Nous avons observé une augmentation ‘’transient’’du taux de cristallisation interfacique de l’a-Si lorsqu’on réimplante du Si à proximité de l’interface amorphe/cristal. Après amorphisation et traitement thermique à 650°C pendant 5s de la couche a-Si crée par implantation ionique, une partie a été réimplantée. Les défauts produits par auto-réimplantation à 0.7MeV se trouvent à (302±9) nm de l’interface initiale. Cela nous a permis d’étudier d’avantage la variation initiale de la vitesse SPE (Épitaxie en phase solide). Avec des recuit identiques de 4h à 500°C, nous avons déterminé les positions successives des interfaces et en déduit les taux de cristallisation SPE. La cristallisation débute à l’interface et continue graduellement vers la surface. Après le premier recuit, (252±11) nm s’est recristallisé dans la zone réimplantée soit un avancement SPE de 1.26x10^18at./cm2. Cette valeur est environ 1.50 fois plus importante que celle dans l’état relaxé. Nous suggérons que la présence de défauts à proximité de l’interface a stimulé la vitesse initiale. Avec le nombre de recuit, l’écart entre les vitesses diminue, les deux régions se cristallisent presque à la même vitesse. Les mesures Raman prises avant le SPE et après chaque recuit ont permis de quantifier l’état de relaxation de l’a-Si et le transfert de l’état dé-relaxé à relaxé. / We observed a ‘’transient’’ increase of planar crystallization rate of a-Si when one reimplanted Si near the interface amorphous / crystal. After amorphization and heat treatment at 650°C for 5s, one part has been re-implanted. The defects produced at 0.7 MeV by self-re-implantation are located at (302±9) nm of the initial interface. This allows us to better study the initial variation of SPE speed (solid phase epitaxy). With recrystallisation anneals at 500±4°C for 4h, we have determined the successive positions of the interfaces and have deduced the SPE recrystallization rate. Crystallization began at the interface and continues gradually to the surface. After the first annealing, (252±11)nm was recrystallized in the re-implanted state. That means 1.26x10^18at./cm2 SPE enhancement. This value is approximately 1.50 times greater than that in the relaxed state. We suggest that the presence of defects near the interface stimulate the speed. Raman measurements taken after each annealing allowed us to know the transfer of the un-relaxed state to the relaxed state. After the number of anneals treatments, both areas progress almost at the same speed / Dans ce travail nous avons étudié le phénomène de diffusion du cuivre et de l’argent dans a-Si en présence de l’hydrogène à la température de la pièce et de recuit. Une couche amorphe de 0.9μm d’épaisseur a été produite par implantation de 28Si+ à 500 keV sur le c-Si (100). Après celle-ci, on procède à l’implantation du Cu et de l’Ag. Un traitement thermique a produit une distribution uniforme des impuretés dans la couche amorphe et la relaxation de défauts substantiels. Certains défauts dans a-Si sont de type lacune peuvent agir comme des pièges pour la mobilité du Cu et de l’Ag. L’hydrogène implanté après traitement thermique sert à dé-piéger les impuretés métalliques dans certaines conditions. Nous n’avons détecté aucune diffusion à la température de la pièce au bout d’un an, par contre un an après à la température de recuit (1h à 450°C) on observe la diffusion de ces métaux. Ce qui impliquerait qu’à la température de la pièce, même si l’hydrogène a dé-piégé les métaux mais ces derniers n’ont pas pu franchir une barrière d’énergie nécessaire pour migrer dans le réseau. / In this work we studied the diffusion phenomenon of copper and silver in a-Si in the presence of hydrogen at room temperature and annealing temperature. The 0.9 μm -thick a-Si layers were formed by ion implantation 28Si + at 500 keV on c-Si (100). After this Cu ions and Ag ions were implanted at 90keV.The heat treatment produces a uniform distribution of impurities in the amorphous layer and the relaxation of substantial defects. Vacancies defects in a-Si can act as traps for the mobility of Cu and Ag. Hydrogen implanted is used to de-trap metal impurities such as Cu and Ag. However we did not detect any diffusion at room temperature during 1 year, but after one year at the annealing temperature (450°C for 1h) we observe the distribution of these metals. Implying that the room at temperature, although the hydrogen de-trapping metals but they could not crossed an energy barrier required to migrate in the network.

