Les transistors monoélectroniques (SET) sont des dispositifs de tailles nanométriques qui permettent la commande d'un électron à la fois et donc, qui consomment peu d'énergie. Une des applications complémentaires des SET qui attire l'attention est son utilisation dans des circuits de mémoire. Une mémoire monoélectronique (SEM) non volatile a le potentiel d'opérer à des fréquences de l'ordre des gigahertz ce qui lui permettrait de remplacer en même temps les mémoires mortes de type FLASH et les mémoires vives de type DRAM. Une puce SEM permettrait donc ultimement la réunification des deux grands types de mémoire au sein des ordinateurs. Cette thèse porte sur la fabrication de mémoires monoélectroniques non volatiles. Le procédé de fabrication proposé repose sur le procédé nanodamascène développé par C. Dubuc et al. à l'Université de Sherbrooke. L'un des avantages de ce procédé est sa compatibilité avec le back-end-of-line (BEOL) des circuits CMOS. Ce procédé a le potentiel de fabriquer plusieurs couches de circuits mémoirestrès denses au-dessus de tranches CMOS. Ce document présente, entre autres, la réalisation d'un simulateur de mémoires monoélectroniques ainsi que les résultats de simulations de différentes structures. L'optimisation du procédé de fabrication de dispositifs monoélectroniques et la réalisation de différentes architectures de SEM simples sont traitées. Les optimisations ont été faites à plusieurs niveaux : l'électrolithographie, la gravure de l'oxyde, le soulèvement du titane, la métallisation et la planarisation CMP. La caractérisation électrique a permis d'étudier en profondeur les dispositifs formés de jonction de Ti/TiO2 et elle a démontré que ces matériaux ne sont pas appropriés. Par contre, un SET formé de jonction de TiN/Al2 O3 a été fabriqué et caractérisé avec succès à basse température. Cette démonstration démontre le potentiel du procédé de fabrication et de la déposition de couche atomique (ALD) pour la fabrication de mémoires monoélectroniques.[symboles non conformes]

Nous avons développé un microscope versatile combinant microscopie de force (AFM) et microscopie à effet tunnel (STM) à très basse température. Ce microscope permet d'étudier la densité locale d'états électroniques (LDOS) sur des nanocircuits supraconducteurs polarisables en courant.<br />La sonde du microscope est basée sur un diapason en quartz qui permet une détection entièrement électrique des interactions pointe-surface en mode AFM et qui hors résonance propose la rigidité nécessaire à la stabilité de la jonction tunnel en mode STM. Le diapason est bien adapté à un environnement cryogénique, dissipant une énergie inférieure à 1 nW. Notre microscope atteint en mode AFM la résolution atomique selon l'axe vertical et autorise en mode STM des jonctions tunnels de consigne Rtunnel < 10 MOhms<br />Nous avons développé un procédé de nanofabrication pour mettre au point des fils supraconducteurs de niobium (Nb) ayant pour section 10 x 300 nm2. Ce procédé permet d'obtenir une surface de Nb avec une rugosité subnanométrique.<br />Nous décrivons également la fabrication des pointes que nous collons sur les diapasons pour en faire des sondes.<br />Les LDOS mesurées à T=100 mK sur les fils de Nb sont comparées à la théorie BCS prenant en compte une énergie relative au processus inélastique, appelée paramètre de Dynes. Nos mesures sont en très bon accord avec ce modèle, en prenant en compte une température électronique effective supérieure à la température du cryostat. Enfin nous mesurons la LDOS sur un fil de Nb polarisé en courant qui démontrent la faisabilité des mesures de supraconductivité hors-équilibre par STM.

