The thesis introduces a novel alloy system based on submicron distributions of intermetallic phases realised through eutectic solidification in the ternary system Ni-Al-Zr. Various compositions in this system comprising of intermetallic phases distributed in different eutectic structures show ultra-high strength at temperatures upto 700°C combined with reasonable tensile plasticity, exceptional oxidation resistance and high temperature structural stability. Intermetallics have long been used in high temperature alloys systems such as in the classical Ni-base superalloys that derive their strength from nanoscale dispersions of the aluminide, Ni3Al(γ’) in a matrix of disordered fcc Ni (γ), alloyed with expensive, high density refractory elements such as Re and Ru. The high temperature applications of intermetallics derive from their strength retention to high temperatures, creep resistance enabled by low diffusion rates, and attractive oxidation resistance based on high concentration of elements such as Al that forms stable oxides. Several decades of effort on the development of new generation of intermetallic alloys through the 80’s and 90’s have gone unrewarded, with the exception of TiAl based alloys that are now used in recent generation aircraft engines. The promise of intermetallics as high temperature candidate materials is limited by their poor ductility or toughness arising from several intrinsic properties such as low grain boundary cohesive strength (in the case of Ni3Al) or an insufficient number of slip systems (as in NiAl) or extrinsic effects such as embrittlement by hydrogen (Fe3Al) that derive fundamentally from the existence of directionality in bonding. However, low ductility or toughness can often be alleviated by limiting the length scale for slip. We have therefore examined the possibility of combining intermetallics in the form of eutectic structures, potentially limiting slip lengths within each intermetallic constituent. Eutectic structures in binary systems limit the choice of intermetallic combinations so that finding such combinations with engineering potential is difficult. On the other hand combinations of three elements or more would enable a significantly larger set of permutations of eutectic intermetallics, provided the constituent binary phase diagrams contain either eutectic or peritectic reactions involving intermetallic phases, as well as intermediate intermetallic phases. The ternary Ni-Al-Zr system met our criterion in several ways. The Ni-Al binary phase diagram shows a peritectic reaction from liquid and NiAl (Pm 3m, B2 with a lattice parameter of 0.288nm) to form Ni3Al (Pm 3m, L12 with a lattice parameter of 0.356 nm), intermetallics that have been extensively investigated in earlier literature. The Ni-Zr system shows a peritectic reaction between liquid and the Ni7Zr2 (C12/m1 with a lattice parameters a=0.469nm, b=0.823nm, c=1.219nm) phase to form the intermetallic Ni5Zr (F 43m with a lattice parameter of 0.670nm). Further the NiAl and Ni7Zr2 are both intermediate phases and should therefore form a mono-variant eutectic on the composition line joining these two phases in the ternary system. We note that Zr participates in many glass forming systems. In the Ni-Zr system, for example, glass forming ability has been associated with the structure of the liquid phase and associated low diffusivity. As a consequence, a fine scale eutectic structure may be expected. Zr has also been reported to strengthen and ductilise Ni3Al and NiAl. Finally, both Al and Zr form stable oxides and might promote oxidation resistance. After introducing the thesis in Chapter 1, the experimental details are outlined in the Chapter 2. The experimental results and subsequent discussions are presented in three subsequent chapters. Chapter 3 reports the microstructural aspects of as cast alloys in this ternary system Previous literature and our analysis of phase equilibria in the Ni-Al-Zr system based on Thermo-Calc, suggested that solidification from the liquid to form the Ni3Al + Ni5Zr, Ni3Al + Ni7Zr2 and NiAl+ Ni7Zr2 eutectics is possible. We obtained eutectic structures involving combinations of these intermetallic phases along a constant zirconium section at 11 at. %. The alloy A (Ni-77 at.%, Zr-11at.% and rest Al) contains eutectic structures containing the Ni3Al and Ni5Zr phases in two morphologies, a planar, lamellar structure and a more irregular form. The alloys B (Ni-74 at.%, Zr-11at.% and rest Al) and C (Ni-71 at.%, Zr-11at.% and rest Al) contain two different eutectic structures that combine the Ni3Al and Ni7Zr2 phases, and the NiAl and Ni7Zr2 phases. These phases were identified by a combination of X-ray diffraction, transmission electron microscopy coupled with energy dispersive spectroscopy and electron probe microanalysis. The volume fraction of each eutectic constituent is different in the two compositions in that alloy B(Ni-74 at.%, Zr-11at.% and rest Al) contains significantly higher volume fractions of the eutectic containing the Ni3Al and Ni7Zr2 phases than the alloy C (Ni-71 at.%, Zr¬11at.% and rest Al). In order to understand effect of individual phases we have melted several other alloys (alloy D to I) bounding these eutectic alloys (7-25 at.% Al, 5-15 at.% Zr and rest Ni) that form primary solidification phases of the intermetallic structures that constitute the eutectics. Chapter 4 discusses the mechanical behaviour of the fully eutectic alloys alloys as well as alloys with a combination of primary phases along with a eutectic. Mechanical behaviour was assessed in vacuum arc melted and suction cast material. The compressive strength of eutectic and off-eutectic compositions has been evaluated as a function of temperature. Very high strength levels of around 2 GPa could be achieved accompanied by reasonable room temperature tensile plasticity in the range 3-4%. The introduction of the respective primary phases of NiAl, Ni3Al, Ni5Zr and Ni7Zr2 results in decrease of strength. We have explored the origins of strength and tensile plasticity in alloys through micro and pico indentation (hardness) measurements and an examination of slip lines and crack initiation on pre-polished surface of the tensile tested samples as well as by transmission electron microscopy. Chapter 5 explores the oxidation resistance of these alloys in isothermal tests. The oxidation resistance of alloys compares well with recently developed cast single crystal alloys. Clearly, the oxide scale is extremely adherent and no spalling occurs. Electron microprobe analysis shows the presence of a fine scale, layered oxide structures and reaction zones within the substrate. The oxidation behaviour has been characterized using TGA, XRD and EPMA. We have attempted to understand the mechanism of oxidation through analysis of rate constants and activation energy coupled with microstructural observations. Chapter 6 presents a summary of the current work and present the scope for further work.

