Cette thèse porte sur l’étude de la génération, la propagation et la détection d’ondes de spin dans des nanostructures et microstructures élaborées à partir de couches ultra-minces (quelques nanomètres d’épaisseur) de Y₃Fe₅O₁₂ (YIG). Ce travail se trouve à l’interface entre deux thématiques du magnétisme : la magnonique et la spintronique. Grâce aux effets spin-orbite dans des microstrutures YIG|Pt, il a été possible d’étudier et de manipuler la dynamique d’aimantation du YIG, un matériau utilisé de longues dates sous forme de films épais ou billes pour ses très faibles pertes magnétiques. Ce travail ouvre la voie au développement de circuits magnoniques submicroniques soit pour le traitement des signaux hyperfréquences pour les applications télécom soit pour la réalisation de circuits logiques dans la perspective du remplacement de la technologie CMOS (beyond-CMOS). Ce travail repose sur une expertise dans la croissance de films de YIG développée au laboratoire. Les couches ultra-minces de YIG ont été élaborées par ablation laser pulsée. Pour les meilleurs films ayant une épaisseur de 20 nm, la constante d’amortissement de Gilbert caractérisant les pertes des films, estimée par résonance ferromagnétique, est typiquement de α=3x10⁻ 4. Cette avancée cruciale sur l’aspect matériau a ouvert au début de ma thèse un champ de possibilités pour la réalisation et l’étude de dispositifs magnoniques. En effet, la diminution des épaisseurs a permis d’ouvrir le YIG au domaine de la micro/nanofabrication, levant ainsi un verrou technologique vieux de plusieurs décennies. Nous avons donc pu montrer par des mesures inductives et optiques que la propagation d’ondes de spin dans des guides d’onde de YIG de 20 nm d’épaisseur pouvait être faite sur plusieurs dizaines de microns. Prouvant que la structuration des films de YIG n’altère pas la propagation des ondes de spin ouvrant la voie vers la réalisation de circuits magnoniques plus complexes. En structurant ces films de YIG pour obtenir des cristaux magnoniques, il est possible de générer une modulation spatiale du potentiel vu par les ondes de spin, se traduisant par l’apparition de bande interdite (ou gap) dans la transmittance de fréquences. L’étude de la propagation des ondes de spin dans un cristal a montré l’apparition d’un gap par des mesures BLS, accompagnée par une augmentation de l’atténuation pour la longueur d’onde de Bragg. Pour la première fois dans des films ultra-minces de YIG, ce gap montre la possibilité de réaliser une fonctionnalité de filtrage fréquentiel. La preuve de concept a été validée pour un cristal magnonique adapté pour l’intégration à des dispositifs magnoniques. Afin de manipuler et exciter la dynamique d’aimantation du YIG, nous avons dans une deuxième partie réalisée des microstructures à base de bicouche YIG|Pt. L’injection d’un courant électrique dans le Pt donne naissance, grâce à l’effet Hall de spin, à une accumulation de spin qui se couple à l’interface avec l’aimantation du YIG et permet ainsi d’exercer un couple de transfert de spin (STT) et de générer une dynamique d’aimantation du YIG. Nous avons mis en évidence la modulation d’un facteur cinq de la longueur d’atténuation des ondes de spin se propageant dans une piste YIG|Pt grâce à l’amplification des ondes de spin par STT. Ce contrôle efficace de l’atténuation s’avère très intéressant pour le transport d’information porté par les ondes de spin, afin d’amplifier ou supprimer les ondes de spin et donc sélectionner l’information transmise. Par ailleurs, au-delà d’un courant critique d’injection, nous avons pu observer des auto-oscillations de l’aimantation du YIG à la fois dans des plots ou des pistes. Ce résultat confirme la possibilité d’exciter