Tableau d’honneur de la Faculté des études supérieures et postdoctorales, 2008-2009 / Le présent mémoire propose une étude sur la caractérisation biophysique et in vivo de peptides formant des canaux ioniques artificiels nommés LS2 et LS3. Ces molécules servant de modèles ont d'abord été mises au point par DeGrado et al en 1988, pour être ensuite caractérisées et modélisées jusqu'en 2007. Nous nous appuyons donc sur ces travaux ainsi que sur des études antérieures effectuées au sein de notre laboratoire pour éclaircir davantage les phénomènes d'auto-assemblage propres à ces peptides modèles. La première partie introduit le sujet des nanostructures peptidiques et la problématique de l'auto-assemblage à l'aide de plusieurs exemples tirés de la littérature récente. Les chapitres 1 et 2 traitent, dans un premier temps, des canaux ioniques naturels et offrent une analyse des éléments structuraux qu'ils partagent. Par la suite, une analyse des critères visés pour la création d'un canal ionique modèle est offerte. Celle-ci est suivie d'une présentation détaillée de LS2 et LS3. Le troisième chapitre présente la synthèse d'analogues fluorescents destinés aux caractérisations biophysiques et in vivo. Les chapitres 4 et 5 se consacrent aux études de dichroïsme circulaire et d'incorporation transmembranaire en infrarouge, respectivement. Le dernier chapitre présente les études de localisation in vivo réalisées avec les analogues fluorescents que nous avons synthétisés.

Titre de l'écran-titre (visionné le 9 mai 2023) / La thèse suivante examine la conversion du CO₂ à partir d'énergie solaire en utilisant des photocatalyseurs, qui est considérée comme l'un des techniques les plus intéressantes pour résoudre les problématiques du réchauffement climatique et de la crise énergétique. Il convient de souligner que cette thèse propose trois nouveaux composites hybrides nanostructurés pour la réduction photocatalytique du CO₂. La récolte de la lumière, la séparation des charges et les réactions de surface sont des aspects critiques qui ont un impact énorme sur la photoréduction du CO₂. Les cadres organiques covalents (COF) sont des candidats appropriés pour ces processus car ils offrent des caractéristiques et des propriétés structurelles exceptionnelles. De nombreux photocatalyseurs nanostructurés sont activement développés pour la photoréduction du CO₂. Les nanostructures multidimensionnelles et les hétérostructures sont largement étudiées en raison de leurs excellents attributs tels que la séparation efficace et la longue durée de vie des porteurs de charges. De manière prometteuse, les nanostructures et les nanocomposites des cadres organiques covalentes avec le graphène et ses dérivés, les dichalcogénures métalliques et les matériaux plasmoniques présentent d'excellentes performances photocatalytiques, selon des études de la littérature. D'abord, un cadre organique covalente, à base de céto-énamine TpPa-1 et de nanofeuillets d'oxyde de graphène réduit (rGO en anglais), a été développé par la technique d'assemblage in situ pour la photoréduction du CO₂ sous la lumière du soleil. Les interactions covalentes entre TpPa-1 et le rGO ont facilité la formation des bandes avec le potentiel requis, ainsi qu'une séparation de charge améliorée et une migration rapide des porteurs de charges vers la surface pour la réduction sélective du CO₂. Le médiateur électronique [Co(bpy)₃]²⁺ a servi pour apporter sites actifs pour la coordination, l'activation et la réduction des molécules de CO₂ en CO. De plus, un cadre organique covalente (COF) nanosphérique creux à base de TpPa-1, intégrée à un atome unique de Co-1T-MOS₂ (TpPa-1/Co-1T-MOS₂), a été conçu et développé via une stratégie à double ligand pour ajuster le potentiel des bandes et améliorer la séparation des charges afin d'optimiser l'efficacité de la photoréduction du CO₂. Les interactions entre TpPa-1 et Co-1T-MoS₂ ont facilité et amélioré la séparation des charges ainsi que la migration des porteurs de charge vers la surface, ce qui a entraîné une conversion sélective du CO₂ en CO. Finalement, les nanoparticules plasmoniques Au adhérés à une structure organique covalente tridimensionnelle, à base de porphyrine creuse (COF-366-Co) et avec un atome unique de Co (COF-366-Co[indice (H)]/Au), augmentent considérablement l'efficacité de la photoréduction du CO₂. Le nanocomposite conçu utilise le transfert d'électrons énergétiques induit par le plasmon, une meilleure collecte de lumière et des réactions de surface facilitées pour conduire les réactions redox photocatalytiques. Le nanocomposite développé (COF-366-Co[indice (H)]/Au) a montré une activité prometteuse vis-à-vis de la réduction photocatalytique du CO₂ sous irradiation à la lumière visible, qui a produit CO à un taux allant jusqu'à ~1200 