Board-to-board connectors are used for electrically connecting one printed circuit board to another. In this thesis, a method for assessing the reliability of such connectors will be developed and tested with the goal of determining the reliability of a selection of connectors. Board-to-board connectors are widely used for connecting different electronic modules to each other, forming a modular system. Today, one of the limiting factors when it comes to modularizing electronic systems, is the lack of data on the long-term reliability of board-to-board connectors. The methods detailed in this thesis are meant to enable electronic designers to make informed decisions on connector selection when modularizing electronic systems. Modularization of electronic systems has several advantages, for example an increased first-pass yield (FPY) during assembly, and the ability to modify or replace certain parts of the system without re-spinning the entire thing. The method by which the reliability of connectors will be tested, is to continuously measure the contact resistance of the connectors during a selection of stress tests. The stress tests in question are mechanical vibration tests, thermal cycling tests, and actuation tests, all of which represent conditions that products from Hitachi Energy may be subjected to. There already exist standards on how to measure contact resistance, but those standards are not necessarily scalable to the measurement of thousands of contacts, nor are they made with the expectation that contacts can be measured during stress tests. The methods presented in this report are developed with the existing standards as basis, but have been modified in order to facilitate the measurement of thousands of contacts during stress tests. The results show that there are advantages to continuous monitoring of contact resistances during tests, as behaviors can be observed, which would not have been captured had the tests been performed conventionally. Furthermore the system which was developed forms the groundwork for a more convenient and cost effective method for testing the reliability of a large selection of board-to-board connectors. / Kontaktdon för kort-till-kort-anslutning används för att elektriskt koppla ett kretskort till ett annat. I denna avhandling utvecklas och testas en metod för att bedöma pålitligheten hos sådana anslutningar, med målet att fastställa pålitligheten hos ett urval av existerande kontaktdon. Kontaktdon för anslutning av kretskort till varandra används allmänt för att knyta ihop olika elektroniska moduler till varandra och bilda ett modulärt system. Idag är en av de begränsande faktorerna när det gäller att modularisera elektroniska system, bristen på data för långtidstålighet hos kontaktdon för kort-till-kort-anslutning. De metoder som beskrivs i denna avhandling är avsedda att möjliggöra för elektronikdesigner att fatta korrekta beslut om kontaktdonsval vid modularisering av elektroniska system. Modularisering av elektroniska system har flera fördelar, till exempel en förbättrad “first-pass yield”, FPY, när det gäller montering och möjligheten att modifiera eller ersätta vissa delar av systemet utan att behöva göra om hela systemet. Metoden som här används för att testa pålitligheten hos kontaktdon är att kontinuerligt mäta kontaktresistansen hos kontaktdonen under ett antal stresstester. De aktuella stresstesterna är mekaniska vibrationsprov, termocykeltester och aktiveringstester, vilka alla representerar vanliga situationer som Hitachi Energy’s produkter kan utsättas för. Det finns redan standarder för hur man mäter kontaktresistans, men dessa standarder är ofta inte skalbara till mätningar av tusentals kontakter samtidigt, och de är inte heller utformade för att mäta kontakter under stresstester. De metoder som presenteras i denna rapport är utvecklade med befintliga standarderna som grund, men har modifierats för att underlätta mätning av tusentals kontakter under olika stresstester. Resultaten visar att det finns fördelar med kontinuerlig övervakning av kontaktresistanser under tester, eftersom vissa beteenden kan observeras som inte skulle ha upptäckts om testerna hade utförts på ett konventionellt sätt. Dessutom utgör det system som utvecklades grunden för en mer bekväm och kostnadseffektiv metod för att testa pålitligheten hos ett stort urval av kontaktdon för kort-till-kort-anslutningar.