électriquement la dynamique d’aimantation du YIG par STT. Une étude rigoureuse de ce régime a été effectuée dans des microdisques YIG|Pt pour déterminer le comportement des auto-oscillations et imager les modes d’ondes de spin excités dans le YIG. / The aim of this thesis is to study the generation, propagation and detection of spin waves in nanostructures and microstrutures based on ultrathin (a few nanometers thickness) Y₃Fe₅O₁₂ (YIG) films. This work is at the interface between two fields of magnetism: magnonics and spintronics. Thanks to spin-orbit effects in YIG|Pt microstructures, it has been possible to study and manipulate YIG magnetization dynamic, a material known and used for a long time as thick films or spheres due to its very low magnetic losses. This work opens the path towards the development of submicronic magnonic circuits either for processing radiofrequency signals of for the realization of spin waves logic devices for a future beyond-CMOS technology. Prior to the present work, a significant efforts have been made in the lab to grow epitaxial nanometer thick YIG films by pulsed laser deposition (PLD). It was possible to reduce the film thickness down to a few nanometers while preserving excellent magnetic properties. For the best YIG films having a thickness of 20 nm, ferromagnetic resonance measurements yield a Gilbert magnetic damping of α=3x10⁻ 4 . This value is comparable to micrometer thick YIG films grown by liquid phase epitaxy (LPE). This important step forward on the material aspect opened new possibilities for the realization of magnonic devices that can have a large impact on the ICT industry. Indeed, microfabrication of YIG is now possible thanks to the advent of high quality nanometer thick YIG films. Thus, we have observed the propagation of spin waves in 20-nm thick, 2.5 µm wide YIG waveguides over large distances using inductive and optical detection. Spin-wave propagation characteristics are not affected by microstructuration opening the path to the reliable design of complex magnonic circuits.By structuring YIG films to obtain magnonic crystals, it is possible to generate spatial modulation of the potential seen by spin waves, resulting in the appearance of gaps in the transmittance in frequency. To do so, magnonic crystals implemented in form of microscopic waveguides whose width is periodically varied, were fabricated. The study of spin-wave propagation showed the appearance of a gap accompanied by an increase of the spin-wave attenuation length due to Bragg reflection. For the first time in ultrathin YIG films, this gap shows the possibility to realize radiofrequency filtering. In order to manipulate and excite YIG magnetization dynamics, we have designed YIG|Pt microstructures either stripes or microdisks. Thanks to the spin Hall effect, an electrical current passing in Pt generates a transverse spin accumulation coupled at the interface to the YIG’s magnetization making it possible to exert spin transfer torque (STT). We have highlighted an efficient modulation, by a factor of five, of the spin-wave attenuation length. This control on the decay constant proves to be very interesting for the transport of information using spin waves as data carriers, in order to be able to amplify or suppress spin waves and to select transmitted information. In addition, beyond a critical current, we have induced auto-oscillations of YIG magnetization, either in stripes of microdisks, confirming the possibility to electrically excite YIG magnetization dynamics using STT. A rigorous study of this nonlinear regime has been carried out in YIG|Pt microdisks to determine auto-oscillations behavior and to observe directly dynamic modes excited in YIG.

