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.

L’intégration 3D séquentielle représente une alternative potentielle à la réduction des dimensions afin de gagner encore en densité d’une génération à la suivante. Le principal défi concerne la fabrication du transistor de l’étage supérieur avec un faible budget thermique; ceci afin d’éviter la dégradation du niveau inférieur. L’étape de fabrication la plus critique pour la réalisation du niveau supérieur est l’activation des dopants. Celle-ci est généralement effectuée par recuit à une température supérieure à 1000 °C. Dans ce contexte, cette thèse propose des solutions pour activer les dopants à des températures inférieures à 600 °C par la technique dite de recristallisation en phase solide. Les conditions de dopage ont été optimisées pour améliorer le niveau d’activation et le temps de recuit tout en réduisant la température d’activation jusqu’à 450°C. Les avancées obtenues ont été implémentées sur des dispositifs avancés FDSOI et TriGate générant des dispositifs avec des performances inférieures aux références fabriquées à hautes températures (supérieures à 1000 °C). En utilisant des simulations TCAD et en les comparant aux mesures électriques, nous avons montré que la région la plus critique en termes d’activation se trouve sous les espaceurs de la grille. Nous montrons alors qu’une intégration dite « extension first » est le meilleur compromis pour obtenir de bonnes performances sur des dispositifs fabriqués à faible température. En effet, l’implantation des dopants avant l’épitaxie qui vise à surélever les sources et drains compense l’absence de diffusion à basse température. Ces résultats ont par la suite été étendus pour des dispositifs TriGate et FinFETs sur isolants. Pour la première fois, l’intégration « extension first » a été démontrée pour des N et PFETs d’une technologie 14 nm FDSOI avec des résultats prometteurs en termes de performances. Les résultats obtenus montrent notamment qu’il est possible d’amorphiser partiellement un film très mince avant d’effectuer une recroissance épitaxiale sur une couche dopée. Finalement, une implantation ionique à relativement haute température (jusqu’à 500 °C) a été étudiée afin de doper les accès sans amorphiser totalement le film mince, ce qui est critique dans le cas des dispositifs FDSOI et FinFET. Nous montrons que les niveaux d’activation après implantation sont trop faibles pour obtenir des bonnes performances et que l’implantation ionique « chaude » est prometteuse à condition d’être utilisée avec un autre mécanisme d’activation comme le recuit laser. / 3D sequential integration is a promising candidate for the scaling sustainability for technological nodes beyond 14 nm. The main challenge is the development of a low temperature process for the top transistor level that enables to avoid the degradation of the bottom transistor level. The most critical process step for the top transistor level fabrication is the dopant activation that is usually performed at temperature higher than 1000 °C. In the frame of this Ph.D. work, different solutions for the dopant activation optimization at low temperature (below 600 °C) are proposed and integrated in FDSOI and TriGate devices. The technique chosen for the dopant activation at low temperature is the solid phase epitaxial regrowth. First, doping conditions have been optimized in terms of activation level and process time for low temperatures (down to 450 °C) anneals. The obtained conditions have been implemented in FDSOI and TriGate devices leading to degraded electrical results compared to the high temperature process of reference (above 1000 °C). By means of TCAD simulation and electrical measurements comparison, the critical region of the transistor in terms of activation appears to be below the offset spacer. The extension first integration scheme is then shown to be the best candidate to obtain high performance low temperature devices. Indeed, by performing the doping implantation before the raised source and drain epitaxial growth, the absence of diffusion at low temperature can be compensated. This conclusion can be extrapolated for TriGate and FinFET on insulator devices. Extension first integration scheme has been demonstrated for the first time on N and PFETs in 14 nm FDSOI technology showing promising results in terms of performance. This demonstration evidences that the two challenges of this integration i.e. the partial amorphization of very thin films and the epitaxy regrowth on implanted access are feasible. Finally, heated implantation has been investigated as a solution to dope thin access regions without full amorphization, which is particularly critical for FDSOI and FinFET devices. The as-implanted activation levels are shown to be too low to obtain high performance devices and the heated implantation appears a promising candidate for low temperature devices if used in combination with an alternative activation mechanism.

CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / CENAPAD - Centro Nacional de Processamento de Alto Desempenho em São Paulo / FAPEMIG - Fundação de Amparo a Pesquisa do Estado de Minas Gerais / Utilizando cálculos de primeiro princípios, nós encontramos propriedades estruturais, eletrônicas e magnéticas dos metais de transição (MTs) Co, Fe e Mn depositados em InAs(110) e InAs(001), uma superfície semicondutora III-V. Em relação às propriedades estruturais, obtidas através de relaxação iônica e imagens STM (do inglês, scanning tunneling microscopy) teóricas, nós verificamos que os MTs se posicionaram mais próximos aos arsênios quando comparado com as distâncias interatômicas MTs-In. Utilizando NEB (do inglês Nudged Elastic Band, nós verificamos que os MTs substituem a posição de um cátion da primeira camada da superfície InAs(110). Verificamos ainda que a formação de trilhas de MTs é mais estável na direção [110]. Por outro lado, os MTs causaram grande deformação no topo das reconstruções InAs(001)-^2(2 x 4) (rica em arsênios) e InAs(001)-Z(4 x 2) (rica em In). Através da comparação de energia de adsorção, foi verificado que o cobalto é o elemento que possui maior adesão em InAs(110) e InAs(001), enquanto a incorporação de MTs sobre o substrato se mostrou um processo exotérmico. Através da aproximação de Bader para o cálculo de carga eletrônica, nós encontramos que os MTs atuam como átomos aceitadores de elétrons e, consequentemente, foi constatado a redução dos momentos magnéticos de spin dos íons magnéticos. O acoplamento magnético entre os MTs (a partir de dois íons magnético por supercélula) em InAs(110) é sempre antiferromagnético (AF) via superexchange, cuja interação sfoi mediada pelos orbitais p do ânions da rede. Contudo o acomplamento magnético entre os MTs nas reconstruções /32(2 x 4) e Z(4 x 2) se mostrou dependente da posição final dos MTs sobre o substrato, por exemplo, os íons magnéticos apresentaram acomplamento ferromagnético em Co2/InAs(001)-^2(2 x 4). Por fim, foi verificado que a energia de anisotropia magnética se mostrou sensível à concentração e à posição dos íons magnéticos na rede semicondutora. Sendo assim, baseados nestes resultados, nós concluimos que as propriedades estruturais, eletrônicas e magnéticas dos sistemas MTs/InAs são expressivamente anisotrópicas. A reconstrução superficial do B/Si(1 1 1)- (/3 x //3) R30° tem sido utilizada recentemente como uma plataforma de montagem supramolecular. Porém, o nosso entendimento dos defeitos nativos desse sistema á-dopado e de suas correspondentes assinaturas via microscopia de tunelamento com varredura é incompleto. Neste trabalho, portanto, estudamos esse sistema fazendo uso de cálculos de energia total ab initio e da técnica de Microscopia de Tunelamento. Descobrimos que, embora perturbações à geometria de equilíbrio da superfície sejam geralmente fracas, as perturbações causadas às estruturas eletrônicas podem ser um tanto quanto fortes devido à presença de ligações pendentes compostas de orbitais Si-3p^. Além disso, propomos uma possível estrutura para um defeito anteriormente identificado que aparece em imagens STM a corrente constante e tensão de polarização positiva como um arranjo na forma de um triângulo equilátero de átomos adsorvidos de Si com intensidade atenuada. / Based on first principles calculations, we have studied the structural, electronic, and magnetic properties of transition metals (MTs) Co, Fe, and Mn adsorbed on the III-V semiconductor surfaces, namely, InAs (110) and InAs (001). As regards the structural properties, obtained through ionic relaxation and theoretical scanning tunneling microscopy (STM) images, we found that MTs were positioned closer to the arsenic, while the MTs-In interatomic distances are larger. Using NEB (Nudged Elastic Band), we have verified that MTs replace the topmost cation of the InAs (110) surface. We also verified the energetic preference to the formation MTs chains along the direction [110]. On the other hand, MTs induce large structural deformation on the InAs(001)-S2(2 x 4) (As-rich), and InAs(001)- Z(4 x 2) (In-rich) surfaces. By comparing adsorption energies, we verified the energetic preference of cobalt adatoms,compared with the other MTs, on the InAs(110) and InAs(001) surface, while MTs incorporation on the substrate express an exothermic process. Using Bader’s approach for charge transfer calculations, we find that the MTs act as acceptor dopants and, consequently, the reduction of the magnetic moments of spin of magnetic ions was observed. The magnetic coupling between the MTs (two, three or four magnetic ions per supercell) no InAs (110) is always antiferromagnetic (AF) via superexchange, whose interaction is mediated by the p orbitals of the substrate anions. However, the magnetic coupling between the MTs in the /32(2 x 4) and Z (4 x 2) reconstructions has been shown to be dependent on the location of the MTs on the substrate, for example, the magnetic ions have a ferromagnetic coupling in Co2/InAs(001)-S2(2 x 4). Finally, the magnetic anisotropy energy is sensitive to the concentration