. The microfluidic pump is used to drive the fluid flow powered by pressurized air or the user’s pulse, and the microneedle array is used to inject the fluid through the skin painlessly. Using pressurized air-driven flow testing, we have tested the flow rate across microfluidic pumps of various flow channel widths over a range of physiologically relevant actuation frequencies and pressures. We have found that for the specific channel design we have been using, the flow rate generally positively correlates with the actuation pressure. For devices with wider flow channels, the flow rate generally negatively correlates with the actuation frequency, whereas the flow rate increases and then decreases with increasing actuation frequency for devices with narrower flow channels. This property of these devices is beneficial in insulin delivery because the demand for insulin is generally reduced in vigorous exercise (with elevated heart rate/actuation frequency) and increased in hypertension patients (with elevated blood/actuation pressure). A major future direction of the study is to test a wide range of device designs in a sample of human subjects by attaching the device onto the wrist and measuring the pulse-driven flow across the device. We can further change the channel design parameters of the device so that it will be ideal for insulin delivery. Using the ex vivo flow testing and human subject data, we can further tailor the device design to specific patients using a genetic algorithm-guided optimization based on the heart rate and blood pressure of the patient and the desired flow rate. We will also perform computational modeling using COMSOL Multiphysics to predict the flow across devices of different designs as well as to understand the physics behind the pulse-driven flow. Finally, a 3D-printed insulin reservoir will be incorporated into our patch-pump system for the storage of U-500 insulin. / M.S. / The InsulPatch is a slim, powerless device (“patch-pump”) that can be used to deliver drugs through the skin, especially designed for drugs that are difficult to deliver orally. The patch technology is a promising replacement for conventional injection using syringes and bulky battery-powered pumps. At this stage, the primary drug that our device aims to deliver is insulin, which generally needs to be delivered through the skin. In this thesis, we demonstrate how our patch-pump is made and how its performance is tested. The patch-pump has two parts: the microfluidic pump and the microneedle array. The microfluidic pump is fabricated using a technique called photolithography, in which a photosensitive polymer is selectively cured by UV light, and replica molding, in which the precursor of another polymer is poured on a mold and cured. The microneedle array is made using 3D printing and designed in such a way so that it can be readily connected to the microfluidic pump. The microfluidic pump is used to drive the fluid flow powered by the user’s pulse, and the microneedle array is used to inject the fluid through the skin painlessly. Through testing the flow across the microfluidic pump prototypes using pressurized air, we characterized the correlation between the flow rate of fluid across the device and parameters including the actuation pressure and frequency of the pressurized air as well as the width of the flow channel. Future directions of the study include testing the devices in human subjects to characterize pulse-driven flow across the devices, computational modeling of the devices, and further changes of the device design to optimize the performance of the device. We will also optimize the device design computationally to tailor the device design to specific diabetic patients. Finally, we will incorporate a 3D-printed insulin reservoir into our system for the storage of insulin solution. / Withhold all access to the ETD for 1 year / patent / I hereby certify that, if appropriate, I have obtained and submitted with my ETD a written permission statement from the ower(s) of each third part copyrighted matter to be included in my thesis or dissertation, allowing distribution as specified above. I certify that the version I submitted is the same as that approved by my advisory committee.

Un échange vigoureux au travers des frontières de la biologie et de la physique se développe autour de nouvelles méthodes et outils, et autour de nouveaux phénomènes. Les objets d’étude au cœur de ce recouvrement multidisciplinaire sont très divers. De manière non exhaustive, il s’agit de nanoparticules, de cellules ou encore d’objets encore plus petits et élémentaires tels que les molécules. Aussi bien pour des applications dans le domaine de la microélectronique que pour l’étude de mécanismes biologiques fondamentaux, l’intégration des objets d’intérêt à l’échelle de l’objet unique est essentielle. Dans le cadre de cette thèse, l’objectif que nous nous sommes fixés est de développer un volet technologique qui permette l’assemblage d’objets micro- ou nanométriques uniques à des endroits bien définis d’une surface solide de façon simple, fiable, bas-coût et parallèle. Pour ce développement, nous nous sommes intéressés tout particulièrement aux nanoparticules d’Au de 100 nm de diamètre, aux bactéries, puis aux molécules d’ADN. Nous décrirons les stratégies développées reposant sur la lithographie douce puis leurs potentialités pour différentes applications dans les domaines de l’analyse médicale et de la détection. / A vigorous trade across the borders of biological and physical sciences is developing around new methods and tools, and around new phenomena. The objects at the heart of this multidisciplinary overlapping are numerous. In a non exhaustive manner, the objects of study can be nanoparticles, cells, or even smaller and more elementary objects such as molecules. For applications in the field of microelectronics as for studies of fundamental biological mechanisms, the integration of these objects of interest at the single object scale is essential. In the frame of this Ph.D. thesis, the objective we pursued is the development of a technological tool-box allowing the assembly of micro- and nano-objects at pre-determined locations of a solid surface, in a simple, reliable, low-cost and parallel manner. For this development, we focused on gold nanoparticles 100 nm in diameter, bacterial cells and DNA molecules in particular. We will describe the strategies developed relying on soft-lithography and their potentialities for different applications in the fields of medical analysis and sensing.

