I detta arbete så har en uppsättning aromatiska ditiol-ligander framställts (3,5-dimerkaptobensoesyra I, methyl-3,5-dimerkaptobensoat II, 3,5-dimerkaptotoluen III, 4,6-dimerkaptoisoftalaldehyde IV). En trestegssyntes innehållande Newman-Kwart omlagring som nyckelsteg användes för framställning av föreningarna I-III medan förening IV togs fram via en annan syntesväg. De fyra föreningarna syntetiserades I relativt bra utbyte (5-80% över 3, 4 eller 6 steg) och karaktäriserades med hjälp av 1H-NMR, 13C-NMR, och högupplösande masspektrometri. I en framtida fortsättning av projektet så kommer föreningarna I-IV användas som organiska ligander i koordinationspolymerer, vilka kommer karaktäriseras i termer av elektriska och termiska egenskaper. / In this work, a family of aromatic dithiol ligands were synthesized in the laboratory (3,5-dimercapto benzoic acid I, methyl 3,5-dimercapto benzoate II, 3,5-dimercapto toluene III, 4,6-dimercaptoisophthalaldehyde IV). A three-step synthesis strategy, involving the Newman-Kwart rearrangement as key step, for the formation of I, II and III was used, whereas compound IV required a different synthetic route. The four compounds were synthesized with relatively good yields (5-80% over 3, 4 or 6 steps) and were fully characterized using 1H-NMR, 13C-NMR, and high-resolution mass spectrometry. In a future extension of this work, compounds I-IV will be used as organic ligands in coordination polymers (CPs), which will be characterized in terms of electric and thermal properties.

Thermoelectric materials are solid state devices having the capability to convert heat to electrical energy and vice versa. These materials are simple, have no moving parts and use no greenhouse gases. But the major drawback of these materials is their low conversion efficiency. Hence enhancement of thermoelectric efficiency is required to make the use of these devices widespread. Thermoelectric efficiency is related to a parameter termed figure of merit, ZT which is associated with the inter-related transport properties such as Seebeck coefficient, electrical and thermal conductivity. Efficient thermoelectric material should possess high Seebeck coefficient (S), high electrical conductivity () and low thermal conductivity (). The present investigation revolves around improvement of ZT of CoSb3 either by chemical doping or through microstructural modifications. These materials possess structural voids, which can be filled with foreign atoms. The rattling motion of these filler atoms reduces the thermal conductivity of these materials, thereby increasing the thermoelectric efficiency. The rattler atoms chosen for the present study are Mn and Yb. Both coarse and fine-grained MnxCo4Sb12 (x = 0. 0.2, 0.4, 0.8, 1.2 and 1.6) and Yb0.19Co4Sb12 have been synthesized and subjected to various structural and functional property characterizations. The structural study based on Rietveld Analysis and the corresponding difference Fourier maps confirms the void occupancy by Mn and Yb in MnxCo4Sb12 (x 0.2, 0.4 and 0.8) and Yb0.19Co4Sb12. In higher Mn content, x=1.2 and 1.6, Mn was found to partially substitute Co site and partially fill the voids and the remaining precipitated out as free particles. A comparative study of coarse and fine-grained CoSb3 has thrown light in to the grain size effect on the thermoelectric properties. Lowering of grain size helped in enhancement of ZT in CoSb3. Seebeck coefficient (thermoelectric power), electrical and thermal conductivity have been measured for different concentrations of the filler Mn atoms between 300K and 673K. A change in sign of the Seebeck coefficient from negative to positive occurs, when Mn concentration exceeds x=0.8. Electrical resistivity values was found to decrease initially with Mn filling with the minimum value at Mn content, x=0.4 and then gradually increase as Mn content increases. The thermal conductivity value decreases with Mn content in the CoSb3 indicating their rattling property which helps in the enhancement of the overall thermoelectric efficiency. There is a reduction in the value of ktotal in Mn filled CoSb3 than that of the unfilled counterpart. This decrease in the ktotal is a clear indication of the rattling motion of the filler Mn atom in the structural void of CoSb3. Highest ZT of 0.36 is achieved by Mn0.4Co4Sb12 at 373K. Higher concentration of Mn (with x= 1.2 and 1.6) proved to be detrimental in terms of improvement of the value of ZT. Grain size reduction helped in improvement of ZT in Mn0.2Co4Sb12. Maximal ZT of 0.06 at 523K is achieved in hot pressed Mn0.2Co4Sb12. The corresponding coarse-grained material is found to possess ZT of 0.01 at the said temperature. The enhancement can be attributed to high / ratio and high density. Similarly, fine grained Yb0.19Co4Sb12 shows higher ZT compared to the coarse-grained sample because high / and high S.