This thesis is focused on nanofabrication and its application in plasmonic chemical and bio- sensors. The contribution thus is the development of novel nanofabrication techniques and nano- structures for the sensors based on surface plasmon (SP). Part I (Chapter 1-3) is about novel nanofabrication techniques, especially nanoimprint lithography (NIL) and electron beam lithography (EBL). For NIL, the four major aspects of NIL were discussed, including the resist, mold, imprint process and equipment for NIL. Combined with NIL and soft lithography, hybrid nanoimprint-soft lithography was investigated. To overcome the difficulty of mold fabrication, a more robust solution of mold fabrication through a sacrificial poly(dimethyl glutarimide) (PMGI) master mold was designed in this work. Based on this method, the mold was fabricated without structure distortion, and pattern replication with sub-10 nm resolution was demonstrated. For EBL, several aspects were discussed to improve the performance of EBL, including the resist, development, and exposure condition. The charging effect to the pattern distortion was studied systemically for the electron beam exposure in large area with high current (>nA). Tilted periodic nanostructure was achieved by electron beam scanning on tilted sample with dynamic focus mode. EBL on irregular surface was realized by the exposure on evaporated polystyrene. Part II (Chapter 4-6) is the application in surface plasmonic chemical and bio-sensors. The first type of sensors is surface enhanced Raman scattering (SERS) sensor based on localized SP. Bowtie-shape nano-antenna structures of sub-10 nm gap were fabricated with the breakthrough of EBL resolution to 3 nm by exposing resist on Si3N4 membrane. By controlling the gap size during lithography, the surface plasmon enhancement was tuned accurately. High sensitivity of Au bowties antenna with sub-10 nm gap was achieved at low concentration of the target molecule (10^-7 mM, 1,2-di(4-pyridyl)ethylene in ethanol solution) and high enhancement of 10^7 resulting from the corresponding bowtie structure. The second type of sensors is extraordinary optical transmission (EOT) sensor based on propagating SP. The process of double liftoff was developed for the fabrication of nano-hole arrays on 100 nm-thick Au film utilizing EBL. This technique is versatile for the fabrication of many kinds of high-aspect-ratio noble metal structures. Additionally, annealing method was employed in this work to improve the smoothness of Au film. It was found that the RMS roughness of the deposited film was reduced by 72 % and the sensitivity was increased by 32 nm/RIU as a result of annealing. It was also found that the optical transmission intensity of the annealed NHA of similar hole diameter was increased more than twice which is due to the smaller absorption/scattering of the incident light and surface waves from the Au film surface. Besides the double liftoff process, several techniques were developed for EOT structures, including electroplating, imprint method, and deposition on membrane.

This Thesis describes the development of hard X-ray zone plates intended for focusing radiation at X-ray free-electron lasers (XFELs). XFELs provide unprecedented brightness and zone plates which are put in the intense X-ray beam are at risk of being damaged. Therefore, it is crucial to perform damage tests in order to design zone plates which can survive the XFEL beam. Zone plates are diffractive nanofocusing optics and are regularly used at high brightness synchrotron beamlines in the soft and hard X-ray regime. The resolution of a zone plate is proportional to its outermost zonewidth and thus depends on the smallest feature that can be fabricated. State-of-the-art nanofabrication processes developed for zone plates are able to produce zonewidths down to 10 nm. However, for hard X-rays, the zone plates need to be of sufficient thickness to efficiently focus the radiation. Thus, the limit in the fabrication of hard X-ray zone plates lies in the high aspect-ratios. This Thesis describes two processes developed for high aspect-ratio nanostructuring. The first process uses tungsten as diffractive material. Aspect-ratios up to 1:15 have been accomplished. Furthermore, a mounting method of a central stop directly on the zone plate is also presented. The other fabrication process uses diamond, in which aspect-ratios of 1:30 have been demonstrated. Both processes rely on thin-film deposition techniques, electron-beam lithography, and reactive ion etching. Thanks to the materials’ excellent thermal properties these types of zone plates should be suitable for XFEL applications. Tungsten and diamond diffractive optics have been tested at an XFEL at Stanford (LCLS), and damage investigations were performed in order to determine the maximum fluence that could be imposed on the optics before degradation occured. The conclusion of these damage tests is that tungsten and diamond diffractive optics can survive the XFEL beam and could potentially be used in beamline experiments relying on nanofocused X-ray beams. Finally in this Thesis, characterization of two zone plates using an interferometer is presented, where it is also shown that the interferometric method can be used to pin-point beamline instabilities. / <p>QC 20150112</p>

