Thesis advisor: Zhifeng Ren / Thermoelectric materials have attracted a lot of research interests because of their promising applications in solid-state cooling and power generation. The low ZTs of the current available thermoelectric materials have restricted the device efficiency, and thus the wide application of the thermoelectric technique. We propose a nanocomposite approach to improve ZT by reducing lattice thermal conductivity. The nanocomposite approach was first applied to n-type Si. Since there is no point defect scattering from Ge in pure Si, hence it provides an opportunity to study the scattering of grain boundaries. We found that the thermal conductivity is reduced by a factor of 10 in nanostructured Si in comparison with bulk crystalline Si. By adding 5 at% Ge, the thermal conductivity is further reduced by a factor of 2, thereby leading to a thermoelectric figure of merit 0.95 for Si95Ge5, similar to that of large grained Si80Ge20 alloys. Moreover, thermoelectric properties of In4Se3-x and Zn4Sb3 were investigated. Extremely low thermal conductivity values of 0.41 and 0.69 Wm-1K-1 were obtained in In4Se2.2 and Zn4Sb3 nanocomposites respectively, leading to peak ZTs of 1 and 1.3. / Thesis (PhD) — Boston College, 2011. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

Bismuth telluride based compounds is known to be the best thermoelectric materials within the room temperature regime. In this study, the n-type Bi2Te3-based thermoelectric alloy was synthesized by powder metallurgy method. The Bi2Te2.7Se0.3 thermoelectric materials were prepared via the ball milling, cold pressing, and sintering processes. The effects of sintering time and temperature on the microstructures and thermoelectric properties were investigated and discussed. The X-ray diffraction patterns of Bi2Te2.7Se0.3 reveal that the compounds are single phase after the sintering processes. And the experimental results showed that the pores was reduced by the increased sintering temperature and time. According to the measurement results, the Seebeck coefficient was decreased at firest and then increased by the increased sintering temperature. The optimal Seebeck coefficient of -156.936(£gV/K) was obtained as the sample was sintered at 350¢XC for 3h. The results also showed that the thermal conductivity was increased by the increased sintering temperature, whereas the electrical resistivity was reduced. The lowest thermal conductivity 0.816 (W/m¡EK) was obtained as the sample was sintered at 350¢XC for 1h. On the other hand, the electrical resistivity of 1.6999¡Ñ10-5(£[-m) was obtained as the sample was sintered at 450¢XC for 2h. The figure of merit of 0.31 was obtained at room temperature as the sample was sintered at 375¢XC for 2h.

Sustainable and renewable energy is an incredibly important area in today’s society and investigation into avenues to improve this wide ranging technology are underway in many different fields. Thermoelectric devices possess the ability for the direct solid-state interconversion of heat and electrical power, which not only allows for sustainable refrigeration but also waste heat recovery. One current restriction on the efficiency of thermoelectric devices is the disparity in thermoelectric performance of p-type and n-type materials. Furthermore, a key physical attribute shared by the majority of high performing thermoelectric materials is low thermal conductivity. Thus in this thesis three separate p-type material systems exhibiting low thermal conductivity will be discussed. The Cu-excessed quaternary chalcogenides, CuM2InTe4 (M = Zn, Cd), and ternary chalcogenide, CuSbS2, were investigated due to their intrinsically low thermal conductivity. Whereas, skutterudites typically have good electrical properties but do not exhibit an intrinsically low thermal conductivity. Nevertheless low thermal conductivity can be achieved by taking advantage of their unique crystal structure by filling large voids with loosely bound atoms that act as phonon scattering centers. Therefore double-filled Fe substituted skutterudites with nominal compositions Yb0.4In0.02Co3FeSb12 and Yb0.8In0.02Co2.5Fe1.5Sb12 were also investigated. The CuM2InTe4 (M = Zn, Cd) and skutterudite specimens were synthesized by direct reactions, whereas the CuSbS2 specimens were synthesized by mechanical alloying. Structural and stoichiometric compositions were analyzed by a combination of X-ray diffraction, Rietveld refinement and energy dispersive spectroscopy. High-temperature transport properties were measured for all specimens and will be discussed in detail. The Cu-excessed quaternary chalcogenides display intrinsically low thermal conductivity that appears to be unaffected by the change in electrical properties that is a result of differing stoichiometries. This may provide a possible route to furthering the enhancement of the thermoelectric properties of these materials. Similarly the CuSbS2 ternary chalcogenides display a very low thermal conductivity due to stereochemically active lone-pair electrons and would potentially allow an optimization of the power factor without a significant increase of the very low thermal conductivity, thus improving the figure of merit. For the case of p-type skutterudites, (Yb, In) double-filled skutterudites have a maximum ZT of 0.6, which is promising in the hunt for improved p-type materials. This fundamental investigation provides insight that can lead to a deeper understanding of all three material systems outlined in this thesis and provides a platform for new research in the quest for materials suitable for thermoelectric applications.

