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Thermoelectric materials have been used for cooling and heating systems for over a hundred years. Today practical applications of thermoelectric devices include cooling car seats, power generation, and refrigeration. Thermoelectric materials are special for their ability to convert temperature imbalances into electricity. Their applications can inform the discourse about the transition to renewable energy sources---something that our Earth most desperately needs. The goal of this dissertation is to describe how the effective tensors of two-dimensional thermoelectric composites made from two isotropic materials depend on thermoelectric parameters of the constituents. Using the theory of exact relations and links developed by Grabovsky and his collaborators, we describe all equations satisfied by the thermoelectric effective tensor of a composite without the explicit knowledge of its microstructure. In some special cases, the effective tensor can be determined completely. Even in the general case, four out of 10 components of the two-dimensional thermoelectric tensor can be expressed in terms of the remaining 6, regardless of the microstructure. We started with special cases and worked our way up to the more general ones. / Mathematics

Power harvesting, energy harvesting, power scavenging, and energy scavenging are four terms commonly used to describe the process of extracting useful electrical energy from other ambient energy sources using special materials called transducers that have the ability to convert one form of energy into another. While the words power and energy have vastly different definitions, the terms "power harvesting" and "energy harvesting" are used interchangeably throughout much of the literature to describe the same process of extracting electrical energy from ambient sources. Even though most of the energy coupling materials currently available have been around for decades, their use for the specific purpose of power harvesting has not been thoroughly examined until recently, when the power requirements of many electronic devices has reduced drastically. The overall objective of this research is to typify the power source characteristics of various transducer devices in order to find some basic way to compare the relative energy densities of each type of device and, where possible, the comparative energy densities within subcategories of harvesting techniques. Included in this research is also a comparison of power storage techniques, which is often neglected in other literature sources. An initial analysis of power storage devices explores the background of secondary (rechargeable) batteries and supercapacitors, the advantages and disadvantages of each, as well as the promising characteristics of recent supercapacitor technology developments. Also explored is research into the effectiveness of piezoelectric energy harvesting for the purpose of battery charging, with particular focus on the current output of piezoelectric harvesters. The first objective involved presenting and verifying a model for a cantilever piezoelectric bimorph. Next, an investigation into new active fiber composite materials and macro fiber composite devices utilizing the d31 coefficient is performed in comparison to a monolithic piezoelectric bimorph. The information gathered here was used to design a two bimorph device termed the mobile energy harvester (MEH). Worn by a human being at the waste level, the MEH harvests energy from each footfall during walking or running. The next objective involved characterizing small temperature gradient (less than 200 oC) thermoelectric generators (TEGs). Four TEGs were linked in series and joined with a specially made aluminum base and fin heat sink. This device was then mounted to the exhaust system of an automobile and proved capable of recharging both an 80 and a 300 milliamp-hour battery. A switching circuit concept to step up the output voltage is also presented. However, the circuit proves somewhat difficult to implement, so an alternative DC/DC device is proposed as a possible solution. With the advent of highly efficient, low voltage DC to DC converters, it is shown that their high current, low voltage output can be converted to a higher voltage source that is suitable for many electronic and recharging applications. As extensive literature exists on the capabilities of photovoltaic and electromagnetic energy harvesting, no original experimentation is presented. Instead, only a brief overview of the pertinent technological advances is provided in this document for the purpose of comparison to piezoelectric and thermoelectric energy harvesting. The main research focus, as described above, is dedicated to designing and performing original experiments to characterize cutting edge piezoelectric and thermoelectric transducer materials. To conclude and unify the document, the final section compares the power harvesting techniques with one another and introduces methods of combining them to produce a hybrid, multiple energy domain harvesting device. A piezoelectric-electromagnetic harvesting combination device is presented and scrutinized, revealing that such a device could improve the amount of energy extracted from a single harvesting unit. The research presented here not only expands on the present understanding of these materials, but also proposes a new method of creating a hybrid power harvesting device utilizing two of the energy coupling domains, electromechanical and piezoelectric. The goal is to maximize the harvested energy by tapping into as many ambient sources as are available and practical. / Master of Science

