Organic semiconductors have generated huge interested in recent years for low-cost and flexible electronics. Current and future device applications for semiconducting polymers include light-emitting diodes, thin-film transistors, photovoltaic cells, chemical and biological sensors, photodetectors, lasers, and memories. The performance of conjugated polymer devices depends on two major factors: the chain conformation in polymer film and the device architecture. Highly ordered chain structure usually leads to much improved performance by enhancing interchain interaction to facilitate carrier transport. The goal of this research is to improve the performance of organic devices with the nanoimprint lithography. The work begins with the controlling of polymer chain orientation in patterned nanostructures through nanoimprint mold design and process parameter manipulation, and studying the effect of chain ordering on material properties. After that, step-and-repeat thermal nanoimprint technique for large-scale continuous manufacturing of conjugated polymer nanostructures is developed. The actual chain orientation of molecular groups in polymer micro- and nanostructures patterning by nanoimprint is complicated. However, this information is crucial for intelligently controlling the electrical and photophysical properties of conjugated polymers by nanoimprint. Systematic investigation of polymer chain configuration by Raman spectroscopy is carried out to understand how nanoimprint process parameters, such as mold pattern size, temperature, and polymer molecular weight, affects polymer chain configuration. The results indicate that chain orientation in nanoimprinted polymer micro- and nanostructures is highly related to the nanoimprint temperature and the dimensions of the mold structures. The ability to create nanoscale polymer micro- and nanostructures and manipulate their internal chain conformation establishes an original experimental platform that enables studying the properties of functional polymers at the micro- and nanoscale and understanding their fundamental structure-property relationships. In addition to the impact on basic research, the techniques developed in this work are important in applied research and development. Large-area conjugated polymer micro- and nanostructures can be easily fabricated by thermal step-and-repeat nanoimprint for organic flat-panel displays, organic circuits and organic solar panels. The ability to manipulate chain orientation through nanoimprint presents a new route to fine-tune the electrical and photophysical properties of conjugated polymers, which can lead to improved performance for all organic electronics. The techniques developed here also allow for easy incorporation of other micro- and nanoscale soft functional polymers in miniaturized devices and systems for new applications in electronics, photonics, sensors and bioengineering.

Development of nanoimprint lithography(NIL) has enabled high-throughput and high-resolution patterning over the optical limitation. In recent years, thermal nanoimprint has been used to directly pattern functional materials such as organic semiconductors because heat and pressure used in thermal nanoimprint do not damage functional materials. However, issues such as residual layer removal and mold contamination still limit the application of nanoimprint for organic semiconductor patterning. In this work, nanoimprint-based transfer imprinting of organic semiconductor is studied. In the same time the suggested technique is simulated with COMSOL multi-physics simulator to understand its mechanism. This transfer printing technique utilize thermal nanoimprint scheme to enable residual-layer-free patterning of organic semiconductors without mold contamination. The transfer imprinting technique is amenable to roll-to-roll process for high-throughput patterning of organic semiconductors for low-cost organic electronic applications.

La nano-structuration des surfaces est un intrigant domaine de la physique des matériaux que l’homme s’est approprié aussi bien à des fins esthétiques que fonctionnelles. Les nanostructures peuvent être présentes à l’état naturel (effet déperlant de la feuille de lotus) ou à l’état artificiel pour répondre à des besoins techniques et peuvent alors être fabriquées par lithographie. Le procédé étudié dans cette thèse est la nanoimpression thermique qui permet de répliquer à moindre coût les micro- et nanostructures d’un moule vers la surface d’un substrat. Ce procédé d’embossage consiste à imprimer le moule dans un film mince de polymère thermoplastique (50 à 500 nm d’épaisseur) préalablement déposé sur le substrat. Eventuellement, une étape ultérieure de gravure permet de transférer dans ce dernier les motifs imprimés. On s’intéresse en particulier à l’évaluation des vitesses d’impression des structures dans des films de polystyrène sur substrat de silicium. Un logiciel de simulation numérique a été développé ; il utilise la méthode des éléments naturels contraints (C-NEM). L’accent a été mis sur la prise en compte de trois effets éminemment importants à l’échelle nanométrique : tension de surface, mouillage, glissement à l’interface fluide-solide. Combiné à un comportement visqueux non linéaire, cela permet de rendre partiellement compte des phénomènes physiques qui surviennent lors de l’impression et d’avoir des temps de simulation compatibles avec les contraintes industrielles tout en conservant une évaluation pertinente des vitesses d’impression. Cette démarche nous place à mi-chemin entre des modèles analytiques très simples mais ayant un cadre d’utilisation très restreint et des modèles plus complexes trop onéreux pour la simulation, comme la viscoélasticité en grandes transformations. Ces travaux abordent enfin le problème de la caractérisation du polymère à l’échelle des films minces. Un des défis majeurs relevés ici consistait à appliquer à des films minces le comportement du polymère caractérisé à l’échelle macroscopique. La validation expérimentale de toute la théorie élaborée a permis d’appuyer cette démarche et d’en révéler les limites. Ces approches théorique et expérimentale sont un premier pas vers la conception d’un outil numérique d’optimisation de la nanoimpression thermique. / Surface nanostructuring is an intriguing field of materials physics that has been largely ado-pted for both aesthetic and functional purposes. Nanostructures can be present in nature (water repellent effect of the lotus leaf) or produced for industrial applications, and they can be manufactured by lithography. Thermal nanoimprint is the process studied in this thesis, which is an inexpensive method to replicate the micro- and nanostructures of a mold into the surface of a substrate. This embossing method consists in printing the mold into a thin film of thermoplastic polymer (50 to 500 nm in thickness) previously deposited on the substrate. A further etching step may transfer the imprinted patterns into the latter. The aim of this work is to evaluate the imprint speeds of the structures in thin polystyrene films on a silicon substrate. A numerical simulation software has been developed, which uses the Constrained Natural Elements Method (C-NEM). Our main contribution was to integrate three essential phenomena at the nanoscale: surface tension, wetting, and slip at the fluid-solid interface. Combined with a non-linear viscous behavior, this is shown to describe partially but sufficiently the physical phenomena that occur during printing. Therefore, this work lies halfway between simple analytical models, with a very limited scope of use, and complex models too expensive for simulation, such as finite strain viscoelasticity. Finally, this thesis addresses the problem of the characterization of a polymer in thin films. One of the major challenges faced here was to apply the macroscopic mechanical behavior to thin films. The experimental validation of the theory developed in the first part has corroborated this approach and revealed its limitations. This set of theoretical and experimental developments is a first step towards the design of a numerical tool for optimizing the thermal nanoimprint process