Ce travail porte sur la réalisation de nanostructures d'or sur substrat de verre afin d’en étudier les propriétés plasmoniques et de les optimiser pour des applications dans le domaine des biocapteurs. L'objectif principal a été de démontrer la faisabilité de combiner sur une même biopuce, les biocapteurs à résonance de plasmon de surface propagatif (SPR) et ceux basés sur la diffusion Raman exaltée de surface (SERS). Nous montrons que la présence d’un film d’or sous les nanostructures est très favorable pour une double caractérisation SPR-SERS. Afin d’étudier plus en détails les couplages entre les différents modes plasmoniques existants dans ces substrats et ainsi pouvoir déterminer la structure optimale, l’essentiel des échantillons a été réalisé par lithographie électronique. La nanoimpression assistée par UV (UV-NIL) a aussi été développé au cours de cette thèse afin de réaliser un nombre important d'échantillons et répondre aux futurs besoins de l'industrie des biocapteurs. Les performances de ces échantillons réalisés par UV-NIL ont été comparées avec ceux fabriqués par lithographie électronique. Les diamètres des nanodisques d'or varient de 40 nm à 300 nm et les périodes de 80 nm à 600 nm en fonction de la technique de fabrication. En SERS, des facteurs d’exaltation de 10^6 à 10^8 ont été obtenus grâce à la présence du film d’or continu sous le réseau de nanodisques. Ce gain est fonction de l’épaisseur du film d’or, de la longueur d’onde d’excitation utilisée et du taux de remplissage des nanostructures. En SPR, nous avons démontré expérimentalement et théoriquement la possibilité de couplage entre les modes localisés et propagatifs donnant lieu à un nouveau mode hybride, potentiellement plus sensible car plus confiné. Les calculs numériques développés pour simuler le comportement de structures réelles (présence d’arrondi, de flanc ou de couche d’accroche) confirment les résultats obtenus. L’ensemble de ce travail a permis de manière expérimentale et théorique d’apporter une meilleure compréhension des propriétés plasmoniques aux échelles nanométriques sur des structures constituées de réseaux de nanostructures d'or, notamment sur film d’or. Par ailleurs, une étude précise des différentes étapes technologiques a permis de comprendre quels éléments impactent significativement les propriétés plasmoniques des échantillons et donc améliorent ou dégradent les performances de ces substrats en tant que biocapteur. Au final, les échantillons réalisés ont été testés et validés en tant que biocapteur au sein d'un appareil bimodal SPR-SERS. / This thesis is focused on gold nanostructuration on glass substrate in order to study and optimize their plasmonic properties for biosensing applications. The main goal was to demonstrate the feasibility of combining on a single biochip, Surface Plasmon Resonance Imaging (SPRI) and Surface Enhanced Raman Scattering (SERS) measurements. We have demonstrated that adding a gold film under the nanostructures was highly beneficial for a dual SPRI-SERS characterization. In order to optimize the geometry of the nanostructures and understand the various plasmonic modes, most of the samples were first made by electron beam lithography. Nanoimprinting assisted by UV (UV-NIL) was also developed during this thesis to manufacture samples in large quantities and reply to the future industrial needs for biosensing applications. Performances of these UV-NIL samples were compared with those produced by e-beam lithography. Diameters and periods of gold nanodisks range respectively from 40 nm to 300 nm and 80 nm to 600 nm, depending on the manufacturing technique used. In SERS, enhancement factor of 10^6 to 10^8 were obtained thanks to the presence of the continuous gold film under the nanodisks array. We found that this gain is a function of the thickness of the gold film, the excitation wavelength used and the nanostructures filling factor. In SPRI, we have demonstrated experimentally and theoretically the existence of a coupling between the propagating and localized plasmonic modes, resulting in a new hybrid mode, potentially more sensitive due to its high confinement. Numerical models confirm these results, taking into account the defects found in real samples (rounded edges, imperfect lateral side, adhesion layer). The whole work proposes a better understanding, both experimentally and theoretically, of the plasmonic properties at nanoscale of gold nanostructures with and without an underlying gold film. Moreover, a detailed study of the different technological processes helps to understand which steps significantly impact the plasmonic properties of the samples and their performance as a biosensor. Finally, these samples were characterized and validated on a bimodal instrument SPRI-SERS.