Nanotechnology and nanoscience are experiencing rapid development in the last decade. Intensive research has been carried out on nanostructures synthesis and nanodevices fabrication. Due to its small size, a nanodevice usually requires an extremely small power to operate. However, to make the novel nanodevice work, an external power source is normally needed, which can either be a battery or a power source, thus, the size of the battery is usually much larger than that of the device and its life time is limited. It is highly desired to have a nanoscale size power source that harvests its energy from the environment so that it works independently and wirelessly to provide power to the nanodevices. This dissertation provides a solid solution to this dilemma based on nanotechnology. Starting from the synthesis of well aligned ZnO nanowire arrays on different substrates, an innovative method is presented first to measure the mechanical property of the as-synthesized ZnO nanowire arrays by using AFM without destroying and manipulating the sample. This technique is then extended to converte mechanical energy into electricity by scanning the nanowire arrays using a AFM tip in contact mode. Due to the unique semiconducting and piezoelectric dual properties of ZnO, mechanical energy is converted into electricity and is effectively output. This is the invention of the piezoelectric nanogenerator. Then, by replacing AFM tips using a zigzag top electrode, the first prototype direct-cirrent nanogenerator driven by ultrasonic wave has been fabricated. Further investigations have also been carried out about the effect of ZnO carrier density on the output power, and the power generating property of oligomer functionalized ZnO nanowires. This desertation established the fundamental mechanism for the nanogenerator, and it provides a new path towards self-powered nanosystems, which has key applications in in-vivo biosensing, MEMS, environmental mornitoring, defence technology and even personal electronics.

This thesis summarizes the present status of the nanofabrication of diffractive optics, i.e. zone plates, and test objects for soft x-ray microscopy at KTH. The emphasis is on new and improved fabrication processes for nickel and germanium zone plates. A new concept in which nickel and germanium are combined in a zone plate is also presented. The main techniques used in the fabrication are electron beam lithography for the patterning, followed by plasma etching and electroplating for the structuring of the optical materials. The process for fabricating nickel zone plates has been significantly improved. The reproducibility of the electroplating step has been increased by the implementation of an in-situ rate measurement and an end-point detection method. We have also shown that pulse plating can be used to obtain zone plates with a uniform height profile. New plating mold materials have been introduced and electron-beam curing of the molds has been investigated and implemented to increase their mechanical stability so that pattern collapse in the electroplating step can be avoided. The introduction of cold development has improved the achievable resolution of the process. This has enabled the fabrication of zone plates with outermost zone widths down to 16 nm. The nickel process has also recently been adapted to fabrication of gold structures intended for test objects and hard x-ray zone plates. For the fabrication of germanium zone plates we developed a highly anisotropic plasma-etch process using Cl2 feed and sidewall passivation. Germanium zone plates have been fabricated with zone widths down to 30 nm. The diffraction efficiency is comparable to that of nickel zone plates, but the process does not involve electroplating and thus has for potential for highyield fabrication. The combination of nickel and germanium is a new fabrication concept that provides a means to achieve high diffraction efficiency even for thin nickel. The idea is to fabricate a nickel zone plate on a germanium film. The nickel zone plate itself is then used as etch mask for a highly selective CHF3- plasma etch into the germanium layer. Proof of principle experiments showed an efficiency increase of about a factor of two for nickel zone plates with a 50- nm nickel thickness. / QC 20100728

Enhanced mass transport in carbon-based nanoscale conduits (e.g. carbon nanotubes, graphene nanochannels/capillaries, graphene/graphene oxide membranes) has attracted tremendous interest over the last decade due to its significant implications for water desalination/purification, nanofiltration, electronic cooling, battery/fuel cells, and lab-on-a-chip. Further development of carbon-based nanoscale conduits for practical applications relies on understanding fundamental mechanisms of transport through individual conduits, which have not been well studied due to challenges in fabrication and measurement. In this thesis, the construction of two-dimensional planar graphene nanochannel devices and the studies of enhanced water and ion transport inside the graphene nanochannels are reported for the first time. The graphene nanochannels are fabricated by conformally covering high-quality graphene on the surfaces of silica nanochannels. A new fabrication scheme consisting of graphene wet transfer, graphene patterning and vacuum anodic bonding is developed to create such graphene nanochannels with heights ranging from 24 to 124 nm. Using these nanochannels and a new hybrid nanochannel based capillary flow measurement technique, we successfully measured the hydraulic resistance (water permeability) of single graphene nanochannels. Our results demonstrate that the frictionless surface of graphene induces a boundary slip and enhances water flow inside the graphene nanochannel. The measured slip length of graphene in the graphene nanochannels poses a median value around 16 nm, albeit with a large variation from 0 to 200 nm regardless of the channel height. The small-yet-widely-varying values of the graphene slip length are attributed to the surface charge of graphene and the interaction between graphene and underneath silica substrate, which are in good agreement with the prediction of our molecular dynamics (MD) simulation. In addition, we also investigated enhanced ion transport inside the graphene nanochannels. Higher electroosmotic conductance at low electrolyte concentrations (10-6 M~10-2 M) is observed in graphene nanochannels when compared with silica nanochannels with the same geometry. Our results suggest that the enhanced electroosmotic flow is also due to the boundary slip at the graphene/electrolyte interface. Besides, our analysis shows that the surface charge on the graphene, originating from the dissociation of oxygen-containing functional groups, is crucial to the enhanced electroosmotic flow inside nanochannels.