In this study, it was nanoimprint focused on the anti-adhesion technique between the grating structure silicon molds below 200nm half-pitch and polymer materials (H-PDMS). The nano-groove structure molds with different depths and widths were made by FIB. During the process of molding by soft-lithography, an anti-adhesion layer needed being plated between the silicon and PDMS mold, which was in order to get completely formed H-PDMS soft mold and prevent defective mold caused by the adhesion problem on the surface. There were three kinds of method of plating anti-adhesion layer which were the liquid immersion, vapor deposition, and fluorine doped DLC film. The PFOTCS was used as mold releasing agent in the methods of liquid immersion and vapor deposition, and the contact angle was measured to realize the ability of anti-adhesion. In the method of fluorine doped DLC film, in addition to measuring the anti-adhesion ability for each sample through contact angle with water, the AFM was also applied to measure the degree of adhesion on the surface for each film. And the contact angles with water between each film were also compared. The methods of plating anti-adhesion film with lower degree of adhesion on the surface could be acquired and discussed by means of the above-mentioned ways to fabricate the molds with good formability

In this paper, a new method combining imprint lithography and multiimprint was discussed to improve the generic TFT process. In order to apply the multilayer imprint, the alignment machine is essential for the whole process. Although there are many types of equipment available on the market, the cost of those alignment apparatuses is too expensive. In this paper, a simple theorem is employed to complete a low cost alignment machine with alignment accuracy to 5 £gm. Besides, in order to develop new TFT imprint photoresist, three kind of materials, AZ-series photoresist (AZ-650 a positive photoresist), HOSP (Hygrido Organic Siloxane Polymer) and SE-812, are tested for imprint and evaluate the applications of these materials in the future. The AZ-650 suits imprint process in this experiment.

This research presents grating photoresist structures by imprint and focused ion beam (FIB) techniques. Imprint technique is not limited to the physical properties of optical lithography. In the imprinting process, the quartz mold designed for imprinting process is fabricated by focused ion beam techniques to imprint photoresist (SU-8). To select imprint temperature of resist by Differential Scanning Calorimetry, and several kind of pressure are tested and evaluated for imprint. In this study, trichloro(1H, 1H, 2H, 2H- perfluorooctyl)silane (PFOTCS) are used for self-assembled monolayers (SAM) on mold as releasing and anti-sticking layer for nanoimprint. We use contact angle system to discuss the surface energy of any contact surface. The results demonstrated that the resist surface revealed the lower defect and roughness after separation of imprinting mold with SAMs of PFOTCS monolayer, ascribed to the PFOTCS monolayer with a large amount of -CF2 resulted in lower surface energy. This research has successfully defined 50~400 nm width resist features on the mold and transferred to the polymer after imprinting.

Miniaturization has become a product trend due to technological advancements, thus giving rise to nanoimprint lithography printing. Miniaturization is also a trend regarding process features. nanoimprint lithography has great potential for its simple process, low cost, mass-production capacity, and ease to produce nanoscale microstructure. After making a fence structure of line width less than 100nm on quartz glass with FIB, this study printed the fence structure of line width less than 100nm with the nanoimprint lithography using PDMS mold and quartz soft mold. Though PDMS molding is fast and convenient, it is uncommon with regard to small-size press. This study investigated the application of PDMS molds to nanoimprint lithography in order to verify the optimal parameters of PDMS molding and the results of nanoimprint lithography with PDMS soft modes. After obtaining the optimal molding press, the optimal molding parameters and press pressure were applied to find the optimal experimental results. Results show that the combination can successfully print a fence structure with a line width of 40nm.

