The aim of biomaterials design is to create an artificial environment that mimics the in vivo extracellular matrix for optimized cell interactions. A precise synergy between the scaffolding material, bioactivity, and cell type must be maintained in an effective biomaterial. In this work, we present a technique of nanofabrication that creates chemically nanopatterned bioactive silicon surfaces for cell studies. Using nanoimprint lithography, RGD and mimetic BMP-2 peptides were covalently grafted onto silicon as nanodots of various dimensions, resulting in a nanodistribution of bioactivity. To study the effects of spatially distributed bioactivity on cell behavior, mesenchymal stem cells (MSCs) were cultured on these chemically modified surfaces, and their adhesion and differentiation were studied. MSCs are used in regenerative medicine due to their multipotent properties, and well-controlled biomaterial surface chemistries can be used to influence their fate. We observe that peptide nanodots induce differences in MSC behavior in terms of cytoskeletal organization, actin stress fiber arrangement, focal adhesion (FA) maturation, and MSC commitment in comparison with homogeneous control surfaces. In particular, FA area, distribution, and conformation were highly affected by the presence of peptide nanopatterns. Additionally, RGD and mimetic BMP-2 peptides influenced cellular behavior through different mechanisms that resulted in changes in cell spreading and FA maturation. These findings have remarkable implications that contribute to the understanding of cell-extracellular matrix interactions for clinical biomaterials applications.

The aim of the present work was to design and fabricate all purpose, positioning-tolerant and efficient interconnects between single-mode fibers and integrated waveguides out of polymers. The developed structures are part of the optical packaging of integrated optical chips. Integrated optics have gathered tremendous interest throughout recent years from research as well as from the industry, and most likely the demand will further grow in the future. Today’s trend is to establish optical data communication not only in far-distance transmission but also in end-user or so called fiber-to-home configurations, or, in the near future, also on board or even chip level. In addition, integrated optical sensors are gaining more and more importance. In the future, lab-on-a-chip systems may be able to simplify and accelerate analysis methods within health care or allow for a continuous monitoring of almost any environmental variable. All these applications call for robust optical packaging solutions. Many integrated optical chips are using a silicon-on-insulator design. Technologies which were originally intended for the manufacturing of integrated circuits can be utilized for the fabrication of such silicon-on-insulator chips. Point-of-care testing, which is a considerable part of bio-sensing, in some cases only allows the use of disposable transducer elements. The fabrication of these transducers, also including almost all other system parts, may be possible using polymers. Alternative fabrication methods like nanoimprint lithography can be applied for the patterning of polymers. With these, the extension of already known working principles or even entirely new device architectures become feasible for mass production. The direct patterning of polymers by means of nanoimprint was used to fabricate interconnects for integrated waveguides. In contrast to conventional lithography approaches, where a patterned resist layer is used as a masking layer for subsequent process steps, direct patterning allows the immediate use of the structures as functional elements. Firstly, nanoimprint allows diffraction-unlimited patterning with nanometer resolutions as well as the replication of complex three-dimensional patterns. These unique properties were used within this work to pattern shallow gratings atop an integrated waveguide within only one single manufacturing step. The gratings are used as coupling elements and can be utilized either to couple light from external elements to the chip or vice versa. Considerations regarding the optical effects on single-mode polymer waveguides as well as grating couplers were obtained from simulation. They are specific to the chosen design and the used polymer and cannot be found elsewhere so far. Compared to similar designs and fabrication strategies proposed in literature, the ones followed here allow for a higher efficiency. The dimensions and process windows obtained from simulation did serve as a basis for the subsequent fabrication of the grating couplers. All steps which are necessary to turn the calculated design into reality, ranging from master fabrication, to working mold cast and imprint, are shown in detail. The use of a working mold strategy is of crucial importance for the fabrication process and is discussed in detail. The use of a working mold preserves a costly master and further allows for a cost-efficient production. Parameters which are relevant for the production as well as for the final polymer patterns were analyzed and discussed. On the basis of the obtained data, a process optimization was performed. The optical characterization was also part of the presented work. A comparison with the results obtained from simulation is included and additional effects were revealed. Most of them may be subject to further improvement in future designs. In summary, the present work contributes to the field of optical packaging. It shows a viable route for the design and fabrication of interconnects of single-mode polymer waveguides. The presented design can be used as a building block which can be placed at almost any positions within an integrated optical chip. The fabrication method includes a minimum number of process steps and is still able to increase performance compared to similar approaches. Moreover, all process steps allow for scaling and are potential candidates for mass production.