Dye Sensitized Solar Cells (DSSC) possesses huge potential in solar energy utilisation and immense research has been carried out in order to improve its performance. There are several aspects that affect the solar cell’s performance, such as the photon collection efficiency of the cell, the reflectivity of the semiconductor, the transparency and conductivity of the transparent conductive oxide layer, and the photon-electron conversion efficiency. In this research, a pre-patterned substrate was used as a base to fabricate DSSC for improving the photon collection efficiency of DSSC. The pre-patterned substrate was prepared using maskless dry etching technique, resulting in micro-size features on the substrates and giving a 1% reduction on reflectance. The effect of Aluminium doped ZnO sputtered as the Transparent Conductive Oxide layer (TCO) in comparison with a typical DSSC fabricated on Tin doped Indium Oxide glass (ITO) was also studied. The research was carried out in two parts: substrate texturing of glass fabrication with Al:ZnO deposition, and DSSC cell assembly. The first half was carried out in the nanofabrication laboratory at University of Canterbury, New Zealand, and the second half was in National Nano Device Laboratory, Taiwan. The characteristics of both the substrates and the cells were measured using spectrophotometer with integrating sphere and solar cell simulation system. Decrease in reflectance of the Al:ZnO coated substrate at infrared region from 20% to 10 % was achieved. Due to the high resistivity of Al:ZnO and the problem of incapability in TiO2 coating, DSSC cells fabricated with these substrates have efficiencies around 2%, which is lower than the typical DSSC cells fabricated with ITO glass. Future adjustments on the substrate etching process and the cell assembly are needed for optimizing the results. The relatively high resistivity of Al:ZnO also needs to be lower for better DSSC cell performance.

<p>Promising applications in the design of various biological systems hold critical implications as heralded in the rising field of synthetic biology. But, to achieve these goals, the ability to synthesize and screen in situ DNA constructs of any size or sequence rapidly, accurately and economically is crucial. Today, the process of DNA oligonucleotide synthesis has been automated but the overall development of gene and genome synthesis and error correction technology has far lagged behind that of gene and genome sequencing. What even lagged behind is the capability of screening a large population of information on a single cell, protein or gene level. Compartmentalization of single cells in water-in-oil emulsion droplets provides an opportunity to screen vast numbers of individual assays with quantitative readouts. However these single-emulsion droplets are incompatible with aqueous phase analysis and are not controllable through molecule transports. </p><p>This thesis presents the development of a multi-tool ensemble platform targeted at high-throughput gene synthesis, error correction and screening. An inkjet oligonucleotide synthesizer is constructed to synthesize oligonucleotides as sub-arrays onto patterned and functionalized thermoplastic microchips. The arrays are married to microfluidic wells that provide a chamber to for enzymatic amplification and assembly of the DNA from the microarrays into a larger construct. Harvested product is then amplified off-chip and error corrected using a mismatch endonuclease-based reaction. Bacterial cells baring individual synthetic gene variants are encapsulated as single cells into double-emulsion droplets where cell populations are enriched by up to 1000 times within several hours of proliferation. Permeation of Isopropyl-D-1-thiogalactopyranoside (IPTG) molecules from the external solution allows induction of target gene expression. The induced expression of the synthetic fluorescent proteins from at least ~100 bacteria per droplet generates clearly distinguishable fluorescent signals that enable droplets sorting through fluorescence-activated cell sorting (FACS) technique. The integration of oligo synthesis and gene assembly on the same microchip facilitates automation and miniaturization, which leads to cost reduction and increases in throughput. The capacity of double emulsion system (millions discrete compartments in 1ml solution) combined with high-throughput sorting by FACS provide the basis for screening complex gene libraries for different functionality and activity, significantly reducing the cost and turn-around time.</p> / Dissertation