Indiana University-Purdue University Indianapolis (IUPUI) / Infrared (IR) polarizers have been widely used in military and commercial applications. Controlling the polarization of incident light is one of major issues in the detector systems. However, conventional polarimetric IR detectors require series of polarizers and optical components, which increase the volume and weight of the system. In this research, stacked 1-dimensional (1-D) subwavelength grating structures were studied to develop compact size IR polarimetric detector by using surface plasmonic polariton. Experimental parameters were optimized by Finite Difference Time Domain (FDTD) simulation. Effects of gold (Au) grating size, numbers of stacked gratings, and dielectric space height were tested in the FDTD study. The fabrication of grating layers was conducted by using nanoimprint lithography. The samples were characterized by scanning electron microscopy. IR transmissions in transverse magnetic (TM) and transverse electric (TE) modes were measured by Fourier transform infrared spectroscopy (FTIR).

Durant la dernière décennie, la résonance de plasmon de surface (SPR) est devenue très populaire pour effectuer des analyses au cours d’un greffage chimique (ou biochimique) et étudier ainsi des réactions chimiques. Ce travail de thèse avait pour but de développer une méthode lithographique alternative, la nanoimpression assistée UV dite «douce», qui permet de fabriquer des réseaux de nanomotifs sur de très grandes surfaces (voir chapitre 1 - état de l’art) pour générer des nanostructures métalliques SPR intégrables. Les chapitres 2 et 3 étudient les paramètres expérimentaux de la nanoimpression pour obtenir des nanostructures hautement résolues et avec un minimum de défaut. Notre étude optique a été menée ensuite sur des réseaux de nanotrous imprimés dans des films d’or (chapitre 4). Le mécanisme physique du phénomène de transmission assistée par les plasmon est étudié de manière systématique d’après l’évolution de la position du pic de transmission avec les paramètres structuraux. Des mesures réalisées dans un système fluidique ont ensuite montré une réponse à un faible changement de l’indice de réfraction à la surface du réseau. Enfin, le dernier chapitre (chapitre 5) présente une nouvelle géométrie de biocapteurs optique basé sur une structure tri-couche dans une géométrie de type «nanocavité» à plasmon localisé (LSPR). Ces capteurs LSPR à nanocavités permettent d’améliorer le facteur de mérite d’un ordre de grandeur par rapport aux LSPR classiques. Leurs propriétés de résonance sont discutées à l’aide d’outils de simulation numérique. Enfin, nous démontrons qu’un tel capteur possède une grande sensibilité à la détection de biomolécules et serait donc adapté à l’étude d’interactions immunochimiques. / During the last decade, surface plasmon resonance (SPR) has become widely used to characterize a biological surface and to characterize binding events in the fields of chemistry and biochemistry. Research in this field has been favoured by the tremendous growth in nanofabrication methods among which soft lithographies are alternatively emerging. The purpose of this thesis work was to develop soft UV nanoimprint lithography, an emerging flexible technology allowing patterning on large area of subwavelength photonic nanostructures. The main advantages offered by soft UV nanoimprint lithography concern the simple patterning procedure and the low cost of the experimental setup (see state-of-art presented in chapter 1). Chapters 2 and 3 present the fabrication of master stamps, the study of nanoimprinting parameters coupled with the optimization of the etching process in order to get metallic nanostructures with limited pattern defects. The physical mechanisms of the transmission phenomenon exalted by surface plasmons were studied based on arrays of imprinted gold nanoholes (chapter 4). Extraordinary light transmission has been experimentally demonstrated. The geometrical effects on the position transmission peak were systematically analyzed. Proof-of-concept measurements performed in simple fluidic device indicate a response to small changes in refractive index in the surface vicinity. Finally, chapter 5 proposes a novel design for the optical sensor which is based on “nanocavities” exhibiting coupled localized plasmons. This LSPR sensor offers an improvement of one order of magnitude of the Figure of Merit compared to classical LSPR sensors. The resonance properties of these innovative nanocavities have been studied from numerical simulations and discussed based on their geometrical dependence. Since this system has demonstrated higher sensitivity for detection of biomolecules, it is thus fully adapted to study immunochemical binding interactions.

This diploma thesis deals with the investigation of the metal-assisted catalytic etching (MaCE) of Si. One of the main goals is to study fabrication of stamps for nanoimprint lithography using MaCE. Formation of nanoporous silicon (PSi), Si nanowires (SiNWs) and three-dimensional nanostructures in Si by MaCE is demonstrated. For this purpose optical lithography, electron beam lithography (EBL), shadow mask evaporation and aerosol nanoparticles deposition techniques have been utilized. The etching rate and surface morphology of Si (with Au lift-off films as a catalyst) as functions of time and concentrations of chemicals are measured in the current diploma work using optical microscope and scanning electron microscopy (SEM). In the current thesis it is shown that Si structures with sub-150 nm lateral sizes, high aspect ratio (up to 1:21), well-defined shapes, and various complexity can easily be fabricated by means of MaCE process.