xviii, 192 p. / Gold nanoparticles in the 1-2 mn core diameter size regime have generated a great deal of interest due to their size-dependent electronic, optical, and catalytic properties. A number of proof-of-concept experiments have demonstrated that small metal nanoparticles can be integrated into single electron transistors and optical waveguides. Still, reliable incorporation of gold nanoparticles into devices requires practical methods for their assembly on surfaces. Additionally, surface modification methods must be developed in order to control interparticle interactions and nanoparticle-environment interactions for use in sensing and catalysis. In this research, nanoparticle-substrate interactions were utilized to assemble surface-bound gold nanoparticle monolayers with interesting electronic and catalytic properties. Gold nanoparticles (1.5 nm diameter) with a thiol ligand shell containing phosphonic acid terminal functionality were synthesized and assembled selectively onto hafnium-modified silicon dioxide substrates through bonding of the terminal phosphonate to Hf(IV) surface groups. By increasing the surface coverage of Hf, it was possible to assemble monolayers of gold nanoparticles dense enough to exhibit nonlinear current-voltage properties across a 5-μm electrode gap at room temperature. Moreover, by taking advantage of the selectivity of this ligand shell for ZnO over SiO 2 , small gold nanoparticles were utilized as catalysts for selective growth of patterned, vertical ZnO nanowire arrays. In addition to engineering nanoparticle-substrate interactions, new surface modification methods were introduced to manipulate the interaction of the as-deposited gold nanoparticle monolayers with the environment. For example, thiol-thiol ligand exchange reactions were carried out on the surface-bound nanoparticle monolayers by immersion in dilute thiol solutions. Contact angle and XPS measurements indicate that the upper, surface-exposed phosphonic acid ligands are replaced by incoming thiol ligands. TEM measurements indicate that nanoparticle monolayers remain surface-bound and are stable to this exchange process, as the average particle size and surface coverage are preserved. As another example, the ligand shell can be partially removed by UV/ozone treatment to expose bare gold cores to the surrounding environment. On metal oxide substrates, this approach activates the particles for room temperature oxidation of carbon monoxide to carbon dioxide. This dissertation includes both my previously published and my co-authored materials. / Adviser: James E. Hutchison