Thesis (M.A.)--University of Hawaii at Manoa, 2005. / Includes bibliographical references (leaves 202-209). / ix, 209 leaves, bound .ill, maps 29 cm

歷史，是人生經驗的總合；史學，則是萃取其中菁華加以會通，意圖有補於人世的大 業；資治通鑑，更可以視為此中最典型的標的。但是，由於若干偏見和卷帙浩繁的局 限，使這一代鉅著往往束諸高閣。本篇即在嘗試撥開層層障礙，直指司馬光潛心構建 的理相國。 一、研究方法：針對上述目的，循此直接而明確的脈絡，逼近上述理想。所以，本篇 的工作流程也因而畫分為六：（一）蒐羅材料、（二）閱讀分析、（三）製作檢索、 （四）分疏章節、（五）詳訂敘例、（六）正式撰述。 二、研究文獻：以啟業書局六六年台版的點校本資治通鑑、商務印書館五四年二月台 初版的萬有文庫薈要本司馬文正公傳家集為基礎，網羅了近百種相關的書籍、期刊、 論文。 三、研究內容：本篇歸納四大課題，共分九章、廿六節－－ （一）背景分析：研究動機暨方法、編年史傳統回顧、時代背景；通鑑的編纂成員、 準備、成書；體例、羽翼以及臣光曰概況。計三章。 （二）主題推演：臣光曰的君、臣道；取才、行政；立法、司法、監察及其他理念的 脈絡呈現。計三章。 （三）批判：臣光曰的思想特色、得失；司馬光的文學觀以及臣光曰的題旨趨勢、文 章手法。計二章。 （四）歸結：計一章。 四、研究結果：集中於第九章－－ （一）提示特徵：春秋之意、左傳之法、儒家之旨、本朝背景、個人創獲。 （二）平議爭端：疏通歷來攻擊最厲的因襲、保守、主觀論點。 （三）略述影響：穩定型政治觀的承先啟後。

A major focus is on integrated Silicon-based optoelectronics for the creation of low-cost photonics for mass-market applications. Especially, the growing demand for sensitive and portable optical sensors in the environmental control and medicine follows in the development of integrated high resolution sensors [1]. In particular, since 2013 the quick onsite verification of pathogens, like legionella in drinking water pipes, is becoming increasingly important [2, 3]. The essential questions regarding the establishment of portable biochemical sensors are the incorporation of electronic and optical devices as well as the implementations of fundamental cross-innovations between biotechnology and microelectronics. This thesis describes the design, fabrication and analysis of high-refractive-index-contrast photonic structures. Besides silicon nitride (Si3N4) strip waveguides, lateral tapers, bended waveguides, two-dimensional photonic crystals (PhCs) the focus lies on monolithically integrated waveguide butt-coupled Silicon-based light emitting devices (Sibased LEDs) [4, 5] for use as bioanalytical sensor components. Firstly, the design and performance characteristics as single mode regime, confinement factor and propagation losses due to the geometry and operation wavelength (1550 nm, 541 nm) of single mode (SM), multi mode (MM) waveguides and bends are studied and simulated. As a result, SM operation is obtained for 1550 nm by limiting the waveguide cross-section to 0.5 μm x 1 μm resulting in modal confinement factors of 87 %. In contrast, for shorter wavelengths as 541 nm SM propagation is excluded if the core height is not further decreased. Moreover, the obtained theoretical propagation losses for the lowestorder TE/TM mode are in the range of 0.3 - 1.3 dB/cm for an interface roughness of 1 nm. The lower silicon dioxide (SiO2) waveguide cladding should be at least 1 μm to avoid substrate radiations. These results are in a good correlation to the known values for common dielectric structures. In the case of bended waveguides, an idealized device with a radius of 10 μm was developed which shows a reflection minimum (S11 = - 22 dB) at 1550 nm resulting in almost perfect transmission of the signal. Additionally, tapered waveguides were investigated for an optimized light coupling between high-aspect-ratio devices. Here, adiabatic down-tapered waveguides were designed for