By means of advanced molecular dynamic techniques, we predict the stability of novel materials based on carbon, germanium and PbSe. This topological solutions have been studied and characterised at a DFT/DFTB level of theory and interesting optical, mechanical, electronic and heat transport properties have been pointed out.

De récentes études montrent que les films minces présentent des performances thermoélectriques nettement plus importantes (jusqu'à un facteur 3) que celles obtenues dans les matériaux massifs. Nous avons choisi de développer des couches minces thermoélectriques Bi0,5Sb1,5Te3 de type p et Bi2Te2,7Se0,3 de type n présentant les performances thermoélectriques les plus intéressantes à des températures proches de l'ambiante. La technique de dépôt utilisé est la PVD magnétron. L'optimisation des conditions de dépôt (pression Ar, puissance plasma, distance cible-substrat et temps de dépôt) ainsi que du traitement thermique de recuit a permis obtenir des figures de mérite ZT les plus élevées possibles. De plus, les phénomènes physiques mis en jeu dans les films minces étant différents de ceux des massifs, il a été nécessaire des les étudier pour améliorer les performances thermoélectriques des couches minces. De petits dispositifs thermoélectriques en couche minces ont pu être réalisé et caractérisé. En parallèle nous avons exploré la possibilité de faire croître des filaments thermoélectriques de compositions semblables aux couches et de dimensions manométriques au sein d'une matrice d'alumine nanoporeuse. En effet la réduction des dimensions géométriques permet d'augmenter les performances thermoélectriques des matériaux. Nous avons pu réaliser les premiers fils n et p ainsi que les premières caractérisations thermoélectriques. / Recent studies showed that thermoeletrical performances are larger for thin films (factor 3) than for bulk materials. We chose to develop p-type Bi0,5Sb1,5Te3 and n-type Bi2Te2,7Se0,3 thermoelectrical thin films in order to work at room temperature. Thin films have been realized using magnetron sputtering process. The optimisation of the deposition conditions (Ar pressure, power plasma, target-substrate distance, deposition time) as well as the annealing treatments has helped to obtain figure of merits as high as possible. On the other hand, the physical mechanisms in thin films are different than those of bulk materials so it was necessary to study such mechanisms for a better understanding. In parallel, we explore the possibility to grow thermoelectrical wires with nanometric dimensions inside of a nanoporous alumina matrix. It has been recently shown theoretically and experimentally that thermoelectrical properties are strongly improved when the nanometric dimensions are obtained.

L’effet thermoélectrique permet la conversion directe et réversible d’un flux de chaleur en courant électrique via l’utilisation de semi-conducteurs de type-p et de type n. Les polymères conjugués, comme le poly(3,4-éthylènedioxythiophène) (PEDOT) sont pressentis pour être des alternatives aux alliages de tellurure de bismuth (Bi2Te3) coûteux, toxiques et difficiles à synthétiser.Cette thèse se propose d’améliorer la conductivité électrique d’un PEDOT et de faciliter sa mise en œuvre par une technique d’impression grande surface comme le spray.La première partie porte sur l’amélioration de la synthèse par tournette du PEDOT : OTf dont le dopage est stabilisé par le contre-ion trifluorométhanesulfonate (OTf-). Plusieurs co-solvants sont testés comme la pyridine ou la NMP. Ces co-solvants permettent de ralentir la polymérisation et d’améliorer ainsi la structure du matériau. Des conductivités électriques de 3600 S.cm-1 avec un coefficient Seebeck aux environs de 20 µV.K-1 sont atteintes.La seconde partie étudie les avantages et les inconvénients d’une synthèse de ce PEDOT : OTf amélioré par spray ultrasonique. Cette technique permet de conserver la formulation développée pour le dépôt par tournette. Il est possible d’obtenir des films épais (~ 1 µm) avec une conductivité électrique supérieure à 1650 S.cm-1. Des études par diffraction des rayons X et de transports permettent de comparer les deux méthodes de dépôt et d’orienter les choix de formulation et de procédé.Finalement, avec ces améliorations apportées, des exemples de modules thermoélectriques imprimés sont présentés et évalués. Ainsi en imprimant plus de 300 thermocouples connectés en série puis roulés, un tel module thermoélectrique occupe une surface inférieure à une pièce de 50 centimes d’euro et peut générer 1 µW avec un gradient de température de 35 °C.Cette thèse souhaite pouvoir apporter des éléments de réponse sur la relation entre la mise en œuvre et les propriétés électriques des polymères conducteurs. / Thermoelectricity can convert directly and reversibly a heat flux into an electric current with p and n-type semiconductors. Conjugated polymers, such as poly(3,4-ethylenedioxithiophene) (PEDOT), offers an alternative to the best room temperature thermoelectric materials based on bismuth telluride alloys which used scarce, hazardous and hard to process raw materials.This PhD work aims to enhance the electrical conductivity of an in-situ polymerised PEDOT and make it easy to process with large scale printing techniques like spray-coating.The first part focus on the optimisation of this synthetized PEDOT through spin-coating. The doping of this PEDOT is stabilised with the counter-ion trifluoromethanesulfonate (OTf-). One way of enhancement is to add co-solvents like pyridine and NMP in order to slow down the polymerisation rate. Consequently, PEDOT:OTf get a better structure and reach an outstanding electrical conductivity of 3,600 S.cm-1 without decreased the Seebeck coefficient which remains around 20 µv.K-1.The second part studies pro and cons of the ultrasonic spray as a coating technic to this enhanced PEDOT:OTf. This technic allows to keep an ink formulation closed of the spin-coating one and can print thick films (~ 1 µm) with an electrical conductivity above 1650 S.cm-1. XRD and transport measurements are achieved in order to understand and compare both spray and spin-coating techniques. And therefore, to enlighten improvement on formulation and process.At last, several examples of spray-coated thermoelectric generators are shown and tested. Thus by printing more than 300 thermocouples connected in series and rolled into a cylinder, such devices could produce 1 µW with a gradient of temperature of 35 °C on a surface less than a 5 cm2 (size of a coin).This thesis work wishes to provide insight on the process-electrical relationship in conducting polymers.