µmolg⁻¹h⁻¹ et avec une sélectivité de 98 % sur H₂. / The ensuing thesis examines the conversion of carbon dioxide (CO₂) to value-added chemical and fuels under solar light irradiation by employing some of the emerging photocatalytic materials known as covalent organic frameworks (COFs). This approach of photocatalytic process is considered to be one of the most viable remedies to global warming and energy crisis dilemmas. Importantly, this thesis delivers three novel nanostructured hybrid composites based on COFs for photocatalytic CO₂ reduction to value-added chemicals and fuels. Light-harvesting, charge separation, and surface reactions are critical aspects that have an enormous impact on CO₂ photoreduction. Covalent organic frameworks can be suitable candidates for these processes as they offer outstanding structural features and properties. Diverse nanostructured photocatalysts are actively being developed for CO₂ photoreduction. Multidimensional nanostructures and nanocomposite heterostructures are widely studied because of their excellent attributes such as efficient separation and long lifetime of the excited charge carriers. Promisingly, nanostructures and nanocomposites of the covalent organic frameworks with graphene and its derivatives, metal dichalcogenides and plasmonic materials exhibit excellent photocatalytic performance, according to the literature reports. In this investigation, a keto-enamine TpPa-1 covalent organic framework and reduced graphene oxide nanosheet nanocomposite are developed by an in-situ assembling technique. The covalent interactions between TpPa-1 and rGO facilitated the formation of band edges with required potential and thereby to achieve an improved charge separation along with rapid migration of charge carriers to the surface toward the selective reduction of CO₂. By the support of the electron mediator [Co(bpy)₃]²⁺ in the hybrid served as the active sites for the coordination, activation, and reduction of CO₂ molecules to CO. A hollow nano spherical TpPa-1 covalent organic framework (COF) integrated with single atom Co-1T-MoS₂ (TpPa-1/Co-1T-MoS₂) is further designed and developed through a dual-ligand strategy to tune the band edge potential and enhance the charge separation to improve CO₂ photoreduction efficiency of the system. The interactions between TpPa-1 and Co-1T-MoS₂ aided and enhanced the charge separation as well as charge carrier migration to the surface resulted in selective conversion CO₂ to CO. Au plasmonic nanoparticles adorned three-dimensional hollow porphyrin-based covalent organic framework with Co single atom (COF-366-Co[subscript (H)]/Au) is developed via dual-ligand strategy and post-synthetic metallization method and found that this system significantly boosted up the CO₂ photoreduction efficiency. It utilizes the plasmon-induced energetic electron transfer, enhanced light harvesting, and surface reactions to drive the photocatalytic redox reactions. The developed COF-366-Co[subscript (H)]/Au exhibited fine activity toward photocatalytic CO₂ reduction under visible light irradiation, which yielded the CO at a rate up to ~1200 µmolg⁻¹h⁻¹ with a selectivity of 98% over H₂.

In this dissertation, I present that at a vacuum of 3×10-7 Torr, residual O2, CO2, H2 and Ar exposure do not significantly degrade the field emission (FE) properties of ZnO nanorods, but N2 exposure significantly does. I propose that this could be due to the dissociation of N2 into atomic nitrogen species and the reaction of such species with ZnO. I also present the effects of O2, CO2, H2O, N2, H2, and Ar residual gas exposure on the FE properties of GaN and ZnS nanostructure. A brief review of growth of ZnO, GaN and ZnS is provided. In addition, Cs deposition on GaN nanostructures at ultra-high vacuum results in 30% decrease in turn-on voltage and 60% in work function. The improvement in FE properties could be due to a Cs-induced space-charge layer at the surface that reduces the barrier for FE and lowers the work function. I describe a new phenomenon, in which the resistivity of CVD-grown graphene increases to a higher saturated value under light exposure, and depends on the wavelength of the light—the shorter the wavelength, the higher the resistivity. First-principle calculations and theoretical analysis based on density functional theory show that (1) a water molecule close to a graphene defect is easier to be split than that of the case of no defect existing and (2) there are a series of meta-stable partially disassociated states for an interfacial water molecule. Calculated disassociation energies are from 2.5 eV to 4.6 eV, that match the experimental observation range of light wavelength from visible to 254 nm UV light under which the resistivity of CVD-grown graphene is increased.

