In this thesis work, novel planar nanodiodes (PNDs) using an amorphous indium-gallium-zinc oxide (IGZO) film as the active layer have been electrically characterised for the first time. Simulation techniques and experimental methods, such as e-beam lithography (EBL) and nanoimprint lithography (NIL), have been explored for these devices. In addition, a novel approach was realized that produced self-aligned contacts for the nanostructured devices. A preliminary parameter space for experimentation of the PNDs was ascertained by simulating the devices using a technology computer aided design (TCAD) simulator. In this study Silvaco’s ATLAS default IGZO material system was adopted. These simulations showed device performance to be heavily dependent on the carrier concentration of the film, owing to the high leakage current during the off-state of device operation. Furthermore, device geometry had a significant influence on the device’s electrical response. Channel width, length and trench width were all examined. Experimental characterisation of PNDs were attained by fabricating devices using EBL. These devices are the first to exhbit diode-like DC electrical response from an IGZO-based PND. Full current rectification was obtained with a rectification ratio of 10^4 for devices with a long, narrow channel with a width of 50nm and a length of 4μm. This particular device geometry had a turn-on voltage, Von, of 2.2V and did not breakdown within the −10V bias range tested. An output drive current of 0.1μA at 10V was obtained by the single PND device. It was also demonstrated that by increasing the channel width, Von could be reduced; however, rectification also diminished. It is reasoned that the exposed IGZO surface was subject to contamination from the ambient which changed the device’s electrical response after 17 days. An ultraviolet NIL (UV-NIL) technique was developed to produce the PNDs. This fabrication method offers a suitable route towards high-volume manufacture of these nanodevices, which is critical for them to be incorporated into a low-cost RF energy harvester. A novel NIL process was established in which the contact pads were self-aligned to within ~ 200nm of the channel by patterning both metal and semiconductor layers with a single imprint. DC electrical characterisation of the imprinted PNDs produced high rectifications ratios at a lower Von. The greater number of devices tested allowed a coarse parameter space for channel width and length to determined. PNDs with a channel aspect ratio (length divided by width) of more than 20 exhibited the greatest DC rectification of 10^4. An alumina capping layer was found to eliminate hysteresis in the electrical response; however, the greater permittivity value had no noticeable effect on device performance. Finally, a large-signal RF analysis is carried out on a device which suggest no deterioration in device perfromance up to at least 1GHz.

L'oxyde de zinc (ZnO) est un semi-conducteur à large gap direct (3,37 eV) qui possède de nombreuses propriétés intéressantes (piézoélectrique, optique, catalytique, chimique…). Un large champs d'applications fait de lui l'un des matériaux les plus étudiés de la dernière décennie, notamment sous forme nanostructurée. Dans ce travail, nous nous intéressons à la synthèse par électrochimie des couches minces, des micro- & nano-plots, et des nanofils de ZnO. Deux méthodes ont été utilisées : la première dite Template consiste à la fabrication des micro- et nanopores en réseau ordonné à l'aide de la technique lithographique dans lesquels a lieu la croissance du ZnO ; la seconde consiste à la croissance libre de réseau de nanofils. Les caractérisations structurales, morphologiques et optiques du ZnO ainsi élaboré ont été réalisées par diffractométrie des rayons-X (DRX), microscopie électronique à balayage (MEB), microscopie électronique en transmission (MET), spectroscopie Raman, spectroscopie UV et photoluminescence (PL). Les propriétés électriques des couches minces et des réseaux de nanofils (sous l'effet collectif) de ZnO ont été étudiées par des mesures «courant tension» (I-V) à température ambiante dans la configuration métal/semi-conducteur/métal à l'aide d'un réseau de micro-électrodes métalliques déposé en surface du ZnO. Cette étude nous a permis de déterminer qualitativement la conductivité électrique du ZnO et les différents paramètres de la jonction Schottky entre le ZnO et le substrat doré. Celle-ci est fondamentale et indispensable pour la réalisation d'un dispositif de récupération d'énergie tel que le nanogénérateur de courant piézoélectrique à base de nanofils de ZnO / Abstract Zinc oxide (ZnO) is direct wide band gap semiconductor (3.37 eV) with many interesting properties (piezoelectric, optical, catalytic, chemical …). A wide range of applications makes it one of the most studied materials in the past decade, particularly when elaborated as nanostructures. In this work, we focus on electrochemical synthesis of ZnO thin films, micro- and nano-pillars as well as nanowires. Two methods were used: the first, called “Template”, consists of growing ZnO into organized arrays of micro- and nanopores made by lithographic methods ; the second consists of the free growth of nanowires array. The morphological and optical characterizations of the obtained ZnO were carried out using scanning and transmission electron microscopy (SEM and TEM), X-ray diffraction (XRD), Raman and UV spectroscopy, and photoluminescence (PL). Electrical properties of the electrodeposited ZnO (thin films and nanowire networks) were studied using I-V measurements at room temperature in metal/semiconductor/metal configuration, by the use of an array of metallic micro-electrodes deposited on the surface of ZnO. This allows determining qualitatively the electrical conductivity of ZnO and the different parameters of the Schottky junction between ZnO and the substrate (Au). This study is necessary for future applications based on ZnO nanowires array such as the solar cell and the piezoelectric nanogenerator