La thermoélectricité est considérée comme une source prometteuse de l'énergie puisqu'elle est capable de convertir directement la chaleur en électricité. Ceci permet de récupérer la chaleur dissipée sans causer de la pollution. Cependant, les options applicatives à grande échelle sont encore en restriction en raison du faible rendement de conversion thermoélectrique. Par conséquent, de nombreux travaux de recherche sont consacrés à l'amélioration de la performance thermoélectrique de différents matériaux, qui est caractérisée par la figure de mérite ZT. Un ZT favorable comprend simultanément un coefficient Seebeck satisfaisant, une conductivité électrique élevée et une faible conductivité thermique. Rechercher un matériau approprié avec une meilleure performance thermoélectrique est l'objectif de nos analyses. Avec les techniques de dopage, différents éléments peuvent être ajoutés dans des semi-conducteurs à différentes concentrations. La densité de charge pourrait ainsi être modifiée pour améliorer les propriétés thermoélectriques. En raison des obstacles liés à la synthèse des matériaux, des simulations numériques basées sur différentes méthodes, telles que la théorie fonctionnelle de la densité (DFT), la dynamique moléculaire (DM), sont ensuite mises en oeuvre pour estimer l'approche d'amélioration la plus prometteuse. Au cours de cette thèse, les propriétés thermoélectriques de plusieurs matériaux sont étudiées pour des applications dans différentes situations, à savoir CsSnI₃ comme un candidat potentiel avec sa haute conductivité électrique, ZnO comme un matériau thermoélectrique transparent, Bi₂Te₃ comme un traditionnel matériau avec d'autres améliorations et la cellulose comme futur semi- conducteur organique. Comme la DFT ne concerne que les propriétés des électrons (coefficient de Seebeck, conductivité électrique, conductivité thermique due aux électrons), la conductivité thermique du réseau n'est pas incluse ici. Par conséquent, DFT avec des déplacements finis et DM sont utilisés comme méthodes complémentaires pour établir la conductivité thermique due aux phonons. De cette façon, cette thèse est divisée en deux parties. Dans la première partie, des contextes théoriques de DFT sont introduits à partir de l'équation de Schrödinger. Les résultats des simulations DFT classiques sont présentés par la suite. En utilisant des positions atomiques issues de mesures expérimentales, nous avons lancé la relaxation de la structure cristalline pour assurer que chaque atome dans le système est à sa position d'équilibre. Les structures de bande d'énergie électronique sont également calculées pour valider les configurations de calcul (énergie de coupure, conditions de convergence, etc.). Une cartographie complète des valeurs propres dans l'espace réciproque est faite et les propriétés thermoélectriques sont calculées en résolvant les équations de transport de Boltzmann. Dans la deuxième partie, les théories de base des phonons sont mentionnées, suivies des introductions des méthodes en DFT avec des déplacements finis et en DM. Nous avons mis en oeuvre des simulations DM pour étudier l'influence du dopage à l'aluminium sur la conductivité thermique du réseau pour ZnO. Nous avons également utilisé la méthode en DFT avec des déplacements finis pour étudier la variation de la conductivité thermique de l'alliage Bi₂Te₃₋ₓSeₓ. / Thermoelectricity is considered a promising source of energy since it is able to directly convert heat into electricity. This makes it possible to recover dissipated heat without causing pollution. However, large-scale applicative options are still under restriction because of the dim thermoelectric conversion yield. Therefore, numerous research works are dedicated to improving thermoelectric performance of different materials, which is characterized by the dimensionless figure of merit ZT. A favorable ZT includes simultaneously a satisfying Seebeck coefficient, a high electrical conductivity and a low thermal conductivity. To seek a suitable material with a better thermoelectric performance is the objective of our analyses. With doping technics, different elements can be added into semi-conductors within different concentrations. The charge density could be thus modified in order to change thermoelectric properties. Due to hurdles related to materials synthesis, numerical simulations based on different methods, such as density functional theory (DFT), molecular dynamics (MD), are then implemented to estimate the most promising improvement approach. During this thesis, thermoelectric properties of several materials are investigated for applications in different situations, i.e. CsSnI₃ as a potential candidate with its high electronic conductivity, ZnO as a transparent thermoelectric material, Bi₂Te₃ as a traditional material with further improvements and cellulose as future organic semi-conductor. As DFT concerns only properties of electrons (Seebeck coefficient, electric conductivity, thermal conductivity due to electrons), lattice thermal conductivity is not included herein. Therefore, DFT with finite displacement and MD are used as a complementary method to establish thermal conductivity due to phonons. In this way, this thesis is divided into two parts. In the first part, theoretical backgrounds of DFT are introduced starting with Schrödinger equation. Results of classical DFT simulations are presented afterwards. By using atomic positions from experimental measurements, we launched crystal structure relaxation to ensure that every atom in the system is at its equilibrium position. Electronic band structures are also calculated to validate calculation configurations (cutoff energy, convergence conditions, etc.). A full mapping of Eigenvalues in reciprocal space is realized and thermoelectric properties are calculated by solving Boltzmann transport equations. In the second part, basic theories of phonons are mentioned, followed by introductions of DFT with finite displacements and MD methods. We implemented MD simulations to study the influence of aluminum doping on lattice thermal conductivity for ZnO. We also used DFT with finite displacements method to study lattice thermal conductivity variation of Bi₂Te₃₋ₓSeₓ alloy.