and position of the magnetic ions in the semiconductor substrate. Therefore, based on these results, we conclude that the structural, electronic and magnetic properties of the MTs/InAs systems are expressively anisotropic. The B/Si(111)-(\/3 x \/3)R300 surface reconstruction has recently been used as a platform for supramolecular assembly. However, our understanding of the native defects in this delta- doped system and their corresponding STM signatures is incomplete. So we have studied this system using ab initio total energy calculations and scanning tunneling microscopy. We find that although perturbations to the equilibrium geometry of the surface are in general weak, the perturbations to the electronic structure can be quite strong due to the presence of dangling bonds composed of Si-3p^ orbitals. Additionally, we propose a possible structure for a previously unidentified defect that appears in positive bias constant-current STM images as an equilateral triangular arrangement of Si adatoms with attenuated intensity. / Tese (Doutorado)

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Eu3+:SiO2 PMMA hybrid nanocomposites were prepared by sol-gel process aiming to study its structure and luminescent properties. Thermal treatment and dopant concentration experimental variables were sequentially altered in order to evaluate their influences on the properties of the final material. At the start, the precursors (MPTS and MMA) were studied and the process of hybrid nanocomposites formation was analyzed by FTIR and TG techniques. As regards to thermal treatments, it was noticed that its execution at 100 and 200 °C for 3 hs don´t change significantly the basic structure of samples, behavior attested by the profile of FTIR spectra and by small variations of TG/DTG curves. There was, however, changes in silicon structures of samples (noticed at 29Si NMR spectra), besides great alterations in the sites occupied by Eu3+ ions, perceptible by photoluminescence spectroscopy. Luminescent behavior indicates a change in the symmetry of lanthanide sites caused by the temperatures imposed in thermal treatments. From the values calculated for a set of spectroscopic parameters, the symmetry change was attributed to the removal of water molecules coordinated to Eu3+ ions, which could coordinate to hybrid matrix groups and so interact stronger with it. The study of Eu3+ concentration influences showed that the higher this variable the broader some bands of FTIR spectra. TG analysis indicate an increase of sample´s residue percentage, assigned to Eu2O3 formation at high temperatures. In these samples, it was noticeable luminescence quenching caused by the increase of Eu3+ concentration, which wasn´t expected owing to the presence of silica network. It was supposed that clusters were formed when Eu3+ amount increases, decreasing Eu-host interaction and quenching the luminescence by energy transfer between Eu3+ ions. / Nanocompósitos híbridos Eu3+:SiO2 PMMA foram preparados pelo processo sol-gel com o objetivo de estudar suas estrutura e propriedades luminescentes. As variáveis experimentais tratamentos térmicos e concentração de dopante foram sequencialmente alteradas visando avaliar as influências exercidas por cada uma sobre as propriedades do material final. Inicialmente estudou-se os precursores (MPTS e MMA) e o processo de formação dos nanocompósitos híbridos foi avaliada por meio das técnicas de FTIR e TG. Quanto aos tratamentos térmicos, observou-se que a realização destes a 100 e 200 °C por 3 horas não alterou significativamente a estrutura básica das amostras, comportamento atestado pelo perfil dos espectros de FTIR e pelas pequenas variações das curvas TG/DTG. Houve, contudo, mudanças nas estruturas de silício presentes nos materiais (notadas nos espectros de RMN 29Si) além de grande alteração dos sítios ocupados pelos íons Eu3+, perceptível por espectroscopia de fotoluminescência. Pelo comportamento de emissão, inferiu-se a ocorrência de mudança da simetria dos sítios ocupados pelos íons lantanídeos causada pelas temperaturas empregadas nos tratamentos. A partir dos valores calculados para um conjunto de parâmetros espectroscópicos, atribuiu-se a mudança de simetria à remoção de moléculas de água coordenadas aos íons Eu3+, que passaram a se coordenar a grupos presentes na matriz híbrida e interagir mais fortemente com esta. O estudo da influência da concentração de íons Eu3+ mostrou que com o aumento deste valor há alargamento de algumas bandas nos espectros de FTIR. As análises por TG demonstraram aumento do percentual de resíduo das amostras, atribuído à formação de Eu2O3 a altas temperaturas. Nestas amostras, pôde-se observar efeitos de supressão de luminescência causados pelo aumento da concentração de íons Eu3+, o que não era esperado tendo em vista a presença da rede de sílica nas amostras. Supôs-se que com o aumento da concentração de íons Eu3+ houve a formação de clusters , os quais provocam a diminuição da interação Eu matriz e provocam efeitos de supressão de luminescência por meio da transferência de energia entre íons Eu3+.