the elimination of higher-order modes and perfect signal transmission. Secondly, fabrication lines including Electron-beam (E-beam) lithography and reactive ion etching (RIE) with an Aluminum (Al) mask were developed and lead to well fabricated optical devices in the (sub)micrometer range. The usage of focused ion beam (FIB) milling is invented for smoother front faces which were analyzed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). As a result, the anisotropy of the RIE process was increased, but the obtained surface roughness parameters are still too high (10 – 20 nm) demonstrating a more advanced lithography technique is needed for higher quality structures. Moreover, this study presents an alternative fabrication pathway for novel designed waveguides with free-edge overlapping endfaces for improving fiber-chipcoupling. Thirdly, the main focus lies on the development of a monolithic integration circuit consisting of the Si-based LED coupled to an integrated waveguide. The light propagation between high-aspect-ratio devices is enabled through low-loss adiabatic tapers. This study shows, that the usage of CMOS-related fabrication technologies result in a monolithic manufacturing pathway for the successful implementation of fully integrated Si-based photonic circuits. Fourth, transmission loss measurements of the fabricated photonic structures as well as the waveguide butt-coupled Si-based LEDs were performed with a generated setup. As a result, free-edge overlapping MM waveguides show propagation loss coefficients of ~ 65 dB/cm in the range of the telecommunication wavelength. The high surface roughness parameters (~ 150 nm) and the modal dispersion in the core are one of the key driving factors. These facts clearly underline the improvement potential of the used fabrication processes. However, electroluminescence (EL) measurements of waveguide butt-coupled Si-based LEDs due to the implanted rare earth (RE) ion (Tb3+, Er3+) and the host material (SiO2/SiNx) were carried out. The detected transmission spectra of the coupled Tb:SiO2 systems show a weak EL signal at the main transition line of the Tb3+-ion (538 nm). A second emission line was detected in the red region of the spectrum either corresponding to a further optical transition of Tb3+ or a Non Bridging Oxygen Hole Center (NBOHC) in SiO2. Unfortunately, no light emission in the infrared range was established for the Er3+-doped photonic circuits caused by the low external quantum efficiencies (EQE) of the Er3+ implanted Si-based LEDs. Nevertheless, transmission measurements between 450 nm – 800 nm lead again to the result that an emission at 650 nm is either caused by an optical transition of the Er3+-ion or initialized by the NBOHC in the host. Overall, it is difficult to assess whether or not these EL signals are generated from the implanted ions, thus detailed statements about the coupling efficiency between the LED and the integrated waveguide are quite inadequate. Nevertheless, the principle of a fully monolithically integrated photonic circuit consisting of a Si-based LED and a waveguide has been successfully proven in this study.