This thesis describes investigations into the optical and device design of organic light-emitting diodes (OLEDs) with the aim of exploring the factors controlling the spatial emission pattern of OLEDs and developing novel OLEDs with directional emission by applying wavelength-scale photonic microstructure. The development of directional OLEDs was broken down into two steps: the development of efficient narrow linewidth OLEDs and the integration of wavelength-scale photonic microstructures into narrow linewidth OLEDs. The narrow linewidth OLEDs were developed using europium (Eu) complexes. The electrical optimisation of solution-processed Eu-based OLEDs using commercially available materials was investigated. The optimised Eu-based OLEDs gave an external quantum efficiency of 4.3% at a display brightness of 100 cd/m². To our knowledge, this is the highest efficiency reported for solution-processed Eu-based OLED devices, and the efficiency roll-off has been reduced compared with other reported references. Photonic microstructures were applied to develop directional OLEDs using the efficient Eu-based OLEDs. Two contrasting strategies were used. One was to embed photonic microstructures into Eu-based OLEDs, the other was to couple photonic microstructures externally onto the devices. The microstructured devices developed by the former strategy boosted the emitted power in desired angles in both s- and p-polarisations and doubled the fraction of emission in an angle range of 4⁰. The devices developed by the external coupling strategy achieved even higher directionality and the out-coupled emission was a confined beam with easy control of beam steering. Around 90% of the emitted power was confined in an angular range of 20⁰ in the detection plane. The optical properties can be optimised independently without compromising the electrical properties of devices, which gives major advantages in terms of effectiveness and versatility. Optical models were also developed to investigate the out-coupling mechanism of various trapped modes and develop OLEDs with stronger directionality.

Trilayer polypyrrole microactuators that can operate in air have previously been developed. They consist of two outer layers ofthe electroactive polymer polypyrrole (PPy) and one inner layer of a porous poly(vinylidene flouride) (PVDF) membranecontaining a liquid electrolyte. The two outer layers of PPy are each connected with gold electrodes and separated by the porousPVDF membrane. This microtool is fabricated by bottom-up microfabrication However, porous PVDF layer is not compatible with bottom upmicrofabrication and highly swollen SPE suffers from gold electrode delamination. Hence, in this MSc project/thesis a novelmethod of flexible electrode fabrication with conducting polymers was developed by soft lithography and drop-on-demandprinting. The gold electrodes were replaced by patterned vapor phase polymerized (VPP) poly(3,4-ethylenedioxythiophene) (PEDOT)electrodes due to its high electrical conductivity and versatile process ability. The replacement of the stiff gold electrodes byflexible and stretchable PEDOT allowed high volume change of the material and motions. The PEDOT electrodes werefabricated by patterning the oxidant iron tosylate using microcontact printing and drop-on-demand printing. Moreover, thePVDF membrane has been replaced by a nitrile butadiene rubber/poly(ethylene oxide) semi-interpenetrating polymer network(IPN) to increase ion conductivity and strechability and hence actuator performance.

Materials based on novel Off-Stoichiometry Thiol-Ene polymers, abbreviated OSTE, show promising properties as materials forlow cost and scalable manufacturing of micro- and nanosystems such as lab-on-chip devices. The OSTE materials have tunablemechanical properties, offer possibility for low temperature bonding to many surfaces via tunable surface chemistry, and can beused in soft lithography. Unlike the commonly used elastomer poly(dimethylsiloxane), PDMS, the OSTE materials have lowpermeability for gasses, are resistant to common solvents and can be more permanently surface modified.In this master’s thesis project, the OSTE materials have been evaluated with focus on compatibility with cells, possibility fornanostructuring using soft lithography and the use of OSTE as a flexible support for conducting polymers.Results from cell seeding studies with HEP G2 cells suggest that cells can proliferate on a low thiol off-stoichiometry OSTEmaterial for at least five days. The biocompatibility for this type of OSTE material may be similar to poly(styrene). However, highlevels of free thiol monomers in the material decrease cell viability considerably.By using soft lithography techniques it is possible to fabricate OSTE nanochannels with at least the dimensions of 400 nm x 15nm. Combined with the advantages of using the OSTE materials, such as low temperature bonding and possibility for stablesurface modifications, a candidate construction material for future development of systems for DNA analysis is at hand.OSTE can serve as a flexible support for an adsorbed film of a conducting polymer with the possibility for future applicationssuch as electronic interfaces in microsystems. In this project, a film of PEDOT:PSS with the electrical resistance of ~5 kΩ wascreated by adsorption to an flexible OSTE material. Furthermore, results suggest that it is possible to further optimize theconductivity and water resistance of PEDOT:PSS films on OSTE.