New Generation Lithographic (NGL) techniques have been recently investigated in order to overcome the limitations of the long-used UV lithography. Several techniques have been proposed during the last decades, but the continued improvement of UV lithography rendered them useful only for a limited number of applications. More recently, nanoimprint lithography (NIL), invented in the nineties, has been considered as the new NGL due to its extreme simplicity and high resolution. Thermal NIL consists in the deformation of a thermoplastic under pressure and temperature by a nanostructured mold, while UV-NIL consists in the polymerization by UV light of a monomer at room temperature and under a lower pressure than Thermal NIL. One of the main problems of this technique is mold-polymer separation after the process. This problem is especially important for UV-NIL, because the working treatments for Thermal NIL degrade with UV light. In order to assess this problem, thin diamond-like amorphous carbon films (DLC) have been proposed as an alternative to existing treatments for their low chemical reactivity and the possibility to incorporate other chemical elements to further reduce their surface energy. Amorphous carbon exists in different forms, depending on how it is grown. Its mechanical properties range from polymer or graphite-like to almost as resistant as diamond. Besides the excellent mechanical properties of DLC (high hardness, elasticity and wear resistance, and low dry friction), amorphous carbon has also been found useful in applications requiring inert and/or biocompatible surfaces. The project DPI2007-61349 of the Science and Innovation Department of Spain, named “Amorphous carbon molds for micro and nanoimprint of polymeric surfaces”, aims to study the effect of the incorporation of different elements in DLC films for the improvement of NIL molds. This thesis has focused on a series of objectives of this project: - Design and construction of a very high vacuum reactor for deposition processes and ionic etch - Incorporation of fluorine to amorphous carbon films and subseqüent characterization by different surface, mechanical and tribological techniques, as well as spectroscopy for the characterization of the plasma used for the process. - Set up and optimization of a deep ion etch technique with ion beam for the production of molds. - The use of different lithographic techniques oriented to the production in large scale of nanometric patterns. - The exploration of mold coating to increase its durability and antisticking properties in nanoimprint processes. The incorporation of fluorine in DLC films has demonstrated to be useful in the improvement of the properties of NIL molds, because it avoids the use of the current surface treatments, which in addition to being less durable, can react with polymers in presence of UV light. In this thesis, the influence of fluorine incorporation in the films has been studied. Fluorinated amorphous carbon films have been deposited by pulsed-DC plasma enhanced chemical vapor deposition, by progressively replacing methane by trifluoromethane. The experimental device used for deposition has been designed and built to allow a number of multiple processes in the same reactor. The results of the study demonstrate the feasibility of this technique, of easy industrial implementation, for the deposition of this type of coatings. The characterization of both the active species in the plasma and the groups incorporated into the deposited films has helped to understand the process of fluorine incorporation, as well as the change in the surface properties that it entails. / La dificultad de extender el uso de la litografía de luz ultravioleta (UV) a los cada vez más estrictos requisitos de resolución, llevaron desde hace ya un par de décadas, a plantearse la necesidad de buscar técnicas litográficas llamadas de “Nueva Generación” (NGL) que las superasen. Son diversas las técnicas se han ido proponiendo durante estos años, pero la mejora de la litografía UV las ha ido relegando fuera del ámbito industrial. Más recientemente, la litografía por nanoestampación (NIL), ha tomado fuerza como la nueva NGL por su extrema sencillez y por su demostrada elevada resolución. La NIL térmica (T-NIL) consiste en la deformación de un termoplástico bajo presión y temperatura por un molde con estructuras nanométricas, mientras que la NIL por UV (UV-NIL) consiste en la polimerización de un monómero a temperatura ambiente con menor presión ejercida por un molde transparente al UV. Uno de los principales problemas de esta técnica es la separación de molde y polímero, una vez finalizado el proceso. Como alternativa a los tratamientos existentes, se han propuesto los recubrimientos de carbono amorfo tipo diamante (DLC) por su baja reactividad química, elevada dureza y posibilidad de incorporación de otros elementos químicos a fin de reducir su energía superficial. El proyecto del Ministerio de Ciencia e Innovación DPI2007-61349, “Moldes de carbono amorfo para micro y nanograbado de superficies poliméricas”, en el cuál se ha enmarcado esta tesis, pretende estudiar los efectos de la incorporación de diferentes elementos en capas de DLC para la mejora de los moldes de NIL. La incorporación de flúor en capas de DLC ha demostrado recientemente ser útil en la mejora de las propiedades de los moldes de NIL, porque evita el uso de los actuales tratamientos superficiales (por ejemplo siloxanos), los cuales, además de ser menos duraderos, pueden reaccionar con los polímeros en presencia de luz UV. Así, en esta tesis se ha estudiado la influencia de la incorporación de flúor a capas de DLC en la composición y en las propiedades de superfície obtenidas.