Les filtres CRIGFs sont une nouvelle génération de filtres optiques réflectifs nanostructurés qui présentent un très fort intérêt pour de nombreuses applications. Cependant, leur fabrication est relativement complexe : il s'agit de composants structurés à des échelles petites devant la longueur d'onde d'utilisation, mais de surface totale relativement grande. Ils sont usuellement fabriqués en utilisant des procédés de lithographie de type lithographie électronique, qui présente une résolution suffisante mais qui est séquentielle et donc lente pour de telles surfaces de composant. En outre, les CRIGFs sont souvent réalisés sur des substrats isolants, ce qui complexifie encore plus l'utilisation de cette lithographie. Lors de cette thèse, un procédé de fabrication des CRIGFs a été développé à partir de la lithographie par nanoimpression via moule souple (SNIL). Cette technologie collective et à haut rendement contourne les inconvénients et garde les avantages de la traditionnelle lithographie électronique. Elle permet de fabriquer des motifs nanométriques par simple pressage d'un moule souple sur une couche de résine de polymères sous insolation d'ultraviolets. Après avoir stabilisé le procédé et établi les limites de la technologie, de nombreux filtres CRIGFs ont ainsi été créés. Ils présentent des résultats optiques équivalents dans le proche infrarouge (NIR) à ceux fabriqués par lithographie électronique. Dans un deuxième temps, le caractère générique du procédé mis en place a été démontré de plusieurs façons. Premièrement, nous avons montré qu'il était possible à l'aide de celui-ci de dépasser les compromis usuels de conception en structurant directement le guide d'onde, qui sera ensuite ré-encapsulé. Deuxièmement, nous avons montré que ce même procédé pouvait être directement transféré pour réaliser des filtres CRIGF dans la gamme du moyen infrarouge, bien que les filtres soient alors réalisés sur un matériau cristallin III-V et présentent des dimensions micrométriques plutôt que nanométriques. Enfin, nous avons démontré la grande souplesse et stabilité du procédé en l'utilisant pour explorer différentes géométries potentiellement intéressantes de cette nouvelle famille de filtres optiques nanostructurés. Nous avons notamment étudié des CRIGFs comportant un gradient de période qui ont permis pour la première fois d'obtenir un filtre CRIGF accordable. Pour finir, nous nous sommes attachés à étudier le potentiel de réalisation de filtres CRIGFs plus complexes et présentant plusieurs niveaux de corrugation. / Cavity resonator integrated grating filters (CRIGFs) are a new generation of nanostructured reflective filters. They present a strong interest for many applications. However, their manufacturing is relatively complex: CRIGFs are components structured at small scales compared to the wavelength of interest but on a relatively large area. They are usually made by electron beam lithography technique which presents a sufficient resolution but does not allow parallel patterning and is thereby time consuming for large area components. Furthermore, CRIGFs are often fabricated on insulating wafers which make the e-beam lithography process more complicated. In this PhD, a CRIGF process manufacturing has been implemented through soft mold nanoimprint lithography (SNIL). This high throughput collective technology keeps the benefits of the traditional electron beam lithography while overcoming its limits. Nano-scale patterns can be made by a simple stamping under UV exposure of a soft mold on a polymer resist layer. After stabilizing the process and assessing the technique limits, plenty of CRIGFs have been manufactured. They exhibit optical performances in the near- infrared range equivalent to those manufactured by e-beam lithography. Secondly, it has been demonstrated that the implemented process is generic. We have shown the possibility to overcome the usual design trade-offs by structuring directly the waveguide, before embedding. Moreover, this same process has been shown to be applied in a straightforward way to fabricate CRIGFS in the mid-infrared range using a III-V crystalline material and micrometric sized patterns. Finally, we have demonstrated the great flexibility and sustainability of the process by testing different potential geometries of CRIGFs. Notably, we have designed a CRIGF with a period gradient leading to the first tunable CRIGF ever demonstrated. Lastly, we have evaluated the potential manufacturing of complex CRIGFs with several corrugation levels.