Thermoelectric devices with the ability to convert rejected heat into electricity are widely used in nowadays technology. Several studies have been done to improve the efficiency of these devices. However, because of the strong correlation between thermoelectric properties (electrical conductivity, Seebeck coefficient, and thermal conductivity including lattice and electron counterpart), improving ZT has always been a challenging task. In this study, thermal conductivity of group IV-based binary and ternary alloys such as SiGe, SiSn, GeSn, and SiGeSn has been studied. Phonon Boltzmann Transport Equation has been solved in the relaxation time approximation including intrinsic and extrinsic (in the presence of boundary and interfaces in the low-dimensional material) scattering mechanisms. Full phonon dispersion based on the Adiabatic Bond Charge model has been calculated for Si, Ge, and Sn. Virtual crystal approximation has been adapted to calculate the dispersion of SiGe, SiSn, GeSn, and SiGeSn. Two approaches have been introduced to reduce the lattice thermal conductivity of the materials under study. First, alloying results in a significant reduction of thermal conductivity. But, this reduction has been limited by the mass disorder scattering in the composition range of 0.2 to 0.8. Second, nanostructuring technique has been proposed to further reduce the thermal conductivity. Our study shows that, due to the atomic mass difference which gives rise to the elastic mass scattering mechanism, SiSn has the lowest thermal conductivity among the other materials under study. SiSn achieved the thermal conductivity of 1.18 W/mK at 10 nm at the Sn composition of 0.18, which is the experimentally stable state of SiSn. The results show that SiSn alloys have the lowest conductivity (3 W/mK) of all the bulk alloys, more than two times lower than SiGe, attributed to the larger difference in mass between the two constituents. In addition, this study demonstrates that thin films offer an additional reduction in thermal conductivity, reaching around 1 W/mK in 20 nm SiSn, GeSn, and ternary SiGeSn films, which is close to the conductivity of amorphous SiO$_2$. This value is lower than the thermal conductivity of SiGe at 10 nm which is 1.43 W/mK. Having lattice thermal conductivity reduced, electron transport has been studied by solving Boltzmann Transport Equation under low electric field including elastic and inelastic scattering mechanisms. Rode's iterative method has been applied to the model for obtaining perturbation of distribution function under a low electric field. This study shows that nanostructuring and alloying can reduce $\kappa_{ph}$ without significantly changing the other parameters. This is because of the phonon characteristics in solids in which MFP of phonons is much larger than those of electrons, which gives us the possibility of phonons confinement without altering electrons transport. Thermoelectric properties of SiGe in the bulk and nanostructure form have been studied to calculate ZT in a wide range of temperatures. The results demonstrate that ZT reaches the value of 1.9 and 1.58 at the temperatures of 1200 K and 1000 K respectively, with the Ge composition of 0.2 and carrier concentration of 5$\times$10$^{19}$ cm$^{-3}$ at 10 nm thickness. This model can be applied to SiSn and other binary and ternary alloys, to calculate the improved ZT. Hence, we conclude that group IV alloys containing Sn have the potential for high-efficiency TE energy conversion.