This research was mainly focused on the design and optimization of aperture-based structures to achieve the greatest third harmonic conversion efficiency. It was discovered that by tuning the localized surface plasmon resonance to the fundamental beam wavelength, and by tuning the propagating surface plasmons resonance to the Bragg resonance of the aperture arrays, both the directivity and conversion efficiency of the third harmonic signal were enhanced. The influence of the gap plasmon resonance on the third harmonic conversion efficiency of the aperture arrays was also investigated. The resulted third harmonic generation (THG) from an array of annular ring apertures as a closed loop structure were compared to arrays of H-shaped, double nanohole and rectangular apertures as open-loop structures. The H-shaped structure had the greatest conversion efficiency at approximately 0.5 %. Moreover, it was discovered that the maximum THG did not result from the smallest gap; instead, the gap sizes where the scattering and absorption cross sections were equal, led to the greatest THG. The finite difference time domain (FDTD) simulations based on the nonlinear scattering theory were also performed. The simulation results were in good agreement with the experimental data. Moreover, a modified quantum-corrected model was developed to study the electron tunneling effect as a limiting factor of the THG from plasmonic structures in the sub-nanometer regime. / Graduate / 0544 / 0794 / 0752 / 0756 / mrnezami@gmail.com

An important goal of nanoscience is the self-assembly of nanoscale building blocks into complex nanostructures. DNA is an important and versatile building block for nanostructures because of its small size, predictable base pairing, and numerous sequence possibilities. I use DNA origami to design and fold DNA into predesigned shapes, to assemble thin, branched DNA nanostructures as templates for nanoscale metal features. Using a PCR-based scaffold strand generation procedure, several wire-like nanostructures with varying scaffold lengths were assembled. In addition, more complex prototype circuit element structures were designed and assembled, demonstrating the utility of this technique in creating complex templates. My fabrication method for DNA-templated nanodevices involves a combination of techniques, including: solution assembly of the DNA templates, surface orientation and placement, and selective nanoparticle attachment to form nanowires with designed gaps for the integration of semiconducting elements to incorporate transistor functionality. To demonstrate selective surface placement of DNA templates, DNA origami structures have been attached between gold nanospheres assembled into surface arrays. The DNA structures attached with high selectivity and density on the surfaces. In a similar base-pairing technique, 5 nm gold nanoparticles were aligned and attached to specific locations along DNA templates and then plated to form continuous metallic wires. The nanoparticles packed closely, through the use of a high density of short nucleotide attachment sequences (8 nucleotides), enabling a median gap size of 4.1 nm between neighboring nanoparticles. Several conditions, including hybridization time, magnesium ion concentration, ratio of nanoparticles to DNA origami, and age of the nanoparticle solution were explored to optimize the nanoparticle attachment process to enable thinner wires. These small, branched nanowires, along with the future addition of semiconducting elements, such as carbon nanotubes, could enable the formation of high-density self-assembled nanoscale electronic circuits.

Highly ordered nanoparticle arrays have been successfully fabricated by our group recently using ultra-thin porous alumina membranes as masks in the evaporation process. The sizes of the nanoparticles can be adjusted from 5-10 nm to 200 nm while the spacing between adjacent particles can also be adjusted from several nanometers to about twice the size of a nanoparticle. The configuration of the nanoparticles can be adjusted by changing the height of the alumina masks and the evaporation direction. Due to the high pore regularity and good controllability of the particle size and spacing, this method is useful for the ordered growth of nanocrystals. Different kinds of nanoparticle arrays have been prepared on silicon wafer including semiconductors (e.g., germanium) and metals (e.g., nickel). The germanium nanoparticle arrays have potential applications in memory devices while the nickel catalyst nanoparticle arrays can be used for the growth of ordered carbon nanotubes. / Singapore-MIT Alliance (SMA)