<p dir="ltr"><i>The high heat fluxes generated in electronic devices must be effectively diffused through </i><i>the semiconductor substrate and packaging layers to avoid local, high-temperature “hotspots” </i><i>that govern long-term device reliability. In particular, advanced semiconductor packaging </i><i>trends toward thin form factor products increase the need for understanding and improving </i><i>in-plane conduction heat spreading in anisotropic materials. Furthermore, predicting thermal </i><i>transport in vertical stacks of thinned and bonded die hinges on accurately characterizing </i><i>unknown buried interfacial thermal resistances. The design of semiconductor thermal packaging </i><i>solutions is hence limited by the functionality and accuracy of metrology available </i><i>for thermal properties characterization of engineered anisotropic heat spreading materials </i><i>and buried interfaces. This work focuses on the development of two separate innovative </i><i>metrology techniques for characterizing in-plane thermal properties of both isotropic and </i><i>anisotropic materials, and the measurement of low thermal interfacial resistances embedded </i><i>in stacks of semiconductor substrates.</i></p><p dir="ltr"><i>In the first portion of this thesis, a new measurement technique is developed for characterizing </i><i>the isotropic and anisotropic in-plane thermal properties of thin films and sheets, </i><i>as an extension of the traditional Ångstrom method and other lock-in thermography techniques. </i><i>The measurement leverages non-contact infrared temperature mapping to quantify </i><i>the thermal response to laser-based periodic heating at the center of a suspended thin film </i><i>sample. This novel data extraction method does not require precise knowledge of the boundary </i><i>conditions. To validate the accuracy of this technique, numerical models are developed </i><i>to generate transient temperature profiles for hypothetical anisotropic materials with known </i><i>properties. The resultant temperature profiles are processed through a fitting algorithm to </i><i>extract the in-plane thermal conductivities, without the knowledge of the input properties </i><i>to the forward model. Across a wide range of in-plane thermal conductivities, these results </i><i>agree well with the input values. The limits of accuracy of this technique are identified based </i><i>on the experimental and sample parameters. Further, numerical simulations demonstrate </i><i>the accuracy of this technique for materials with thermal conductivities from 0.1 to 1000 W </i><i>m</i><i>−1 </i><i>K</i><i>−1</i><i>, and material thicknesses ranging from 0.1 to 10 mm. This technique effectively</i> <i>measures anisotropy ratios up to 1000:1. Data from multiple heating frequencies can be </i><i>combined to fit for a single set of thermal properties (independent of frequency), which improves </i><i>measurement sensitivity as the thermal penetration depth varies across frequencies. </i><i>The post-processing algorithm filters out regions within the laser absorber and heat sink to </i><i>eliminate regions in the sample domain with boundary effects. Based on these guidelines, </i><i>experiments demonstrate the accuracy of this measurement technique for a wide range of </i><i>known isotropic and anisotropic heat spreading materials across a thermal conductivity range </i><i>of 0.3 to 700 W m</i><i>−1 </i><i>K</i><i>−1</i><i>, and in-plane anisotropy ratios of 30:1. These steps contribute </i><i>towards standardization of this measurement technique, enabling the development and characterization </i><i>of engineered heat spreading materials with desired anisotropic properties for </i><i>various applications.</i></p><p dir="ltr"><i>The second portion of this thesis focuses on characterization of thermal resistances across </i><i>“buried” interfaces that are challenging to characterize in situ due to their low relative magnitude </i><i>and embedded depth within a material stack. In particular, we target characterization </i><i>of interfaces that are buried deeper than the thermal penetration depth of available transient </i><i>measurement techniques, such as thermoreflectance, but have low thermal resistances </i><i>that prohibit the use of steady-state techniques, such as the reference bar method, due to </i><i>the very high temperature gradients that would be necessary resolve the resistances, among </i><i>other sample preparation challenges. This work develops a technique for the non-destructive </i><i>characterization of such deeply buried interfaces having thermal contact resistances of the </i><i>order of 0.001 cm</i><i>2</i><i>K/W. Two different embodiments of the measurement approach are first </i><i>assessed before down-selecting to a single experimental implementation. The working principle </i><i>for both embodiments includes a combination of non-contact periodic heating and </i><i>thermal sensing to measure the transient temperature response of a two-layer stack of materials </i><i>with a bonded interface of unknown thermal resistance. The approaches aim to </i><i>eliminate the preparation requirement of cutting samples to investigate their temperature in </i><i>cross-section. In the first embodiment, the sample stack is heated periodically at the center </i><i>of the sample, and cooled at the periphery, to create a radial temperature gradient. The </i><i>second embodiment involves generating a one-dimensional temperature gradient across the </i><i>stack by periodic heating of one face and steady cooling of the other face. The corresponding </i><i>ing amplitude and phase delay of the temperature responses are used to fit for the thermal </i><i>interfacial resistance, assuming a time-periodic solution for the heat diffusion equation for </i><i>a system with periodic heating. Numerical models developed for both approaches simulate </i><i>the transient temperature profiles across a two-layer bonded silicon stack of known thermal </i><i>properties, and enable an assessment of both approaches. The one-dimensional (1D) gradient </i><i>approach is found to have higher sensitivity and measurable signal compared to the </i><i>radial spreading approach, at the same mean temperature of the sample. </i></p><p dir="ltr"><i>Based on this 1D gradient concept, an experimental facility is developed, which includes </i><i>a IR-transparent heat sink, laser-based heating, and two IR temperature sensors for noncontact </i><i>temperature measurement of both sides of the sample. The unique IR transparent </i><i>heat sink design allows for simultaneous cooling and non-contact temperature measurement </i><i>of the bottom surface of the sample. An inverse fitting method is developed to extract </i><i>the thermal resistances using the steady periodic temperature amplitude and phase delay </i><i>across the thickness of the material. Thermal data generated using numerical simulations, </i><i>along with the data fitting method, is first leveraged to validate the extracted thermal resistance </i><i>values for two-layer material systems with an bonded interface, as well as for the </i><i>thermal conductivity measurement of bulk materials without an interface. The data extraction </i><i>process is shown to accurately extract thermal contact resistances on the order of </i><i>0.0001 cm</i><i>2</i><i>K/W in silicon-based packages for interfaces that are a few millimeters from the </i><i>exposed surface. For bulk materials, this technique demonstrates accuracy in extracting </i><i>the thermal conductivity of a wide range of materials ranging from thermal insulators to </i><i>highly conductive materials, spanning a range of 0.1 to 2000 W m</i><i>−1 </i><i>K</i><i>−1</i><i>. Physical measurements </i><i>of thermal conductivity of bulk silicon nitride and zinc oxide agree well with expected </i><i>reference values, and these measurements also align well with data from independently performed </i><i>experiments on the same materials using an established ASTM D5470 standard, </i><i>thereby validating this new measurement technique experimentally. Two-layer dry-contact </i><i>stacks of these two materials demonstrate the extraction of the thermal resistance across </i><i>interfaces buried up to 2 mm from the exposed surface. This work contributes toward standardization </i><i>of this technique for measurement of thermal resistances with low magnitudes </i><i>and buried depths, which are commonly found in modern electronic packages, ranging from </i><i>near-junction epitaxial semiconductor films to interconnect layers in emerging die-to-die and </i><i>wafer hybrid bonding technologies.</i></p><p dir="ltr"><i>Ultimately, these measurement techniques of in-plane thermal conductivity measurement </i><i>of anisotropic materials and the interfacial contact resistance measurements across buried </i><i>interfaces offer an important contribution to the area of thermal metrology, and advance the </i><i>field of next-generation semiconductor packaging.</i></p>

Soft matter, here, liquids and polymers, have adaptability to a surrounding geometry. They intrinsically have advantageous characteristics from a mechanical perspective, such as flowing and wetting on surrounding surfaces, giving compliant, conformal and deformable behavior. From the behavior of soft matter for heterogeneous surfaces, compliant structures can be engineered as embedded liquid microstructures or patterned liquid microsystems for emerging compliant microsystems. Recently, skin electronics and soft robotics have been initiated as potential applications that can provide soft interfaces and interactions for a human-machine interface. To meet the design parameters, developing soft material engineering aimed at tuning material properties and smart processing techniques proper to them are to be highly encouraged. As promising candidates, Ga-based liquid alloys and silicone-based elastomers have been widely applied to proof-of-concept compliant structures. In this thesis, the liquid alloy was employed as a soft and stretchable electrical and thermal conductor (resistor), interconnect and filler in an elastomer structure. Printing-based liquid alloy patterning techniques have been developed with a batch-type, parallel processing scheme. As a simple solution, tape transfer masking was combined with a liquid alloy spraying technique, which provides robust processability. Silicone elastomers could be tunable for multi-functional building blocks by liquid or liquid-like soft solid inclusions. The liquid alloy and a polymer additive were introduced to the silicone elastomer by a simple mixing process. Heterogeneous material microstructures in elastomer networks successfully changed mechanical, thermal and surface properties. To realize a compliant microsystem, these ideas have in practice been useful in designing and fabricating soft and stretchable systems. Many different designs of the microsystems have been fabricated with the developed techniques and materials, and successfully evaluated under dynamic conditions. The compliant microsystems work as basic components to build up a whole system with soft materials and a processing technology for our emerging society.