Neste trabalho foram efetuados estudos importantes e pioneiros sobre as propriedades estruturais, eletrônicas e termodinâmicas dos nitretos e de suas ligas, através de dois métodos de primeiros princípios distintos, o FLAPW (\"Full-potential Linear Augmented Plane Wave\") e o pseudopotencial combinado com a aproximação quasequímica generalizada. Na primeira parte, utilizando o método FLAPW, calculamos as estruturas de bandas para os nitretos cúbicos do grupo-IH, BN, AIN, GaN e InN. Foram obtidos valores para a constante de rede e \"bulk modulus\" para os nitretos do grupo-III através de cálculos relativísticos da energia total. Através das estruturas de bandas e analisando o topo da banda de valência e o fundo da banda de condução perto do ponto r ou, no ponto k correspondente ao mínimo da banda de condução, derivamos os respectivos valores para as massas efetivas de elétron e de buraco pesado, leve e de \"split-off\' e correspondentes parâmetros de Luttinger. Todos os resultados são comparados com dados experimentais e teóricos existentes na literatura. Na segunda parte, utilizando o método FLAPW, estudamos a influência da impureza de Mg na estrutura eletrônica do GaN cúbico (c-). Realizamos cálculos da otimização da geometria, incluindo deslocamentos dos primeiros e segundos vizinhos, para os casos da impureza com estados de carga neutro e negativo. Obtivemos o valor de 190 meV para o deslocamento de Franck-Condon da energia térmica, o qual apresenta um bom acordo com os dados experimentais de fotoluminescência e efeito Hall. Nós concluímos que os primeiros e segundos vizinhos desempenham um papel importante na determinação das energias do nível aceitador resultante da dopagem do c-GaN com Mg. Na terceira parte, nós apresentamos cálculos das propriedades eletrônicas, estruturais e termodinâmicas de ligas cúbicas envolvendo os nitretos do grupo-III, InxGa1-xN, InxAl-xN, AlxGal-xN, BxGal-xN e BxA1-xN. Nós combinamos o método de expansão de \"clusters\" através da aproximação quasequímica generalizada (\"Generalized Quasichemical Approximation -GQCA\") com cálculos de pseudopotenciais \"ab initio\" DFT-LDA. Para todas a ligas, exceto a de AlxGal-xN, encontramos separação de fase para temperaturas próximas das temperaturas de crescimento. Generalizamos o método de expansão de \"c1usters\" para estudar a influência da tensão biaxial. Encontramos uma significativa supressão da separação de fase induzida pela tensão para as ligas de InxGal-xN e InxAh-xN, sendo no caso da liga de InxGal_xN confirmado experimentalmente. Observamos também que flutuações da energia do \"gap\" da liga de InxGal-xN permitem definir valores mínimo e médio para a energia do \"gap\" com diferentes valores para o \"bowing\". Observamos que a tensão biaxial reduz as flutuações da energia do \"gap\", resultando em uma diminuição do valor do \"bowing\". Através deste estudo mostramos uma possível explicação para a discrepância experimental para valores do \"bowing\". / In this work we performed a pioneer theoretical study of structural, electronic and thermodynamic properties of the group-III nitrides and their alloys, by using two distinct first principles methods, the FLAPW full potential linear augmented plane wave and the pseudopotential-plane-wave method combined with the generalized quasichemical approximation. In the first part of our work, by using the FLAPW, we present the electronic band structures ofthe zinc-blende-type group-III nitrides compounds, BN, AIN, GaN, and InN. Lattice constant and bulk modulus are obtained from fuH relativistic total-energy calculations. Electron, heavy-, light-, and split-off-hole effective masses and corresponding Luttinger parameters are extracted from the band-structure calculations. A comparison with other available theoretical results and experimental data is made. In the second part of our work, by using the FLAPW method, the electronic structure of Mg impurity in zinc-blende (c-) GaN is investigated. Full geometry optimization calculations, including nearest and next-nearest neighbor displacements, were performed for the impurity in the neutral and negatively charged states. A value of 190 meV was obtained for the Franck-Condon shift to the thermal energy, which is in good agreement with that observed in recent low temperature photoluminescence and Hall-effect measurements. We conclude that the nearest and the next-nearest neighbors of the Mg impurity replacing Ga in c-GaN undergo outward relaxations which play an important role in the determination ofthe center acceptor energies. In the third part of our work, we present a study of electronic, structural, and thermodynamic properties of the cubic group-III nitrides alloys, InxGal-xN, InxAll_xN, AlxGal-xN, BxGal-xN e BxAll-xN. We combined the generalized quasichemical approximation (GQCA) with an ab initio pseudopotential-plane-wave method. For alI alIoys, except the AlxGal-xN, we observe a miscibility gap for temperatures near those of the growth. The cluster treatment is generalized to study the influence of biaxial strain. We find a remarkable suppression ofphase separation in InxGal-xN and InxAll-xN induced by strain which is confirmed by experiments on the InxGal_xN alloy. We also observed that the gap fluctuations in the InxGal-xN alloy allow the definition of a minimum gap and an average gap with different bowing parameters. Biaxial strain drastically reduces the gap fluctuations, resulting in a reduction of the bowing. The different gaps and the strain influence investigated provide an explanation for the discrepancies found in the experimental values of the bowing parameter.