Metasurfaces are arrays of subwavelength meta-atoms that shape waves in a compact and planar form factor. During recent years, metasurfaces have gained a lot of attention due to their compact form factor, easy integration with other devices, multi functionality and straightforward fabrication using conventional CMOS techniques. To provide and evaluate an efficient metasurface, an optimized design, high resolution fabrication and accurate measurement is required. Analysis and design of metasurfaces require accurate methods for modeling their interactions with waves. Conventional modeling techniques assume that metasurfaces are locally periodic structures excited by plane waves, restricting their applicability to gradually varying metasurfaces that are illuminated with plane waves. In this work, we will first provide a novel technique that enables the development of accurate and general models for 1D metasurfaces. This approach can be easily extended to 2D metasurfaces. Due to the remarkable importance of accurate characterization of metasurfaces, we will provide a rigorous method to characterize 1D metasurfaces. Finally, we will provide an accurate approach to fabricate and characterize 2D metasrufaces.

Porous metal oxide materials, particularly those comprised of silica or titania, find use in many applications such as low-k dielectric materials for microelectronics as well as chemical sensors, micro/nanofluidic devices, and catalyst substrates. For this dissertation, the focus will be on the processing of porous metal oxide materials covering two subjects: hierarchical porosity exhibited over two discrete length scales and incorporation of functional nanomaterials. To generate the porous silica materials, the technique of supercritical carbon dioxide infusion (scCO2) processing was heavily relied upon. Briefly, the scCO2 infusion processing utilizes phase selective chemistries within a pre-organized amphiphilic block copolymer template using scCO2 as the reaction medium to selectively hydrolyze and condense silica precursors to yield mesoporous materials. To further develop the scCO2 infusion processing technique, hierarchically porous silica materials were generated on unique substrates. Hierarchically structured silica nanochannels were created using a combination of scCO2 infusion processing and nanoimprint lithography (NIL) patterned sacrificial polymer templates to yield mesopores and airgap structures respectively. Hierarchically porous silica materials were also generated on alternative substrates, in the form of cellulose filter paper, which were used to host the amphiphilic block copolymer template to yield tri-modal porosity silica materials. To extend the applicability of mesoporous silica generated from scCO2 infusion processing, functional nanomaterials, in the form of pre-synthesized gold nanoparticles, fullerene derivatives, and polyhedral oligomeric silsequioxanes (POSS) were embedded within the mesoporous silica to produce unique composite materials. The functional nanomaterials were able to impart specific properties, typically only affored to the functional nanomaterials, upon the mesoporous silica thin film with an example being enhanced thermal and hydrothermal properties of mesoporous silica doped with POSS molecules. To continue research with functional nanomaterials, nanoparticle composite materials, comprised of crystalline metal oxide nanoparticles and binder/filler materials, either organic or inorganic, were also evaluated as novel NIL resist materials. Patterning of the nanoparticle composite materials, specifically, but not limited to, titanium dioxide based materials, into two dimensional, arbitrarily shaped, sub-micron features was readily achieved on either rigid or flexible substrates. True three-dimensional structures, based on nanoparticle composite materials, were fabricated by utilizing release layers and pre-patterned substrates.

