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Ce travail de thèse concerne la réalisation et l'analyse des propriétés optiques de nanocristaux de silicium. Ces objets de taille nanométrique possèdent des propriétés optiques remarquables, en particulier de photoluminescence. Les propriétés de confinement quantique qui les caractérisent permettent d'obtenir un signal de luminescence intense dans le domaine du visible. Des composants optoélectroniques et photoniques ont été envisagés à base de nanocristaux de silicium. Les raisons physiques du fort signal de luminescence en revanche sont encore mal comprises. Les nanocristaux de silicium sont élaborés par évaporation. L'élaboration et le recuit thermique de multicouches SiO/SiO2 permet d'obtenir des nanocristaux de silicium de diamètre moyen bien contrôlé. Ceux-ci sont issus de la démixtion de la couche de SiO selon la réaction SiOx --> Si + SiO2. Le contrôle du diamètre des nanocristaux de silicium permet de maîtriser la région spectrale de luminescence dans la région du visible.La première partie de ce travail de thèse vise à isoler un ou quelques nanocristaux de silicium. L'objectif est de remonter à la largeur homogène de ces nano-objets. Dans un premier temps, une étude centrée sur le matériau SiOx est réalisée afin de réduire la densité surfacique de nanocristaux de silicium. Dans un deuxième temps, des moyens de lithographie ultime sont mis en oeuvre afin de réaliser des masques percés de trous de diamètres de l'ordre de la centaine de nanomètre. Des expériences de spectroscopie optique sont réalisées sur ces systèmes.La deuxième partie de ce travail vise à contrôler l'émission spontanée de lumière issue des nanocristaux de silicium. Ceci se fait en couplant les modes électroniques aux modes optiques confinés d'une microcavité optique. Le manuscrit détaille les moyens développés afin d'obtenir une microcavité optique dont les modes optiques puissent se coupler efficacement aux nanocristaux de silicium. Les propriétés optiques de ces systèmes sont finalement analysées. / This work concerns the implementation and analysis of optical properties of silicon nanocrystals. These nanoscaled objects have remarkable optical properties, especially in photoluminescence. The properties of quantum confinement that characterize them allow obtaining an intense luminescence signal in the visible range. Optoelectronic and photonic devices have been proposed based on silicon nanocrystals. The physical reasons of the strong luminescence signal, however, are still poorly understood. The silicon nanocrystals are prepared by evaporation. The preparation and thermal annealing of multilayers SiO/SiO2 leads to silicon nanocrystals with a well controlled average diameter. They are created during the demixing of the SiO layer by the reaction SiO ? Si + SiO2. The control the diameter of the silicon nanocrystals influences directly the spectral region of luminescence in the visible region.The aim of first part of this work is to isolate one or a few silicon nanocrystals. The intent is to trace the homogeneous width of these nano-objects. Initially, a study focusing on the SiOx material is conducted to reduce the surface density of silicon nanocrystals. In a second step, lithography is implemented to make masks with holes with diameters of about one hundred nanometers. Optical spectroscopy experiments were performed on these systems.The second part of this work aims controlling the spontaneous emission of light from silicon nanocrystals. This is done by coupling the electronic transmission to optical modes confined in an optical microcavity. The manuscript describes the methods developed to obtain an optical microcavity whose optical modes can be coupled effectively to the silicon nanocrystals. The optical properties of these systems are finally analyzed

Este trabalho trata do estudo das condições para a produção de padrões em escala nano e micrométricas, utilizando o processo de litografia eletrônica. A parte inicial refere-se ao estudo do elétron-resiste de PMMA incluindo a preparação da solução, o recobrimento do substrato e a secagem. Em seguida, são apresentados estudos sobre o funcionamento do sistema de litografia por feixe de elétrons em detalhe. São tratados problemas com o resiste, o substrato e a interação com a amostra. São apresentados os aspectos mais importantes dos substratos utilizados, sendo dado um enfoque a heteroestruturas semicondutoras com gás de elétrons bidimensionais. As condições para revelação do resiste e das etapas de processamento para que seja feita a replicação para o substrato do padrão gerado no resiste são também abordadas. Diversos estudos foram realizados para mostrar a influência de alguns efeitos comuns na litografia como a influência da espessura do filme de resiste e os efeitos de proximidade. Também trata da produção de padrões sobre substratos diversos como GaAs, VIDRO, ALUMINA e PRATA. A última etapa estuda a utilização de um resiste híbrido PMMA-Sílica como um método de conformação cerâmica. Finalmente é apresentado um estudo relativo a produção de diversos padrões diferentes sobre