Durante las últimas décadas, la construcción de anillos de almacenamiento de electrones exclusivamente dedicados a la producción de radiación sincrotrón ha sido la clave para justificar el gran desarrollo de los componentes ópticos para rayos X. Se requieren nuevos elementos ópticos para una explotación óptima de las propiedades de esta luz, que puede usarse para descubrir los secretos de la materia y para revelar el mundo microscópico. El uso de radiación sincrotrón como sonda ha hecho posible una gran cantidad de experimentos para expandir el conocimiento de muchas áreas científicas. Paulatinamente, la radiación sincrotrón se ha convertido en un instrumento indispensable para muchos científicos, que trabajan en disciplinas muy diferentes como la biología, la química, la ciencia de materiales o incluso la arqueología. La microscopía de rayos X ha emergido como técnica para observar estructuras que no son accesibles con microscopia óptica convencional, y que tiene ventajas respeto a la microscopía electrónica debido a la mayor longitud de penetración y a la sensibilidad química de la radiación X. La óptica de los microscopios de rayos X incluye componentes como las lentes zonales de Fresnel que se producen con técnicas de microfabricación. En este trabajo, se han fabricado lentes zonales de Fresnel utilizando distintas técnicas y se han testado en diversas Fuentes de Luz Sincrotrón. Describiremos en detalle las técnicas de micro- y nanofabricación que son necesarias para la producción de estos elementes, des de la litografía por haz de electrones a la transferencia del patrón a distintos materiales. En particular, presentamos lentes para rayos X blandos hechas de silicio. Mostraremos que éstas funcionan bien en las fuentes de luz existentes y que debido a su robustez serán también apropiadas para las fuentes de rayos X de 4a generación. También preparamos un elemento óptico difractivo que produce una mancha iluminación cuadrada y llana, y que puede usarse como lente condensadora en microscopía de rayos X de transmisión. Finalmente, también demostramos un nuevo método de fabricación que puede mejorar la resolución espacial última de las lentes difractivas para rayos X. Se fabricaron lentes zonales de Fresnel con una última zona de 20 nm y líneas de 15 nm han sido claramente resueltas en microscopía de rayos X de rastreo. Este trabajo se ha realizado en el Laboratorio de Luz Sincrotrón en Barcelona, con la participación del Centro Nacional de Microelectrónica de Barcelona (CSIC-CNM) y del Grupo de Óptica del Departamento de Física de la Universidad Autónoma de Barcelona. Al mismo tiempo, partes esenciales de este trabajo se han realizado con la colaboración del Dr. C. David y el Dr. K. Jefimovs del Labor fur Mikro- und Nanotechnologie al Paul Scherrer Institut en Villigen (Suiza). / During the last decades, the construction of electron storage rings exclusively dedicated to the production of synchrotron radiation has been a key reason to explain the large development of x-ray optics. New optical elements are required for an optimal exploitation of the properties of this light, which can be used to find out the secrets of matter and to reveal the microscopic world. The use of synchrotron light as a probe has made possible a large quantity of experiments to expand the knowledge in many scientific areas. Little by little, synchrotron radiation sources have become an indispensable tool for the research of lots of scientists, who work in very different disciplines such as biology, chemistry, physics, material science or even archaeology. X-ray microscopy has emerged as a technique to observe structures which are not accessible with conventional optical microscopy, and that has advantages in respect to electron microscopy due to the longer penetration depth and chemical sensitivity of the x-ray radiation. The optics of the x-ray microscopes includes components such as the Fresnel zone plate lenses which are made by means of microfabrication techniques. Within this work, Fresnel zone plate lenses were produced using different approaches and they have been tested in several Synchrotron Light Sources. We will describe in detail the micro- and nanofabrication techniques that are necessary for the production of such elements, from the electron beam lithography to the pattern transfer into different materials. In particular, we will present lenses for soft x-rays made of silicon. We show that they perform well at the current light sources and we think that due to their robustness they will also be suitable for the 4th generation x-ray sources. We also prepared a diffractive optical element which produces a square flat top illumination spot, and that can be used as a condenser lens in full-field transmission x-ray microscopy. Finally, we will also demonstrate a novel fabrication method which can push the ultimate spatial resolution of x-ray diffractive lenses. Fresnel zone plates with an outermost zone width of 20 nm have been fabricated and 15 nm lines have been clearly resolved in scanning transmission x-ray microscopy. This work has been carried out in the Laboratori de Llum Sincrotró in Barcelona, with the participation of the Centro Nacional de Microelectrònica de Barcelona (CSIC - CNM) and the Grup d'Òptica del Departament de Física de la Universitat Autònoma de Barcelona. At the same time, essential parts of this work have been done in close collaboration with Dr. C. David and Dr. K. Jefimovs from the Labor für Mikro- und Nanotechnologie at the Paul Scherrer Institut in Villigen (Switzerland).