High temperature waste heat recovery has been gaining attention in recent years as it forms one of the largest sources of available energy. A rapid development of thermoelectric (TE) materials that can directly convert heat into electricity through the Seebeck effect, opens promising pathway for harvesting the thermal energy from the surroundings. In order to harvest the high-quality waste heat at elevated temperature, excellent thermal and mechanical stability of the TE materials is critical for a sustainable energy harvesting. In this respect, half-Heusler (hH) alloys are one of the promising high-temperature TE materials due to their high dimensionless thermoelectric figure of merit (zT) along with excellent mechanical and thermal stability. This dissertation demonstrates novel hH compositions and microstructures for the waste heat recovery systems. Focus in the thesis is on development of high performance hH TE materials with excellent in-air thermal stability at high temperatures (>700K). This will allow manufacturing of high efficiency and durable high temperature thermoelectric generators (TEGs). In chapter 3 and 4, a comprehensive optimization of n-type MNiSn and p-type MCoSb (M = Hf, Zr, and Ti) compounds is investigated through systematic control of processing parameters during melting and sintering. The synthesis conditions were controlled to achieve the phase purity, desired microstructure and the enhanced charge-carrier transport. Optimized n-type and p-type compositions are found to exhibit zTmax ~ 1 at 773 K. Chapter 5 describes breakthrough in decoupling of TE parameters in n-type half-Heusler (hH) alloys through multi-scale nanocomposite architecture with tungsten nanoinclusions. The tungsten nanoparticles not only assist electron injection, thereby improving electrical conductivity, but also enhance the Seebeck coefficient through energy filtering effect. The microstructure comprises of disordered phases with feature sizes at multiple length scales, which assists in effective scattering of heat-carrying phonons over diverse mean-free-path ranges. Cumulatively, these effects are shown to result in outstanding thermoelectric performance of zTmax ~ 1.4 at 773 K and zTavg ~ 0.93 between 300 and 973 K. In order to deploy TE materials into a thermal energy conversion device, it is essential to understand the transformation behavior under thermal cycling at high temperatures. In-air thermal stability of the hH compositions is demonstrated in chapter 6. All the optimized compositions are found to be stable below 673 K in-air condition. The n-type MNiSn and p-type NbFeSb compounds were found to show good thermal stability even at higher temperatures (>773K), whereas MCoSb compounds did not exhibit similar level of stability. Building upon the improved material performance and thermal stability, uni-coupled TE generators are demonstrated that exhibit high power density of 13.81 W⸱cm-2 and conversion efficiency of 10.9 % under a temperature difference of 674 K. The uni-couple TEG device shows stable performance for more than 150 hours at 873 K in air. These results are very promising for deployment of TE materials in waste heat recovery systems. / Doctor of Philosophy / Based on the 2012 international energy agency (IEA) report, global waste heat energy is estimated to be in the range of 246 Exajoule (1 EJ = 10¹⁸ J). Tapping even small fraction of this wasted energy through thermal energy harvesting techniques will allow us to generate significant magnitude of green energy. Thermoelectrics (TEs) are one of the most promising thermal energy conversion materials as they offer cost-effective and environmentally friendly option with solid-state silent operation and scalability. Among many different options for high temperature TE materials, half-Heusler system is one of the leading candidates as it has the potential to provide high performance and thermal stability at temperatures as high as 873 K. The progress in developing practical half-Heusler materials has been limited for last two decades. Despite many publications, the maximum figure of merit (zT) of n-type half-Heusler materials has been stagnant (zT ~ 1.0). Further, there has been a lack of focus towards module development that can operate under realistic conditions. This dissertation provides comprehensive studies on novel thermoelectric compositions and nanocomposites that are suitable for manufacturing of high temperature modules. Microstructural architectures proposed here provide the ability to tailor electronic transport and phonon scattering beyond the commonly demonstrated regimes. Optimized materials were successfully implemented in efficient and stable thermoelectric generator exhibiting power density on the order of 13.81 W⸱cm⁻² , which is 1400 % higher than that of the fuel cell (~1 W⸱cm⁻² ).

