In an age in which the microchip is ubiquitous, the rewards for novel methods of microfabrification are great, and the vast possibilities of nanotechnology lie just a little ahead. Various methods of microlithography offer differing benefits, and even as older techniques such as optical lithography are being refined beyond what were once considered their upper limits of resolution, new techniques show great promise for going even further once they reach their technological maturity. Recent developments in optical lithography may allow it to break the 100-nm limit even without resorting to x-rays.

This Thesis describes the development of a cost-effective process for patterning nanoscale metal antenna arrays. Soft ultraviolet (UV) Nanoimprint Lithography (NIL) into bilayer resist was chosen since it enables repeatable large-scale replication of nanoscale patterns with good lift-off properties using a simple low-cost process. Nanofabrication often involves the use of Electron Beam Lithography (EBL) which enables the definition of nanoscale patterns on small sample regions, typically < 1 mm 2 . However its sequential nature makes the large scale production of nanostructured substrates using EBL cost-prohibitive. NIL is a pattern replication method that can reproduce nanoscale patterns in a parallel fashion, allowing the low-cost and rapid production of a large number of nanopatterned samples based on a single nanostructured master mold. Standard NIL replicates patterns by pressing a nanostructured hard mold into a soft resist layer on a substrate resulting in exposed substrate regions, followed by an optional Reactive Ion Etching (RIE) step and the subsequent deposition of e.g. metal onto the exposed substrate area. However, non-vertical sidewalls of the features in the resist layer resulting from an imperfect hard mold, from reflow of the resist layer, or from isotropic etching in the RIE step iii may cause imperfect lift-off. To overcome this problem, a bilayer resist method can be used. Using stacked resist layers with different etch rates, undercut structures can be obtained after the RIE step, allowing for easy lift-off even when using a mold with non-vertical sidewalls. Experiments were carried out using a nanostructured negative SiO2 master mold. Various material combinations and processing methods were explored. The negative master mold was transferred to a positive soft mold, leaving the original master mold unaltered. The soft mold consisted of a 5 m thick top Poly(methyl methacrylate) (PMMA), or Polyvinyl alcohol (PVA) layer, a 1.5 mm thick Polydimethylsiloxane (PDMS) buffer layer, and a glass supporting substrate. The soft mold was pressed into a bilayer of 300 nm PMMA and 350 nm of silicon based UV-curable resist that was spin-coated onto a glass slide, and cured using UV radiation. The imprinted patterns were etched using RIE, exposing the substrate, followed by metal deposition and lift-off. The experiments show that the use of soft molds enables successful pattern transfer even in the presence of small dust particles between the mold and the resist layer. Feature sizes down to 280 nm were replicated successfully

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.

Carbon nanotubes are carbon based structures with outstanding electronical and mechanical properties. They are used in a wide range of applications, usually embedded in polymer in the form of composites, in order to affect the electronic behavior of the matrix material. However, as the nanotubes properties are directly dependent on their intrinsic structure, it is necessary to select specific nanotubes depending on the application, which can be a complicated and inefficient process. This makes it attractive to be able to reduce the amount of material used in the composites. In this thesis, focus is placed on the electrical properties of the composites. A simple patterning method is presented which allows the use of extremely low amounts of nanotubes in order to increase the electrical conductivity of diverse polymers such as polystyrene (PS) or poly(3-hexylthiophene) (P3HT). This method is called nanoimprint lithography and uses a flexible mold in order to pattern composite films, leading to the creation of conducting nanotube networks, resulting in vertically conducting samples (from the bottom of the film to the top of the imprinted patterns). In parallel, X-ray diffraction measurements have been conducted on thin P3HT polymer films. These were prepared on either silicon substrate or on graphene, and the influence of the processing conditions as well as of the substrate on the crystallinity of the polymer have been investigated. The knowledge of the crystalline structure of P3HT is of great importance as it influences its electronic properties. Establishing a link between the processing conditions and the resulting crystallinity is therefore vital in order to be able to make opto-electronic devices such as transistor or photovoltaic cells.