La formation et la morphologie des boîtes quantiques est un sujet d'un grand intérêt, ces structures ayant de nombreuses application potentielles, en particulier en microélectronique et optoélectronique. Cette thèse porte sur l'étude théorique et numérique de la croissance et de la morphologie d'ilots par épitaxie par jet moléculaire. Un premier modèle de croissance est une étude non-linéaire de l'instabilité de type Asaro-Tiller-Grinfeld, il convient pour les systèmes à faibles désaccords de maille, et est plus spécifiquement appliquée au cas où le désaccord de maille est anisotrope (voir le cas du GaN sur AlGaN). Le calcul de l'instabilité que nous avons effectué prend en compte les effets élastiques causés par le désaccord de maille, les effets de mouillage et les effets d'évaporation. La résolution numérique de l'instabilité nous permet de constater une croissance plus rapide dans le cas anisotrope comparé au cas isotrope, ainsi que la croissance d'ilots fortement anisotropes.Le deuxième modèle est basé sur des simulations Monte Carlo cinétiques, qui permettent de décrire la nucléation d'ilots 3D. Ces simulations sont utilisées pour les systèmes à fort désaccord de maille, comme Ge sur Si. Nos simulations prennent en compte la diffusion des adatomes, les effets élastiques, et un terme simulant la présence de facettes (105). Des ilots pyramidaux se formaent, conformément aux expériences et subissent un mûrissement interrompu. Les résultats obtenus ont été comparés au cas de la nucléation 2D, et on retrouve en particulier une densité d'ilots en loi de puissance par rapport au rapport D/F du coefficient de diffusion et du flux de déposition. / The growth and morphology of quantum dots is currently a popular subject as these structures have numerous potential uses, specifically in microelectronics and optoelectronics. Control of the size, shape and distribution of these dots is of critical importance for the uses that are being considered. This thesis presents a theoretical and numerical study of the growth of islands during molecular beam epitaxy. In order to study these dots, we used two models : a nonlinear study of an Asaro-Tiller-Grinfeld like instability, and kinetic Monte Carlo simulations. The first model is appropriate for low misfit systems, and is detailed in the case where misfit is anisotropic (this is the case when depositing GaN on AlGaN). In this case we took into account elastic effects, wetting effects and evaporation. Numerical calculations show faster growth, compared to the isotropic misfit case, and the growth of strongly anisotropic islands.The second model is based on kinetic Monte Carlo simulations that can describe 3D island nucleation. We use these simulations to study systems with high misfits, specifically Ge on Si. Adatom diffusion on a surface is considered and takes into account elastic effects, and surface energy anisotropy, that allows us to stabilize (105) facets. Simulation results show the growth of pyramid-shaped 3D islands, as observed in experiments, and their ripening is interrupted. The results of these simulations are then compared to the case of 2D nucleation, and we find that several of the known 2D properties also apply to 3D islands. Specifically, island density depends on a power law of D/F, the diffusion coefficient divided by the deposition flux.