Carbon nanotubes are made into films or bulks, their surface or junction morphology in the networks can be modified to obtain desired electrical transport properties by various surface modification methods. The methods include incorporation of organic molecules or inorganic nanoparticles, debundling of nanotubes by dispersing agents, and microwave irradiation. Because carbon nanotubes have unique carrier transport characteristics along a sheet of graphite in a cylindrical shape, the properties can be dramatically changed by the modification. This is ideal for developing high-performance materials for thermoelectric and photovoltaic energy conversion applications. In this research, decoration of various organic/inorganic nanomaterials on carbon nanotubes was employed to enhance their electrical conductivity, to improve thermoelectric power factor by modulating their electrical conductance and thermopower, or to obtain n-type converted carbon nanotube. The electrical conductivity of double-wall nanotubes (DWNTs) decorated with tetrafluoro-tetracyanoquinodimethane (F4TCNQ) was increased up to 5.9 × 10^5 S/m. The sheet resistances were measured to be 42 Ω/sq at 75% of transmittance for HNO3/SOCl2-treated DWNT films, making their electrical conductivities 200~300% better than those of the pristine DWNT films. A series of experiments at different ion concentrations and reaction time periods were systematically performed in order to find optimum nanomaterial formation conditions and corresponding electronic transport changes for better thermoelectric power factor. For example, the thermoelectric power factors were improved by ~180% with F4TCNQ on DWNTs, ~200% with Cu on SWNTs, and ~140% with Fe on single-walled nanotubes (SWNTs). Also SWNTs was converted from p-type to n-type with a large thermopower (58 μV/K) by using polyethyleneimine (PEI) without vacuum or controlled environment. This transport behavior is believed to be from charge interactions resulted from the difference between the work functions/reduction potentials of nanotubes and nanomaterials. In addition, different dispersing agents were utilized with DWNT and SWNTs to see a debundling effect in a film network. The highest electrical conductivity of ~1.72×10^6 S/m was obtained from DWNT film which was fabricated with a nanotube solution dispersed by chlorosulfonic acid. Debundling of nanotubes in the film network has been demonstrated to be a critical parameter in order to get such high electrical property. In the last experiment, Au nanoparticle decoration on carbon nanotube bundle was performed and a measurement of themophysical properties has done before and after modifying carbon nanotube surface. Carbon nanotube bundle, herein, was bridged on microdevice to enable the measurement work. This study demonstrates a first step toward a breakthrough in order to extract the potential of carbon nanotubes regarding electron transport properties.

In this work, patterns in the behavior of different classes and types of thermoelectric materials are observed, and an alchemy that could help engineer a highly efficient thermoelectric is proposed. A method based on cross-correlation of Seebeck waveforms is also presented in order to capture physics of magnetic transition. The method is used to compute Curie temperature of LaCoO3 with an accuracy of 10K. In total, over 26 systems are analyzed, and 19 presented: Chalcogenides (PbSe, PbTe, Sb2Te3, Ag2Se), Skutterudites and Clathrates (CoSb3, SrFe4Sb12, Cd (CN)2, CdC, Ba8Ga16Si30*), Perovskites (SrTiO3, BaTiO3, LaCoO3, CaSiO3, Ce3InN*, YCoO3*), Half-Heuslers (ZrNiSn, NbFeSb, LiAlSi, CoSbTi, ScPtSb*, CaMgSi*), and an assorted class of thermoelectric materials (FeSi, FeSi2, ZnO, Ag QDSL*). Relaxation time is estimated from experimental conductance curve fits. A maximum upper bound of zT is evaluated for systems that have no experimental backing. In general, thermoelectric parameters (power factor, Seebeck coefficient and zT) are estimated for the aforementioned crystal structures. Strongly correlated systems are treated using LDAU and GGAU approximations. LDA/GGA/L(S)DA+U/GGA+U approach specific errors have also been highlighted. Densities of experimental results are estimated.

