Organic semiconductors are prime candidates for thermoelectric applications, because one can maximize the dimensionless figure of merit ZT (by maximizing the Seebeck coefficient and electrical conductivity) while simultaneously minimizing the thermal conductivity. In this work, we explore a few materials and try to find their thermoelectric characteristics. For the n-leg of the thermogenerator, we studied a modified fullerene (PCBM) which is doped with TDAE vapor. For the p-leg, we studied PEDOT and found the TDAE dedoping level at which the figure of merit is maximized.

This study is centered on modeling and experimental efforts to simulate and optimize the performance of thermoelectric generators (TEGs) for waste heat recovery systems for use in motor vehicles. TEGs are being studied and developed for applications in which waste heat, for example, from the exhaust of motor vehicles is converted into usable electricity. TEGs consisting of TE elements integrated with an exhaust heat exchanger require optimization to produce the maximum possible power output. Important optimization parameters include TE element leg length, fill fraction, leg area ratio between n- and p-type legs, and load resistance. A finite difference model was developed to study the interdependencies among these optimization parameters for thermoelectric elements integrated with an exhaust gas heat exchanger. The present study was carried out for TE devices made from n-type Mg₂Si and p-type MnSi[subscript 1.8] based silicides, which are promising TE materials for use at high temperatures associated with some exhaust heat recovery systems. The model uses specified convection boundary conditions instead of specified temperature boundary conditions to duplicate realistic operating conditions for a waste heat recovery system installed in the exhaust of a vehicle. A numerical model for a new waste heat recovery system configuration was proposed which showed an improvement of 40% in net power output over the conventional systems while using approximately 60% more TEG modules. The 1st generation, and an improved 2nd generation TEG module using n-type Mg₂Si and p-type MnSi[subscritp 1.8] based silicides were fabricated and tested to compare and correlate TE power generation with the numerical model. Important results include parameter values for maximum power output per unit area and the interdependencies among those parameters. Heat transfer through the void areas was neglected in the numerical model. When thermal contact resistance between the TE element and the heat exchangers is considered negligible, the numerical model predicts that any volume of TE material can produce the same power per unit area, given the parameters are accurately optimized. Incorporating the thermal contact resistance, the numerical model predicts that the peak power output is greater for longer TE elements with larger leg areas. The optimization results present strategies to improve the performance of TEG modules used for waste heat recovery systems. / text

For the past decade interest in skutterudites has been significant as a potentially viable material for thermoelectrics. One way to improve the effectiveness of these materials is to lower their thermal conductivity. Lattice thermal conductivity of a series of La- and Yb-filled skutterudite antimonides (with varying filling fraction) has been modeled with different phonon scattering parameters using the debye approximation. It was found that filler atoms both increase point defect scattering and resonance scattering. Subsequently, the thermal conductivity of partially-filled skutterudites AxCo4Sb12, where A = La, Eu and Yb, is analyzed using the Debye model in order to correlate the data with the type of filler atom in evaluating the role of the filler atom in affecting the thermal conductivity. Partial void filling has resulted in relatively high thermoelectric figures of merit at moderately high temperatures. This idea is extended as new materials were synthesized with the intention of filling the voids in the CoGe1.5Se1.5 skutterudite, and analyzing the transport of these novel materials. Results of the analysis of this material are interesting and may indicate an amorphous phase of skutterudite present. Further work is needed to explore fully the implications of this new skutterudite and to fully understand its properties.

The present dissertation investigates the relationship between the structure and thermoelectric properties of ZnO based materials, with a focus on trivalent element doping on engineering the microstructure and altering the electrical and thermal transport properties. Within the solubility range, the addition of trivalent elements, such as In3+, Fe3+ and Ga3+, is observed to increase the electrical conductivity of ZnO and decrease the thermal conductivity. / Engineering and Applied Sciences

In this work, we develop a many-body theory of electronic transport through single molecule junctions based on nonequilibrium Green’s functions (NEGFs). The central quantity of this theory is the Coulomb self-energy matrix of the junction ∑(C). ∑(C) is evaluated exactly in the sequential-tunneling limit, and the correction due to finite lead-molecule tunneling is evaluated using a conserving approximation based on diagrammatic perturbation theory on the Keldysh contour. In this way, tunneling processes are included to infinite order, meaning that any approximation utilized is a truncation in the physical processes considered rather than in the order of those processes. Our theory reproduces the key features of both the Coulomb blockade and coherent transport regimes simultaneously in a single unified theory. Nonperturbative effects of intramolecular correlations are included, which are necessary to accurately describe the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap, essential for a quantitative theory of transport. This work covers four major topics related to transport in single-molecule junctions. First, we use our many-body theory to calculate the nonlinear electrical response of the archetypal Au-1,4-benzenedithiol-Au junction and find irregularly shaped ‘molecular diamonds’ which have been experimentally observed in some larger molecules but which are inaccessible to existing theoretical approaches. Next, we extend our theory to include heat transport and develop an exact expression for the heat current in an interacting nanostructure. Using this result, we discover that quantum coherence can strongly enhance the thermoelectric response of a device, a result with a number of technological applications. We then develop the formalism to include multi-orbital lead-molecule contacts and multi-channel leads, both of which strongly affect the observable transport. Lastly, we include a dynamic screening correction to ∑(C) and investigate the optoelectric response of several molecular junctions.