Primarily, newly developed, high sensitive and accurate methods for thermal characterization of liquids using photothermal radiometry are presented. Two experimental configurations are suggested, tested and validated with usual liquid materials. These methods are used to study polymer dispersed liquid crystal samples. Dynamic thermal properties of samples are analysed verses amplitude varying applied electric field with constant frequency as well as versus frequency varying electric field with constant amplitude. Our results clearly show the thermal properties of the samples are prone to depolarizing field effects at the lower frequencies of the applied electric field. The experimental results are modeled against existing theories to predict electric properties of the sample composites. Second part of the manuscript describes the development of a novel photothermal technique based on thermoelectric effect. This technique is particularly useful for thermally characterizing thermoelectric materials without using a separate sensor for measuring induced temperature changes. A theoretical and experimental study is presented. The experiments are done on polyaniline - carbon nanotube composite pellets by measuring Seebeck voltage generated by the samples upon heating by a modulated laser beam. Additional infrared radiometry experiments are done on the same samples and the results are in good agreement with those previously found. Later on, the possibility of photothermoelectric materials to be used as sensors for finding thermal transport properties of materials with a thermal wave resonant cavity is suggested.

Les matériaux thermoélectriques (TE) permettent de convertir directement de la chaleur en électricité et vice-versa. Les objectifs de cette thèse étaient de tenter d'améliorer les performances TE de trois familles de matériaux et de mieux comprendre le lien entre les propriétés physiques (électriques, thermiques, magnétiques) généralement mesurées dans une large gamme de température (5–700 K) et les microstructures/compositions chimiques observées. Généralement, les matériaux ont été synthétisés par des techniques de métallurgie des poudres et densifiés par spark plasma sintering. La majeure partie de nos travaux a concerné la famille des matériaux tétraédrites, dérivés du minéral naturel (Cu,Ag)10(Zn,Fe)2(Sb,As)4S13, présentant des propriétés TE prometteuses, récemment mises en évidence. D’abord, les propriétés TE de huit tétraédrites naturelles de provenance différente ont été étudiées. Nous avons montré que leurs propriétés physiques sont plutôt prévisibles selon leur composition chimique et finalement peu différentes selon leur origine. Les propriétés TE de mélanges de tétraédrites naturelles et synthétiques obtenus par broyage mécanique ont ensuite été déterminées. Ce procédé fortement énergétique produit des particules de taille nanométrique des deux phases qui forment une solution solide pendant le frittage. Par contre, un broyage manuel conserve la présence des deux phases, ce qui conduit à de plus faibles performances TE. Ensuite, nous avons montré que la substitution Sb <-> As, usuelle dans les spécimens naturels, n’influence que faiblement les propriétés TE. Enfin, les propriétés TE de manganites de calcium et de polymères conducteurs ont également été étudiées / Thermoelectric (TE) materials allow direct conversion between heat and electricity. The aim of this thesis was to try to improve the thermoelectric performance of three different families of materials and to better understand the link between the various physical properties (electrical, thermal, magnetic) generally measured in a broad temperature range (5–700 K) and the observed microstructure/chemical composition. In general, the materials were synthesized by powder metallurgy techniques and densified by spark plasma sintering (SPS). The major part of our studies concerns the tetrahedrite family of materials, derived from the mineral tetrahedrite, (Cu,Ag)10(Zn,Fe)2(Sb,As)4S13, whose promising thermoelectric properties were only recently discovered. In a first approach, the TE properties of eight natural tetrahedrites of different geographic origin are studied. It is shown that they all behave rather predictably and uniformly. Next, the properties of ball milled mixtures of natural and synthetic tetrahedrites are investigated. This high-energy process yields nanoscale particles of the two phases, which form a solid solution during the sintering. Low-energy hand grinding preserves the two-phase nature and results in inferior TE performance. Because arsenic is a common substituent in natural specimens, several As-substituted tetrahedrites are synthesized and characterized. It is shown that the TE properties are only weakly influenced by the substitution of As for Sb. Besides tetrahedrites, calcium manganese oxides and conductive polymers are also studied

