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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.

The efficiency of an organic photovoltaic cell depends mainly on its morphology where an exciton has to migrate to a p-n junction to create a photocurrent. Therefore the distance from the bulk of the cell to a junction interface should not exceed the diffusion length of the exciton. In this thesis, two novel lithographical methods, to produce specific polymer morphologies, were developed and evaluated. In the first method, called embedded annealing, self-assembled polystyrene colloids were embedded in a polydimethylsiloxane (PDMS) film and annealed under an electric field to produce a bi-polymer structure consisting of polymer columns in a thin film of PDMS. Polymer colloids were successfully assembled into two dimensional hexagonally close packed arrays. However, the annealing process was unsuccessful. The second method, imprint annealing, aimed to increase the aspect ratio (height/width) of thermally imprinted micrometer sized polystyrene features by annealing them in uniform electric fields. The results showed that the aspect ratio of imprinted features can be significantly increased, 21-fold, while maintaining the periodicity of the original imprint. This is in contrast to previous results where smooth polymer films annealed in uniform fields where the periodicity of the resulting structures cannot be independently controlled, and are highly sensitive to the electrode spacing. Feature sizes down to 1 µm and aspect ratios up to 4.5 were achieved using imprint annealing. / Verkningsgraden hos en hos en solcell beror, för givna material, framförallt på dess uppbyggnad. För att bidra till fotoströmmen måste en genererad exciton vandra till en pn-övergång. På grund av detta bör det längsta avståndet till närmaste pn-övergång i solcellen inte vara längre än excitonens diffusionslängd. I detta examensarbete testas två olika litografiska metoder för att åstadkomma en specifik filmgeometri lämpad för organiska solceller. Den första metoden, kallad embedded annealing, går ut på att bädda in spontant ordnade sfäriska polystyrenkolloider i en polydimetylsiloxan (PDMS) -film för att sedan vid förhöjd temperatur applicera ett elektiskt fält över filmen. Förhoppningen var att på detta sätt töja ut kolloiderna till pelare genom PDMS-filmen. I det första steget ordnades kolloiderna sponant i tätpackade hexagonala tvådimensionella gitter på kiselsubstrat. Experimenten lyckades inte med hjälp av elektriska fält töja ut kolloiderna. Den andra metoden, imprint annealing, syftar till att öka höjd/bredd -förhållandet och minska diametern hos präglade polystyrenstrukturer. Dessa ursprungliga topografiska stukturer skapas med hjälp av en tryckpressmetod kallad nanoimprinting. Dessa strukturer värmdes upp, och ett uniformt elekrisk fält applicerades över dem. Mina resultat visar att man med elektriska fält avsevärt kan öka höjd-breddförhållandet hos polymerstrukturer och samtidigt bevara periodiciteten hos de ursprungliga strukturerna. Detta står i kontrast mot tidigare resultat på släta filmer, där periodiciteten inte kan kontrolleras oberonde av andra parametrar. Med imprint annealing ökades höjd-breddförhållandet hos enskilda strukturer upp till 21 gånger. Diametrar ner till 1 µm och höjd/breddförhållanden upp till 4,5 uppnåddes.

Cette thèse présente des résultats théoriques et expérimentaux portant sur des écoulements à l'échelle nanoscopique de polymères fondus. L'étude analytique et numérique de l'écoulement d'un film de polymère, préalablement nanostructuré par nanoimpression puis recuit au dessus de sa température de transition vitreuse, a permis de dégager différentes dynamiques de nivellement selon la topographie initiale du film. Certaines ont été appliquées à l'élaboration d'éléments optiques par recuit de nanostructures complexes. Une méthode de mesure de la viscosité Newtonienne et du temps terminal de relaxation d'un polymère déposé en film mince a également pu être développée. Enfin, un travail exploratoire portant sur un procédé de nanoimpression sans épaisseur résiduelle par démouillage est présenté. L'accent a porté sur le calcul précis de la pression de disjonction dans un milieu stratifié en utilisant la théorie moderne de Lifshitz basée sur les propriétés optiques des matériaux en interaction. / This thesis presents a theoretical and experimental work on nanoscale flows of polymer melts. Different leveling dynamics emerge from the analytical and numerical study of the reflow of a polymer film that is first nanoimprinted and then annealed above its glass transition temperature, depending on the initial topography of the film. These concepts were applied to the manufacturing of optical devices from the reflow of complex nanostructures. A method to measure the Newtonian viscosity and the terminal relaxation time of a thin polymer film was also developed. Finally, an exploratory work on a residual-layer-free nanoimprint process based on dewetting is presented. Emphasis was put on the accurate computation of the disjoining pressure in stratified media with the modern Lifshitz theory based on the optical properties of the interacting materials.

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.

A low-cost plasmonic nanopillar array was synthesized using soft thermal nanoimprint lithography, and its sensitivity was determined through far-field spectroscopic measurements. Its transmission spectrum was highly dependent on the refractive index of the surrounding medium, with its sensitivity being 375 nm per refractive index unit according to the spectral shift. Moreover, a simple sensor whose reflected color changed with a change in the plasma frequency on varying the surrounding medium was fabricated.