Durant ces dernières années, l’apparition de nouvelles architectures (FDSOI, FinFETs ou NW-FETs) et l’utilisation de nouveaux matériaux (notamment SiGe) ont permis de repousser les limites des performances des dispositifs MOS et de contourner l’effet canal court inhérent à la miniaturisation des composants. Cependant, pour toutes ces nouvelles architectures, la résistance de contact se dégrade au fil des nœuds technologiques. Celle-ci dépend fortement de deux paramètres physiques : la concentration de dopants actifs proches de la surface du semi-conducteur et de la hauteur de barrière Schottky du contact siliciuré. De multiples procédés avancés ont été proposé pour améliorer ces deux paramètres physiques (pré-amorphisation, recuit laser, ségrégation de dopants, etc…). Afin d’optimiser les conditions expérimentales de ces nouvelles techniques de fabrication, il est primordial de pouvoir caractériser avec fiabilité leur impact sur les deux grandeurs physiques citées. Dans le cadre de cette thèse, deux thématiques dédiées à l’étude de chacun des paramètres sont abordées, explicitant les méthodes de caractérisation développées ainsi que des exemples concrets d’applications. La première partie concerne l’étude de la concentration de dopants actifs proches de la surface du semi-conducteur. Dans cet axe, nous avons mis en place une méthode d’Effet Hall Différentiel (DHE). Cette technique combine gravures successives et mesures par effet Hall conventionnel afin d’obtenir le profil de concentration de dopants actifs en fonction de la profondeur. Nous avons développé et validé une méthode de gravure chimique et de mesure électrique pour des couches ultra-minces de SiGe et de Si dopées. Les profils de concentration générés ont une résolution en profondeur inférieure à 1 nm et ont permis d’étudier de façon approfondie dans les premiers nanomètres proches de la surface de couches fabriquées grâce à des techniques d’implantation et de recuit avancées comme par exemple, la croissance en phase solide activée par recuit laser. La deuxième partie porte sur la mesure de hauteurs de barrière Schottky pour des contacts siliciurés. Durant cette étude, nous avons transféré une technique se basant sur des diodes en tête bêche pour caractériser l’impact de la ségrégation de différentes espèces à l’interface siliciure/semi-conducteur sur la hauteur de barrière Schottky d’un contact en siliciure de platine. Cette méthode de mesure associée à des simulations physiques a permis d’une part, d’extrairer avec fiabilité des hauteurs de barrières avec une précision de 10meV et d’autre part, d’effectuer une sélection des meilleures conditions de ségrégation de dopants pour la réduction de la hauteur de barrière Schottky. Pour conclure, ce projet a rendu possible le développement de méthodes de caractérisation pour l’étude de matériaux utilisés en nanoélectronique. De plus, nous avons pu apporter des éclaircissements concernant l’impact de techniques d’implantation ionique alternatives sur des couches de Si et SiGe ultrafines, et ce, dans le but de réduire la résistance de contact entre siliciure et semi-conducteur dans le module source-drain de transistors ultimes. / During the past few decades, the emergence of new architectures (FDSOI, FinFETs or NW-FETs) and the use of new materials (like silicon/germanium alloys) allowed to go further in MOS devices scaling by solving short channel effect issues. However, new architectures suffer from contact resistance degradation with size reduction. This resistance strongly depends on two parameters: the active dopant concentration close to the semi-conductor surface and the Schottky barrier height of the silicide contact. Many solutions have been proposed to improve both of these physical parameters: pre-amorphisation, laser annealing, dopant segregation and others. In order to optimize the experimental conditions of these fabrication techniques, it is mandatory to measure precisely and reliably their impact on cited parameters.Within the scope of this thesis, two parts are dedicated to each lever of the contact resistance, each time precising the developed characterization method and concrete application studies. The first part concerns the study of the active dopant concentration close to the semi-conductor surface. In this axis, we developed a Differential Hall Effet method (DHE) which can provide accurate depth profiles of active dopant concentration combining successive etching processes and conventional Hall Effect measurements. To do so, we validated layer chemical etching and precise electrical characterization method for doped Si and SiGe. Obtained generated profiles have a sub-1nm resolution and allowed to scan the first few nanometers of layers fabricated by advanced ion implantation and annealing techniques, like solid-phase epitaxy regrowth activated by laser annealing. In the second part, we focused on the measurement of Schottky barrier height of platinum silicide contact. We transferred a characterization method based on back-to-back diodes structure to measure platinum silicide contacts with different dopant segregation conditions. The electrical measurements were then fitted with physical models to extract Schottky barrier height with a precision of about 10meV. This combination between measurements and simulations allowed to point out the best ion implantation and annealing conditions for Schottky barrier height reduction.To conclude, thanks to this project, we developed highly sensitive characterization methods for nanoelectronics application. Moreover, we brought several clarifications on the impact of alternative ion implantation and annealing processes on Si and SiGe ultra-thin layers in the perspective of contact resistance reduction in FDSOI source-drain module.