O presente trabalho apresenta o desenvolvimento de uma bancada didática de baixo custo para estudo dos materiais termoelétricos para a realização de ensaios de obtenção de curvas de desempenho dos módulos termoelétricos no que se refere a geração de energia pelo Efeito Seebeck e resfriamento através do Efeito Peltier de forma a difundir os conhecimentos nas áreas afim em escolas de Engenharia, refletindo na compreensão dos princípios e funcionalidades destas tecnologias. O sistema proposto permite ler simultaneamente até 3 geradores termoelétricos, e é composto por dois principais circuitos eletrônicos: sendo um estágio aquisição de dados compostos por 3 canais para leitura de tensão, 3 canais para corrente e 6 canais para aquisição do sinal dos termopares (<400°C) além de sistema térmico que terá as funções de aquecimento e resfriamento. Os dados medidos são adquiridos para um computador com um software customizado a aplicação que permite o monitoramento das grandezas envolvidas (tensão, corrente, potência e temperatura) para acompanhamento do ensaio dos materiais termoelétricos, tanto por meio de uma indicação numérica como gráfica. O sistema de aquisição de dados possui precisa o para temperatura de ±2,5%, para tensão de ±2,5% e para corrente de ±1,5%. / The present work describes the development of a low cost didactic bench for Study of thermoelectric materials for performing obtaining performance curves testing of thermoelectric modules in regard to energy generation effect Seebeck and cooling via Peltier Effect order to disseminate knowledge in areas related to engineering schools, reflecting the understanding of the principles and features of these technologies. The proposed system can be read simultaneously up to 3 thermoelectric generators, and consists of two main electronic circuits: being a stage data acquisition composed of 3 channels for reading voltage and 3 channels for current using ACS712 instrumentation amplifiers and 6 channels signal acquisition thermocouples (<400 ° C) as well as thermal system will have the heating and cooling functions. The measured data is acquired to a computer with software developed in Delphi language, which allows monitoring of the quantities involved (voltage, current, power and temperature) to monitor the testing of thermoelectric materials, either through a digital display as a graphic . The data acquisition system has a temperature accuracy to ± 2,5% to ± 2.5% voltage and current of ± 1.5%.

abstract: Studying charge transport through single molecules is of great importance for unravelling charge transport mechanisms, investigating fundamentals of chemistry, and developing functional building blocks in molecular electronics. First, a study of the thermoelectric effect in single DNA molecules is reported. By varying the molecular length and sequence, the charge transport in DNA was tuned to either a hopping- or tunneling-dominated regimes. In the hopping regime, the thermoelectric effect is small and insensitive to the molecular length. Meanwhile, in the tunneling regime, the thermoelectric effect is large and sensitive to the length. These findings indicate that by varying its sequence and length, the thermoelectric effect in DNA can be controlled. The experimental results are then described in terms of hopping and tunneling charge transport models. Then, I showed that the electron transfer reaction of a single ferrocene molecule can be controlled with a mechanical force. I monitor the redox state of the molecule from its characteristic conductance, detect the switching events of the molecule from reduced to oxidized states with the force, and determine a negative shift of ~34 mV in the redox potential under force. The theoretical modeling is in good agreement with the observations, and reveals the role of the coupling between the electronic states and structure of the molecule. Finally, conclusions and perspectives were discussed to point out the implications of the above works and future studies that can be performed based on the findings. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2017