Abstract not available

L’aluminium et ses alliages sont très largement exploités en industrie car ils sont légers, peu sensibles à la corrosion et parfois ont une dureté comparable à celle de l’acier. Souvent, le matériau est utilisé brut de fonderie, dans ce cas, la composition, la macro et microstructure de matériau issues de la solidification, définissent son comportement suivant les conditions d’utilisation. Cependant, au cours des procédés d’élaboration sur terre, l’écoulement convectif apparaît à cause de la gravité et modifie les conditions locales de la solidification, la distribution du soluté et influe sur les propriétés de matériau. Afin d’analyser et contrôler ces phénomènes, des études expérimentales et numériques ont été réalisés.Deux fours de type Brdigman ont été construits à l’Université de Miskolc par MTA-ME Materials Science Research Group dans le cadre du ESA-MAP MICAST pour étudier l’effet de l’écoulement convectif lors de la solidification des alliages. Ces fours ont été équipés de systèmes électromagnétiques permettant de générer des champs magnétiques rotatif et glissant .Des modèles multiphases développés à SIMAP/EPM, Grenoble, France, ont été utilisés pour la simulation numérique de la solidification d’alliages binaire et ternaire en présence d’un écoulement convectif créé par des forces électromagnétiques. La modélisation de la solidification d’un alliage Al-Si avec un brassage rotatif a été réalisée pour des configurations 2D et 3D avec un couplage entre un modèle macroscopique de transport et des modèles à l’échelle mésoscopique, l’un basé sur la règle de levier et l’autre sur une moyenne d’ensemble Euler-Euler. De plus, les effets de deux modes de brassage par champs glissants sur la solidification d’un alliage ternaire ont été étudiés dans une géométrie 3D à l’aide d’un modèle macroscopique basé sur la règle de levier. Les résultats des modélisations numériques permettent d’expliquer la ségrégation observée sur les échantillons expérimentaux. / Aluminium and aluminium-based alloys are widely in industry due to the corrosion passivity, lighter weight, yet – in several cases – comparable strength with steel. Often, the material is used “as-cast“, that means that composition, macro- and microstructure of the material emerged during the casting defines its behaviour under different loads. Yet, convective flows generally arise in casting processes performed on-ground because of gravity and modify local solidification conditions, and, consequently, solute distribution and affect properties of material. To understand and to be able to control such phenomena, detailed experimental and numerical work has been needed.Two Bridgman-type furnaces were constructed in the University of Miskolc, Hungary, by MTA-ME Materials Science Research Group in the framework of the ESA funded MICAST project for experimental study of the effect of convective flow in solidification of alloys. These facilities were equipped with electromagnetic systems capable to generate rotating and travelling magnetic fields of various intensities.Multiphase models developed at SIMaP/EPM, Grenoble, France, were applied for numerical study of the solidification of binary and ternary aluminium alloys under electromagnetically generated convective flow. Solidification of a binary Al-Si alloy under RMF stirring was done with Euler-Euler ensemble averaging and lever rule mesoscale models coupled with the macroscale transport both in 2D and 3D geometries. Further, effect of various modes of TMF stirring during solidification of a ternary alloys was studied in 3D geometry with lever rule based macroscopic model. Results of numerical simulations well explain the segregation observed in the experimental samples.

Neste trabalho foram efetuados estudos importantes e pioneiros sobre as propriedades estruturais, eletrônicas e termodinâmicas dos nitretos e de suas ligas, através de dois métodos de primeiros princípios distintos, o FLAPW (\"Full-potential Linear Augmented Plane Wave\") e o pseudopotencial combinado com a aproximação quasequímica generalizada. Na primeira parte, utilizando o método FLAPW, calculamos as estruturas de bandas para os nitretos cúbicos do grupo-IH, BN, AIN, GaN e InN. Foram obtidos valores para a constante de rede e \"bulk modulus\" para os nitretos do grupo-III através de cálculos relativísticos da energia total. Através das estruturas de bandas e analisando o topo da banda de valência e o fundo da banda de condução perto do ponto r ou, no ponto k correspondente ao mínimo da banda de condução, derivamos os respectivos valores para as massas efetivas de elétron e de buraco pesado, leve e de \"split-off\' e correspondentes parâmetros de Luttinger. Todos os resultados são comparados com dados experimentais e teóricos existentes na literatura. Na segunda parte, utilizando o método FLAPW, estudamos a influência da impureza de Mg na estrutura eletrônica do GaN cúbico (c-). Realizamos cálculos da otimização da geometria, incluindo deslocamentos dos primeiros e segundos vizinhos, para os casos da impureza com estados de carga neutro e negativo. Obtivemos o valor de 190 meV para o deslocamento de Franck-Condon da energia térmica, o qual apresenta um bom acordo com os dados experimentais de fotoluminescência e efeito Hall. Nós concluímos que os primeiros e segundos vizinhos desempenham um papel importante na determinação das energias do nível aceitador resultante da dopagem do c-GaN com Mg. Na terceira parte, nós apresentamos cálculos das propriedades eletrônicas, estruturais e termodinâmicas de ligas cúbicas envolvendo os nitretos do grupo-III, InxGa1-xN, InxAl-xN, AlxGal-xN, BxGal-xN e BxA1-xN. Nós combinamos o método de expansão de \"clusters\" através da aproximação quasequímica generalizada (\"Generalized Quasichemical Approximation -GQCA\") com cálculos de pseudopotenciais \"ab initio\" DFT-LDA. Para todas a ligas, exceto a de AlxGal-xN, encontramos separação de fase para temperaturas próximas das temperaturas de crescimento. Generalizamos o método de expansão de \"c1usters\" para estudar a influência da tensão biaxial. Encontramos uma significativa supressão da separação de fase induzida pela tensão para as ligas de InxGal-xN e InxAh-xN, sendo no caso da liga de InxGal_xN confirmado experimentalmente. Observamos também que flutuações da energia do \"gap\" da liga