Ce mémoire de thèse porte sur l'exploitation de l'effet Seebeck pour la caractérisation thermo-physique des matériaux thermoélectriques (TE) solides et liquides. Lors de travaux récents au sein du laboratoire, la technique photothermoélectrique (PTE) a été développée pour la caractérisation thermique de matériaux TE solides de faibles conductivités électriques. Dans ce travail, l'utilisation de cette technique a été généralisée à tous les matériaux TE solides (de faibles ou de hautes conductivités électriques). Cela est rendu possible par la prise en compte de la nature gaussienne de l'excitation thermique modulée à laquelle le matériau est soumis ainsi que par la compréhension des effets de couplage des mécanismes de transport thermique et électrique dans les matériaux TE. Dans cette thèse, plusieurs matériaux thermoélectriques solides ont été étudiés : le trisulfure de titane (TiS₃), les oxydes types Bi₂Ca₂Co₁,₇Oₓ, le séléniure du tellurure de bismuth (Bi₂Te₂,₄Se₀,₆). La tension auto-induite par effet Seebeck a été aussi exploitée pour la détection des transitions de phases que présentent certains matériaux thermoélectriques, ici le cas du séléniure de cuivre a été étudié. Une nouvelle procédure qui permet de déterminer l'évolution de la diffusivité thermique d'un matériau TE en fonction de la température est présentée. En plus des matériaux TE solides, la technique PTE a été étendue à l'étude des matériaux thermoélectriques liquides (LTE). Un modèle théorique qui décrit le signal délivré par un matériau LTE soumis à une excitation thermique périodique a été développé. Ensuite, une étude de l'évolution des propriétés thermiques d'un matériau LTE en fonction de la concentration d'un soluté a été réalisée. Enfin, l'approche dite de cavité résonnante d'ondes thermiques (TWRC) a été utilisée pour investiguer thermiquement des matériaux LTE. À notre connaissance, c'est la première fois que l'approche TWRC est utilisée pour l'analyse du signal généré par un liquide thermoélectrique. L'utilisation des LTE comme capteurs thermiques a été aussi abordée dans ce travail. / The use of the self-induced Seebeck effect in thermophysical characterization of solid and liquid thermoelectric (TE) materials is described in this manuscript. In previous works, the photothermoelectric technique (PTE) has been developed in our laboratory for the thermal characterization of solid TE materials having low electrical conductivities. In this work, we first generalized the use of the PTE technique to all solid thermoelectric materials (with high or low electrical conductivities). This is achieved by taking into account the Gaussian shape of the thermal source exciting the material as well as by the understanding of the coupling effects between thermal and electrical transport mechanisms when a TE material is submitted to a modulated thermal excitation. In this thesis, several solid thermoelectric materials were studied : Titanium trisulfide (TiS₃),Bi₂Ca₂Co₁,₇Oₓ oxydes and Bismuth Selenido-telluride (Bi₂Te₂,₄Se₀,₆). Then, the self-induced Seebeck voltage was used for the detection of phase transitions exhibited by certain thermoelectric materials. The case of the copper selenide (Cu₂Se) was studied. A new procedure allowing to follow the temperature dependance of the thermal diffusivity of solid TE materials is also presented. In this work, the PTE technique was extended to liquid thermoelectric (LTE) materials. Indeed, a theoretical model describing the signal delivered by a LTE material subject to a periodic thermal excitation has been developed. Then, a study of the evolution of the thermal properties of an electrolyte as function of a solute concentration was performed. Finally, the thermal-wave resonator cavity (TWRC) approach was used to characterize thermally LTE materials. As far as we know, this is the first method proposing a TWRC approach applied directly to the sensor itself. The use of LTE such as heat sensors was also addressed here.

In this work synthesis of structure cobaltites based on Ca-Co-O system is discussed. As major way of synthesis was chosen citric acid method. The document is devided into theoretical and experimental part and also into discussion of observed results. Main focus of literary research is general utilization and function of thermoelectric materials, related thermoeletric effects according to structural defects in crystals. Also topic of cobaltite ceramics is described. Due to the fact that calcium-cobalt oxides are conductive, their use is point of interest in high-temperature and energy applications. During experiments differential thermal and thermogravimetric analysis (TG-DTA), X-Ray diffraction, heat microscopy and scanning electron microscopy were used.

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Thermoelectric (TE) ZrNiSn samples with a half-Heusler atomic structure were synthesized by mechanical alloying (MA) and consolidation by either Spark Plasma Sintering (SPS) or hot pressing (HP). X-Ray diffraction patterns of as milled powders and consolidated samples were compared and analyzed for phase purity. Thermal conductivity, electrical conductivity and Seebeck coefficient are measured as a function of temperature in the range 300 K to 800 K and compared with measurements reported for high temperature solid state reaction synthesis of this compound. HP samples, compared to SPS samples, demonstrate increased grain growth due to longer heating times. Reduced grain size achieved by MA and SPS causes increased phonon scattering due to the increased number of grain boundaries, which lowers the thermal conductivity without doping the base system with addition phonon scattering centers. Mechanical characterization of the samples by microindentation and depth sensing indentation for hardness and elastic modulus will be discussed.