The knowledge of diffusion parameters provides important understanding of many physical and mechanical properties of materials. In most of the applications silicides are grown by a diffusion controlled process mainly in thin film condition. Because of this reason, most of the studies till date are available in thin film condition. Although more than one phase is present in all these systems, mainly disilicides were found at the interface. In this thesis bulk interdiffusion studies are conducted by coupling pure refractory metals (group IVB, VB and VIB elements) with single crystal Si. Several phase layers grow between binary refractory metal and Si systems. The layer thicknesses of the phases are measured from the microstructures. Composition profiles were measured in electron probe microanalyzer. Different diffusion parameters are estimated such as parabolic growth constants, integrated diffusion coefficients, activation energy for diffusion and ratio of tracer diffusivities of the components are estimated. Growth mechanisms of the phases are discussed with the help of diffusion parameters. The atomic mechanism of the diffusion is discussed considering crystal structure of the phases along with possible defects present. Solid diffusion couple experiments are conducted to analyse the growth mechanism of the phases and the diffusion mechanism of the components in the Ti-Si system. The calculation of the parabolic growth constant and of the integrated diffusion coefficients substantiates that the analysis is intrinsically prone to erroneous conclusions if it is based just on the parabolic growth constants determined for a multiphase interdiffusion zone. The location of the marker plane is detected based on the uniform grain morphology in the TiSi2 phase, which indicates that this phase grows mainly because of Si diffusion. The growth mechanism of the phases and morphological evolution in the interdiffusion zone are explained with the help of imaginary diffusion couples. The activation enthalpies for the integrated diffusion coefficient of TiSi2 and the Si tracer diffusion are calculated as 190±9 and 170±12 kJ/mol, respectively. The crystal structure, details on the nearest neighbours of the elements and the relative mobilities of the components indicate that the vacancies are mainly present on the Si sublattice. Diffusion controlled growth of the phases in the Hf-Si and Zr-Si are studied by bulk diffusion couple technique. Only two phases grow in the interdiffusion zone, although several phases are present in both the systems. The location of the Kirkendall marker plane detected based on the grain morphology indicates that the disilicides grow by the diffusion of Si. Diffusion of the metal species in these phases is negligible. This indicates that vacancies are present mainly on the Si sublattice. The activation energies for integrated diffusion coefficients in the HfSi2 and ZrSi2 are estimated as 394 ± 37 and 346 ± 34 kJ/mol, respectively. The same is calculated for the HfSi phase as 485±42 kJ/mol. The activation energies for Si tracer diffusion in the HfSi2 and ZrSi2 phases are estimated as 430 ± 36 and 348 ± 34 kJ/mol, respectively. We conducted interdiffusion studies to understand the atomic mechanism of the diffusing species and the growth mechanism of the phases. Integrated diffusion coefficients and the ratio of tracer diffusion coefficients were estimated for these analyses. The activation energies for the integrated diffusion coefficients were calculated as 550 ± 70 and 410 ± 39 kJ/mol in the TaSi2 and the Ta5Si3 phases, respectively. In the TaSi2 phase, Ta has a slightly lower but comparable diffusion rate with respect to Si, although no TaTa bonds are present in the crystal. In the Ta5Si3 phase, Si has higher diffusion rate, which is rather unusual, if we consider the atoms in the nearest-neighbor positions for both the elements. The ratio of Si to Ta tracer diffusion coefficients is found to be lower in the Si-rich phase, TaSi2, compared to the Si-lean phase, Ta5Si3, which is also unusual. This indicates the type of structural defects present. An analysis on the growth mechanism of the phases indicates that duplex morphology and the Kirkendall marker plane should only be present in the TaSi2 phase. This is not present in the Ta5Si3 phase because of the very high growth rate of the TaSi2 phase, which consumes most of the Ta5Si3 phase layer. The problems in the calculation method used previously by others in this system are also explained. Experiments are conducted in the W-Si system to understand the diffusion mechanism of the species. The activation energies for integrated diffusion are found to be 152±7 and 301±40 kJ/mol in the WSi2 and W5Si3 phases, respectively. In both the phases, Si has a much higher diffusion rate compared to W. The result found in the WSi2 phase is not surprising, if we consider the nearest neighbors in the crystal. However, it is rather unusual to find that Si has higher diffusion rate in the W5Si3 phase, indicating the presence of high concentration of Si antisites in this phase. In the group IVB, VB and VIB M-Si systems are considered to show an interesting pattern in diffusion of components with the change in atomic number in a particular group. MSi2 and M5Si3 are considered for this discussion. Except in the Ta-Si system, activation energy for integrated diffusion of MSi2 is always lower than M5Si3. Interestingly, in both the phases, the relative mobilities measured by the ratio of tracer D* diffusion coefficients, S i decreases with the increase in atomic number in both the DM* groups. Both the phases have similar crystal structures in a particular group in which these parameters are calculated. In both the phases Si has higher diffusion rate compared to M. Absence of any M-M bonds in MSi2 and increase in the diffusivities of M with the increase in atomic number substantiates the increasing concentration of M anti-sites and higher interactions of M with vacancies. Only one or two Si-Si bonds are present in M5Si3, however, the higher diffusion rate of Si indicates the presence of vacancies mainly D* on its sublattice. On the other hand, increase in S i with increasing atomic number in DM* Both the groups substantiates increasing interactions of M and vacancies.