La nano-impression est une technique de lithographie qui consiste à reproduire les motifs contenus dans un moule, par pressage de celui-ci sur un film de résine. Cette technologie – rapide et peu coûteuse à mettre en oeuvre – est prometteuse mais son utilisation à l’échelle industrielle nécessite encore des améliorations notamment en termes de limitation de la défectivité des motifs reproduits. Des solutions existent pour pallier cette limitation, à travers notamment l’utilisation de traitements antiadhésifs qui se greffent en surface des moules et permettent de favoriser les étapes de démoulage. Cependant, ces traitements de moules ont une durée de vie limitée, ce qui limite la rentabilité globale du procédé de nano-impression.Ce projet de thèse s’intéresse à la question de la durabilité des moules et propose des matériaux alternatifs pour la fabrication de moules de nano-impression.Pour répondre aux exigences des acteurs de la nano-impressions, quatre matériaux (le Diamond-like carbon, le carbure de silicium et leurs versions dopées en fluor) ont été développés pour une utilisation en tant que matériaux de moules alternatifs au silicium et au quartz. La caractérisation des propriétés physiques et physico-chimiques a été réalisée de sorte à sélectionner les matériaux les plus prometteurs qui ont ensuite été structurés pour une utilisation en tant que moules fonctionnels.Les propriétés d’adhérence de ces matériaux ont ensuite été caractérisées tant en nano-impression assistée par ultraviolets qu’en nano-impression thermique. Ces essais ont permis de montrer que les matériaux développés, malgré une grande énergie de surface, présentent intrinsèquement un caractère antiadhésif lié à leur inertie chimique. / Nanoimprint is a lithography technology which consists in structuring a polymer film by pressing a structured mold into it. This promising method is low-cost and has a high throughput, but its implementation in industry still requires improvements, particularly regarding the defectivity of imprinted structures. To circumvent this defectivity, the use of antiadhesive treatments, grafted to the mold surface has been developed to facilitate the demolding step. However, these treatments have a limited lifespan, thereby empeding the global nanoimprint cost-effectiveness.This thesis focuses on mold durability and suggests alternative materials for the fabrication of nanoimprint molds.To match nanoimprint requirements, four materials (Diamond-like carbon, Silicon carbide and their fluorine-doped versions) were developed to be used as alternatives to silicon and quartz. Physical and physico-chemical characterization were carried out, so as to determine the best candidates that were then patterned, leading to usable molds.Adhesion properties of these materials were then characterized both in UV-nanoimprint and thermal-nanoimprint procedures. These investigations showed that despite their high surface energies, the developed materials exhibit intrinsically antiadhesive properties, thanks to their chemical inertness.