Thermoelectric materials can convert thermal energy into electrical energy and vice-versa. They are widely used in energy harvesters, thermal sensors, and cooling systems. However, the low efficiency and high cost of the known material compositions limit their widespread utilization in electricity generation applications. Therefore, there is a strong interest in identifying new thermoelectric materials with high figure of merit. In response to this need, this dissertation works on the synthesis, structure, doping mechanism, and thermoelectric properties of zinc oxide (ZnO) and lead tellurium (PbTe). The main focus is on ZnO based materials and in improving their performance. The influences of micro- or nano-structures on thermal conductivity, as well as the correlation between the electrical property and synthesis conditions, have been systematically investigated. ZnO is a likely candidate for thermoelectric applications, because of its good Seebeck coefficient, high stability at high temperature, non-toxicity and abundance. Its main drawbacks are the high thermal conductivity (κ) and low electrical conductivity (σ). To decrease κ, two novel structures—namely, precipitate system and layered-and-correlated grain microstructure—have been proposed and synthesized in ZnO. The mechanisms iii governing the nature of thermal behavior in these structures have been explored and quantified. Due to strong phonon scattering, the nano-precipitates can reduce the thermal conductivity of ZnO by 73%. The ZnO with layered-and-correlated grains can further reduce κ by about 52%, which compares favorably with the dense ZnO with nanoprecipitates. The figure of merit of this ZnO based structure was 0.14×10⁻³ K⁻¹ at 573 K. In order to understand the electrical behavior in nanostructured ZnO, the impact of Al doping and chemical defects in ZnO under different synthesis conditions were studied. Under varying sintering temperatures, atmospheres and initial physical conditions, ZnO exhibited very distinct σ. High temperature, lack of oxygen, vacuum condition, and chemically synthesized powder can increase the carrier concentration and σ of ZnO. A promising alloy system, PbTe-PbS, undergoes natural phase separation by nucleation and growth, and spinodal decomposition depending on the thermal treatment. The correlation between the thermal treatment, structure, and the thermoelectric properties of Pb0.9S0.1Te has been studied. The nano-precipitates were incorporated in the annealed alloy resulting in a 40% decrease in κ. The PbS precipitation was shown to enhance the carrier concentration and improves the Seebeck coefficient. These concomitant effects result in a maximum ZT of 0.76 at 573 K. Throughout the thesis, the emphasis was on understanding the impact of the microstructures on thermal conductivity and the effect of the synthesis condition on thermal and electrical properties. The process and control variables identified in this study provide practical ways to optimize the figure of merit of ZnO and PbTe materials for thermoelectric applications. / Ph. D.

The dissertation solved some critical issues in thermoelectric energy harvesting and tried to broaden the thermoelectric application for energy recovery and sensor powering. The scientific innovations of this dissertation were based on the new advance on thermoelectric material, device optimization, fabrication methods, and system integration to increase energy conversion efficiency and reliability of the thermoelectric energy harvester. The dissertation reviewed the most promising materials that owned a high figure of merit (ZT) value or had the potential to increase ZT through compositional manipulation or nano-structuring. Some of the state-of-art methods to enhance the ZT value as well as the principles underneath were also reviewed. The nanostructured bulk thermoelectric materials were identified as the most promising candidate for future thermoelectric applications as they provided enormous opportunities for material manipulation. The optimizations of the thermoelectric generator (TEG) depended on the accuracy of the mathematical model. In this dissertation, a general and comprehensive thermodynamic model for a commercial thermoelectric generator was established. Some of the unnecessary assumptions in the conventional models were removed to improve the accuracy of the model. This model can quantize the effects of the Thomson effect, contact thermal and electrical resistance, and heat leakage, on the performance of a thermoelectric generator. The heat sink can be another issue for the