de InxGal-xN permitem definir valores mínimo e médio para a energia do \"gap\" com diferentes valores para o \"bowing\". Observamos que a tensão biaxial reduz as flutuações da energia do \"gap\", resultando em uma diminuição do valor do \"bowing\". Através deste estudo mostramos uma possível explicação para a discrepância experimental para valores do \"bowing\". / In this work we performed a pioneer theoretical study of structural, electronic and thermodynamic properties of the group-III nitrides and their alloys, by using two distinct first principles methods, the FLAPW full potential linear augmented plane wave and the pseudopotential-plane-wave method combined with the generalized quasichemical approximation. In the first part of our work, by using the FLAPW, we present the electronic band structures ofthe zinc-blende-type group-III nitrides compounds, BN, AIN, GaN, and InN. Lattice constant and bulk modulus are obtained from fuH relativistic total-energy calculations. Electron, heavy-, light-, and split-off-hole effective masses and corresponding Luttinger parameters are extracted from the band-structure calculations. A comparison with other available theoretical results and experimental data is made. In the second part of our work, by using the FLAPW method, the electronic structure of Mg impurity in zinc-blende (c-) GaN is investigated. Full geometry optimization calculations, including nearest and next-nearest neighbor displacements, were performed for the impurity in the neutral and negatively charged states. A value of 190 meV was obtained for the Franck-Condon shift to the thermal energy, which is in good agreement with that observed in recent low temperature photoluminescence and Hall-effect measurements. We conclude that the nearest and the next-nearest neighbors of the Mg impurity replacing Ga in c-GaN undergo outward relaxations which play an important role in the determination ofthe center acceptor energies. In the third part of our work, we present a study of electronic, structural, and thermodynamic properties of the cubic group-III nitrides alloys, InxGal-xN, InxAll_xN, AlxGal-xN, BxGal-xN e BxAll-xN. We combined the generalized quasichemical approximation (GQCA) with an ab initio pseudopotential-plane-wave method. For alI alIoys, except the AlxGal-xN, we observe a miscibility gap for temperatures near those of the growth. The cluster treatment is generalized to study the influence of biaxial strain. We find a remarkable suppression ofphase separation in InxGal-xN and InxAll-xN induced by strain which is confirmed by experiments on the InxGal_xN alloy. We also observed that the gap fluctuations in the InxGal-xN alloy allow the definition of a minimum gap and an average gap with different bowing parameters. Biaxial strain drastically reduces the gap fluctuations, resulting in a reduction of the bowing. The different gaps and the strain influence investigated provide an explanation for the discrepancies found in the experimental values of the bowing parameter.

No description available.

Durant ces travaux, nous nous sommes intéressés à l’étude des transferts thermiques aux nano-échelles dans les couches minces par spectroscopie pompe-sonde femtoseconde. Dans un premier temps, nous nous sommes intéressés à la mesure haute-cadence de la conductivité thermique d’alliages de Fe-Si-Ge et Ti-Ni-Sn, dans le but d’optimiser leur processus de fabrication et de créer une base de données des propriétés thermiques de ces matériaux. Afin de pouvoir mesurer une grande quantité d’échantillons en un temps réduit, un système de mesure haute cadence entièrement automatisé a été développé et utilisé avec succès. Dans un second temps,ces travaux ont portés sur l’étude du transport thermique dans trois matériaux (Ge, GaAs In-GaAs) par spectroscopie pompe-sonde femtoseconde. Une nouvelle méthode de mesure de la réponse spectrale des nanomatériaux sur une gamme de fréquences allant de quelques centaines de kHz jusqu’au THz a été développée. Les mesures à l’aide de cette méthode ont permis de confirmer la présence d’un régime de transport qualifié de quasi-balistique dans certains matériaux,et une méthode d’extraction de propriétés thermiques à partir de la réponse spectrale mesurée, et prenant en compte ces effets quasi-balistiques, a été développée. L’ensemble des résultats obtenus par ces nouvelles méthodes confirment les travaux précédents décrits dans la littérature. Enfin, la mesure de la réponse spectrale d’un nano-matériau à haute fréquence est en grande partie limitée par la gigue des cavités lasers utilisées par l’expérience. Ainsi, la dernière étape a été de développer un système de mesure de cette gigue et de synchronisation de cavités laser qui pourra permettre de repousser la limite des fréquences mesurables par spectroscopie pompe-sonde femtoseconde. / In this work, we studied ultrafast thermal transport at nanoscale in thin films by femtosecond pump-probe thermal spectroscopy. We first developed a high-throughput heterodyne thermoreflectance setup that allows the extraction of thermal properties of a large number of sample in a minimum time, aiming at creating a database of these properties for a large numberof thin film ternary alloys with thermoelectric potential. In the second part of this work, wefocused on the study of thermal transport in three materials : Ge, GaAs and InGaAs. A high resolution phonon spectroscopy setup, along with a spectral reconstruction method allowed usto measure the response of these materials up to several tens of GHz in Fourier domain, which highlighted the presence of non-diffusive thermal transport in InGaAs. Non-diffusive theory,based on Lévy dynamics, allowed us to model this superdiffusion phenomenon and to extract coherent, frequency-independant thermal properties of these materials. Also, high frequency(>GHz) measurements of these spectral responses have shown interesting effects related to the ultrafast thermalisation in transducer-like very thin films. Finally, high-frequency thermal spectroscopy is inherently limited by the intrinsic timing jitter of laser cavities. Thus, the last partof this work was dedicated to developing a timing jitter measurement and active laser synchronisation system in order to increase the signal-to-noise ratio and access higher frequencies in pump-probe thermal spectroscopy experiments.