We report on the process parameters of nanoimprint lithography (NIL) for the fabrication of two-dimensional (2-D) photonic crystals. The nickel mould with 2-D photonic crystal patterns covering the area up to 20mm² is produced by electron-beam lithography (EBL) and electroplating. Periodic pillars as high as 200nm to 250nm are produced on the mould with the diameters ranging from 180nm to 400nm. The mould is employed for nanoimprinting on the poly-methyl-methacrylate (PMMA) layer spin-coated on the silicon substrate. Periodic air holes are formed in PMMA above its glass-transition temperature and the patterns on the mould are well transferred. This nanometer-size structure provided by NIL is subjective to further pattern transfer. / Singapore-MIT Alliance (SMA)

In an age in which the microchip is ubiquitous, the rewards for novel methods of microfabrification are great, and the vast possibilities of nanotechnology lie just a little ahead. Various methods of microlithography offer differing benefits, and even as older techniques such as optical lithography are being refined beyond what were once considered their upper limits of resolution, new techniques show great promise for going even further once they reach their technological maturity. Recent developments in optical lithography may allow it to break the 100-nm limit even without resorting to x-rays.

Focused Ion Beam (FIB) has several advantages such as high sensitivity, high material removal rates, low forward scattering and directing fabrication. Without any etched mask, processing time can be reduced. Pyrex glass etched by FIB is used for fast fabrication of 3-D submicron structure mold. In this study, glass is used as substrate. The UV-cured resin that spin-coated onto a mold has 3-D structure patterns. 3-D structure patterns are transferred on the plate to investigate the effects of parameters of UV cured, pressure and exposure time on the occurrence of defects. The relationship of these processing parameters for the imprinting process is also realized. Besides, the material property of UV-cured resin is investigated. UV-Cured resin is investigated by thermogravimetric Analysis (TGA) to measure the degradation temperature (Td). The hardness and modulus of UV-Cured resin was measured by nanoindentation to realize deformed ability of material for the imprinting process. Moreover, the contact angle of Pyrex glass is measured to investigate its surface quality for the imprint process.

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.

Les nanotechnologies représentent un potentiel de développements et d’applications considérables dans le domaine des matériaux ouvrant la voie à d’innombrables développements pour l’énergie, le transport, la santé, l’industrie, etc. Le biomimétisme a ainsi trouvé un nouveau moteur d'étude et de développement. La feuille de lotus est capable de faire perler l’eau avec une efficacité remarquable transformant n’importe quelle goutte d’eau en une bille répondant aux lois de la physique des solides. Cette propriété extraordinaire est due à l’association d’une composition chimique intrinsèquement hydrophobe avec une texturation hiérarchique de sa surface.Cette thèse s’intéresse à la compréhension des principes physiques qui régissent l'interaction des gouttes d'eau avec les surfaces de films polymères structurées de FEP, PMMA et PET. Deux technologies ont été mises en oeuvre pour la fabrication de surfaces superhydrophobes hiérarchiques : la nanoimpression (NIL) thermique et la gravure plasma. Nous avons mesuré les angles de contact et hystérésis de ces surfaces structurées afin d’identifier leur état de mouillage de Wenzel ou de Cassie-Baxter. Nous avons attaché une importance particulière au développement de solutions de fabrication et de caractérisations sur de grandes surfaces.Les propriétés antigivre ont été caractérisées, ainsi le rôle de la condensation dans la propagation du givre a été corrélé à la structuration de surface. De plus, nous avons mis en évidence le rôle du potentiel électrostatique de surface sur les retards de gel. Enfin, au vue du potentiel applicatif de ces surfaces, nous avons ajouté une dimension dynamique à l’étude en considérant les vitesses d’impact des gouttes. Un modèle de prédiction de la littérature a été comparé avec succès aux résultats expérimentaux. / Nanotechnologies represent a considerable potential of development and application in the field of material science opening the way to innumerable developments for energy, transport, health, industry, and so on. Thus, biomimicry found a new driving force for study and development. The lotus leaf is able to repulse water with a remarkable efficiency transforming any drop of water into a ball following the laws of solid physics. This extraordinary property is due to the association of a hydrophobic chemical composition with a hierarchical texturing of its surface.This thesis focuses on the understanding of the physical principles governing the interaction of water drops on the surfaces of structured polymer films of FEP, PMMA and PET. Two technologies have been implemented for the production of hierarchical superhydrophobic surfaces: thermal nanoimprint lithography (NIL) and plasma etching. We have measured the contact angles and hysteresis of these structured surfaces in order to identify their Wenzel or Cassie-Baxter wetting state. We have attached particular importance to the development of manufacturing and characterization solutions on large surfaces.The anti-icing properties have been characterized and the role of condensation in the propagation of frost has been correlated with the surface texturing. In addition, we have highlighted the role of the electrostatic surface potential on frost delays. Finally, in view of the applicative potential of these surfaces, we added a dynamic dimension in the study considering the velocity of drops impact. A model of prediction from the literature was successfully compared to our experimental results.