Le projet de thèse est divisé en deux parties. D’une part, la génération directionnelle et singulière de plasmons de surface (SPPs) par des ouvertures nanométriques a été réalisé et optimisé par le biais de microscopie de fuites radiatives (LRM). Nous démontrons expéri- mentalement qu’une structure plasmonique composée de nano-ouvertures en forme de T et Λ permet de contrôler le couplage unidirectionnel et radialdes SPPs grâce au spin de la lumière incidente. Pour confirmer nos résultats expérimentaux, nous développons un modèle analytique qui décrit les coupleurs plasmoniques constitués de nano-ouvertures par représentation multidipolaire, permettant ainsi une explication théorique de la directionalité et de la formation de vortex plasmonique. L’optimisation des paramètres géométriques tels que l’angle au sommet des ouvertures en forme de Λ montre la possibilité de maximiser la directivité et le taux d’extinction à la fois pour le couplage directionnel et la génération des vortex dans le champ lointain. Parailleurs, notre méthode basée sur la détection LRM, permet une analyse quantitative et est avérée être une technique de caractérisation sophistiquée pour cartographier le champ plasmonique. Il fournit également plusieurs nouvelles possibilités pour la focalisation de SPP contrôlée en polarisation.D’autre part,le couplage spin-orbite de la lumière dans un guide et son effet réciproque sont réalisées et confirmées expérimentalement et théoriquement. Les coupleurs et découpleurs réseaux sur le guide d’ondes sont d’abord développés et étudiés. La sortie parfaite de la lumière confinée par le découpleur nous offre la possibilité de détecter les ondes guidées. La fluorescence des nanocristaux déposés sur la surface de l’échantillon montre une autre possibilité de visualiser directement la propagation de la lumière dans le guide d’onde. Le couplage directionnel contrôlé par spin est réalisé par des antennes en forme de Λ et est confirmé par des images en champ sombre avec des découpleurs et des images de fluorescence. En outre, l’effet réciproque est observé avec une imperfection de polarisation de sortie qui est expliqué théoriquement par le fait que les ordres de diffraction par les antennes en forme de Λ influent sur les états de polarisation finaux. Ainsi, l’effet réciproque est parfaitement réalisé par la sélection d’une région spécifique de diffraction dans le plan de Fourier. La caractérisation quantitative des interactions spin-orbite nous permet d’envisager le développement de nouveaux coupleurs directionnels dans le domaine de la nanophotonique tels que le traitement quantique de l’information. / In this project, two contributions are reported. Firstly, the directional and singular generation of Surface Plasmon Polaritons (SPPs) in the nanoapertures is investigated using the Leakage Radiation Microscopy (LRM). We demonstrate experimentally spin-driven directional coupling as well as singularity (inward) and vortex (outward radial coupling) of SPPs by nanostructures built with T-shaped and Λ-shaped apertures.To support our experimental findings, we develop an analytical model based on a multidipolar representation of Λ- andT-shaped aperture plasmonic couplers, allowing a theoretical explanation of both directionality and singular SPP formation. The optimal apex angle of Λ-shaped apertures shows the possibility to maximize the directiviy and extinction ratio for both directional coupling and singular SPP generation in the far field. Besides, our method based on LRM detection, allows quantitative analysis and is proven to be a sophisticated characterization technique for mapping the SPP vortex field.It also provides several new possibilities for polarization-controlled SPP sub-wavelength focusing.Secondly, the spin-orbit coupling of light into a photonic waveguide and its reciprocal effect are realized and confirmed both experimentally and theoretically. Coupler and decoupler gratings on the waveguide are firstly developed and investigated. The radiation of the confined light from the decoupler provides us a possibility to detect the guided waves. The fluorescence of nanocrystals deposited on the sample surface shows another possibility to directly visualize the light propagation in the waveguide. The spin-driven directional coupling is achieved by Λ-shaped antennas and is certified by the dark field images with decouplers and the fluorescence images. Furthermore, the reverse effect is observed with an imperfection of output polarization which is explained that the diffraction orders by the Λ-shaped apertures influence the final polarization states based on an analytical model. Thus, the reciprocal effect is realized by selecting the specific diffraction region on the Fourier plane. We believe that the quantitative characterization of spin-orbit interactions will pave the way for developing new directional couplers in the field of nanophotonics such as quantum information processing and so forth.