A major focus is on integrated Silicon-based optoelectronics for the creation of low-cost photonics for mass-market applications. Especially, the growing demand for sensitive and portable optical sensors in the environmental control and medicine follows in the development of integrated high resolution sensors [1]. In particular, since 2013 the quick onsite verification of pathogens, like legionella in drinking water pipes, is becoming increasingly important [2, 3]. The essential questions regarding the establishment of portable biochemical sensors are the incorporation of electronic and optical devices as well as the implementations of fundamental cross-innovations between biotechnology and microelectronics. This thesis describes the design, fabrication and analysis of high-refractive-index-contrast photonic structures. Besides silicon nitride (Si3N4) strip waveguides, lateral tapers, bended waveguides, two-dimensional photonic crystals (PhCs) the focus lies on monolithically integrated waveguide butt-coupled Silicon-based light emitting devices (Sibased LEDs) [4, 5] for use as bioanalytical sensor components. Firstly, the design and performance characteristics as single mode regime, confinement factor and propagation losses due to the geometry and operation wavelength (1550 nm, 541 nm) of single mode (SM), multi mode (MM) waveguides and bends are studied and simulated. As a result, SM operation is obtained for 1550 nm by limiting the waveguide cross-section to 0.5 μm x 1 μm resulting in modal confinement factors of 87 %. In contrast, for shorter wavelengths as 541 nm SM propagation is excluded if the core height is not further decreased. Moreover, the obtained theoretical propagation losses for the lowestorder TE/TM mode are in the range of 0.3 - 1.3 dB/cm for an interface roughness of 1 nm. The lower silicon dioxide (SiO2) waveguide cladding should be at least 1 μm to avoid substrate radiations. These results are in a good correlation to the known values for common dielectric structures. In the case of bended waveguides, an idealized device with a radius of 10 μm was developed which shows a reflection minimum (S11 = - 22 dB) at 1550 nm resulting in almost perfect transmission of the signal. Additionally, tapered waveguides were investigated for an optimized light coupling between high-aspect-ratio devices. Here, adiabatic down-tapered waveguides were designed for the elimination of higher-order modes and perfect signal transmission. Secondly, fabrication lines including Electron-beam (E-beam) lithography and reactive ion etching (RIE) with an Aluminum (Al) mask were developed and lead to well fabricated optical devices in the (sub)micrometer range. The usage of focused ion beam (FIB) milling is invented for smoother front faces which were analyzed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). As a result, the anisotropy of the RIE process was increased, but the obtained surface roughness parameters are still too high (10 – 20 nm) demonstrating a more advanced lithography technique is needed for higher quality structures. Moreover, this study presents an alternative fabrication pathway for novel designed waveguides with free-edge overlapping endfaces for improving fiber-chipcoupling. Thirdly, the main focus lies on the development of a monolithic integration circuit consisting of the Si-based LED coupled to an integrated waveguide. The light propagation between high-aspect-ratio devices is enabled through low-loss adiabatic tapers. This study shows, that the usage of CMOS-related fabrication technologies result in a monolithic manufacturing pathway for the successful implementation of fully integrated Si-based photonic circuits. Fourth, transmission loss measurements of the fabricated photonic structures as well as the waveguide butt-coupled Si-based LEDs were performed with a generated setup. As a result, free-edge overlapping MM waveguides show propagation loss coefficients of ~ 65 dB/cm in the range of the telecommunication wavelength. The high surface roughness parameters (~ 150 nm) and the modal dispersion in the core are one of the key driving factors. These facts clearly underline the improvement potential of the used fabrication processes. However, electroluminescence (EL) measurements of waveguide butt-coupled Si-based LEDs due to the implanted rare earth (RE) ion (Tb3+, Er3+) and the host material (SiO2/SiNx) were carried out. The detected transmission spectra of the coupled Tb:SiO2 systems show a weak EL signal at the main transition line of the Tb3+-ion (538 nm). A second emission line was detected in the red region of the spectrum either corresponding to a further optical transition of Tb3+ or a Non Bridging Oxygen Hole Center (NBOHC) in SiO2. Unfortunately, no light emission in the infrared range was established for the Er3+-doped photonic circuits caused by the low external quantum efficiencies (EQE) of the Er3+ implanted Si-based LEDs. Nevertheless, transmission measurements between 450 nm – 800 nm lead again to the result that an emission at 650 nm is either caused by an optical transition of the Er3+-ion or initialized by the NBOHC in the host. Overall, it is difficult to assess whether or not these EL signals are generated from the implanted ions, thus detailed statements about the coupling efficiency between the LED and the integrated waveguide are quite inadequate. Nevertheless, the principle of a fully monolithically integrated photonic circuit consisting of a Si-based LED and a waveguide has been successfully proven in this study.

