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Drawing of standard telecommunication-type optical fibres has been optimised in terms of optical and physical properties. Specialty fibres, however, typically have more complex dopant profiles. Designs with high dopant concentrations and multidoping are common, making control of the fabrication process particularly important. In photonic crystal fibres (PCF) the inclusion of air-structures imposes a new challenge for the drawing process. The aim of this study is to gain profound insight into the behaviour of complex optical fibre structures during the final fabrication step, fibre drawing. Two types of optical fibre, namely conventional silica fibres and PCFs, were studied. Germanium and fluorine diffusion during drawing was studied experimentally and a numerical analysis was performed of the effects of drawing parameters on diffusion. An experimental study of geometry control of PCFs during drawing was conducted with emphasis given to the control of hole size. The effects of the various drawing parameters and their suitability for controlling the air-structure was studied. The effect of air-structures on heat transfer in PCFs was studied using computational fluid dynamics techniques. Both germanium and fluorine were found to diffuse at high temperature and low draw speed. A diffusion coefficent for germanium was determined and simulations showed that most diffusion occurred in the neck-down region. Draw temperature and preform feed rate had a comparable effect on diffusion. The hole size in PCFs was shown to depend on the draw temperature, preform feed rate and the preform internal pressure. Pressure was shown to be the most promising parameter for on-line control of the hole size. Heat transfer simulations showed that the air-structure had a significant effect on the temperature profile of the structure. It was also shown that the preform heating time was either increased or reduced compared to a solid structure and depended on the air-fraction.

Les nanofils de silicium (Si) sont des nano-objets à une dimension. Ils font l'objet de beaucoup d'intérêt ces dernières années en raison de leurs bonnes propriétés et leur grand potentiel d'applications. Pour ces applications, il est important de parfaitement contrôler la croissance de ces objets ainsi que leurs dopages. Dans ce contexte, l'objectif de ce travail de thèse est la modélisation de la croissance des nanofils de Si et la métrologie à l'échelle atomique de la composition des nanofils. Dans la première partie de ce travail, nous avons étudié le taux de croissance (longueur) ainsi que l'évolution de la morphologie des nanofils, en particulier l'effet d'effilage. Plusieurs modèles sont proposés selon la nature des nanofils synthétisés via différentes méthodes d'élaboration: Dépôt Chimique en phase Vapeur et Epitaxie par Jets Moléculaires. Les taux de croissance varient selon les méthodes de synthèse. Le modèle reproduit fidèlement les données expérimentales. L'influence des conditions expérimentales sur la morphologie des nanofils est également étudiée dans cette partie. L'objectif de la seconde partie de ce travail est la métrologie des impuretés (catalyseur et dopant) dans les nanofils de Si. Cette étude est réalisée à l'aide de la technique de Sonde Atomique Tomographique (SAT). Cette technique permet une analyse à l'échelle atomique, dans l'espace réel et en trois dimensions de l'objet analysé. Des nanofils synthétisés par différentes techniques telles : la gravure chimique, la méthode Vapeur-Liquide-Solide (VLS) et la méthode Solide-Liquide-Solide (SLS), en utilisant différents catalyseurs de croissance tels Au, In et Sn, sont étudiés. La présence d'atomes des catalyseurs dans les nanofils se trouve être un phénomène général. Un travail sur la métrologie des dopants a également été réalisé. La concentration des dopants et leurs distributions dans les nanofils synthétisé par gravure chimique est inchangée. En revanche, dans les nanofils de Si dopés via un mécanisme de croissance VLS, une structure cœur-coquille avec un cœur sous-dopé et une coquille sur-dopée est observée. Ceci est retrouvé quelque soit la morphologie du nanofil et la nature chimique du dopant. Un modèle basé sur la diffusion latéral (via la surface du nanofil) des dopants est proposé afin de reproduire les profils expérimentaux observés et aussi préciser une voie d'incorporation possible des dopants.