Dans ces travaux de thèse on s’intéresse au développement d’un outil numérique pour résoudre le problème de conduction instationnaire avec changement de phase dans un milieu composite constitué d’une mousse de graphite infiltrée par un matériau à changement de phase tel que le sel, dans le contexte du stockage de l’énergie thermique solaire.Au chapitre 1, on commence par présenter le modèle sur lequel on va travailler. Il estséparé en trois sous-parties : un problème de conduction de chaleur dans la mousse, un problème de changement de phase dans les pores remplis de sel et une condition de résistance thermique de contact entre les deux matériaux qui est traduite par une discontinuité du champ de température.Au chapitre 2, on étudie le problème stationnaire de conduction thermique dans un milieu composite avec résistance de contact. Ceci permet de se focaliser sur la plus grande difficulté présente dans le problème qui est le traitement de la condition de saut à l’interface.Deux méthodes d’éléments finis sont proposées pour résoudre ce problème : une méthode basée sur les éléments finis Lagrange P1 et une méthode hybride-duale utilisant les éléments finis Raviart-Thomas d’ordre 0 et P0. L’analyse numérique des deux méthodes est effectuée et les résultats de tests numériques attestent des efficacités des deux méthodes [10]. Les matériaux à changement de phase qu’on étudie dans le cadre de cette thèse sont des matériaux pures, par conséquent le changement de phase s’effectue en une valeur de température fixe qui est la température de fusion. Ceci est modélisé par un saut dans la fonction fraction liquide et par conséquent dans la fonction enthalpie du matériau. Cette discontinuité représente une difficulté numérique supplémentaire qu’on propose de surmonter en introduisant un intervalle de régularisation autour de la température de fusion.Cette procédure est présentée dans le chapitre 3 où une étude analytique et numérique montre que l’erreur sur la température se comporte comme " en dehors de la zone de mélange, où " est la largeur de l’intervalle de régularisation. Cependant, à l’intérieur l’erreur se comporte comme p " et on montre que cette estimation est optimale. Cette diminution de vitesse de convergence est due à l’énergie qui reste bloquée dans la zone de mélange [58].Dans le chapitre 4 on présente quatre des schémas les plus utilisés pour le traitement de la non-linearité due au changement de phase: mise à jour du terme source, linéarisation de l’enthalpie, la capacité thermique apparente et le schéma de Chernoff. Différents tests numériques sont réalisés afin de tester et comparer ces quatre méthodes pour différents types de problèmes. Les résultats montrent que le schéma de linéarisation de l’enthalpie est le plus précis à chaque pas de temps tans dis que le schéma de la capacité thermique apparente donne de meilleurs résultats au bout d’un certain temps de calcul. Cela indique que si l’on s’intéresse aux états transitoires du matériaux le premier schéma est lemeilleur choix. Cependant, si l’on s’intéresse au comportement thermique asymptotique du matériau le second schéma est plus adapté. Les résultats montrent également que le schéma de Chernoff est le plus rapide parmi les quatre schémas en terme de temps de calcul et donne des résultats comparables à ceux des deux plus précis.Enfin, dans le chapitre 5 on utilise le schéma de Chernoff avec la méthode d’éléments finis hybride-duale Raviart-Thomas d’ordre 0 et P0 pour résoudre le problème non-linéaire de conduction thermique dans un milieu composite réel avec matériau à changement de phase. Le but étant de déterminer si un matériau composite avec une distribution uniforme de pores est assimilable à un matériau à changement de phase homogènes avec des propriétés thermo-physiques équivalentes. Pour toutes les expériences numériques exposées dans ce manuscrit on a utilisé le logiciel libre d’éléments finis FreeFem++ [41]. / In this thesis we aim to develop a numerical tool that allow to solve the unsteady heatconduction problem in a composite media with a graphite foam matrix infiltrated witha phase change material such as salt, in the framework of latent heat thermal energystorage.In chapter 1, we start by explaining the model that we are studying which is separated in three sub-parts : a heat conduction problem in the foam, a phase change problem in the pores of the foam which are filled with salt and a contact resistance condition at the interface between both materials which results in a jump in the temperature field.In chapter 2, we study the steady heat conduction problem in a composite media withcontact resistance. This allow to focus on the main difficulty here which is the treatment of the thermal contact resistance at the interface between the carbon foam and the salt. Two Finite element methods are proposed in order to solve this problem : a finite element method based on Lagrange P1 and a hybrid dual finite element method using the lowest order Raviart-Thomas elements for the heat flux and P0 for the