Philosophiae Doctor - PhD / Electroanalytical and optical properties of nanoscale materials are very important for biosensing applications as well as for understanding the unique one-dimensional carrier transport mechanism. One-dimensional semiconductor nanomaterials such as semiconductor quantum dots are extremely attractive for designing high-density protein arrays. Because of their high surfaceto-volume ratio, electro-catalytic activity as well as good biocompatibility and novel electron transport properties make them highly attractive materials for ultra-sensitive detection of biological macromolecules via bio-electronic or bio-optic devices. A genosensor or gene based biosensor is an analytical device that employs immobilized deoxyribonucleic acid (DNA) probes as the recognition element and measures specific binding processes such as the formation of deoxyribonucleic acid-deoxyribonucleic acid (DNA-DNA), deoxyribonucleic acid- ribonucleic acid (DNA-RNA) hybrids, or the interactions between proteins or ligand molecules with DNA at the sensor surface.In this thesis, I present four binary and two ternary-electrochemically and optically modulated selenide and telluride quantum dots, all synthesised at room temperature in aqueous media. Cationic gallium (Ga3+) synthesized in form of hydrated gallium perchlorate salt[Ga(ClO4)3.6H2O] from the reaction of hot perchloric acid and gallium metal was used to tailor the optical and electrochemical properties of the selenide and telluride quantum dots. The synthesized cationic gallium also allowed successful synthesis of novel water soluble and biocompatible capped gallium selenide nanocrystals and gallium telluride quantum dots. Cyclic voltammetric studies inferred that presence of gallium in a ZnSe-3MPA quantum dot lattice improved its conductivity and significantly increased the electron transfer rate in ZnTe-3MPA.Utraviolet-visible (UV-vis) studies showed that incorporation of gallium into a ZnSe-3MPA lattice resulted in a blue shift in the absorption edge of ZnSe-3MPA from 350 nm to 325 nm accompanied by decrease in particle size. An amphiphilic bifunctional molecule, 3-Mercaptopropionic acid (3-MPA) was used as a capping agent for all quantum dots. It was found that 3-MPA fully solubilised the quantum dots, made them stable, biocompatible, non agglomerated and improved their electron transfer kinetics when immobilized on gold electrodes.Retention of the capping agent on the quantum dot surface was confirmed by Fourier transform infrared spectroscopy (FTIR) which gave scissor type bending vibrations of C-H groups in the region 1365 cm-1 to 1475 cm-1, stretching vibrations of C=O at 1640 cm-1, symmetric and asymmetric vibrations of the C-H in the region 2850 cm-1 to 3000 cm-1 as well as stretching vibrations of –O-H group at 3435 cm-1. The particle size and level of non-agglomeration of the quantum dots was studied by high resolution transmission electron microscopy (HRTEM). The optical properties of the quantum dots were studied using UV-vis and fluorescence spectroscopic techniques.Quantum dot/nanocrystal modified gold electrodes were prepared by immersing thoroughly cleaned electrodes in the quantum dot/nanocrystal solution, in dark conditions for specific periods of time. The electrochemical properties of the modified electrodes were characterized by cyclic voltammetry (CV), square wave voltammetry (SWV), electrochemical impedance and spectroscopy (EIS). Six sensing platforms were then prepared using quantum dot/nanocrystal, one of which was used for detection of dopamine while the rest were used for detection of a DNA sequence related to 5-enolpyruvylshikimate-3-phosphate synthase, a common vector gene in glyphosate resistant transgenic plants.The first sensing platform, consisting of ZnSe-3MPA modified gold electrode (Au|ZnSe-3MPA) gave rise to a novel method of detecting dopamine in presence of excess uric acid and ascorbic acid. Using a potential window of 0 to 400 mV, the ZnSe-3MPA masked the potential for oxidation of uric and ascorbic acids, allowing detection of dopamine with a detection limit of 2.43 x 10-10 M (for SWV) and 5.65 x 10-10 M (for steady state amperometry), all in presence of excess uric acid (>6500 higher) and ascorbic acid (>16,000 times higher). The detection limit obtained in this sensor was much lower than the concentration of dopamine in human blood(1.31 x 10-9 M), a property that makes this sensor a potential device for detection of levels of dopamine in human blood.The other sensing platforms were prepared by bioconjugation of amine-terminated 20 base oligonucleotide probe DNA (NH2-5′-CCC ACC GGT CCT TCA TGT TC-3′) onto quantum dot modified electrodes with the aid of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS). The prepared DNA electrodes were electrostatically hybridized with different sequences which included 5′-GAA CAT GAA GGA CCG GTG GG-3′ (complementary target), 5′-CATAGTTGCAGCTGCCACTG-3′ (non complementary target) and 5′-GATCATGAAGCACCGGAGGG-3′ (3-base mismatched target).The hybridization events were monitored using differential pulse voltammetry (DPV) and SWV by monitoring the guanine oxidation signal or using EIS by monitoring changes in the charge transfer resistance. The quantum dot genosensors were characterized by low detection limits (in the nanomolar range), long linear range (40 - 150 nM) and were able to discriminate among complementary, non-complementary and 3-base mismatched target sequences.