No description available.

The study of nanomaterials is a developing science with potentially large benefits in the development of catalysts, optical and chemical sensors, and solid state memory devices. As several of these devices require large arrays of nanoparticles, one of the greatest obstacles in material characterization and device development is the reliable manufacture of nanopatterns over a large surface area. In addition, various applications require different nanoparticle size and density. High density arrays with small nanoparticle sizes are difficult to achieve over a large surface area using current manufacturing processes. Herein, Nanoimprint Lithography (NIL) and Dynamic Templating are combined to create a new manufacturing process capable of developing high density arrays with small nanoparticle sizes. The NIL process involves the stamping of a polymer coated substrate by a silicon stamp with patterned nanofeatures. The stamp is then removed, leaving the pattern in the polymer, which is first etched and then coated with a thin layer of metal, filling the recessed regions of the pattern. The excess polymer is dissolved, leaving a pattern of nanoparticles on the substrate matching the pattern on the stamp. When Dynamic Templating is applied, a very thin layer of metal can be coated, which forms small nanoparticle sizes when dewetted. A custom NIL system has been developed to combine these two processes together, which has now proven to yield consistent large-area, dense arrays with a small nanoparticle size. An array spacing of 700 nm has been achieved, along with a nanoparticle size of 90 nm. Arrays have been created in gold and palladium, where there is now the potential to combine them with other solution-based syntheses which should lead to complex nanoparticle geometries suitable for sensor applications. / Mechanical Engineering

In the pursuit of economical and rapid fabrication solutions on the micro and nano scale, polymer replication has proven itself to be a formidable technique, which despite zealous development by the research community, remains full of promise. This thesis explores the potential of elastomers in what is a distinctly multidisciplinary field. The focus is on developing innovative fabrication solutions for planar photonic devices and for nanoscale devices in general. Innovations are derived from treatments of master structures, imprintable substrates and device applications. Major contributions made by this work include fully replicated planar integrated optical devices, nanoscale applications for photolithographic standing wave corrugations (SWC), and a biologically templated, optical fiber based, surface-enhanced Raman scattering (SERS) sensor. The planar devices take the form of dielectric rib waveguides which for the first time, have been integrated with long-period gratings by replication. The heretofore unemployed SWC is used to demonstrate two innovations. The first is a novel demonstration of elastomeric sidewall photolithographic mask, which exploits the capacity of elastomers to cast undercut structures. The second demonstrates that the corrugations themselves in the absence of elastomers, can be employed as shadow masks in a directional flux to produce vertical stacks of straight lines and circles of nanowires and nanoribbons. The thesis then closes by conceptually combining the preceding demonstrations of waveguides and nanostructures. An optical fiber endface is em ployed for the first time as a substrate for patterning by replication, wherein the pattern is a nanostructure derived from a biological template. This replicated nanostructure is used to impart a SERS capability to the optical fiber, demonstrating an ultra-sensitive, integrated photonic device realized at great economy of both time and money, with very real potential for mass fabrication.