heteroestruturas semicondutoras de AlGaAs/GaAs. / The work describe the conditions for pattern production at nano and micrometric scale using the electronic lithographic process. In the first part many types of lithographic technics are compared and the aim why the electron beam lithographic nanostructured production was chosen. Detailed results about operation with the lithographic system and some problems related to electron resist, substrate and interaction between electron beam and sample are presented. The most important substrate aspects are shown. The two dimensional electron gas (2DEG) semiconductors heterostrutures and the M B E process to grow samples are discussed too. The conditions to develop electron resist and steps for pattern transfer over the substrate are discussed. Many experimental studies were realized to show the influence and some effects, common to the lithographic process, such as electron resist thickness and the proximity effect. A production of pattern on some kind of substrate like GaAs, Glass, Aluminum, Silver can also be observed. In the last part of this work some discussion about utilisation of hybrid electron resist composite PMMA-Silica was done, as well as very important technics for ceramic conformation. Finally, the main goal of this work is presented: the production of different nanostructure samples using AlGaAs/GaAs substrates.

Ces travaux de thèse portent sur les phénomènes d’amplification du signal de diffusion Raman par effet de surface et par effet de pointe. Des réseaux de motifs métalliques de taille nanométrique arrangés spatialement ont été fabriqués par la méthode de transfert Langmuir-Blodgett et par lithographie à faisceau d’électrons. De telles structures de géométries contrôlées déposées à la surface de lamelles de microscope ont été développées afin d’amplifier le signal Raman de molécules adsorbées par effet SERS (Surface Enhanced Raman Spectroscopy). Ces nanostructures triangulaires en or de taille proche de la longueur d’onde ont des bandes de résonance plasmon dans le domaine spectral visible. En utilisant une source de laser appropriée dans ce domaine spectral, les facteurs d’amplification Raman d’une couche mono-moléculaire d’un dérivé azobenzène sont de plusieurs ordres de grandeur, et ce pour les deux techniques de nano-lithographie employées. Afin de compléter ces premiers résultats, des réseaux de fils d’or avec de grands facteurs de forme ont été fabriqués. Ces derniers montrent des résonances plasmons multipolaires et des facteurs d’amplification de l’ordre de 105. Les techniques de microscopie en champ proche ont également été développées afin de localiser précisément l’exaltation Raman et d’accroitre la résolution spatiale de mesures Raman. Des pointes métalliques en or de taille nanométrique ont ainsi permis d’amplifier localement le signal de diffusion de molécules placées à leur proximité par effet TERS (Tip Enhanced Raman Spectroscopy). Les développements logiciels et mécaniques entre un microscope confocal Raman et un microscope à force atomique ont été implémentés afin de contrôler simultanément les deux instruments. Ce montage expérimental a été appliqué à l’étude de nanofils semi-conducteurs de nitrure de gallium permettant de suivre leur signal vibrationnel avec une résolution spatiale inférieure à 200 nm. / This thesis work focuses on Raman scattering enhancements by metallic nanostructures. In the first part of this work, arrays of metallic patterns with nanometer dimensions were fabricated by the Langmuir-Blodgett deposition technique and electron-beam lithography. Such structures made of gold were fabricated onto microscope slides with the goal to enhance the Raman signal through SERS effect (Surface Enhanced Raman Spectroscopy). These patterns formed by an assembly of triangular nanostructures with sizes of hundreds of nanometers, exhibit plasmon resonance bands in the visible spectral region. By using an appropriate excitation laser source with respect to the plasmon frequency, Raman enhancement factors of a monolayer were found to be of several order of magnitude for both Langmuir-Blodgett and electron-beam lithography platforms. To further complement these results, gold wires arrays with large aspect ratio made by electron-beam lithography showed multipolar plasmon resonances with enhancement factors up to 105. In the second part of this thesis, near-field Raman microscopy has been developed with the aim to localize precisely the Raman enhancement and improve spatial resolution of Raman measurements. Atomic force microscopy gold tips have been used to locally enhance scattering signal of molecules in close proximity to the tip opening new opportunities. This approach known as TERS (Tip Enhanced Raman Spectroscopy) is of significant interest to probe nanomaterials, nanostructures or monolayers. Software and mechanical developments have been made between a confocal Raman microscope and an atomic force microscope to control simultaneously both instruments. This experimental setup was used to characterize gallium nitride semi-conductors nanowires with spatial resolution better than 200 nm.