FePt/B4C multilayer thin films are deposited on silicon substrates using magnetron sputtering with different B4C layer thickness. Experimental results suggest that the B4C layers effectively serve as spacers to separate the FePt layers, making the multilayer configuration stable even after film annealing at elevated temperatures. On the other hand, B and C are found to be incorporated into the FePt layer, which is responsible for the FePt grain growth confinement and grain separation, and eventually affects the properties of the composite film. Based on the experimental results of multilayer composite film, particle (FePt)/matrix (B4C) monolayer composite thin films on Si substrate are synthesized, in which a record coercivity of 2200 Oe is achieved compared to similar system. The size uniformity of the FePt nanoparticles, the well-defined particle-particle separation, together with the good magnetic property and high temperature thermal stability of the overall composite film, make it a very promising candidate for the ultrahigh density magnetic storage media. / Functional nanostructures serve as the basic building blocks for nanodevices and significant efforts have been devoted to their morphology control and properties optimization. In present study, four functional nanostructures, i.e., FePt/B4C multilayer composite film, particle (FePt)/matrix (B4C) monolayer composite film, Ga-doped ZnO nanowire arrays, and CdSe nanotube arrays are designed, synthesized and characterized in detail, in which the first two are expected to be prominent candidates for ultrahigh-density magnetic storage media while the later two have potential applications in solar energy conversion. / Semiconductor based one-dimensional nanostructures are investigated as promising building blocks for solar energy conversion devices. Two aspects are explored, aiming at increasing the energy conversion efficiency, i.e., facilitating electron transport and enhancing photon absorbing. In the first case, large area Ga-doped ZnO nanowire arrays are grown on transparent conducting substrate. Experimental results reveal the well-aligned array morphology and the uniform Ga concentration in these nanowires. In particular, direct I-V measurements performed on single nanowire-on-ITO substrate disclose its Ohmic contact with the conducting substrate and the significant conductivity improvement compared to undoped ZnO nanowire, In the second case, a novel synthesis strategy for nanotube arrays is developed and CdSe is used for demonstration, which material possessing more appropriate band gap as effective light harvester compared to that of materials for existing semiconductor nanotube arrays. The controllable tube wall thickness that can be increased until continuous CdSe porous network is obtained. The experimental results suggest a nanotube array formation mechanism that can be generally applied to a wide range of materials. / Zhou, Minjie = 功能纳米结构在磁性和能源方面的应用 / 周民杰. / Adviser: Li Quan. / Source: Dissertation Abstracts International, Volume: 72-11, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 91-100). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Zhou, Minjie = Gong neng na mi jie gou zai ci xing he neng yuan fang mian de ying yong / Zhou Minjie.

La manipulation de parois de domaine magnétique – qui séparent des régions d’aimantation uniforme dans les matériaux – est associée à des enjeux à la fois fondamentaux et technologiques. De nombreux travaux portent sur l’utilisation de champs magnétiques et de courants électriques pour leur déplacement. Cependant, des préoccupations particulières – notamment la dissipation d’énergie - motivent la recherche d’alternatives. Parmi les solutions potentielles, le couplage magnétoélectrique par l’intermédiaire de contraintes mécaniques dans des hétérostructures magnétoélastique/piézoélectrique paraît prometteur. Dans cette thèse, il est montré que l’association d’un champ magnétique de biais et de contraintes mécaniques uniformes peut engendrer le déplacement unidirectionnel d’une paroi de domaine transverse dans des nanostructures à anisotropie uniaxiale. Les considérations statiques et dynamiques de ce phénomène sont étudiées par le biais de procédures numériques ad hoc simulant le couplage mécanique entre substrat de PMN-PT de coupe 011 générant des contraintes, et nanostructures multicouches magnétoélastiques TbCo2/FeCo. Le design du profil de section des nanostructures permet de moduler la réponse du système, par exemple pour contrôler la position de parois confinées. La dynamique du système se distingue des régimes habituels de par la forme de la paroi de domaine. L’atteinte de régimes permanents dans des nanorubans montre que des vitesses comparables aux autres techniques sont obtenues, pour une dissipation d’énergie beaucoup plus faible. Des travaux expérimentaux ont permis de mettre au point un process de fabrication sur PMN-PT et d’explorer l’effet magnétoélectrique / The manipulation of magnetic domain walls – that separate regions of uniform magnetization – is associated with both fundamental and technological research interests. A large part of the literature on domain wall motion deals with the use of magnetic fields and electric currents. However, several concerns – most notably energy dissipation – motivates the search for alternatives. Among potential candidates, the mechanical stress-mediated magnetoelectric coupling in magnetoelastic/piezoelectric heterostructures seems promising. In this thesis, it is shown that the combination of a bias magnetic field and uniform mechanical stress can induce unidirectional domain wall motion in nanostructures