This master's thesis deals with study of the injected charge contrast mechanism of doped semiconductors by using the ultra – high vacuum scanning low electron energy microscope (UHV SLEEM). The aims of this work were to explain the injected charge contrast mechanism, to ability of this contrast mechanism to map the dopant density quantitatively and to identify the influencing factors.

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.

Cette thèse présente une analyse approfondie et comparative des résultats de mesures µ-XRD et µ-XAS sur des combustibles UO2 standard, dopé au sesquioxyde de chrome (Cr2O3) et MOX, irradiés ou non. Elle présente également l'interprétation des résultats en regard des effets induits par le chrome en tant que dopant ainsi que par la présence de plusieurs produits de fission. Les paramètres de maille de l’UO2 et les paramètres de densité d'énergie de déformation élastique dans les matériaux irradiés ou non ont été mesurés et quantifiés. Les données de µ-XRD ont en outre permis l'évaluation de la taille des domaines cristallins, ainsi que l’étude de la formation de sous-grains à différentes positions au sein des pastilles de combustibles irradiés. Le paramètre de maille et l'environnement atomique local du chrome dans des précipités d’oxyde de chrome présents dans les pastilles de combustible non-irradié ont également été déterminés. La structure locale du Cr dans la matrice du combustible dopé et l'influence de l'irradiation sur l'état du chrome dans la matrice de combustible ont été étudiées. Enfin, pour une comparaison du comportement des gaz de fission et du phénomène de re-solution induite par l'irradiation dans l’UO2 standard ou dopé, la dernière partie de ce travail propose une tentative d'analyse de l’environnement atomique du Kr dans ces deux combustibles irradiés. Le travail effectué par micro-faisceau XAS sur ce gaz de fission a permis la détermination des distances du Kr avec ses proches voisins, une estimation des densités atomiques des gaz de fission dans les agrégats et des pressions internes apparentes dans ces nano-phases de gaz inertes. / This thesis work reports in depth analyses of measured µ-XRD and µ-XAS data from standard UO2, chromia (Cr2O3) doped UO2 and MOX fuels, and interpretation of the results considering the role of chromium as a dopant as well as several fission product elements. The lattice parameters of UO2 in fresh and irradiated samples and elastic strain energy densities in the irradiated UO2 samples have been measured and quantified. The µ-XRD patterns have further allowed the evaluation of the crystalline domain size and sub-grain formation at different locations of the irradiated fuel pellets. Attempts have been made to determine lattice parameter and next neighbor atomic environment in chromia-precipitates found in fresh chromia-doped fuel pellets. The local structure around Cr in as-fabricated chromia-doped UO2 matrix and the influence of irradiation on the state of chromium in irradiated fuel matrix have been addressed. Finally, for a comparative understanding of fission gases behavior and irradiation induced re-solution phenomenon in standard and chromia-doped UO2, the last part of the present work tries to clarify the fission gas Kr atomic environment in these irradiated fuels. The work performed on Kr, by micro-beam XAS, comprises the determination of Kr next neighbor distances, an estimation of gas atom densities in the aggregates, and apparent internal pressures in the gas bubbles.