temperature. The numerical analysis of both methods is conducted and numerical examples are given to assert the analytic results. The work presented in this chapter has been published in the Journal of Scientific Computing [10].The phase change materials that we study here are mainly pure materials and as a consequence the change in phase occurs at a single point, the melting temperature. This introduces a jump in the liquid fraction and consequently in the enthalpy. This discontinuity represents an additional numerical difficulty that we propose to overcome by introducing a smoothing interval around the melting temperature. This is explained in chapter 3 where an analytical and numerical study shows that the error on the temperature behaves like " outside of the mushy zone, where _ is the width of the smoothing interval. However, inside the error behaves like p " and we prove that this estimation is optimal due to the energy trapped in the mushy zone. This chapter has been published in Communications in Mathematical Sciences [58].The next step is to determine a suitable time discretization scheme that allow to handle the non-linearity introduced by the phase change. For this purpose we present in chapter 4 four of the most used numerical schemes to solve the non-linear phase change problem : the update source method, the enthalpy linearization method, the apparent heat capacity method and the Chernoff method. Various numerical tests are conducted in order to test and compare these methods for various types of problems. Results show that the enthalpy linearization is the most accurate at each time step while the apparent heat capacity gives better results after a given time. This indicates that if we are interestedin the transitory states the first scheme is the best choice. However, if we are interested in the asymptotic thermal behavior of the material the second scheme is better. Results also show that the Chernoff scheme is the fastest in term of calculation time and gives comparable results to the one given by the first two methods.Finally, in chapter 5 we use the Chernoff method combined with the hybrid-dual finiteelement method with P0 and the lowest order Raviart-Thomas elements to solve thenon-linear heat conduction problem in a realistic composite media with a phase change material. Numerical simulations are realised using 2D-cuts of X-ray images of two real graphite matrix foams infiltrated with a salt. The aim of these simulations is to determine if the studied composite materials could be assimilated to an equivalent homogeneous phase change material with equivalent thermo-physical properties. For all simulationsconducted in this work we used the free finite element software FreeFem++ [41].

This thesis investigates the electrical and electrochemical properties and the long-term stability of anodes of the solid oxide fuel cell (SOFC). A model is suggested, which describes the impedance spectra of symmetrical anode cells. According to this, the series resistance in the spectra is caused by the resistance of the electrolyte (YSZ), ohmic parts of the anodes, which are described as porous electrodes, and by the partial contacting of the anodes. A major contribution to it is provided by the nickel matrix in the anodes. The high frequency relaxation in the spectra is assigned to the transfer reaction, the low frequency to a gas diffusion inhibition along the gas supply channels. The degradation of the symmetrical anode cells, which has been observed in long-term experiments, is ascribed to a degradation of the electrolyte material, of the transfer reaction, of the nickel matrix in the anodes and of the contact resistance between the anodes and the current collecting nickel grids. The degradation rate of the last two depends on the gas composition. A model for the observed behaviour in time is presented. / Diese Arbeit untersucht die elektrischen und elektrochemischen Eigenschaften und die Langzeitbeständigkeit der Anoden von Festoxid-Brennstoffzellen (SOFC). Ein Modell wird vorgestellt, mit dem die Impedanzspektren symmetrischer Anodenzellen beschrieben werden können. Demnach ist der Serienwiderstand in den Spektren verursacht durch den Widerstand des Elektrolyten (YSZ), ohmsche Anteile in den Anoden, die als poröse Elektroden beschrieben werden, und durch die partielle Kontaktierung der Anoden. Maßgebliche Beiträge liefert hier die Nickelmatrix in den Anoden. Die hochfrequente Relaxation in den Spektren wird der Durchtrittsreaktion, die niederfrequente einer Gasdiffusionshemmung entlang der Gasversorgungskanäle zugeordnet. Die in Langzeitversuchen beobachtete Degradation der symmetrischen Anondenzellen wird zurückgeführt auf eine Degradation des Elektrolytmaterials, der Durchtrittsreaktion, der Nickelmatrix in den Anoden und des Kontaktwiderstandes zwischen den Anoden und den stromabnehmenden Nickelnetzen. Die Degradation der beiden letzteren ist in ihrer Rate abhängig von der Gaszusammensetzung. Ein Modell für das beobachtete zeitliche Verhalten wird vorgestellt.