with uniaxial anisotropy. Static and dynamic aspects of this phenomenon are studied by means of ad hoc numerical procedures simulating the mechanical coupling of 011-cut PMN-PT generating the stress, and TbCo2/FeCo multilayers magnetoelastic nanostructures. The design of the cross section profile in nanostructures allows to tailor the response of the system, enabling for instance the control of domain wall position in confined geometries. The associated dynamics stands apart from known regimes because of the shape of the domain wall. The existence of steady-state regimes in nanostripes of constant width shows that velocities comparable to those of other techniques can be obtained, for a fraction of the energy required. Experimental investigations resulted in the development of a successful fabrication process on PMN-PT and the exploration of the magnetoelectric effect

"There is plenty of room at the bottom." This bold and prophetic statement from Nobel laureate Richard Feynman back in 1950s at Cal Tech launched the Nano Age and predicted, quite accurately, the explosion in nanoscience and nanotechnology. Now this is a fast developing area in both science and technology. Many think this would bring the greatest technological revolution in the history of mankind. To understand electronic and optical properties of nanostructures, the following problems have been studied. In particular, intensity of mid-infrared light transmitted through a metallic diffraction grating has been theoretically studied. It has been shown that for s-polarized light the enhancement of the transmitted light is much stronger than for p-polarized light. By tuning the parameters of the diffraction grating enhancement can be increased by a few orders of magnitude. The spatial distribution of the transmitted light is highly nonuniform with very sharp peaks, which have the spatial widths about 10 nm. Furthermore, under the ultra fast response in nanostructures, the following two related goals have been proved: (a) the two-photon coherent control allows one to dynamically control electron emission from randomly rough surfaces, which is localized within a few nanometers. (b) the photoelectron emission from metal nanostructures in the strong-field (quasistationary) regime allows coherent control with extremely high contrast, suitable for nanoelectronics applications. To investigate the electron transport properties of two dimensional carbon called graphene, a localization of an electron in a graphene quantum dot with a sharp boundary has been considered. It has been found that if the parameters of the confinement potential satisfy a special condition then the electron can be strongly localized in such quantum dot. Also the energy spectra of an electron in a graphene quantum ring has been analyzed. Furthermore, it has been shown that in a double dot system some energy states becomes strongly localized with an infinite trapping time. Such states are achieved only at one value of the inter-dot separation. Also a periodic array of quantum dots in graphene have been considered. In this case the states with infinitely large trapping time are realized at all values of inter-dot separation smaller than some critical value.

In this thesis, a systematic study has been carried out on the synthesis, characterization and device fabrication of piezoelectric ZnO nanstructures. The achieved results are composed of the following four parts. Firstly, through a systematic investigation on the Sn-catalyzed ZnO nanostructure, an improved understanding of the chemical and physical process occurring during the growth of hierarchical nanostructures has been achieved. Decomposed Sn from SnO2 has been successfully demonstrated and proved to be an effective catalyst guiding the growth of not only aligned ZnO nanowires, but also the hierarchical nanowire-nanoribbon junction arrays and nanopropeller arrays. During the vapor-liquid-solid (VLS) catalyzing growth process at high temperature, Sn in the liquid state has been proved to be able to guide the growth of nanowires and nanoribbons in terms of growth directions, side facets, and crystallographic interfaces between Sn and ZnO nanostructures. Secondly, using pure ZnO as the only source material, by precisely tuning and controlling the growth kinetics, a variety of hierarchical polar surface dominated nanostructures have been achieved, such as single crystal nanorings, nanobows, nanosprings and superlattice nanohelices. High yield synthesis of ZnO nanosprings over 50% has been successfully obtained by mainly controlling the pre-pumping level associated with the partial pressure of residual oxygen during the vapor-solid growth process. The rigid superlattice nanohelices of ZnO have been discovered, which is a result of minimization of the electrostatic energy induced by polar surfaces. The formation process of the nanohelix has been systematically characterized. Thirdly, two new strategies have been successfully developed for fabricating ZnO quantum dots and synthesis of ZnO nanodiskettes and nanotubes. The formation process is based on a common concept of self-assembly. Finally, a series of devices and applications studies based on several piezoelectric ZnO nanostructures, such as nanobelts, nanopropellers and nanohelices, have been carried out utilizing the electro-mechanical resonance, bio-surface functionalization, devices fabrication and electrical characterization. Individual nanobelt and nanohelix based nanodevices have been successfully fabricated for applications in chemical and biological sensing. The study opens a few new areas in oxide nanostructures and applications.