Abstract This research is designed to investigate the occurrence of interdiffusion-induced mesopores, Brownian motion, cleaving and healing and defect clusters in three binary composites, i.e. Ni1-xO/Co1-xO, Ni1-xO/ZrO2 and Co1-xO/ZrO2 of the Ni1-xO-Co1-xO-ZrO2 system. Firstly, the (NimCo1-m)1-£_O/Ni-doped Co3-dO4 composites prepared by reactive sintering Ni1-xO and Co1-xO powders (1:2 molar ratio, denoted as N1C2) at 1000oC with or without further annealing at 720oC in air were studied by X-ray diffraction and electron microscopy to clarify the formation mechanism of mesoporous spinel precipitates. Submicron-sized inter- and intragranular pores, due to incomplete sintering and grain boundary detachment, prevails in (Ni0.33Co0.67)1-£_O protoxide with rock salt structure; whereas nanosize pores due to Kirkendall effect were restricted to the spinel precipitates having Ni component progressively expelled upon annealing. A rapid net vacancy flux and a tensile misfit stress perpendicular to the protoxide/spinel interface caused the formation of elongated and aligned {100}-faceted mesopores in the spinel precipitates with a relatively low equilibrium vacancy concentration. Aligned mesopores in diffusion zone of nonstoichiometric metal oxides have potential applications on thermal barrier bond coating and mass-transport limited heterogeneous catalysis. Also, this thesis deals with the reorientation and shape change of low-crystal-symmetry (non-cubic) ZrO2 within the high-crystal-symmetry grains of Co1-xO/Ni1-xO cubic rock salt-type structure. ZrO2/Co1-xO composites 1:99 and ZrO2/Ni1-xO composites 1:9 in molar ratio were sintered and then annealed at 1650oC for 24 and 100 h in air to induce reorientation of the embedded particles. Transmission electron microscopic observations in both systems indicated that the submicron tetragonal/monoclinic (t/m) ZrO2 particles fell into three topotaxial relationships with respect to the host Co1-xO/Ni1-xO grain: (1) parallel topotaxy, (2) ¡§eutectic¡¨ topotaxy i.e. [100]Z//[111]C,N, [010]Z//[0 1]C,N and (3) ¡§occasional¡¨ topotaxy [100]Z//[111]C,N, [01 ]Z//[0 1]C,N. The parallel topotaxy has a beneficial low energy for the family of {100}Z/C,N and {111}Z/C,N interfaces. The change from the occasional topotaxy to an energetically more favorable eutectic topotaxy was likely achieved by a rotation of the ZrO2 particles over a specific (100)Z/(111)C,N interface. Brownian-type rotation is probable for the embedded t-ZrO2 particles in terms of anchorage release at the interphase interface with the Co1-xO/Ni1-xO host. Detachment or bypassing of rock salt type grain boundaries could also cause orientation as well as shape changes of intergranular ZrO2 particles. Zirconia-polymorphism-induced cleaving and spontaneous healing by precipitation was studied in Co1-xO polycrystals containing a dispersion of ZrO2 particles. Conventional, analytical, and high-resolution transmission electron microscopy indicated that the Co1-xO matrix cleaves parallel to {100} and {110} planes and heals itself by co-precipitation of parallel-topotaxial ZrO2/Co3-£_O4 particles upon cooling. Due to size effect and matrix constraint, nanometer-size ZrO2 precipitates at cleavages were able to retain tetragonality upon further cooling to room temperature. Paracrystalline array of defect cluster was shown to form in Zr-doped Ni1-xO and Co1-xO polycrystals while prepared by sintering at relative high temperature, i.e., 1650oC to increase the defect concentration. Paracrystalline array of defect clusters in Co3-£_O4 spinel structure also occurred when doped with Zr4+ at high temperature or cooled below 900oC to activate oxy-precipitation of Co3-dO4 at dislocations. transmission electron microscopic observations indicated the spinel precipitate and its paracrystal predominantly formed at the ZrO2/Co1-xO interface and the cleavages/dislocations of the Co1-xO host. Defect chemistry consideration suggests the paracrystal is due to the assembly of charge- and volume-compensating defects of the 4:1 type with four octahedral vacant sites surrounding one Co3+-filled tetrahedral interstitial site. The spacing of paracrystalline distribution is 3.3, 2.9 and 4.9 times the lattice parameter for Zr-doped Ni1-xO, Zr-doped Co1-xO and Zr-doped Co3-dO4. This spacing between defect clusters is about 0.98 times that of the previously studied undoped Co3-dO4. There is much larger (3.4 times difference) paracrystalline spacing for Zr-doped Co3-£_O4 than its parent phase of Zr-doped Co1-xO.