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Conducting vertical nanopillar arrays can serve as three-dimensional nanostructured electrodes with improved performance for electrical recording and electrochemical sensing in bio-electronics applications. However, vertical nanopillar-array electrodes made of inorganic conducting materials by conventional nanofabrication approach still faces challenges in high manufacturing costs, poor scalability, and limited choice of carrier substrates. Here, we report a new type of conducting nanopillar arrays composed of multi-walled carbon nanotubes (MWCNTs) doped polymeric nanocomposites, which are manufactured over the wafer-scale on both rigid and flexible substrates by direct nanoimprinting of perfluoropolyether nanowell-array templates into uncured MWCNT/polymer mixtures. By controlling the MWCNT ratios and the annealing temperatures during the fabrication process, MWCNT/polymer nanopillar arrays can possess outstanding electrical properties with high DC conductivity (~4 S/m) and low AC electrochemical impedance (~104 Ω at 1000 Hz). Moreover, by electrochemical impedance spectroscopy (EIS) measurements and equivalent circuit modeling-analysis, we can decompose the overall impedance of MWCNT/polymer nanopillar arrays in the electrolyte into multiple bulk and interfacial circuit components, and thus can illustrate their different dependence on the MWCNT ratios and the annealing temperatures. In particular, we find that a proper annealing process can significantly reduce the anomalous ion diffusion impedance and improve the impedance properties of MWCNT/polymer nanopillars in the electrolyte. / Master of Science / Conducting vertical nanopillar arrays can serve as three-dimensional nanostructured electrodes with improved performance for electrical recording and electrochemical sensing in nano-bioelectronics applications. However, vertical nanopillar-array electrodes made of inorganic conducting materials by conventional nanofabrication approach still faces challenges in high manufacturing costs, poor scalability, and limited choice of carrier substrates. Compared to conventional nanofabrication approaches, nanoimprint lithography exhibits unique advantages for low-cost scalable manufacturing of nanostructures on both rigid and flexible substrates. Very few studies, however, have been conducted to achieve the scalable nanoimprinting fabrication of conducting nanopillar arrays made of MWCNT/polymer nanocomposites. Here, I'm reporting a new type of conducting nanopillar arrays composed of multi-walled carbon nanotubes (MWCNTs) doped polymeric nanocomposites, which can be manufactured over the wafer-scale on both rigid and flexible substrates by direct nanoimprinting of the perfluoropolyether nanowell-array template into uncured MWCNT/polymer mixtures. We find that the nanoimprinted conducting nanopillar arrays can possess appealing electrical properties with a high DC conductivity (~4 S/m) and a low AC electrochemical impedance (~104 Ω at 1000 Hz) in the physiologically relevant electrolyte solutions (1X PBS). Furthermore, I've conducted a systematic equivalent circuit modeling analysis of measured EIS results to understand the effects of the MWCNT ratios and the annealing temperatures on the impedance of different bulk and interfacial circuit components for MWCNT/polymer nanopillar arrays in the electrolyte.

Planar electronic devices represent an attractive approach towards roll-to-roll printed electronics without the need for the sequential, precisely aligned, patterning steps inherent in the fabrication of conventional ‘3D’ electronic devices. Self-switching diodes (SSDs) and in-plane-gate field-effect transistors (IPG-FETs) can be patterned using a single process into a substrate precoated with semiconductor.These devices function in depletion mode, requiring the semiconductor to be doped in order for the devices to function. To achieve this, a reliable and controllable method was developed for doping organic semiconducting polymers by the immersion of optimally deposited films in a solution of dopant. The process was shown to apply both semicrystalline and air-stable, amorphous materials indicating that the approach is broadly applicable to a wide range of organic semiconductors.Simultaneously with the development of the doping protocol specialised hot-embossing equipment was designed and constructed and a high-yielding method of patterning the structures of IPG-FETs and SSDs was arrived at. This method allowed for consistent and reliable patterning of features with a minimum line-width of 200nm.Following the development of these doping and patterning processes these were combined to fabricate controllably doped, functioning planar devices. SSDs showed true zero-threshold rectification behaviour with no observed breakdown in the reverse direction up to 100 V. IPG-FETs showed switching behaviour in response to an applied gate potential and were largely free of detectable gate leakage current, verifying the quality of the patterning process.Furthermore, high-performance semiconducting polymer PAAD was synthesised and characterised in field-effect transistors as steps towards its use in planar electronic devices. It was also shown that this material could be doped using the developed immersion doping protocol and that this protocol was compatible with top-gated device architectures and the use of fluoropolymer CYTOP as a dielectric.