The present thesis investigates the grain refinement in solidifying Al-7wt%Si hypoeutectic alloy driven by electric currents. The grain size reduction in alloys generated by electric currents during the solidification has been intensively investigated. However, since various effects of electric currents have the potential to generate the finer equiaxed grains, it is still argued which effect plays the key role in the grain refinement process. In addition, the knowledge about the grain refinement mechanism under the application of electric currents remains fragmentary and inconsistent. Hence, the research objectives of the present thesis focus on the role of electric current effects and the grain refinement mechanism under the application of electric currents. Chapter 1 presents an introduction with respect to the subject of grain refinement in alloys driven by electric current during the solidification process in particular, including the research objectives; the research motivation; a brief review about the research history; a short introduction on the electric currents effects and a review relevant to the research status of grain refinement mechanism. Chapter 2 gives a description of research methods. This chapter shows the employed experiment materials, experimental setup, experimental procedure, the analysis methods of solidified samples, and numerical method, respectively. Chapter 3 focuses on the role of electric current effects in the grain refinement process. A series of solidification experiments are performed under various values of effective electric currents for both, electric current pulse and direct current. The corresponding temperature measurements and flow measurements are carried out with the increase of effective electric current intensity. Meanwhile, numerical simulations are conducted to present the details of the flow structure and the distribution of electric current density and electromagnetic force. Finally, the role of electric current effects is discussed to find the key effect in the grain refinement driven by electric currents. Chapter 4 investigates the grain refinement mechanism driven by electric currents. This chapter mainly focuses on the origin of finer equiaxed grain for grain refinement under the application of electric current on account of the importance of the origin for understanding the grain refinement mechanism. A series of solidification experiments are carried out in Al-7wt%Si alloy and in high purity aluminum. The main origin of equiaxed grain for grain refinement is concluded based on the experiment results. Chapter 5 presents three further investigations based on the achieved knowledge in chapter 3 and 4 about the role of electric current effects and the grain refinement mechanism. According to the insight into the key electric current effect for the grain refinement shown in chapter 3, this chapter presents a potential approach to promote the grain refinement. In addition, the solute distribution under the influence of electric current is examined based on the knowledge about the electric current effects. Moreover, the grain refinement mechanism under application of travelling magnetic field is investigated by performing a series of solidification experiments to compare with the experiments about the grain refinement mechanism driven by electric currents shown in chapter 4. Chapter 6 summarizes the main conclusions from the presented work.