With the advancements in the field of wireless sensor networks (WSNs), more and more applications require the sensor nodes to have long lifetime. Energy harvesting sources, e.g. thermoelectric generators (TEGs), can be used to increase the lifetime and capability of the WSNs. Integration of energy harvesters into sensor nodes of WSNs can realize self powered systems, providing the possibility for maintenance free WSNs. TEGs can convert the existing temperature differences into electricity. The efficiency of TEGs is directly related to the dimensionless figure of merit (ZT) of materials, which is given as ZT=σS^2 T/k, where σ is the electrical conductivity, S is the Seebeck coefficient, k is the thermal conductivity, T is the temperature and σS^2 is the power factor. Traditional thermoelectric (TE) materials are based on inorganic materials, of which the thermal conductivity is high. Over the past decade, the use of nanostructuring technology, e.g. superlattice, could decrease the thermal conductivity in order to enhance the efficiency of TE materials. However, the high cost and the rigidity of inorganic TE materials are limiting factors. As alternatives, polymer based materials have become the research focus due to their intrinsic low thermal conductivity, high flexibility and high electrical conductivity. Moreover, polymer based materials could be fabricated in solution form, giving the possibility for employing printing techniques hence a decrease in the production cost. Unlike the typical approach, in which secondary dopants are added into PEDOT:PSS solutions to modify the power factor of polymer films, this thesis is focused on a more efficient method to improve TE properties. This thesis demonstrates for the first time that post treatment of PEDOT:PSS films with the secondary dopant DMSO as the medium results in a much larger power factor than the traditional addition method. The post treatment method also avoids the usually required mixing step involved in the addition method. Different solvents were selected to discuss the impact factors in the modification of the power factor by this post treatment approach. The post treatment of PEDOT:PSS films was then extended to utilize a green solvent EMIMBF_4 (an ionic liquid) as the medium. EMIMBF_4 is found to exchange ions with PEDOT:PSS films. As a result, the EMIM^+ cations remain in the films and reduce the oxidation level of PEDOT chains, which affects the Seebeck coefficient and the electrical conductivity. Furthermore, TE materials based on hybrid composites with polymer as the matrix and Te nanostructures as the nanoinclusions were investigated. This thesis successfully developed a green synthesis method to obtain Te nanostructures, in which a non toxic reductant and a non toxic Te sources were used. Well controlled Te nanostructures including nanorods, nanowires and nanotubes were synthesized by wet chemical and hydrothermal synthesis. Those as synthesized Te nanowires were then integrated into PEDOT:PSS solution for composite films fabrication. A high Seebeck coefficient up to 200 μV/K was observed in the composite film. / Mit den Weiterentwicklungen der Drahtlosen Sensornetzwerke (engl. WSN, wireless sensor networks) stellen immer mehr Anwendungen die Forderung einer langen Lebensdauer der Sensorknoten. Energiegewinnungssysteme (engl. Energy Harvesters) wie z.B. thermoelektrische Generatoren (TEGs) können genutzt werden, um die Lebensdauer und Leistungsfähigkeit der WSN zu steigern. Mit der Integration von Energy Harvesters können WSN ohne äußere Stromversorgung realisiert und somit die Möglichkeit zur Wartungsfreiheit geschaffen werden. TEGs liefern Energie durch die Umwandlung einer Temperaturdifferenz in Elektrizität. Die Effektivität der TEG ist direkt verbunden mit der Material-Kennzahl ZT und ist gegeben durch ZT=σS^2 T/k, wobei σ die elektrische Leitfähigkeit ist, S der Seebeck Koeffizient, k die thermische Leifähigkeit, T die Temperatur und σS^2 der Leistungsfaktor. Herkömmliche