Electron Beam Induced Deposition (EBID) is a direct write fabrication process with applications in circuit edit and debug, mask repair, and rapid prototyping. However, it suffers from significant drawbacks, most notably low purity. Work over the last several years has demonstrated that deposition from bulk liquid precursors, rather than organometallic gaseous precursors, results in high purity deposits of low resistivity (LPEBID). In this work, it is shown that the deposits resulting from LP-EBID are only highly conductive when deposited at line doses below 25μC/cm. When the dose exceeds this value, the resulting structure is highly porous providing a poor conductive pathway. It is also shown that beam current has no significant effect on the resistivity of the deposits. Nanowires with resistivity significantly lower than the previous best result of 67μΩ•cm were achieved, with the lowest resistivity being only 6.6μΩ•cm, only a factor of 4 higher than that bulk copper of 1.7μΩ•cm.

Heavy Ion Elastic Recoil Detection Analysis (HIERDA) is a versatile Ion Beam Analysis technique well suited to multi-elemental depth profiling of thin layered structures and near-surface regions of materials. An existing limitation is the inability to accurately account for the pronounced broadening and tailing effects of multiple scattering typically seen in HIERDA spectra. This thesis investigates the role of multiple large angle scattering in heavy ion applications such as HIERDA, and seeks to quantify its contribution to experimental output. This is achieved primarily by the development of a computer simulation capable of predicting these contributions and using it to classify and quantify the interactions that cause them. Monte Carlo ion transport simulation is used to generate simulated HIERDA spectra and the results are compared to experimental data acquired using the Time of Flight HIERDA facility at the Australian Nuclear Science and Technology Organisat ion. A Monte Carlo simulation code was adapted to the simulation of HIERDA spectra with considerable attention on improving the modelling efficiency to reduce processing time. Efficiency enhancements have achieved simulation time reductions of two to three orders of magnitude. The simulation is shown to satisfactorily reproduce the complex shape of HIERDA spectra. Some limitations are identified in the ability to accurately predict peak widths and the absolute magnitude of low energy tailing in some cases. The code is used to identify the plural scattering contribution to the spectral features under investigation, and the complexity of plurally scattered ion and recoil paths is demonstrated. The program is also shown to be useful in the interpretation of overlapped energy spectra of elements of similar mass whose signals cannot be reliably separated experimentally. The effect of large angle scattering on the transmission of heavy ions through a nano-scale aperture mask, used to collimate an ion beam to a very small beam spot, is modelled using a version of the program adapted to handle the more complex geometry of the aperture mask. The effectiveness of nano-aperture collimation was studied for a variety of ion-energy combinations. Intensity, energy, and angular distributions of transmitted ions were calculated to quantify the degree to which scattering within the mask limits the spatial resolution achievable. The simulation successfully predicted the effect of misaligning the aperture and the beam, and the result has subsequently been observed experimentally. Transmitted ion distributions showed that the higher energy heavier ions studied are more effectively collimated than are lower energy lighter ions. However, there is still a significant probability of transmission of heavy ions with substantial residual energy beyond the perimeter of the aperture. For the intended application, ion beam lithography, these ions are likely to be problematic. The results indicate that medium energy He ions are the more attractive option, as the residual energy of scattered transmitted ions can be more readily managed by customising the etching process. Continuing research by experimentalists working in this area is proceeding in this direction as a result of the conclusions from this work.