design of high-performance TEG. An innovative heat sink design integrated with self-oscillating impinging jet generated by the fluidic oscillator arrays were adopted to enhance the heat convection. The performance of the heat sink was characterized by large eddy simulation. The compatibility mismatch had been a practical problem that hindered the further improvement of energy conversion efficiency of thermoelectrics. In this dissertation, a novel method to optimize the geometry of the thermo-elements was developed. By varying the thickness and cross-sectional area of each thermoelectric segment along the length of the thermo-element, the compatibility mismatch problem in the segmented TEG construction was eliminated. The optimized segmented TEG can make the best of the existing thermoelectric materials and achieve the maximum energy conversion efficiency in a wide temperature range. A segmented TEG with an unprecedented efficiency of 23.72% was established using this method. The complex geometry structure of the established thermo-elements would introduce extra difficulty in fabrication. Thus selective laser melting, a high-temperature additive manufacture method, was proposed for the fabrication. A model was built based on the continuous equations to guide the selective-laser-melting manufacturing of thermoelectric material with other nanoparticles mixed for high thermoelectric performance. Thermoelectric energy harvesting played a critical role in the self-powered wireless sensors, as it was compact and quiet. In this dissertation, various thermoelectric energy harvesters were established for self-powered sensors to in-situ monitor the working condition in the gas turbine and the interior conditions in nuclear canisters. The sensors, taking advantage of the thermal energy existing in the local environment, can work continuously and provide tremendous data for system monitor and diagnosis without external energy supply. / Doctor of Philosophy / The dissertation addressed some critical issues in thermoelectric energy harvesting and broadened its application for energy recovery and sensor powering. Some of the most advanced technologies were developed to improve the energy conversion efficiency and reliability of the thermoelectric energy harvesters. In this dissertation, a general and comprehensive thermodynamic model for a commercial thermoelectric generator (TEG) was established. The model can be used to optimize the design of the existing commercial TEG modules. High performance heat sink design was critical to maximize the temperature drop in the TEG module, thus increase the power output and energy conversion efficiency of the TEG. An innovative heat sink design integrated with self-oscillating impinging jet generated by the fluidic oscillator arrays were designed to cool the cold end of the TEG, thus enhance the performance of the TEG. The performance of the heat sink was characterized by large eddy simulation. A single thermoelectric material only had high thermoelectric performance in a narrow temperature range. A segmented TEG could achieve a high energy conversion efficiency over a wide temperature range by adopting different materials which had high thermoelectric performance at low, moderate, and hight temperature ranges. However, the material compatibility mismatch had been a practical problem that hindered the further improvement of energy conversion efficiency of the segmented TEG. In this dissertation, a novel method was developed to eliminate the compatibility mismatch problem via optimizing the geometry of the thermo-elements. A segmented TEG with an unprecedented efficiency of 23.72% was constructed using the method proposed in this dissertation. The complex geometry structure of the established thermo-elements would introduce extra difficulty in fabrication. Thus selective laser melting, a high-temperature additive manufacture method, was proposed for the fabrication. A physical model based on the v conservation equations was built to guide the selective-laser-melting manufacturing of the optimized segmented TEG mentioned above. In this dissertation, two thermoelectric energy harvesters were built for self-powered sensors to in-situ monitor the interior conditions in nuclear canisters. The sensors, taking advantage of the thermal energy existing in the local environment, can work continuously and provide tremendous data for system monitor and diagnosis without external energy supply. Also, a compact thermoelectric energy harvester was developed to power the gas sensor for combustion monitoring and control.