A major focus of research in nanotechnology is the development of novel, high throughput techniques for fabrication of arbitrarily shaped surface nanostructures of sub 100 nm to atomic scale. A related pursuit is the development of simple and efficient means for parallel manipulation and redistribution of adsorbed atoms, molecules and nanoparticles on surfaces – adparticle manipulation. These techniques will be used for the manufacture of nanoscale surface supported functional devices in nanotechnologies such as quantum computing, molecular electronics and lab-on-achip, as well as for modifying surfaces to obtain novel optical, electronic, chemical, or mechanical properties. A favourable approach to formation of surface nanostructures is self-assembly. In self-assembly, nanostructures are grown by aggregation of individual adparticles that diffuse by thermally activated processes on the surface. The passive nature of this process means it is generally not suited to formation of arbitrarily shaped structures. The self-assembly of nanostructures at arbitrary positions has been demonstrated, though these have typically required a pre-patterning treatment of the surface using sophisticated techniques such as electron beam lithography. On the other hand, a parallel adparticle manipulation technique would be suited for directing the selfassembly process to occur at arbitrary positions, without the need for pre-patterning the surface. There is at present a lack of techniques for parallel manipulation and redistribution of adparticles to arbitrary positions on the surface. This is an issue that needs to be addressed since these techniques can play an important role in nanotechnology. In this thesis, we propose such a technique – thermal tweezers. In thermal tweezers, adparticles are redistributed by localised heating of the surface. This locally enhances surface diffusion of adparticles so that they rapidly diffuse away from the heated regions. Using this technique, the redistribution of adparticles to form a desired pattern is achieved by heating the surface at specific regions. In this project, we have focussed on the holographic implementation of this approach, where the surface is heated by holographic patterns of interfering pulsed laser beams. This implementation is suitable for the formation of arbitrarily shaped structures; the only condition is that the shape can be produced by holographic means. In the simplest case, the laser pulses are linearly polarised and intersect to form an interference pattern that is a modulation of intensity along a single direction. Strong optical absorption at the intensity maxima of the interference pattern results in approximately a sinusoidal variation of the surface temperature along one direction. The main aim of this research project is to investigate the feasibility of the holographic implementation of thermal tweezers as an adparticle manipulation technique. Firstly, we investigate theoretically the surface diffusion of adparticles in the presence of sinusoidal modulation of the surface temperature. Very strong redistribution of adparticles is predicted when there is strong interaction between the adparticle and the surface, and the amplitude of the temperature modulation is ~100 K. We have proposed a thin metallic film deposited on a glass substrate heated by interfering laser beams (optical wavelengths) as a means of generating very large amplitude of surface temperature modulation. Indeed, we predict theoretically by numerical solution of the thermal conduction equation that amplitude of the temperature modulation on the metallic film can be much greater than 100 K when heated by nanosecond pulses with an energy ~1 mJ. The formation of surface nanostructures of less than 100 nm in width is predicted at optical wavelengths in this implementation of thermal tweezers. Furthermore, we propose a simple extension to this technique where spatial phase shift of the temperature modulation effectively doubles or triples the resolution. At the same time, increased resolution is predicted by reducing the wavelength of the laser pulses. In addition, we present two distinctly different, computationally efficient numerical approaches for theoretical investigation of surface diffusion of interacting adparticles – the Monte Carlo Interaction Method (MCIM) and the random potential well method (RPWM). Using each of these approaches we have investigated thermal tweezers for redistribution of both strongly and weakly interacting adparticles. We have predicted that strong interactions between adparticles can increase the effectiveness of thermal tweezers, by demonstrating practically complete adparticle redistribution into the low temperature regions of the surface. This is promising from the point of view of thermal tweezers applied to directed self-assembly of nanostructures. Finally, we present a new and more efficient numerical approach to theoretical investigation of thermal tweezers of non-interacting adparticles. In this approach, the local diffusion coefficient is determined from solution of the Fokker-Planck equation. The diffusion equation is then solved numerically using the finite volume method (FVM) to directly obtain the probability density of adparticle position. We compare predictions of this approach to those of the Ermak algorithm solution of the Langevin equation, and relatively good agreement is shown at intermediate and high friction. In the low friction regime, we predict and investigate the phenomenon of ‘optimal’ friction and describe its occurrence due to very long jumps of adparticles as they diffuse from the hot regions of the surface. Future research directions, both theoretical and experimental are also discussed.