Conjugated polymers are novel organic electronic materials highly important for organic photovoltaic applications. Charge transport is one of the key properties which defines the performance of conjugated polymers in electronic devices. This work aims to explore the charge transport anisotropy in thin films of P3HT, one of the most common conjugated polymers. Using X-ray diffraction techniques and charge transport measurements, the relation between vertical charge transport through thin P3HT films and structure of the films was established. It was shown that particular orientations of crystalline domains of P3HT, namely face-on and chain-on, are beneficial for vertical charge transport. These orientations provide the efficient pathways for the charges to be transported vertically, either via π-π stacking interaction between the adjacent conjugated chains, or via the conjugated chain backbones. It was also demonstrated that particular orientations of crystallites are favourable for the formation of interconnected percolated pathways providing enhanced vertical charge transport across the film. Deposition of P3HT on most commonly used silicon substrates typically results in the formation of mostly edge-on orientation of crystallites which is unfavourable for vertical charge transport. Nanoimprint lithography was demonstrated as a powerful processing method for reorienting the edge-on crystalline domains of P3HT into chain-on (vertical) orientation. It is also shown that thin P3HT films with preferentially face-on orientations of crystallites can be deposited on graphene surface by spin coating. Using patterning of thin P3HT films by nanoimprint lithography, unprecedentedly high average vertical mobilities in the range of 3.1-10.6 cm2 V-1 s-1 were achieved in undoped P3HT. These results demonstrate that charge transport in thin films of a relatively simple and well-known conjugated polymer P3HT can be significantly improved using optimization of crystallinity,orientation of crystallites, polymer chain orientation and alignment in the films.

Le but de la conception d’un biomatériau est de mimer les modèles qui puissent être représentatifs de la matrice extracellulaire (MEC) existant in vivo. Cet objectif peut être atteint en associant une combinaison de cellules et des facteurs biologiques à un biomatériau sur lequel ces cellules peuvent se développer pour reconstruire le tissu natif. Dans cet étude, nous avons crée des surfaces bioactives nanostructurées en combinant la nanolithographie et la fonctionnalisation de surface, en greffant un peptide RGD ou BMP-2 (bone morphogenetic protein 2). Nous avons étudié l’effet de cette nanodistribution sur le comportement des cellules souches mésenchymateuses en analysant leur adhésion et différentiation. Nous notons que la nanodistribution des peptides induit une bioactivité qui a un impact sur l’organisation du cytosquelette, la conformation des fibres de stresse de l’actin, la maturation des adhésions focales (AFs), et le commitment des cellules souches. En particulier, l’aire, la distribution, et la conformation des AFs sont affectes par la présence des nanopatterns. En plus, le RGD et le BMP-2 changent le comportement cellulaire par des voies et des mécanismes différents en variant l’organisation des cellules souches et la maturation de leurs AFs. La nanodistribution influence de façon évidente les cellules souches en modifiant leur comportement (adhésion et différenciation) ce qui a contribué et ce qui contribuera à améliorer la compréhension des interactions des cellules avec la MEC. / The aim of biomaterials design is to create an artificial environment that mimics the in vivo extracellular matrix for optimized cell interactions. A precise synergy between the scaffolding material, bioactivity, and cell type must be maintained in an effective biomaterial. In this work, we present a technique of nanofabrication that creates chemically nanopatterned bioactive silicon surfaces for cell studies. Using nanoimprint lithography, RGD and mimetic BMP-2 peptides were covalently grafted onto silicon as nanodots of various dimensions, resulting in a nanodistribution of bioactivity. To study the effects of spatially distributed bioactivity on cell behavior, mesenchymal stem cells (MSCs) were cultured on these chemically modified surfaces, and their adhesion and differentiation were studied. MSCs are used in regenerative medicine due to their multipotent properties, and well-controlled biomaterial surface chemistries can be used to influence their fate. We observe that peptide nanodots induce differences in MSC behavior in terms of cytoskeletal organization, actin stress fiber arrangement, focal adhesion (FA) maturation, and MSC commitment in comparison with homogeneous control surfaces. In particular, FA area, distribution, and conformation were highly affected by the presence of peptide nanopatterns. Additionally, RGD and mimetic BMP-2 peptides influenced cellular behavior through different mechanisms that resulted in changes in cell spreading and FA maturation. These findings have remarkable implications that contribute to the understanding of cell-extracellular matrix interactions for clinical biomaterials applications.