La chaleur dégagée par des dispositifs à différentes échelles (microprocesseurs, automobiles, habitations, usines) constitue une source quasi inexploitée d’énergie. La conversion de cette énergie thermique en énergie électrique est possible via l’emploi de générateurs thermoélectriques. Cependant actuellement leur usage est peu répandu du fait de leur faible rendement, de la toxicité et du coût des matériaux. L’objectif de cette thèse qui fait suite à la thèse théorique de Kinga Niedziolka (Université Montpellier, 2014) était l’obtention de nouveau matériaux thermoélectriques performants à base de ZnSb sur la base des résultats obtenus par modélisation. Conformément aux calculs réalisés et en accord avec le partenaire industriel (Hutchinson), les dopants choisis pour ZnSb ont été l’aluminium (1% en substitution du zinc), le tellure (1% en substitution de l’antimoine, le titane (1% en substitution du zinc) et l’yttrium (1% en substitution du zinc). L’objectif ici est de synthétiser et de caractériser les matériaux qui ont été calculés de type n (conduction électrique assurée par les électrons). Les matériaux ont été synthétisés par fusion, trempe et recuit et ont été obtenus sous forme de lingot polycristallin. Ils ont été caractérisés par diffraction des rayons X, microscopie électronique à balayage et microsonde de Castaing. Leur mise en forme pour les caractérisations thermoélectriques a ensuite été mise au point. C’est en utilisant la technique du Spark Plasma Sintering (SPS) que nous avons atteint des densités très intéressantes de l’ordre de 98% pour tous les matériaux contenant un dopant. Les caractérisations thermoélectriques ont été conduites en fonction de la température jusqu’à 600 K au moyen d’un appareillage de type ZEM-3.Les travaux de dopage se sont concentrés sur les matériaux dopés au tellure présentant les résultats les plus prometteurs. Cependant les caractérisations thermoélectriques des matériaux synthétisés n’ont pas permis de mettre en évidence le passage au type n souhaité. Cependant, une avancée a été réalisée en ce qui concerne ZnSb non dopé qui est naturellement un matériau de type p (conduction électrique assurée par les trous): grâce à la mise en œuvre de la mécanosynthèse nous avons obtenu un matériau présentant de meilleurs propriétés que ceux existants. Des analyses de ce matériau au microscope électronique en transmission ainsi que des analyses par la méthode XPS ont conduit à l’identification de certains précipités responsables de l’amélioration de ses propriétés thermoélectriques. De plus, le matériau ZnSb obtenu, présente une grande stabilité en température ce qui renforce d’autant plus son intérêt d’utilisation par rapport à d’autres matériaux dans la même gamme de température. / The heat loss from different sources at different scales (microprocessors, cars, houses, factories) is an almost untapped source of energy. The conversion of this thermal energy into electrical energy is possible through the use of thermoelectric generators. However at the present time their use is not widespread due to their low efficiency, toxicity and because of the cost of the existing materials. The aim of this thesis that follows the DFT calculations previously made during Kinga Niedziolka’s thesis, (University of Montpellier, 2014) was to obtain new efficient thermoelectric materials based on ZnSb relying on the calculation results. Based on the calculations and in agreement with the industrial partner Hutchinson, aluminum (1 % at. in substitution of Zn), tellurium (1 % at. in substitution of Sb), titanium (1 % at. in substitution of Zn) and yttrium (1 % at. in substitution of Zn) were selected as dopants. The objective, was to synthesize and characterize the materials which were calculated as n type semiconductors (electron conduction). The materials were synthesized by melting, quenching and annealing. They were obtained in the form of polycrystalline ingots. They were characterized by X-ray diffraction, scanning electron microscopy and EDS and WDS microanalysis. Their shaping for thermoelectric characterization was then developed. The technique of Spark Plasma Sintering (SPS) was chosen to this aim and we achieved very interesting densities of around 98% for all doped materials. Thermoelectric characterizations were carried out up to 600 K by means of a ZEM-3 type apparatus. Only tellurium doped materials with the most promising results were thoroughly studied. However, the thermoelectric characterization of the synthesized doped materials didn’t show the expected transition to an n-type conduction. However, progress was made regarding ZnSb as a p-type material. The optimization of the mechanical alloying process led to a very promising ZnSb material. The analyses of this material by transmission electron microscopy and XPS analysis led to the identification of some precipitates which give rise to improved thermoelectric properties compared to existing p-type ZnSb. Furthermore the obtained material has a high thermal stability reinforcing its interest compared to other materials for applications in the same temperature range.