Cette thèse concerne le dépôt de couches minces par la méthode de co-pulvérisation assistée par plasma micro-onde dans le contexte de leurs applications potentielles pour la thermoélectricité. Deux volets principaux ont été développés au cours de ce travail: la synthèse et l'étude des propriétés de couches minces à base de Mg2Si et Mg2(Si,Sn) pour une mise en œuvre au sein de modules thermoélectriques miniaturisés, et l'étude de matériaux susceptibles d’agir comme barrières de diffusion entre un thermoélément à base de Mg2Si et les joints de brasage utilisés pour connecter les contacts électriques. Dans la première partie de l'ouvrage, des couches minces de solutions solides de Mg2(Si,Sn), avec une stœchiométrie proche de Mg2Si0.4Sn0.6, ont été déposées sur différents substrats. Les propriétés thermomécaniques de ces couches ont été étudiées en fonction du processus de dépôt et de la nature du substrat, tandis que la stabilité thermique et la réactivité avec les substrats ont été examinées, ont fonction de la composition, dans le domaine de températures intermédiaires. En outre, les propriétés de transport des couches minces de Mg2Si dopé au Sb ont été caractérisées, en s’intéressant, en particulier, à l’effet de la texturation de la couche mince sur les propriétés thermoélectriques (coefficient Seebeck, conductivité électrique et thermique). La deuxième partie de cette thèse est dédiée au dépôt de couches barrières sur des échantillons massifs de Mg2(Si,Ge) dopés Bi afin de limiter la diffusion et la réactivité entre le thermoélément et le joint de brasage à base d'alliage Al-Si dans le but d’obtenir un contact électrique chimiquement stable et de faible résistance. Deux options ont été étudiées : l'une est basée sur des couches à gradient destinées à ajuster progressivement la composition entre celle du thermoélément et une couche supérieure de Ni qui constitue la barrière de diffusion. L'autre option concerne les bi-couches M/Ni, où M est un métal (Ti, Ta, W ou Cr). Globalement, le travail présenté ici offre un aperçu du potentiel des couches minces à base de Mg2Si et Mg2(Si,Sn) dans la réalisation d'un module thermoélectrique miniaturisé et l'étude de faisabilité de différents matériaux comme barrières de diffusion dans des modules conventionnels. / In this thesis are presented the deposition of thin films by microwave plasma-assisted co­sputtering and their characterization within the context of thermoelectric applications. The aims of the work are split into two categories: the investigation of Mg2Si and Mg2(Si,Sn) thin films in terms of their potential to be implemented in a miniaturized thermoelectric module and the inquiry of materials which may act as diffusion barriers at the interface between Mg2Si-based thermoelements and the brazing joints used in the preparation of electrical contacts. In the first part of the work, thin films of Mg2(Si,Sn) solid solutions with a stoichiometry close to Mg2Si0.4Sn0.6 have been deposited on various substrates. The thermo­mechanical properties of these films have been investigated with respect to their dependence on the deposition process and the nature of the substrate on which they are grown, while the thermal stability and reactivity with the substrates at intermediate temperatures based on their composition has been explored. Furthermore, the transport properties of Sb-doped Mg2Si thin films have been also characterized. This was done in the context of finding the evolution and dependence of the thermoelectric properties (Seebeck coefficient, electrical and thermal conductivities) to the level of texturing within the thin film. The second part of this thesis involves the deposition of diffusion barriers on bulk Bi-doped Mg2(Si,Ge) thermoelements in order to disrupt the diffusion and reactivity between the thermoelectric leg and the Al-Si alloy-based brazing joint and to obtain a chemically stable, low resistive electrical contact. With this objective, two options have been pursued. One is based on the deposition of gradient layers that are meant to gradually inverse the composition from the Mg2(Si,Ge) thermoelements to a top layer of Ni that is used in the deposition of the potential diffusion barrier. The other option concerns the deposition of a M/Ni bi­layer on the TE legs, where M is a metallic layer (Ti, Ta, W or Cr). Overall, the work presented here offers a glimpse of the potential use of Mg2Si and Mg2(Si,Sn) thin films in the making of a miniaturized thermoelectric module and the efficiency of various materials as diffusion barriers in the industry of thermoeletrics.