High temperature thermal energy harvesting has attracted much attention recently. In order to achieve stable operation at high temperatures there is emerging need to develop efficient and oxidation-resistant materials. Most of the well-known materials with high dimensionless figure of merit (ZT) values such as Bi2Te3, PbTe, skutterudites, and half-Heusler alloys, are not thermally stable at temperatures approaching 500°C or higher, due to the presence of volatile elements. Oxide thermoelectric materials are considered to be potential candidates for high temperature applications due to their robust thermal and chemical stability in oxidizing atmosphere along with the reduced toxicity, relatively simpler fabrication, and cost. In this dissertation, nanoscale texturing and interface engineering were utilized for enhancing the thermoelectric performance of oxide polycrystalline Ca3Co4O9 materials, which were synthesized using conventional sintering and spark plasma sintering (SPS) techniques. In order to tailor the electrical and thermal properties, Lu and Ga co-doping was investigated in Ca3Co4O9 system. The effect of co-doping at Ca and Co sites on the thermoelectric properties was quantified and the anisotropic behavior was investigated. Because of the effective scattering of phonons by doping-induced defects, lower thermal conductivity and higher ZT were achieved. The layered structure of Ca3Co4O9 has strong anisotropy in the transport properties. For this reason, the thermoelectric measurements were conducted for the samples along both vertical and horizontal directions. The ZT value along the vertical direction was found to be 3 to 4 times higher than that along the horizontal direction. Metallic inclusions along with ionic doping were also utilized in order to enhance the ZT of Ca3Co4O9. The texturing occurring in the nanostructured Ca3Co4O9 through ion doping and Ag inclusions was studied using microscopy and diffraction analysis. Multi-length scale inclusions and heavier ion doping in Ca3Co4O9 resulted in higher electrical conductivity and reduced thermal conductivity. The maximum ZT of 0.25 at 670°C was found in the spark plasma sintered Ca2.95Ag0.05Co4O9 sample. In literature, limited number of studies have been conducted on understanding the anisotropic thermoelectric performance of Ca3Co4O9, which often results in erroneous estimation of ZT. This study addresses this limitation and provides systematic evaluation of the anisotropic response with respect to platelet microstructure. Textured Ca3Co4O9/Ag nanocomposites were fabricated using spark plasma sintering (SPS) technique and utilized for understanding the role of microstructure towards anisotropic thermoelectric properties. The thermoelectric response was measured along both vertical and horizontal direction with respect to the SPS pressure axis. In order to achieve enhanced degree of texturing and increase electrical conductivity along ab planes, a two-step SPS method was developed. Ag nanoinclusions was found to increase the overall electrical conductivity and the thermoelectric power factor because of improved electrical connections among the grains. Through two-step SPS method, 28% improvement in the average ZT values below 400°C and 10% improvement above 400°C in Ca3Co4O9/Ag nanocomposites was achieved. Lastly, this dissertation provides significant progress towards understanding the effect of synthesis method on thermoelectric properties and evolution of textured microstructure. The anisotropy resulting from the crystal structure and microstructural features is systematically quantified. Results reported in this study will assist the continued progress in developing Ca3Co4O9 materials for practical thermoelectric applications. / PHD / Among the wide range of renewable energy sources, wasted thermal energy has attracted worldwide interest as it is freely available from most of the industrial and natural processes. Among various choices for converting thermal energy into electricity, thermoelectric devices are attractive as they are solid state, noiseless, no moving parts, and can be easily integrated with most of the heat sources. Thus, there has been significant efforts to develop high efficiency thermoelectric energy harvesting devices. However, currently available thermoelectric materials are not thermally stable in oxidizing environments because of heavy metals’ evaporation and reactivity. In order to overcome this limitation of thermoelectric materials, in this dissertation, the focus is on developing calcium cobalt oxide (Ca₃Co₄O₉) materials through innovation in the processing, composition design, and modulation of the thermal transport mechanism by exploiting the anisotropy. Ca₃Co₄O₉ is promising candidate for high temperature thermoelectric applications due to its thermal and chemical stability in oxidizing atmosphere, reduced toxicity, easy fabrication, and low cost. Its main disadvantages are the high thermal conductivity and low electrical conductivity. In order to tailor the electrical and thermal properties, Lu and Ga co-doped Ca₃Co₄O₉ were synthesized and characterized. The thermoelectric measurements were conducted along both vertical and horizontal directions with respect to pressure axis during spark plasma sintering. Layered structure