The present thesis deals with Nb-Si alloy composites in both bulk and multilayer forms. The work has been divided into two parts. First part (chapter 4-6) deals with Nb based silicides binary and ternary alloys with alloying additions like Ga and Al. These alloys are synthesized by vacuum arc melting and suction casting (non-equilibrium processing techniques). The studies on intermetallic coatings of Nb-Si alloys and Nb/Si multilayer synthesized by pulsed laser deposition technique have been presented in the second part (chapter7-8). Nb-Si alloys are one of the candidate materials for the advanced structural and microelectronic applications. There are few issues with these materials like poor oxidation resistance, low fracture toughness and brittleness which need to be solved. Microstructure plays a crucial role to control these properties. The main focus of this work is to understand the process of phase transformation and thereby control the microstructure in both bulk alloys and thin films. We have also investigated in a limited manner mechanical and environmental properties of bulk alloys. This thesis is subdivided into nine chapters. After a brief introduction in the first chapter, a brief overview on Nb-Si phase diagram and literature reviews on Nb-Si based alloys are presented with emphasis on the current work in the second chapter. Literature reviews on the phase formations sequence and stability in Nb-Si alloys thin films and Nb/Si multilayers are also discussed in the same chapter. In the third chapter different experimental techniques, processing parameters and characterization tools like XRD, SEM, TEM etc. are briefly discussed. Special emphasis is given on two non-equilibrium techniques: laser deposition technique to deposit the thin film/multilayer and vacuum suction casting to produce the 3 mm diameter rods of different Nb-Si alloys. The fourth chapter discusses the microstructural aspects of Nb-Si alloys prepared by suction casting and its mechanical behavior. The samples have the compositions hypoeutectic (Nb-10at.%Si and Nb-14at.%Si), eutectic (Nb-18.7at.%Si) and hypereutectic (Nb-22at.% Si and Nb-25at.% Si). SEM microstructural analyses of all the samples clearly show the enhancement in the volume fraction of eutectic and decease in the eutectic spacings in microstructure due to large undercooling. Rod eutectic is observed in most of places with irregular eutectic a few places in all samples. First check of phases has been done by XRD in all samples. Phase confirmation using TEM showed the eutectic between Nbss and Nb3Si phases in all samples. The primary phase for hypoeutectic alloys is Nbss (dendritic structure), Nb3Si phase for eutectic composition and β-Nb5Si3 phase for hypereutectic alloys. Compositional analysis using EDS and EPMA also supported the above results. No signature of eutectoid reaction (Nb3Si→Nb+α-Nb5Si3) is observed. Mechanical properties like hardness, strength, ductility and indentation fracture toughness have been determined for above mention alloy compositions. SEM micrographs showed that silicides fractured by cleavage and Nb phase in a ductile manner during the compression tests carried out at room temperature. We attempt to explain how the above mention mechanical properties change with alloy compositions and processing. Chapter five deals with the effect of Ga addition on the microstructure and mechanical properties of the Nb-Si alloy. The composition selected for this study is Nb-20.2at.%Si-2.7at.%Ga. The results of ternary alloy have been compared with the binary alloy composition Nb-18.7at.%Si. Phase analysis has been carried out using TEM and XRD. Ga addition has suppressed the formation of Nb3Si phase and promoted the formation of β-Nb5Si3 phase. Ga addition also established the eutectic between Nbss and β-Nb5Si3, which is a metastable eutectic. Ga added ternary alloy, on suction casting, yields ultrafine eutectic with nanometer length scale (50-100nm). From the compression tests, it is concluded that the combination of ultrafine eutectic (Nbss-β-Nb5Si3) and primary β-Nb5Si3 in ternary alloy results in a high compressive strength ~2.8±0.1 GPa with 4.3% plasticity. In contrast binary alloy under identical conditions shows the compressive strength ~1.35±0.1 GPa and 0.2% plasticity. Ga addition also enhances the indentation fracture toughness from 9.2±0.05 MPa√m (binary) to 24.11±0.5 MPa√m (ternary). Composite hardness values of the ternary and binary alloys are 1064±20 Hv and 1031±20 Hv respectively. Chapter six deals with Al added Nb-Si ternary alloy. Here we have discussed microstructural and mechanical properties like in chapter 5 along with oxidation behavior for the alloy composition Nb-12.7at.%Si-9at.