thermoelektrische (TE) Materialien basieren auf anorganischen Materialien, von denen die thermische Leitfähigkeit hoch ist. Im Laufe des letzten Jahrzehnts konnte durch den Einsatz der Nanostrukturierung die thermische Leitfähigkeit verringern werden um damit die Effizienz von TE-Materialien zu steigern. Die Steifigkeit dieser Materialien ist ein anderer Aspekt. Als Alternative für anorganische TE Materialien sind Polymer basierte TE Materialien zum Fokus der Forschung geworden aufgrund einer intrinsisch niedrigen thermischen Leitfähigkeit, hohen Flexibilität und hohen elektrischen Leitfähigkeit. Des Weiteren können diese Polymere in gelöster Form verarbeitet werden, was die Möglichkeit für den Einsatz von Drucktechnologien und damit geringeren Produktionskosten gibt. Anders als der herkömmliche Ansatz den Leistungsfaktor der Polymerfilme durch die Ergänzung von sekundären Dotanten in PEDOT:PSS Lösungen zu verändern, wurde in dieser Arbeit eine effizientere Methode zur Verbesserung der TE Eigenschaften gesucht. In dieser Arbeit wird zum ersten Mal gezeigt, dass die Nachbehandlung von PEDOT:PSS Schichten mit sekundären Dotanten Dimethylsulfoxid (DMSO) als Medium der Nachbehandlung zu einem viel höheren Leistungsfaktor führt als bei der Zugabemethode und außerdem die sonst erforderliche Mischprocedur vermeidet. Es wurden verschiedene Lösungsmittel ausgewählt um die Einflussfaktoren bei der Modifikation des Leistungsfaktors durch die Nachbehandlung von Polymerschichten zu diskutieren. Die Nachbehandlung von PEDOT:PSS Schichten wurde nachfolgend erweitert um das umweltfreundliche Lösungsmittel EMIMBF4 (eine ionische Flüssigkeit) als das Medium einzusetzen. EMIMBF4 ist bekannt für den Austausch von Ionen mit PEDOT:PSS Schichten, so dass EMIM Kationen in der Schicht verbleiben, die Oxidationsstufe der PEDOT-Ketten senken und damit den Seebeck-Koeffizient und die elektrische Leitfähigkeit beeinflussen. Des Weiteren konzentriert sich diese Arbeit auf TE Materialien basierend auf Kompositen aus Polymeren mit Nanoeinlagerungen. Erfolgreiche Syntheseansätze wurden für Tellur-Nanostrukturen entwickelt, bei denen keine giftigen Reduktionsmittel und keine giftigen Tellur-Quellen zur Verwendung kamen. Es erfolgte die Erzeugung von kontrollierten Tellur-Nanostrukturen, einschließlich Nanostäben, Nanodrähten und Nanoröhren, mit nass-chemischer und hydrothermaler Synthese. Die so hergestellten Nanodrähte wurden dann in PEDOT:PSS Lösungen integriert für die Herstellung von Komposite-Schichten. Dabei konnte ein hoher Seebeck-Koeffizienten, bis zu 200 μV/K, festgestellt werden.

This thesis work reports in depth analyses of measured µ-XRD and µ-XAS data from standard UO2, chromia (Cr2O3) doped UO2 and MOX fuels, and interpretation of the results considering the role of chromium as a dopant as well as several fission product elements. The lattice parameters of UO2 in fresh and irradiated samples and elastic strain energy densities in the irradiated UO2 samples have been measured and quantified. The µ-XRD patterns have further allowed the evaluation of the crystalline domain size and sub-grain formation at different locations of the irradiated fuel pellets. Attempts have been made to determine lattice parameter and next neighbor atomic environment in chromia-precipitates found in fresh chromia-doped fuel pellets. The local structure around Cr in as-fabricated chromia-doped UO2 matrix and the influence of irradiation on the state of chromium in irradiated fuel matrix have been addressed. Finally, for a comparative understanding of fission gases behavior and irradiation induced re-solution phenomenon in standard and chromia-doped UO2, the last part of the present work tries to clarify the fission gas Kr atomic environment in these irradiated fuels. The work performed on Kr, by micro-beam XAS, comprises the determination of Kr next neighbor distances, an estimation of gas atom densities in the aggregates, and apparent internal pressures in the gas bubbles.