Stainless steel bipolar plates are a possible replacement for graphite and composite bipolar plates in fuel cells. However, due to a native oxide layer they exhibit a high interfacial contact resistance (ICR) which lowers the performance. Conductive coatings like gold are a possible solution because they can reduce the contact resistance of metallic bipolar plates. We investigate the pulsed cathodic arc technique for deposition of carbon-based thin films on austenitic stainless steel 316L as cost-efficient alternative. Different types of coatings were prepared by varying the layer structure and processing parameters. Potentiodynamic polarization tests and ICR measurements were conducted to evaluate the performance of the films as conductive and corrosion resistant coatings. It was found that the corrosion resistance of coated austenitic steel samples is improved by both coatings and that measured ICR-values are well below the DOE 2020 target of 10 mΩ/cm2.

This thesis investigates the electrical and electrochemical properties and the long-term stability of anodes of the solid oxide fuel cell (SOFC). A model is suggested, which describes the impedance spectra of symmetrical anode cells. According to this, the series resistance in the spectra is caused by the resistance of the electrolyte (YSZ), ohmic parts of the anodes, which are described as porous electrodes, and by the partial contacting of the anodes. A major contribution to it is provided by the nickel matrix in the anodes. The high frequency relaxation in the spectra is assigned to the transfer reaction, the low frequency to a gas diffusion inhibition along the gas supply channels. The degradation of the symmetrical anode cells, which has been observed in long-term experiments, is ascribed to a degradation of the electrolyte material, of the transfer reaction, of the nickel matrix in the anodes and of the contact resistance between the anodes and the current collecting nickel grids. The degradation rate of the last two depends on the gas composition. A model for the observed behaviour in time is presented. / Diese Arbeit untersucht die elektrischen und elektrochemischen Eigenschaften und die Langzeitbeständigkeit der Anoden von Festoxid-Brennstoffzellen (SOFC). Ein Modell wird vorgestellt, mit dem die Impedanzspektren symmetrischer Anodenzellen beschrieben werden können. Demnach ist der Serienwiderstand in den Spektren verursacht durch den Widerstand des Elektrolyten (YSZ), ohmsche Anteile in den Anoden, die als poröse Elektroden beschrieben werden, und durch die partielle Kontaktierung der Anoden. Maßgebliche Beiträge liefert hier die Nickelmatrix in den Anoden. Die hochfrequente Relaxation in den Spektren wird der Durchtrittsreaktion, die niederfrequente einer Gasdiffusionshemmung entlang der Gasversorgungskanäle zugeordnet. Die in Langzeitversuchen beobachtete Degradation der symmetrischen Anondenzellen wird zurückgeführt auf eine Degradation des Elektrolytmaterials, der Durchtrittsreaktion, der Nickelmatrix in den Anoden und des Kontaktwiderstandes zwischen den Anoden und den stromabnehmenden Nickelnetzen. Die Degradation der beiden letzteren ist in ihrer Rate abhängig von der Gaszusammensetzung. Ein Modell für das beobachtete zeitliche Verhalten wird vorgestellt.