<p>Materials prepared on the nanoscale often exhibit many different properties compared to the same materials in their bulk-state. Interest in nanostructured materials has increased because of these properties in fields such as microelectronics, catalysis, optics and sensors. This increased interest in nanostructured materials calls for new and more precise fabrication techniques.</p><p>This thesis describes how to use the porous anodic aluminium oxide as a template for the fabrication of a variety of nanostructured materials. Palladium and copper nanoparticles were deposited along the pore walls in anodic aluminum oxide using electroless deposition and atomic layer deposition. In both cases, it was possible to control the size of the nanoparticles by carefully monitoring the deposition parameters. The thesis also describes how Prussian blue nanoparticles and nanotubes can be fabricated using the anodic aluminium oxide as a template. The deposition of Prussian blue was performed by a sequential wet-chemical method. By using atomic layer deposition, it was also possible to deposit thin films of amorphous Nb2O5 on the pore walls. When the template was removed by etching, freestanding nanotubes were obtained. The anodic aluminium oxide membrane was also used as a mask for high energy (MeV) ion irradiation of an underlying substrate. The tracks produced were etched away with hydrogen fluoride. In this way, it was possible to transfer the highly ordered porous pattern from the mask onto other oxides such as SiO2 and TiO2.</p><p>All fabricated structures were characterized using a variety of analysis techniques: scanning electron microscopy for evaluating sample morphology; transmission electron microscopy for better resolved investigations of the morphology; X-ray diffraction to assess crystallinity; energy dispersive spectroscopy and X-ray fluorescence spectroscopy to determine the elemental composition and identify possible contaminants.</p><p>The general aim of the work described in this thesis has been to create a set of tools for use in the fabrication of a variety of nanostructured materials, whose dimensions composition can be tailored by selecting appropriate fabrication methods and parameters.</p>

Nanofabrication techniques were used to manufacture nanometer scale protein templates. The fabrication approach employs electron beam lithography (EBL) patterning on poly(ethylene glycol) (PEG) thiol (CH3O(CH2CH2O)17NHCO(CH2)2SH) self-assembled monolayers (SAM) on Au. The PEG SAM prevented protein surface adhesion and binding sites for protein were created in the SAM by EBL. Subsequent to EBL, the patterns in the PEG SAM were backfilled with 40-nm NeutrAvidin-coated fluorescent spheres (FluoSpheres). The spontaneous and directed immobilization of the spheres from a solution to the patterns resulted in high resolution protein patterns. The FluoSpheres could be arranged in any arbitrary pattern with ultimately only one or a few FluoSpheres at each binding site. Growth dynamics and SAM morphology of PEG on Au were studied by atomic force microscopy (AFM). PEG SAMs on three types of Au with different microstructure were examined: thermally evaporated granular Au and two types of Au films produced by hydrogen flame annealing of granular Au, Au(111) and "terraced" Au (crystal orientation unknown). The different Au surfaces' substructure affected the morphology and mechanical properties of the PEG SAM. On Au(111), AFM imaging revealed monolayer formation through three distinct steps: island nucleation, island growth, and coalescence. The fine-structure of the SAM revealed dendritic island formation - an observation which can be explained by attractive intermolecular interactions and diffusion-limited aggregation. Island growth was not observed on the "terraced" Au. AFM studies of EBL patterned PEG SAMs on Au(111) revealed two different patterning mechanisms. At low doses, the pattern formation occurs by SAM ablation in a self-developing process where the feature depth is directly dose dependent. At higher doses electron beam induced deposition of material, so-called contamination writing, is seen in the ablated areas of the SAM. The balance between these two mechanisms is shown to depend on the geometry of the pattern. In addition to PEG SAMs, fibronectin monolayers on SiO2 surfaces were patterned by EBL. The areas exposed with EBL lose their functionality and do not bind anti-fibronectin. With this approach we constructed fibronectin templates and used them for cell studies demonstrating pattern dependent cell geometries and cell adhesion. / QC 20101008