Effects of biomimetic micro-patterning of polymeric materials on their interfacial properties were studied experimentally. Micropillars of PDMS and SU-8 epoxy were fabricated through soft lithography and UV lithography techniques, respectively. PDMS pillars were topped by thin terminal films of the same material through dipping method with different thicknesses and viscosities. Adhesion and frictional properties of biomimetic microstructures were examined in two modes of contact, i.e. laid and conformal contact. In the first mode of contact, i.e. laid contact, the contact between adhesive and adherent is laid on top of the micro-protrusions or is in contact with side wall of micropillars. Adhesion properties of the smooth and patterned PDMS were characterized through micro-indentation test. Moreover, the friction properties of the smooth PDMS sample and PDMS micropillars with different aspect ratios were examined in unidirectional friction testing. JKR theory of continuum contact mechanics was utilized to interpret the obtained data. To study the effect of second mode of contact, peeling behaviour of a conformal contact between solidified liquid PDMS and SU-8 micropillars was monitored. Kendall’s model of elastic peeling was used to interpret the peeling data. It was found that patterning of the materials would decrease the real area of contact and accordingly adhesion and friction to the mating surface. Termination of the micropillars with a thin layer of the same material result in increment of adhesion as reduction of the real contact area could be compensated and the compliance of the near surface increases. Elastic energy dissipation as a result of enhanced compliance and crack trapping and crack propagation instabilities are the main reasons behind increment of adhesion of thin film terminated structures. Viscoelasticity of the terminal thin film remarkably increased the adhesion as a result of coupling mentioned mechanisms and viscoelastic loss on the surface. Decline of the overall friction could be tailored through use of different aspect ratios. Higher aspect ratios pillars show higher friction comparing to lower aspect ratio pillars. 550 folds enhancement of adhesion was observed for peeling of the PDMS tape from rigid micropillars with aspect ratio ranging from 0 to 6. It is concluded that for the lower aspect ratio micropillars, the elastic energy dissipation is playing the key role in adhesion enhancement. This role shifts toward side-wall friction during separation by increase in aspect ratio. These all give in hand a versatile tool to control and fine tune the interfacial properties of materials, whether they are concerned with adhesion or friction.

This thesis presents the development of a novel atomic force microscope (AFM) based nanofabrication technique termed as thermochemical nanolithography (TCNL). TCNL uses a resistively heated AFM cantilever to thermally activate chemical reactions on a surface with nanometer resolution. This technique can be used for fabrication of functional nanostructures that are appealing for various applications in nanofluidics, nanoelectronics, nanophotonics, and biosensing devices. This thesis research is focused on three main objectives. The first objective is to study the fundamentals of TCNL writing aspects. We have conducted a systematic study of the heat transfer mechanism using finite element analysis modeling, Raman spectroscopy, and local glass transition measurement. In addition, based on thermal kinetics analysis, we have identified several key factors to achieve high resolution fabrication of nanostructures during the TCNL writing process. The second objective is to demonstrate the use of TCNL on a variety of systems and thermochemical reactions. We show that TCNL can be employed to (1) modify the wettability of a polymer surface at the nanoscale, (2) fabricate nanoscale templates on polymer films for assembling nano-objects, such as proteins and DNA, (3) fabricate conjugated polymer semiconducting nanowires, and (4) reduce graphene oxide with nanometer resolution. The last objective is to characterize the TCNL nanostructures using AFM based methods, such as friction force microscopy, phase imaging, electric force microscopy, and conductive AFM. We show that they are useful for in situ characterization of nanostructures, which is particularly challenging for conventional macroscopic analytical tools, such as Raman spectroscopy, IR spectroscopy, and fluorescence microscopy.