The considerable interest in nanomaterials and nanotechnology over the last decade is attributed to Industry's desire for lower cost, more sophisticated devices and the opportunity that nanotechnology presents for scientists to explore the fundamental properties of nature at near atomic levels. In pursuit of these goals, researchers around the world have worked to both perfect existing technologies and also develop new nano-fabrication methods; however, no technique exists that is capable of producing complex, 2D and 3D nano-sized features of arbitrary shape, with smooth walls, and at low cost. This in part is due to two important limitations of current nanofabrication methods. First, 3D geometry is difficult if not impossible to fabricate, often requiring multiple lithography steps that are both expensive and do not scale well to industrial level fabrication requirements. Second, as feature sizes shrink into the nano-domain, it becomes increasingly difficult to accurately maintain those features over large depths and heights. The ability to produce these structures affordably and with high precision is critically important to a number of existing and emerging technologies such as metamaterials, nano-fluidics, nano-imprint lithography, and more. Summary To overcome these limitations, this study developed a novel and efficient method to etch complex 2D and 3D geometry in silicon with controllable sub-micron to nano-sized features with aspect ratios in excess of 500:1. This study utilized Metal-assisted Chemical Etching (MaCE) of silicon in conjunction with shape-controlled catalysts to fabricate structures such as 3D cycloids, spirals, sloping channels, and out-of-plane rotational structures. This study focused on taking MaCE from a method to fabricate small pores and silicon nanowires using metal catalyst nanoparticles and discontinuous thin films, to a powerful etching technology that utilizes shaped catalysts to fabricate complex, 3D geometry using a single lithography/etch cycle. The effect of catalyst geometry, etchant composition, and external pinning structures was examined to establish how etching path can be controlled through catalyst shape. The ability to control the rotation angle for out-of-plane rotational structures was established to show a linear dependence on catalyst arm length and an inverse relationship with arm width. A plastic deformation model of these structures established a minimum pressure gradient across the catalyst of 0.4 - 0.6 MPa. To establish the cause of catalyst motion in MaCE, the pressure gradient data was combined with force-displacement curves and results from specialized EBL patterns to show that DVLO encompassed forces are the most likely cause of catalyst motion. Lastly, MaCE fabricated templates were combined with electroless deposition of Pd to demonstrate the bottom-up filling of MaCE with sub-20 nm feature resolution. These structures were also used to establish the relationship between rotation angle of spiraling star-shaped catalysts and their center core diameter. Summary In summary, a new method to fabricate 3D nanostructures by top-down etching and bottom-up filling was established along with control over etching path, rotation angle, and etch depth. Out-of-plane rotational catalysts were designed and a new model for catalyst motion proposed. This research is expected to further the advancement of MaCE as platform for 3D nanofabrication with potential applications in thru-silicon-vias, photonics, nano-imprint lithography, and more.

The current trend in pushing photo lithography to smaller and smaller resolutions is becoming increasingly difficult and expensive. Extreme ultra-violet lithography is an alternate method that has the potential to provide feature sizes down to 30 nm, however, it will come at an even greater cost. Nanoimprint lithography (NIL) is another lithographic technique which is promising to provide very high resolutions at a relatively low cost. Imprinting works by using a mold with a surface patterned with the required nano structures and pressing it into a substrate coated with a deformable polymer. Due to its direct pattern replication technique, it is very capable of reproducing three-dimensional structures, however limited research has been performed on this to date. In this study, investigations have been performed into developing a reliable process for creating SiN molds with sub-100 nm structures with variable height control. The process relies on a negative tone electron beam resist which can be patterned to various thicknesses by varying the exposure dosage. This allows for the creation of complex multi-layer structures in a single electron beam lithography step. These patterns then have been transferred into the SiN substrate by a single reactive ion etch. From here the mold is ready for use in imprinting. Study has also been performed into imprinting process as well. This includes the development of an imprint press, the manner in which NIL works. Investigations have been performed into the imprinting performance of 3D molds. Thermal expansion issues have been found and addressed, as have adhesion problems. Some other aspects of 3D NIL which have not been addressed in this study have been outlined in future work for further investigation.