Le traitement quantique de l'information est un domaine très actif dont les enjeux sont importants tant d'un point de vue du savoir scientifique fondamental que des applications technologiques. Dans ce contexte le concept de bus de spin consiste à employer en tandem des spins électroniques et nucléaires. Les électrons célibataires servent de tête de lecture et d'écriture sur le registre de bits quantiques constitué par les spins nucléaires. Les électrons sont délocalisés sur un ensemble de spins nucléaires dont les temps de décohérences doivent être longs. Dans ce travail nous avons étudié un ion titane (III) dans l'oxyde de gallium dont nous avons synthétisé et étudié des monocristaux. Une étude approfondie par RPE et ENDOR en onde continue a montré que l'électron porté par le titane était en interaction avec huit noyaux de gallium qui constituent le registre de qubits potentiel. L'étude a également révélé un effet isotopique sur les interactions noyau-noyau véhiculées par l'électron. Lorsque les deux noyaux de gallium entourant le titane sont identiques (mêmes isotopes), cette interaction est d'un ordre de grandeur plus grande que dans le cas d'isotopes différents, un effet qui peut être employé afin de réduire la durée des opérations logiques. Enfin, la dynamique de cet ensemble de spin a été caractérisée par RPE et ENDOR en impulsions. Il s'avère que la décohérence électronique est dominée par des phénomènes de diffusion instantanée et de diffusion spectrale. La dynamique des spins nucléaires les expériences menées permettent de déterminer l'ordre de grandeur des temps de relaxation longitudinaux et de décohérence des spins nucléaires.

Cette thèse présente une étude du transport électronique à basse température dans des transistors à effet de champ nanométriques en silicium sur isolant. Leur comportement électrique dépend notamment de la constitution des jonctions entre les réservoirs et le canal, qui est déterminée lors de la fabrication par l'utilisation d'espaceurs de part et d'autre de la grille. Cette différence de comportement est exacerbée à basse température. Dans des transistors très courts, de longueur de grille typique égale à 30 nm, compte tenu de la diffusion des dopants lors du recuit d'activation, il est possible d'obtenir sous la grille un unique donneur bien couplé aux deux réservoirs. Sa présence est révélée par de l'effet tunnel résonant à travers les niveaux d'énergie associés à ses orbitales, observé à basse température à des tensions de grille inférieures au seuil du transistor. L'estimation de l'énergie d'ionisation de ce donneur donne une valeur supérieure à la valeur attendue pour un donneur dans du silicium massif, ce qui est attribué à l'effet du confinement diélectrique du donneur. À l'inverse, il est possible de définir des résistances d'accès au canal suffisantes pour y confiner les électrons. Un transistor se comporte alors comme un transistor mono-électronique à basse température, dont l'îlot est situé sous la grille. Ce moyen de créer un transistor mono-électronique est étendu à des systèmes d'îlots couplés, en déposant plusieurs grilles entre la source et le drain. Plusieurs comportements sont obtenus selon l'écart entre les grilles et la longueur des espaceurs. Ces systèmes sont utilisés pour réaliser le transfert d'un électron unique.

Heterojunction bipolar transistors (HBT) based on SiGeC havebeen investigated. Two high-frequency architectures have beendesigned, fabricated and characterized. Different collectordesigns were applied either by using selective epitaxial growthdoped with phosphorous or by non-selective epitaxial growthdoped with arsenic. Both designs have a non-selectivelydeposited SiGeC base doped with boron and a poly-crystallineemitter doped with phosphorous. Selective epitaxial growth of the collector layer has beendeveloped by using a reduced pressure chemical vapor deposition(RPCVD) technique. The incorporation of phosphorous and defectformation during selective deposition of these layers has beenstudied. A major problem of phosphorous-doping during selectiveepitaxy is segregation. Different methods, e.g. chemical orthermal oxidation, are shown to efficiently remove thesegregated dopants. Chemical-mechanical polishing (CMP) hasalso been used as an alternative to solve this problem. The CMPstep was successfully integrated in the HBT process flow. Epitaxial growth of Si1-x-yGexCy layers for base layerapplications in bipolar transistors has been investigated indetail. The optimization of the growth parameters has beenperformed in order to incorporate carbon substitutionally inthe SiGe matrix without increasing the defect density in theepitaxial layers. The thermal stability of npn SiGe-based heterojunctionstructures has been investigated. The influence of thediffusion of dopants in SiGe or in adjacent layers on thethermal stability of the structure has also been discussed. SiGeC-based transistors with both non-selectively depositedcollector and selectively grown collector have been fabricatedand electrically characterized. The fabricated transistorsexhibit electrostatic current gain values in the range of 1000-2000. The cut-off frequency and maximum oscillation frequencyvary from 40-80 GHz and 15-30 GHz, respectively, depending onthe lateral design. The leakage current was investigated usinga selectively deposited collector design and possible causesfor leakage has been discussed. Solutions for decreasing thejunction leakage are proposed. <b>Key words:</b>Silicon-Germanium-Carbon (SiGeC),Heterojunction bipolar transistor (HBT), chemical vapordeposition (CVD), selective epitaxy, non-selective epitaxy,collector design, high-frequency measurement, dopantsegregation, thermal stability.