%Al. SEM micrograph shows the presence of primary dendrites structure with ultra fine lamellar eutectic (50-100nm). Detailed TEM studies confirm the Nbss as primary phase present in form of dendrites. These dendrites contain the plate shape precipitates of δ-Nb11Si4 (body centered orthorhombic structure) phase in Nb matrix (primary dendrites). Eutectic phases are Nbss and β-Nb5Si3. The analysis of the results indicates that Al addition promote the formation of β-Nb5Si3 phase in the eutectic. The results of this ternary composition were also compared with the binary alloy composition Nb-18.7at.%Si. Compression tests have been carried out at room and elevated temperatures to measure the strength of the material. Al added ternary alloy yields the compressive strength value 1.6±0.01 GPa whereas binary alloy yields the compressive strength value 1.1±0.01 GPa. Enhancement in indentation fractured toughness is observed in Al added ternary alloy (20.4±0.5MPa√m) compare to binary alloy (9.2±0.05 MPa√m). Thermal analysis by TGA and DTA were used to see the oxidation behavior of Al added ternary alloy. Chapter seven deals with the deposition characteristics and the TEM studies on the laser deposited Nb-Si thin films. Films were deposited on the NaCl crystals and Si single crystal substrates. The compositions chosen in this case are Nb-25at.%Si, Nb-37.5at.%Si and Nb-66.7at.%Si. These compositions correspond to the equilibrium intermetallic compounds Nb3Si, Nb5Si3 and NbSi2 respectively. In this chapter we have briefly discussed the microstructural and phase evolutions in the intermetallic coatings. The smooth films quenched from the vapor and/or plasma state show amorphous structure. The sequence of crystallization was studied by hot stage TEM experiments as well as by cross sectional TEM in the films deposited at the elevated temperatures (600oC and 700oC) on Si substrates. During the hot stage experiment, crystallization is observed in Nb-25at.%Si film around 850oC with nucleation of metastable cubic Nb3Si phase. Occasionally metastable hexagonal Nb3Si3 phase has also been observed (close to Si substrate) along with cubic Nb3Si phase in the films at elevated temperatures. For Nb-37.5at.%Si film, crystallization is observed at 800oC with the nucleation of grains of metastable hexagonal Nb5Si3 phase. Cross-sectional TEM shows the presence of hexagonal Nb5Si3 phase along with few grains of NbSi3 (equilibrium) phase in the films deposited at elevated temperatures. Hot stage experiment of Nb-66.3at.%Si film showed the onset of crystallization much earlier at 400oC and complete crystallization at 600oC. This crystallization leads to the nucleation of grains of NbSi2 phase. Films of this composition deposited at elevated temperatures showed the presence of NbSi2 and metastable hexagonal Nb5Si3 phases (occasionally). The laser ablated films, besides the film matrix also contain the micron and submicron sized spherical droplets of different sizes. These droplets travel at very high velocities and impinge on the substrate resulting in a very high rate of heat transfer during solidification from liquid state. Therefore in this work we have also studied the microstructural evolution in the droplets for each composition. The phases observed in the droplets embedded in the matrix of Nb-25 at% Si alloy film are the bcc Nb and the cubic Nb3Si (metastable phase). The droplets in the matrix of Nb-37.5 at% Si alloy showed the bcc Nb and tetragonal β-Nb5Si3 phases. The phases observed in the droplets of in the Nb-66.3at.%Si alloy are the bcc Nb, tetragonal β-Nb5Si3 and the hexagonal NbSi2 (metastable phase). Chapter eight describes the synthesis and microstructural characterization using TEM of Nb/Si multilayers. The aim of this work is to check the stability and phase formation sequence in Nb/Si multilayer. Nb/Si multilayers were first annealed at different time intervals at 600oC and at different temperatures (for 2 hours) and then characterized by the cross-sectional transmission electron microscopy. As-deposited Nb layer is crystalline while Si layer is amorphous. Microstructural and compositional evidences suggest the intermixing between the Nb and Si layers at the interfaces. Nb/Si multilayer annealed at 600oC for 1 hour, NbSi2 was identified as the first crystalline nucleating phase. However amorphous silicide layers were also observed between Nb and NbSi2 layers. Metastable hexagonal Nb5Si3 was identified as the next crystalline phase that nucleated from the amorphous silicide layers at the interfaces of Nb and NbSi2 layers. Occasionally few grains of cubic Nb3Si phase were also observed after 8 hours of annealing at 600oC. In the chapter we have compared the results to the other reported works in Nb-Si bulk diffusion couples and also thin film couples. The final chapter summarizes the major conclusions of the present work and scope of future work.