L'alliage Si-Ge est utilisé depuis de nombreuses années dans les modules thermoélectriques dans les sondes spatiales de la NASA. Ils convertissent la chaleur résultant de la désintégration radioactive de matériaux riches en un ou plusieurs radio-isotopes en électricité. Cet alliage est performant à haute température (à partir de 700 °C), c'est pourquoi il trouve également un fort intérêt dans l'industrie automobile. De nombreuses recherches dans ce secteur s'orientent vers la thermoélectricité, notamment vers des modules fonctionnant à haute température pour permettre la réduction de consommation de carburant.La meilleure composition de l'alliage en thermoélectricité est Si0,8Ge0,2. Le facteur de mérite réduit (ZT) de ces matériaux est généralement proche de 0,75 et de 0,45 à 700 °C pour les types n et p respectivement. Le germanium étant très onéreux, la composition retenue dans cette étude est Si0,92Ge0,08. Pour améliorer les performances de la composition choisie et se rapprocher de celles de la meilleure composition, la voie retenue est l'incorporation de nanoinclusions à base de siliciures de molybdène dans le matériau, permettant la diminution de la conductivité thermique.L'alliage Si-Ge est synthétisé par mécanosynthèse, et densifié par SPS. Les dopants utilisés sont le phosphore et le bore pour les types n et p respectivement. Le taux de dopage optimal est de 0,7 %. Ainsi, les ZT obtenus à 700 °C sont égaux à 0,7 et 0,5 pour les types n et p respectivement. La nature des inclusions stables dans la matrice est déterminée par la méthode CalPhad qui permet l'obtention du diagramme ternaire Mo-Si-Ge. La phase MoSi2 apparait alors comme étant la seule phase stable dans la matrice Si0,92Ge0,08. La fraction volumique optimale de molybdène est de 1,3 % lorsque les matériaux sont densifiés à 1280 °C. Le ZT obtenu est supérieur à 1 à 700 °C pour le type n, et proche de 0,8 pour le type p. L'ajout de nanoinclusions a permis d'augmenter les performances de 43 % et de 60 % à 700 °C. / Si-Ge alloys has been used for many years in the thermoelectric modules in the NASA space probes in which they convert heat produced by the radioactive decay of a heat source into electricity. This alloy is effective at high temperature (from 700 °C), so it is also a strong interest in the automotive industry. The strong incentive in this area to reduce fuel consumption leads researchers to develop thermoelectric modules that can operate at high temperatures. The composition at which SiGe alloys are the most thermoelectrically efficient is Si0.8Ge0.2. Their figure of merit (ZT) is generally close to 0.75 and 0.45 at 700 °C for type n and p respectively. As Germanium is very expensive, this study aims to develop a Si0.92Ge0.08 alloy that can compare to the existing Si0.8Ge0.2 alloys. To get to a higher level of performance, the thermal conductivity of the chosen composition has to be decreased, which is done by incorporating molybdenum silicides in the Si0.92Ge0.08 alloys.The Si-Ge alloy was synthesized by mechanical alloying, and sintered by SPS. The dopants used are phosphorous and boron for the n and p types respectively. The optimal doping level is 0.7%. ZT obtained for Si0.92Ge0.08 base alloys at 700 °C are equal to 0.7 and 0.5 for n and p types respectively. The nature of stable inclusions in the matrix has been determined by the CALPHAD method to obtain the ternary diagram Mo-Si-Ge. Then, the MoSi2 phase appears to be the only stable phase in the matrix Si0.92Ge0.08. The optimum volume fraction of molybdenum was 1.3% when the materials are sintered at 1280 °C. Therefore, the ZT obtained is higher than 1 at 700 °C for n-type and close to 0.8 for p-type. Adding nanoinclusions has increased performance by 43% (n-type) and 60% (p-type) at 700 °C.