Materials prepared on the nanoscale often exhibit many different properties compared to the same materials in their bulk-state. Interest in nanostructured materials has increased because of these properties in fields such as microelectronics, catalysis, optics and sensors. This increased interest in nanostructured materials calls for new and more precise fabrication techniques. This thesis describes how to use the porous anodic aluminium oxide as a template for the fabrication of a variety of nanostructured materials. Palladium and copper nanoparticles were deposited along the pore walls in anodic aluminum oxide using electroless deposition and atomic layer deposition. In both cases, it was possible to control the size of the nanoparticles by carefully monitoring the deposition parameters. The thesis also describes how Prussian blue nanoparticles and nanotubes can be fabricated using the anodic aluminium oxide as a template. The deposition of Prussian blue was performed by a sequential wet-chemical method. By using atomic layer deposition, it was also possible to deposit thin films of amorphous Nb2O5 on the pore walls. When the template was removed by etching, freestanding nanotubes were obtained. The anodic aluminium oxide membrane was also used as a mask for high energy (MeV) ion irradiation of an underlying substrate. The tracks produced were etched away with hydrogen fluoride. In this way, it was possible to transfer the highly ordered porous pattern from the mask onto other oxides such as SiO2 and TiO2. All fabricated structures were characterized using a variety of analysis techniques: scanning electron microscopy for evaluating sample morphology; transmission electron microscopy for better resolved investigations of the morphology; X-ray diffraction to assess crystallinity; energy dispersive spectroscopy and X-ray fluorescence spectroscopy to determine the elemental composition and identify possible contaminants. The general aim of the work described in this thesis has been to create a set of tools for use in the fabrication of a variety of nanostructured materials, whose dimensions composition can be tailored by selecting appropriate fabrication methods and parameters.

In this study nano-patterning was carried out using two different nano-optic devices namely- the NSOM and Fresnel zone plate. In the first study, NSOM was used to generate nano-patterns on selected semiconducting (Si and Ge) and metallic (Cr, Cu and Ag) targets under different laser pulse durations, laser energies and number of laser pulses. Based on the experimental results, femtosecond laser pulses, provided lower pattern generation thresholds on targets but higher damage thresholds to the NSOM probes at the wavelength (~400-410 nm) studied, compared with nanosecond laser pulses. Three different mechanisms were identified as the dominant processes for pattern generation under different conditions, namely nano-scale laser ablation, nano-scale thermal oxidation and nano-scale melting/recrystallization of the targets. Furthermore, the resulting nano-patterns also showed a significant dependence on the optical properties (i.e., absorption coefficient and surface reflectivity) of the target material. By comparing the obtained experimental results, it was concluded that the optical energy transport from the NSOM probe to the target dominates the pattern generation when femtosecond laser is applied to the NSOM system. When nanosecond laser is applied, both the thermal and optical energy transported from the NSOM probe to the targets attribute to the obtained morphology of nano-patterns on different targets under the experimental conditions studied. In the second study, a traditional Fresnel zone plate with a focus length of 3 micrometres was fabricated with a novel lift-off process in e-beam lithography. The fabrication process involved, using a HSQ/PMMA bi-layer in a negative tone lift-off process with a layer of conducting polyaniline for charge dissipation. HSQ was used as the high resolution negative resist for e-beam patterning and the PMMA under-layer was used to enable a HSQ lift-off process. The fabricated Fresnel zone plate was used to generate nano-patterns on a UV sensitive photoresist using nanosecond laser light with lamda~409nm. The smallest pattern sizes generated was close to the diffraction limit. Nano-pattern sizes generated on the photoresist were comparable with a numerically calculated intensity distribution at the focus spot of the designed Fresnel zone plate obtained from Scalar Diffraction Theory.