<p>Heterojunction bipolar transistors (HBT) based on SiGeC havebeen investigated. Two high-frequency architectures have beendesigned, fabricated and characterized. Different collectordesigns were applied either by using selective epitaxial growthdoped with phosphorous or by non-selective epitaxial growthdoped with arsenic. Both designs have a non-selectivelydeposited SiGeC base doped with boron and a poly-crystallineemitter doped with phosphorous.</p><p>Selective epitaxial growth of the collector layer has beendeveloped by using a reduced pressure chemical vapor deposition(RPCVD) technique. The incorporation of phosphorous and defectformation during selective deposition of these layers has beenstudied. A major problem of phosphorous-doping during selectiveepitaxy is segregation. Different methods, e.g. chemical orthermal oxidation, are shown to efficiently remove thesegregated dopants. Chemical-mechanical polishing (CMP) hasalso been used as an alternative to solve this problem. The CMPstep was successfully integrated in the HBT process flow.</p><p>Epitaxial growth of Si1-x-yGexCy layers for base layerapplications in bipolar transistors has been investigated indetail. The optimization of the growth parameters has beenperformed in order to incorporate carbon substitutionally inthe SiGe matrix without increasing the defect density in theepitaxial layers.</p><p>The thermal stability of npn SiGe-based heterojunctionstructures has been investigated. The influence of thediffusion of dopants in SiGe or in adjacent layers on thethermal stability of the structure has also been discussed.</p><p>SiGeC-based transistors with both non-selectively depositedcollector and selectively grown collector have been fabricatedand electrically characterized. The fabricated transistorsexhibit electrostatic current gain values in the range of 1000-2000. The cut-off frequency and maximum oscillation frequencyvary from 40-80 GHz and 15-30 GHz, respectively, depending onthe lateral design. The leakage current was investigated usinga selectively deposited collector design and possible causesfor leakage has been discussed. Solutions for decreasing thejunction leakage are proposed.</p><p><b>Key words:</b>Silicon-Germanium-Carbon (SiGeC),Heterojunction bipolar transistor (HBT), chemical vapordeposition (CVD), selective epitaxy, non-selective epitaxy,collector design, high-frequency measurement, dopantsegregation, thermal stability.</p>