Le silicium (Si) et le germanium (Ge) sont les matériaux de base utilisés dans les circuits intégrés. Cependant, à cause de leur gap indirect, ces matériaux ne sont pas adaptés à la fabrication de dispositifs d'émission de lumière, comme les lasers ou diodes électroluminescentes. Comparé au Si, le Ge pur possède des propriétés optiques uniques, à température ambiante son gap direct est de seulement 140 meV au-delà du gap indirect tandis qu'il est supérieur à 2 eV dans le cas du Si. Compte tenu du coefficient de dilatation thermique du Ge, deux fois plus grand que celui du Si, une croissance de Ge sur Si à hautes températures suivie d'un refroidissement à température ambiante permet de générer une contrainte en tension dans le Ge. Cependant, l'existence d'un désaccord de maille de 4,2% entre deux matériaux conduit à une croissance Stranski-Krastanov avec la formation des films rugueux et contenant de forte densité des dislocations. Nous avons mis en évidence l'existence d'une fenêtre de température de croissance, permettant de supprimer la croissance tridimensionnelle de Ge/Si. En combinant la croissance à haute température à des recuits thermiques par cycles, une contrainte de 0,30% a pu être obtenue. Le dopage de type n a été effectué en utilisant la décomposition de GaP, ce qui produit des molécules P2 ayant un coefficient de collage plus grand par rapport à celui des molécules P4. En particulier, en mettant en oeuvre la technique du co-dopage en utilisant le phosphore et l'antimoine, nous avons mis en évidence une augmentation de l'émission du gap direct du Ge à environ 150 fois, ce qui constitue l'un des meilleurs résultats obtenus jusqu'à présent. / Silicon (Si) and germanium (Ge) are the main materials used as active layers in microelectronic devices. However, due to their indirect band gap, they are not suitable for the fabrication of light emitting devices, such as lasers or electroluminescent diodes. Compared to Si, pure Ge displays unique optical properties, its direct bandgap is only 140 meV above the indirect one. As Ge has a thermal expansion coefficient twice larger than that of Si, tensile strain can be induced in the Ge layers when growing Ge on Si at high temperatures and subsequent cooling down to room temperature. However, due to the existence of a misfit as high as 4.2 % between two materials, the Ge growth on Si proceeds via the Stranski-Krastanov mode and the epitaxial Ge films exhibits a rough surface and a high density of dislocations. We have evidenced the existence of a narrow substrate temperature window, allowing suppressing the three-dimensional growth of Ge on Si. By combining high-temperature growth with cyclic annealing, we obtained a tensile strain up to 0.30 %. The n-doping in Ge was carried out using the decomposition of GaP to produce the P2 molecules, which have a higher sticking coefficient than the P4 molecules. In particular, by implementing a co-doping technique using phosphorus and antimony, we have evidenced an intensity enhancement of about 150 times of the Ge direct band gap emission. This result represents as one of the best results obtained up to now.

Este trabalho tem como objetivo o estudo da influência do boro na fase αNb5Si3 (Fase T2) a baixas temperaturas analisando suas propriedades elétricas e magnéticas. Para o estudo deste tema as amostras foram preparadas, seguindo a estequiometria Nb5Si3-xBx, via metalurgia do pó e também por fusão a arco, com x dentro do intervalo limitado por 0  X  1,0. Estas amostras foram analisadas através de difratometria de raios x, microscopia eletrônica de varredura, magnetização, transporte elétrico e medidas calorimétricas em baixa temperatura. As medidas das propriedades elétricas e magnéticas destas fases mostram que a substituição de boro por silício induz supercondutividade na fase T2. O caráter volumétrico da transição supercondutora é confirmado pela medida de capacidade calorífica. Assim, este trabalho é o primeiro a mostrar uma nova família de materiais supercondutores que cristalizam na estrutura protótipo Cr5B3. / This work to study the influence of boron during low temperature αNb5Si3 (T2 phase) analyzing their electrical and magnetic properties. For the study of this subject the samples were prepared, following the stoichiometry Nb5Si3-xBx via powder metallurgy and also by arc melting process, with x within the range limited by 0X1.0. These samples were analyzed by X-ray diffraction, scanning electron microscopy, magnetization, electrical transport and calorimetric measurements of low temperature. Measurements of electrical and magnetic properties of these phases show that the substitution of boron by silicon induces superconductivity at the T2 phase. The bulk nature of superconducting transition is confirmed by heat capacity measurement. This study is the first to show a new family of superconducting materials that crystallize in the Cr5B3 prototype structure.