Die erfolgreiche Optimierung der Leistung von thermoelektrischen Materialien, die durch zT beschrieben wird, ist entscheidend für ihre Anwendung für das Wärmemanagement und die Kühlung von Leistungselektronik. Im Gegensatz zu Bulk-Proben bleibt die vollständige zT-Charakterisierung von Dünn- und Dickfilmmaterialien eine große Herausforderung. Dies ist insbesondere relevant für Filme, die durch elektrochemische Abscheidung synthetisiert werden, wo das Material auf eine elektrisch leitende Schicht abgeschieden wird. In dieser Dissertation habe ich ein Transport-Device für eine vollständige zTCharakterisierung von elektrochemisch abgeschiedenen Materialien entwickelt, während der Einfluss der elektrisch leitenden Schicht, sowie des Substrats beseitigt wird. Die zT-Charakterisierung erfolgt unter Verwendung eines auf einer freistehenden Membran suspendierten thermoelektrischen Materials innerhalb des entwickelten Transport-Devices, die durch eine Kombination von Fotolithografie und Mikrostrukturierungstechnik zusammen mit Ätzprozessen hergestellt wurde. Für die Messung der Wärmeleitfähigkeit habe ich eine eindimensionale, analytische, stationäre Methode eingesetzt, welche mit Hilfe von dreidimensionalen Finite-Elemente-Simulationen bestätigt wurde. Darüber hinaus habe ich die temperaturabhängigen thermoelektrischen Eigenschaften von zwei Dickschichten mit Hilfe des entwickelten Devices untersucht und mit Bulk-Proben und Dünnfilmen verglichen. Auf diese Weise konnte die Validität des Transport-Devices nachgewiesen werden. Neben der Optimierung von mikro-thermoelektrischen Materialien, die mit dem Transport- Device charakterisiert werden, ist die Leistung von thermoelektrischen Devices von den Faktoren Design, Geometrie und Konstruktion beeinflusst. Daher habe ich den Einfluss der Geometrie auf die Leistung eines elektrochemisch hergestellten mikrothermoelektrischen Generators mit Hilfe einer Finite-Elemente-Simulation untersucht.

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Global warming and developments of alternative energy technologies have become important issues nowadays. Subsequently, the concept of energy harvesting is rising because of its ability of transferring waste energy into usable energy. Thermoelectric devices play a role in this field since there is tremendous waste heat existing in our lives, such as heat from engines, generators, stoves, computers, etc. Thermoelectric devices can extract the waste heat and turn them into electricity. Moreover, the reverse thermoelectric phenomenon has the function of cooling which can be applied to refrigerator or heat dissipation for electronic devices. However, the energy conversion efficiency is still low comparing to other energy technologies. The efficiency is judged by thermoelectric figure of merit (ZT), defined by Seebeck coefficient, electrical conductivity and thermal conductivity. In order to improve ZT, thin film materials are good candidates because of their structural effects on altering ZT.    Ca3Co4O9 thin films grown by reactive radio frequency magnetron sputtering followed by post-annealing process is studied in this thesis. Structural properties of the films with the evolution of elemental ratio (Ca/Co) of calcium and cobalt have been investigated. For the investigations, three samples having elemental ratio 0.82, 0.72, and 0.66 for sample CCO1, CCO2 and COO3, respectively, have been prepared. Structural properties of the films have been investigated by X-ray diffraction (XRD) θ-2θ and pole figure analyses. Surface morphology of the films has been investigated by scanning electron microscopic (SEM) analyses. The highly oriented and phase pure epitaxial Ca3Co4O9 thin films were obtained in the end.   Mixing of ScN and CrN to obtain ScxCr1-xN solid solution thin films by DC magnetron sputtering is the other task in this thesis. Growth of ScN and CrN thin films were studied first in order to get the best mixed growth conditions. The phase shifts between ScN (111) and CrN (111) peaks were observed in mixed growth films by XRD θ-2θ measurements, indicating the formation of ScxCr1-xN. Surface morphology of the films were investigated by SEM. The (111)-oriented ScxCr1-xN thin films with decent surface smoothness grown by DC magnetron sputtering at 600 °C in pure nitrogen with bias were developed.

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