Neste trabalho apresentamos um estudo sistemático da transmissão da radiação eletromagnética em um conjunto de fendas metálicas individuais depositadas em substratos de vidro BK7 com larguras abaixo do comprimento de onda da luz incidente. As fendas foram obtidas através da evaporação térmica de prata e ouro sobre um substrato dielétrico (vidro BK7). A fabricação das fendas foi feita de forma direta através de um equipamento de feixe de íons de Gálio (FEI Quanta 3D). A transmissão óptica das fendas foi estudada com radiação laser para os comprimentos de onda de 488 nm e 632.8 nm. Observouse uma oscilação de intensidade na transmissão devido ao efeito de interferência dos surface plasmon polariton (SPP) gerados na superfície metálica como função da espessura do filme metálico. Os resultados experimentais obtidos foram confrontados com simulações computacionais, via método de elementos finitos, a partir das quais pode se compreender os mecanismos de propagação da radiação na estrutura em questão, e compará-los com detalhes da fabricação de fendas. Procedimento similar foi realizado ao variar a largura das mesmas. Também foi feita a análise da transmissão óptica em fendas fabricadas em filmes constituídos por camadas alternadas de prata e ouro, a fim de comparar como tal mudança na configuração da estrutura afeta os resultados anteriores. O trabalho serviu para mostrar que as dimensões dos filmes metálicos, assim como das fendas, apresentavam grande influência nas propriedades de transmissão e, além do que foi possível conferir diversos conceitos básicos da teoria eletromagnética num sistema relativamente simples. A compreensão dessas propriedades é fundamental para o desenvolvimento de futuros dispositivos que utilizam efeitos plasmônicos. / This work presents a systematic study of the transmission of electromagnetic radiation on a set of single metallic slits metallic with widths below the wavelength of incident light, deposited on BK7 glass substrates. The slits were obtained by thermal evaporation of silver and gold on a dielectric (BK7 glass). The fabrication of the slits was performed directly through a gallium ion beam equipment (FEI Quanta 3D). The optical transmission of the slits was studied by laser radiation for the wavelengths of 488 nm and 632.8 nm. An oscillation in the transmission intensity was observed due to the interference effect of the surface plasmon polariton (SPP) generated on the metallic surface as a function of the metal film thickness. The experimental results were compared with computational simulations, via finite element method, in order to comprehend the mechanisms of radiation propagation in the structure and compare them with details of slits fabrication. A similar procedure was performed by varying the width of the slits. An analagous analysis of the optical transmission in slits fabricated in films consisting of alternating layers of silver and gold was performed in order to compare how this change in structure configuration affects the previous results. The work served to show that the dimensions of the metal films, as well as of the slits, have a significant influence on the properties of transmission, and, moreover it was possible to confer different basic concepts of electromagnetic theory in a relatively simple system. Understanding these properties is fundamental for the development of future devices that make use of plasmonics effects.

Le sujet de cette thèse concerne la spintronique moléculaire. Des jonctions tunnel magnétiques formées par une barrière tunnel moléculaire (monocouche auto-assemblée) insérée entre deux électrodes métalliques ferromagnétiques ont été étudiées. Afin de fabriquer les dispositifs, un procédé de greffage des molécules sur des substrats ferromagnétiques a été mis en place et une technique de lithographie a été développée pour définir des jonctions de taille submicronique. L’ensemble de ce travail expérimental a permis l’obtention de jonctions non court-circuitées et mesurables, où le transport électronique est bien du transport par effet tunnel.Les mesures de magnétotransport de ces échantillons ont amené des résultats intéressants et nouveaux : les jonctions, dont la barrière est formée par des alcanes-thiols, présentent de la magnétorésistance à température ambiante, allant jusqu’à 12%. Une partie de la thèse s’attelle à la compréhension des différents comportements magnétorésistifs observés : un modèle de barrière tunnel à deux niveaux est proposé pour les décrire.La dernière partie du travail présente des résultats préliminaires obtenus lorsque la barrière moléculaire est formée par des molécules aromatiques ou commutables et met en évidence des phénomènes nouveaux par rapport au cas précédent.L’ensemble des résultats prouve le fonctionnement de jonctions tunnel magnétiques à base de monocouches moléculaires à température ambiante et ouvre la voie à l’utilisation de molécules plus complexes pour une électronique de spin moléculaire multifonctionnelle. / This thesis work enters within the molecular spintronic fields. Magnetic tunnel junctions based on molecular self assembled monolayers have been investigated. The devices structure is a molecular monolayer inserted between two ferromagnetic electrodes.A process to graft molecules on a ferromagnet’s surface and a lithography technique have been developed to define the junctions. This experimental work has led to non short-circuited and measurable junctions, in which an electronic tunnel transport has been demonstrated.Interesting and new results have been found out from magnetoresistance measurement of the samples: junctions made with alkanes-thiols barrier have shown magnetoresistance signal at room temperature (up to 12%). In order to explain the magnetoresistive behaviour, a simple model where the barrier is discribed by two levels has been proposed.The last part of the thesis reports preliminary results obtained when the barrier is made of aromatic molecules or switchable molecules and it points out new phenomenons compared to the alkanes case.The overall work proves that devices made from magnetic tunnel junctions with self-assembled monolayers work at room temperature. It is then possible to consider switchable molecules to build multifunctional molecular spintronics devices.