Thesis (DTech (Engineering))--Cape Peninsula University of Technology, 2017. / The world has been experiencing energy-related problems following pressuring energy demands which go along with the global economy growth. These problems can be phrased in three paradoxical statements: Firstly, in spite of a massive and costless solar energy, global unprecedented energy crisis has prevailed, resulting in skyrocketing costs. Secondly, though the sun releases a clean energy, yet conventional plants are mainly being run on unclean energy sources despite their part in the climate changes and global warming. Thirdly, while a negligible percentage of the solar energy is used for power generation purposes, it is not optimally exploited since more than its half is wasted in the form of heat which contributes to lowering efficiency of solar cells and causes their premature degradation and anticipated ageing. The research is geared at addressing the issue related to unsatisfactory efficiencies and anticipated ageing of solar modules. The methodology adopted to achieve the research aim consisted of a literature survey which in turn inspired the devising of a high-efficiency novel thermal electric solar power panel. Through an in-depth overview, the literature survey outlined the rationale of the research interest, factors affecting the performance of PVs as well as existing strategies towards addressing spotted shortcomings. While photovoltaic (PV) panels could be identified as the most reliable platform for sunlight-to-electricity conversion, they exhibit a shortcoming in terms of following the sun so as to maximize exposure to sunlight which negatively affects PVs’ efficiencies in one hand. On the other hand, the inability of solar cells to reflect the unusable heat energy present in the sunlight poses as a lifespan threat. Strategies and techniques in place to track the sun and keep PVs in nominal operational temperatures were therefore reviewed.

O presente trabalho apresenta o desenvolvimento de uma bancada didática de baixo custo para estudo dos materiais termoelétricos para a realização de ensaios de obtenção de curvas de desempenho dos módulos termoelétricos no que se refere a geração de energia pelo Efeito Seebeck e resfriamento através do Efeito Peltier de forma a difundir os conhecimentos nas áreas afim em escolas de Engenharia, refletindo na compreensão dos princípios e funcionalidades destas tecnologias. O sistema proposto permite ler simultaneamente até 3 geradores termoelétricos, e é composto por dois principais circuitos eletrônicos: sendo um estágio aquisição de dados compostos por 3 canais para leitura de tensão, 3 canais para corrente e 6 canais para aquisição do sinal dos termopares (<400°C) além de sistema térmico que terá as funções de aquecimento e resfriamento. Os dados medidos são adquiridos para um computador com um software customizado a aplicação que permite o monitoramento das grandezas envolvidas (tensão, corrente, potência e temperatura) para acompanhamento do ensaio dos materiais termoelétricos, tanto por meio de uma indicação numérica como gráfica. O sistema de aquisição de dados possui precisa o para temperatura de ±2,5%, para tensão de ±2,5% e para corrente de ±1,5%. / The present work describes the development of a low cost didactic bench for Study of thermoelectric materials for performing obtaining performance curves testing of thermoelectric modules in regard to energy generation effect Seebeck and cooling via Peltier Effect order to disseminate knowledge in areas related to engineering schools, reflecting the understanding of the principles and features of these technologies. The proposed system can be read simultaneously up to 3 thermoelectric generators, and consists of two main electronic circuits: being a stage data acquisition composed of 3 channels for reading voltage and 3 channels for current using ACS712 instrumentation amplifiers and 6 channels signal acquisition thermocouples (<400 ° C) as well as thermal system will have the heating and cooling functions. The measured data is acquired to a computer with software developed in Delphi language, which allows monitoring of the quantities involved (voltage, current, power and temperature) to monitor the testing of thermoelectric materials, either through a digital display as a graphic . The data acquisition system has a temperature accuracy to ± 2,5% to ± 2.5% voltage and current of ± 1.5%.