銅銻硒礦是具有 0.3 eV狹窄能帶間隙的P型半導體，且已被發現是在中溫區下極具潛力的熱電材料。銅銻硒礦的晶體結構具有三維銅硒子框架可提供導電的電洞，而有較高的功率因子900 μW/mK2。銻硒四面體結構可藉由其他元素取代銻的位置，扭曲其鑽石結構以達到提高功率因子以及降低熱傳導的目的。理論預測可藉由 IV 族元素鍺、錫、鉛和過渡金屬鈦等元素取代銻來提供電洞載子。本研究藉由燒結與電漿放電製備樣品，探討鈦、錫、鉛、鍺取代銻的熱電效應。 在上述之元素取代效應後，鈦與鉛並沒有帶來顯卓的熱電效應提升，反之錫與鍺能有效地提升電洞載子濃度，然而與摻錫的研究相似的結果已被其他團隊發表，惟鍺的取代效應則尚未被做完整的探討。2 % 鍺的取代有1200μW/mK2的功率因子，相較於母材(900μW/mK2)有 30 % 的提升，因此我們會對鍺的取代效應做完整一系列的研究。摻雜比例從 1~8 % 的結果裡，發現晶格熱傳導係數隨摻雜比例提升減少的合金效應，然而高於 6 % 的取代造成電導大幅提升，使得熱傳導的載子貢獻高於 50% 並嚴重降低載子移動率，致使功率因子大幅衰減與優質係數降低。 4% 的鍺摻雜在提高功率因子與降低熱傳導係數上皆有顯卓的表現，使得優質係數在溫度650 K達到 0.7 相對於母材 (0.54) 有30 ％的提升。 / Cu3SbSe4 is a p-type semiconductor with a narrow band gap near 0.3 eV, and has been found to be a promising thermoelectric material at medium temperatures. The crystal structure of Cu3SbSe4 consists a three-dimensional [Cu3Se4] framework acting as electron hole conduction pathway which cause high power factor near 900 μW/mK2. The inserting guest atom to the Sb site of tetrahedral [SbSe4] framework cause a more distorted diamond-like structure, thus providing a relatively lower lattice thermal conductivity in relatively large electric conductivity. According to theoretical predication which are based on the defect formation energy and band structure calculations, p-type doping can be achieved by substituting Sb with group IV elements, as Ge, Sn, and Pb, and transition metals as Ti. This study is investigation of the doping effect in Cu3SbSe4 semiconductor which are prepared by melting and spark plasma sintering. Herein, we take a close look at the thermoelectric properties of Cu3SbSe4 which are mentioned in previous paragraph. No significant change in results of Ti and Pb. Carrier concentrations are dramatic increasing in results of Sn and Ge, but the results of Sn substitution were already reported by another group. Power factor of Ge substitution is 1,200μW/mK2 which is 30 % more than raw material. We did more study in germanium doping series because it have high power factor which did not be investigated in Cu3SbSe4. Alloy effects, as description of lattice thermal conductivity reducing with doping fraction increasing, are explored in Ge doping fraction from 1 % to 8 %. Although electric conductivity were largely enhanced, figure of merit were reducing by electric contribution of thermal conductivity were higher than 50 % and carrier mobility were significantly reducing when the doping fraction were higher than 4 %. Doping fraction in 4 % have relatively high power factor and relatively low thermal conductivity. Figure of merit in 4 % doping fraction is 0.7, as 30% more than 0.5 of raw material.

Transparent conductive oxides (TCOs) are key functional materials in existing and future electro-optical devices in the fields of energy efficiency, energy generation and information technology. The main application of TCOs is as thin films transparent electrodes where a combination of maximum electrical conductivity and transmittance in the visible to nearinfrared spectral range is required. However, due to the interdependence of the optical properties and the free electron density and mobility, respectively, these requirements cannot be achieved simultaneously in degenerately doped wide band-gap oxide semiconductors. Therefore, a detailed understanding of the mechanisms governing the generation of free charge carriers by extrinsic doping and the charge transport in these materials is essential for further development of high performance TCOs and corresponding deposition methods. The present work is aimed at a comprehensive investigation of the electrical, optical and structural properties as well as the elemental composition of (Al,Ga) doped ZnO and Nb doped TiO2 thin films prepared by pulsed DC reactive magnetron sputtering. The evolution of the film properties is studied in dependence of various deposition parameters through a combination of characterization techniques including Hall-effect, spectroscopic ellipsometry, spectral photometry, X-ray diffraction, X-ray near edge absorption, Rutherford backscattering spectrometry and particle induced X-ray emission. This approach resulted in the development of an alternative process control method based on the material specific current-voltage pressure characteristics of the reactive magnetron discharge which allows to precisely control the oxygen deficiency of the sputter deposited films. Based on the experimental data, models have been established that describe the room temperature charge transport properties and the dielectric function of the obtained ZnO and TiO2 based transparent conductors. On the one hand, these findings allow the prediction of material specific electron mobility limits by identifying the dominating charge carrier scattering mechanisms. On the other hand, new insight is gained into the origin of the observed transition from highly conductive to electrically insulating ZnO layers upon the incorporation of increasing concentrations of Al at elevated growth temperatures. Moreover, the Al and Ga dopant activation in ZnO have been quantified systematically for a wide range of Al concentrations and deposition conditions. A direct comparison of the Ga and Al doping efficiency demonstrates that Ga is a more efficient electron donor in ZnO. Further, it has been shown that high free electron mobilities in polycrystalline and epitaxial Nb:TiO2 layers can be achieved by reactive magnetron sputtering of TiNb alloy targets. The suppression of rutile phase formation and the control of the Nb dopant activation by fine tuning the oxygen deficiency have been identified as crucial for the growth of high quality TiO2 based TCO layers.