Thermoelectric generators (TEG) are re-emerging technology that can be used to recover heat waste from commercial and industrial processes to generate electricity, enhancing fuel utilization and lowering greenhouse gas emissions. TEG modules are solid-state heat engines that produce no noise or vibration during operation. Notably, TEG modules are also able to operate at low-temperature differences, which makes them ideal for a wide range of heat waste recovery applications. Annular thermoelectric generator (ATEG) modules are optimal in applications where either the heat source or sink are round in shape. Bi2Te3 solution-based compounds are of significant interest in the application of thermoelectric materials (TE) used in low-temperature cooling and power generation applications. The main objective of the current work is to design a mechanically reliable ring-shaped ATEG module with a predictable performance using spark plasma sintered Bi2Te3 TE material for low temperature waste heat recovery applications. In terms of structure, this work is divided into two parts. The first part investigates how the use of a powder pre-treatment technique affects the mechanical and thermoelectric properties of P- and N-type Bi2Te3. In addition, part one also presents the measurements of these materials’ mechanical and thermoelectric properties, which serve as inputs for the finite element models used to design thermoelectric modules with parallel and perpendicular configurations vis-a-vis the sintering pressing direction. The second part evaluates the thermoelectric performance and thermal stresses of a ring-shaped ATEG couple that has been integrated between hot-side and cold-side heat exchangers. To this end, two configurations are compared with respect to their heat/electrical current flow paths: one that allows for radial flow (radial configuration), and one that allows for axial flow (axial configuration). The P- and N-type Bi2Te3 powder was treated using a mechanically agitated fluidized powder reduction facility that was built in-house. The characteristic uniaxial tensile strength of the P-type Bi0.4Sb1.6Te3 increased from 13.9 MPa to 26.3 MPa parallel to the sintering pressure, and from 16.3 MPa to 30.6 MPa perpendicular to the sintering pressure following oxide reduction using 5% H2 ˗ 95% Ar at 380 ℃ for 24 h. The figure of merit, ZT, increased from 0.35 to 0.80 and from 0.42 to 1.13 at room temperature (25 ℃) in the parallel and the perpendicular directions, respectively, after the surface oxide reduction treatment. On the other hand, the annealing effects of the oxide reduction pr-treatment of the N-type (Bi0.95 Sb0.05)2(Se0.05 Te0.95)3 using 5% H2 ˗ 95% Ar at 380 ℃ for 24 h were found to be responsible for the majority of the mechanical properties and ZT enhancement. Additionally, the characteristic uniaxial tensile strengths for this material increased from 30.4 to 34.1 MPa and from 30.8 to 38 MPa in the parallel and the perpendicular directions, respectively. The ZTmax (150 ℃) increased from 0.54 to 0.63 in both the parallel and perpendicular directions due to oxide reduction, while annealing led to an increase to 0.58 and 0.62 in the parallel and the perpendicular directions, respectively. An analytical model was constructed to compare the thermoelectric performance of the two configurations under three different hot-side thermal resistances, and a 3D coupled finite element ANSYS model was constructed to study and compare the thermal stresses of the two configurations at different dimensions. The two models were then used to create 2D maps in order to investigate the effects of ATEG couple configuration and dimensions, as well as the hot-side thermal resistance, with the goal of identifying the optimum design. The optimization of module geometry requires a trade-off between performance and mechanical reliability. The results of these investigations showed that increases in the temperature difference across the ATEG couple (ΔT) led to increases in both power and thermal stresses in both configurations. When both configurations were generating the same power at ΔT = 105 ℃, the thermal stresses in the radial configuration were as much as 67 MPa higher than those in the axial configuration due to the formation of additional tensile hoop stresses. The lowest thermal stress obtained for the axial couple configuration was 67.8 MPa, which was achieved when the couple had an outer diameter of 16 mm, an axial thickness of 1 mm, a ΔT of 14.8 ℃, and power generation of 10.4 mW per couple. The maximum thermal stress values were located at the corners of the interface between the solder and the TE rings due to the mismatched coefficient of thermal expansion. This thesis makes a novel contribution to the state-of-the-art literature in ring-shaped ATEG modules, as it details a well-characterised spark plasma sintered Bi2Te3 TE material and a methodology for designing a ring-shaped ATEG module with reliable, robust, and predictable thermoelectric and mechanical performance. The details of the contribution made by this work have been disseminated in the form of three journal publications, which have been integrated into this sandwich Ph.D. thesis. / Thesis / Doctor of Science (PhD)

Diplomová práca sa zaoberá vplyvom termálnych medzivrstiev na tepelnú kontaktnú vodi- vosť a tepelný kontaktný odpor. Práca sa zameriava na aplikáciu termálnych medzivrstiev pre vylepšenie tepelnej kontaktnej vodivosti v tepelnom spínači a v kozmických zariade- niach obecne. Teoretická časť práce stručne skúma rôzne pasívne termálne kontrolné systémy použí- vane v kozmických zariadeniach, vrátane termálnych medzivrstiev, a vysvetľuje pozadie tejto práce. Táto práca ďalej skúma rôzne termálne medzivrstvy, predovšetkým povlaky a fólie, a uvádza výber vhodnej termálnej medzivrstvy. Experimentálna časť práce skúma povrchové parametre, tepelnú vodivosť a mikrotvr-dosť medených vzoriek, ktoré slúžia ako substrát pre povlak čistého striebra. Ďalej rieši podmienky merania, metódy vyhodnocovania a samotné experimentálne merania. Experimentálne merania sú vykonané v termo-vákuovej testovacej komore a na základe výsledkov sú vyvodené závery. Pre ďalšiu prácu sú uvedené doporučenia.