This thesis examines the development of a high efficiency heat pump system using thermoelectric (TE) and reticulated metal foam (RMF) technologies to power a vehicle`s battery thermal management system. The focus is split into two areas: first a review of TE???s sourcing or removing heat, second an examination of compact heat exchanger (HX) design. Five TE suppliers were investigated to understand the performance and limitations of their TE modules. Testing showed the Kyrotherm product to be superior so it was used as a design basis. RMF???s are known to be an effective means to improve the performance of compact heat exchangers, thus HX???s were evaluated with RMF foams compressed to varying densities in order to understand their potential in conjunction with thermoelectric devices. Experimental results showed performance was limited due to adequate bonding, yet still on par with the highest efficiency technologies currently on the market.

Die Systeme CuBiQX (Q = S, Se; X = Cl, Br, I) konnten um zahlreiche Verbindungen erweitert werden. Den meisten dieser Materialien ist ein rigides Netzwerk der Anionenpolyeder um die Bismutkationen gemein. Der Majorität der Verbindungen ist außerdem zumindest eine lokale Beweglichkeit der Kupfer(I)-Ionen immanent. Diese konnte sowohl mittels isotroper Verfeinerungen als auch durch harmonisch und anharmonisch verfeinerte und mittels JPDF zusammengefasste Elektronendichten nachgewiesen werden. Hieraus waren Berechnungen der Potentiale, der Potentialbarrieren und deren Fehler möglich.

xii, 106 p. : ill. (some col.) / Quantum dots are systems in which all three spatial sizes are comparable to the Fermi wavelength. The strong confinement leads to a discrete energy spectrum. A goal of thermoelectric research is to find a system with a high thermoelectric figure of merit, which is related to the efficiency of solid-state heat engines. The delta-like density of states of quantum dots has been predicted to boost this figure of merit. This dissertation addresses some thermoelectric properties relevant to the thermal-to-electric energy conversion using InAs/InP quantum dots embedded in nanowires. In thermoelectric experiments, a temperature difference must be established and its value needs to be determined. A novel technique for measuring electron temperature across the dot is presented. A strong nonlinearity of the thermocurrent as a function of temperature difference is observed at a small ratio of temperature gradient and cryostat temperature. At large heating currents, a sign reversal is observed. Numerical calculations explore the contribution of the energy dependence of the transmission function to this effect. Depending on the relative contributions from sequential tunneling and co-tunneling, thermovoltages of quantum dots generally have one of two different lineshapes: a sawtooth shape or a shape similar to the derivative of the conductance peak. Here a simple picture is presented that shows that thermovoltage lineshape is accurately predicted from the energy level spacing inside the dot and the width of the transmission function. An important figure of merit of all heat engines is the efficiency at maximum power. Here the thermoelectric efficiency at maximum power of quantum dots is numerically compared to that of two other low-dimensional systems: an ideal one-dimensional conductor (1D) and a thermionic power generator (TI). The numerical calculations show that either 1D or TI systems can produce the highest maximum power depending on the operating temperature, the effective mass of the electron, and the effective area of the TI system. In spite of this, 1D systems yield the highest efficiency at maximum power. / Committee in charge: Dr. Richard Taylor, Chair; Dr. Heiner Linke, Research Advisor; Dr. Dietrich Belitz; Dr. David Johnson; Dr. David Strom

Crystalline open-framework intermetallics have long attracted the attention of chemists, physicists, and materials scientists. The intriguing structures such materials exhibit are often intimately related to the unique physical properties they possess. The present work is focused on the preparation and characterization of open-framework intermetallic materials based on group 14 elements, in particular those crystallizing in clathrate and related structures such as the clathrate-II phases. Materials possessing the clathrate-II crystal structure have received increased attention in recent years, as a result of both the unique properties they exhibit as well as potential for use in technologically important applications such as thermoelectrics, photovoltaics, and optoelectronics. However, in comparison with other clathrate structure types, characterization of clathrate-II materials has in general been far less extensive. Moreover, many conceivable compositions have yet to be realized. The purpose of this work is to expand the current knowledge of the structural, chemical, and physical properties of these materials, while simultaneously exploring new compositions and synthetic routes to clathrate-II phases. One of the unique and promising aspects of clathrate-II materials is the ability to vary the guest concentration, which is shown to have significant implications for the structural and physical properties of NaxSi136 (0< x< 24) materials. It is demonstrated that new compositions can be explored by novel approaches to chemical design. Framework substitution in clathrate-II compounds is explored in an effort to assess possibilities for influencing the physical properties of these materials. A novel zeolite-like framework phase, Na1-xGe3+z, has been discovered, and is shown to be a new low-thermal conductivity crystalline solid, suggesting a new approach to the design of crystalline intermetallic materials with low thermal conductivity. New directions in synthesis of intermetallics are identified, with emphasis on unconventional preparative methods and the opportunities they offer. Processing of reactive precursors by spark plasma sintering is demonstrated as a new preparative tool for crystal growth, identifying the first method for preparation of clathrate-II Na24Si136single-crystals since the discovery of these compounds more than four decades ago.

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