O presente trabalho investiga o fenômeno termodifusivo em dispersões coloidais de nanopartículas magnéticas de óxidos de ferro em água (ferrofluidos), com a formação de dupla camada elétrica em torno das partículas. A estabilidade da partícula em solução é controlada pela concentração de íons. Ao estabelecer uma diferença de temperatura através da amostra líquida, ocorre o efeito de termodifusão (efeito Soret) das partículas e de íons em solução. Este efeito é o movimento das partículas para o lado frio ou quente do gradiente de temperatura. O acúmulo para um dos lados do gradiente de temperatura depende das características da solução. O efeito Soret de ferrofluidos em soluções ácidas e básicas é descrito a partir da determinação experimental das grandezas físicas envolvidas na difusão das partículas. O coeficiente Soret ST e o coeficiente de difusão são determinados em experimentos ópticos de lente de matéria, utilizando o aparato experimental de Varredura-Z, e de espalhamento Rayleigh forçado para termodifusão. Para investigar a resposta dos íons ao gradiente de temperatura, são realizadas medidas do potencial termoelétrico em uma célula termoelétrica, gerado a partir da difusão das cargas dispersas no líquido. O potencial superficial das partículas também é investigado experimentalmente, para descrever a interação das partículas com o campo termoelétrico. Os experimentos são realizados em função da temperatura da amostra e usados para descrever os resultados ST(T) das partículas, a partir de equações dos principais modelos teóricos. Os resultados mostram as diferenças e semelhanças do efeito Soret das nanopartículas em soluções ácidas e básicas, e que em ambos os casos a termodifusão de nanopartículas reflete o comportamento termodifusivo dos íons dispersos em solução. / This work investigates the thermal diffusion phenomena in colloidal dispersions of iron oxide magnetic nanoparticles dispersed in water (ferrofluid). The particles are stable in water due to electrical double layer around the particles, controlled by the ionic concentration. A temperature gradient throughout the ferrofluid sample causes the thermodiffusion (Soret effect) of dispersed particles and ions. This effect is the movement of particles to the cold or hot side of the temperature gradient. The particles migration for a given side depends on the characteristics of the sample. The Soret effect of ferrofluids in acidic and basic solutions is described by the experimental measurements of the physical parameters associated to particles diffusion. The Soret coefficient ST and the mass diffusion coefficient are measured in the matter lens experiment in the Z-scan experimental setup, and by the use of Thermal Diffusion Forced Rayleigh Scattering experiments. Concerning the ionic response to the temperature gradient the thermoelectric field generated by charges diffusion is measured in a thermoelectric cell. The surface potential of the particles is also measured to describe its interactions with the thermoelectric field. These experiments are made as function of the temperature of the sample and the results are applied to describe the ST(T) of particles by the use of equations from the main theoretical models. The results show differences and resemblances of the Soret effect in acidic and basic nanoparticles solutions. In both kind of solutions the thermodiffusion of nanoparticles is mainly ruled by the thermodiffusion of ions dispersed in solution.

O presente trabalho apresenta o desenvolvimento de uma bancada didática de baixo custo para estudo dos materiais termoelétricos para a realização de ensaios de obtenção de curvas de desempenho dos módulos termoelétricos no que se refere a geração de energia pelo Efeito Seebeck e resfriamento através do Efeito Peltier de forma a difundir os conhecimentos nas áreas afim em escolas de Engenharia, refletindo na compreensão dos princípios e funcionalidades destas tecnologias. O sistema proposto permite ler simultaneamente até 3 geradores termoelétricos, e é composto por dois principais circuitos eletrônicos: sendo um estágio aquisição de dados compostos por 3 canais para leitura de tensão, 3 canais para corrente e 6 canais para aquisição do sinal dos termopares (<400°C) além de sistema térmico que terá as funções de aquecimento e resfriamento. Os dados medidos são adquiridos para um computador com um software customizado a aplicação que permite o monitoramento das grandezas envolvidas (tensão, corrente, potência e temperatura) para acompanhamento do ensaio dos materiais termoelétricos, tanto por meio de uma indicação numérica como gráfica. O sistema de aquisição de dados possui precisa o para temperatura de ±2,5%, para tensão de ±2,5% e para corrente de ±1,5%. / The present work describes the development of a low cost didactic bench for Study of thermoelectric materials for performing obtaining performance curves testing of thermoelectric modules in regard to energy generation effect Seebeck and cooling via Peltier Effect order to disseminate knowledge in areas related to engineering schools, reflecting the understanding of the principles and features of these technologies. The proposed system can be read simultaneously up to 3 thermoelectric generators, and consists of two main electronic circuits: being a stage data acquisition composed of 3 channels for reading voltage and 3 channels for current using ACS712 instrumentation amplifiers and 6 channels signal acquisition thermocouples (<400 ° C) as well as thermal system will have the heating and cooling functions. The measured data is acquired to a computer with software developed in Delphi language, which allows monitoring of the quantities involved (voltage, current, power and temperature) to monitor the testing of thermoelectric materials, either through a digital display as a graphic . The data acquisition system has a temperature accuracy to ± 2,5% to ± 2.5% voltage and current of ± 1.5%.