Avec l'augmentation du nombre de dispositifs utilisant des nanostructures, tels les nanofils pour les systèmes photovoltaïques, les détecteurs, etc., il devient nécessaire de développer des techniques de fabrication de réseau d'objets de dimensions nanométrique à faible coût. Dans cette étude, nous utilisons les propriétés d'auto-assemblage combinées avec des méthodes « descendantes » pour créer des réseaux de nanostructures très denses et très organisés. En effet, nous proposons de produire des réseaux hexagonaux parfaits d'alumine poreuse (AAO) et de les utiliser pour la croissance confinée de fils de silicium (Si) par la technique de dépôt chimique en phase vapeur (CVD).L'AAO est naturellement obtenue par oxydation de l'aluminium dans un acide, mais ce processus seul n'apporte qu'une organisation des pores très faible. Nous présentons un procédé innovant utilisant la lithographie par nano-impression thermique pour pré-texturer l'aluminium avant son anodisation. Ainsi, nous obtenons des réseaux poreux hexagonaux parfait sur des surfaces allant jusqu'à 4 cm ². Toutes les caractéristiques géométriques de la membrane poreuse peuvent être ajustées en faisant varier les paramètres expérimentaux de l'anodisation. En outre, pour augmenter la densité du réseau et réduire le coût de fabrication du moule d'impression, nous avons développé des structures originales avec une croissance mixte de pores guidées et générer naturellement.Afin d'étudier les caractéristiques de ces réseaux et suivre leur évolution au cours de leur formation, nous présentons les résultats d'une étude de diffusion des rayons X aux petits angles réalisée in situ pendant la formation de l'AAO.L'AAO est finalement utilisée comme matrice guide pour la croissance auto-organisée de fils de Si par CVD. Nous présentons donc des réseaux hexagonaux parfaits de nanofils crus perpendiculairement à la direction <100 > des substrats de silicium. Les différentes étapes du procédé, du dépôt de catalyseur à la croissance des fils sont présentées. Grâce à cette technique, nous obtenons des densités de fils allant jusqu'à 9.109 cm-2 et la dispersion des diamètres est meilleure que lors d'une croissance colloïdale (CVD). La composition chimique et l'orientation cristalline des nanofils confirme qu'ils sont en silicium et que nous avons à la fois des orientations <100> et <111>. Nous avons étudié également la conductivité entre le sommet des fils et le substrat grâce à la technique du microscope à force atomique conducteur. / With the increased number of devices using functional nanostructures, e.g nanowires for photovoltaic systems, detector etc, it becomes of great importance to develop low-cost and versatile fabrication of systems with nano-objects. In this study, self-assembly properties combined with top-down methods were used to create highly dense and organized nanostructures. Indeed, flawless hexagonal porous anodic alumina arrays (PAA) were successfully used as a template for the epitaxial Silicon (Si) nanowires (NW) growth in a chemical vapor deposition reactor (CVD).PAA is naturally obtained by oxidation of aluminum in acid; however this simple process brings a poor pores organization. We present an innovative route using Thermal NanoImprint Lithography previous to aluminum anodization to prepare perfect hexagonal nanopore array on large surface (4 cm²). All the geometrical characteristics of the porous membrane can be adjusted by varying experimental parameters. Furthermore, to increase the density of the array and reduce the fabrication cost of the imprint mould, original structures with a mixed growth of NIL-guided pores and generation of naturally-guided pores (induced pores) have been developed. Shapes of the pores can be modified varying the electrolyte.To know the characteristic of these arrays and their evolution during formation, we will present the results of the hitherto unseen In Situ study under Grazing Incidence Small Angle X-ray Scattering of PAA formation.The PAA is finally used as templates for the self-organized Si NW growth in a CVD reactor. Hexagonal nanowire arrays grown perpendicularly to <100> silicon substrates were successfully produced. The different process steps from the catalyst deposition to the planarization of the array are presented. The quality of the final silicon array is discussed. Densities up to 9*109 NW.cm-2 and diameter dispersion better than colloidal growth are achieved. The chemical composition and the crystalline orientation of the nanowires confirms the nanowires are in silicon and a mix between <100> and <111> orientation. We also measured the conductivity between the top of the vertical nanowire and the substrate with conductive atomic force microscopy.