of Ca₃Co₄O₉ induces strong anisotropy in the transport properties which indicates that textured microstructure will result in better properties. Texturing and interface engineering were employed to control the grain orientation and thereby improve the electrical and thermal properties. In textured and nanostructured Ca₃Co₄O₉, Ag inclusions along with ionic doping was utilized to enhance the thermoelectric performance. In literature, the importance of the anisotropy in Ca₃Co₄O₉ has been less emphasized, which has restricted accurate thermoelectric evaluation of this material for practical application. In order to address this issue, first textured Ca₃Co₄O₉/Ag nanocomposites were fabricated using spark plasma sintering (SPS) techniques and next detailed investigation was conducted on correlation between microstructure and anisotropic thermoelectric properties. The power factor of the Ca₃Co₄O₉/Ag nanocomposites at high temperatures was almost 50% enhanced, as compared to the pure Ca₃Co₄O₉, which resulted in 50% improvement in ZT both horizontal and vertical directions. The samples with texturing along the vertical direction were used to perform the long-term durability test and almost same value of resistivity was maintained after a long-term heating. Two-step SPS method was developed to improve the in-plane electrical conductivity. Through this newly proposed synthesis process, 28% improvement in the average ZT values below 400°C and 10% improvement above 400°C was obtained in Ca₃Co₄O₉/Ag nanocomposites. Using a wide range of composition and synthesis process, the anisotropy and microstructural effects clarified in this study provides promising pathway towards enhance the thermoelectric performance of Ca₃Co₄O₉ materials.

This work presents the development and application of analytical, numerical, and experimental methods for the study of thermal and electrical transport in nanoscale systems, with special emphasis on those materials and phenomena which can be important in thermoelectric and semiconductor device applications. Analytical solutions to the Boltzmann transport equation (BTE) using the relaxation time approximation (RTA) are presented and used to study the thermal and electrical transport properties of indium antimonide (InSb), indium arsenide (InAs), bismuth telluride (Bi₂Te₃), and chromium disilicide (CrSi₂) nanowires. Experimental results for the thermal conductivity of single layer graphene supported by SiO₂ were analyzed using an RTA-based model and compared to a full quantum mechanical numerical BTE solution which does not rely on the RTA. The ability of these models to explain the measurement results as well as differences between the two approaches are discussed. Alternatively, numerical solutions to the BTE may be obtained statistically through Monte Carlo simulation for complex geometries which may prove intractable for analytical methods. Following this approach, phonon transport in silicon (Si) sawtooth nanowires was studied, revealing that thermal conductivity suppression below the diffuse surface limit is possible. The experimental investigation of energy transport in nanostructures typically involved the use of microfabricated devices or non-contact optical methods. In this work, two such approaches were analyzed to ascertain their thermal behavior and overall accuracy as well as areas for possible improvement. A Raman spectroscopy-based measurement design for investigating the thermal properties of suspended and supported graphene was examined analytically. The resulting analysis provided a means of determining from measurement results the thermal interface conductance, thermal contact resistance, and thermal conductivity of the suspended and supported graphene regions. Previously, microfabricated devices of several different designs have been used to experimentally measure the thermal transport characteristics of nanostructures such as carbon nanotubes, nanowires, and thin films. To ascertain the accuracy and limitations of various microdevice designs and their associated conduction analyses, finite element models were constructed using ANSYS and measurements of samples of known thermal conductance were simulated. It was found that designs with the sample suspended were generally more accurate than those for which the sample is supported on a bridge whose conductance is measured separately. The effects of radiation loss to the environment of certain device designs were also studied, demonstrating the need for radiation shielding to be at temperatures close to that of the device substrate in order to accurately calibrate the resistance thermometers. Using a suspended microdevice like those analyzed using finite element analysis, the thermal conductivities of individual bismuth (Bi) nanowires were measured. The results were correlated with the crystal structure and growth direction obtained by transmission electron microscopy on the same nanowires. Compared to bulk Bi in the same crystal direction, the thermal conductivity of a single-crystal Bi nanowires of 232 nm diameter was found to be 3 - 6 times smaller than bulk between 100 K and 300 K. For polycrystalline Bi nanowires of 74 nm to 255 nm diameter the thermal conductivity was reduced by a factor of 18 - 78 over the same temperature range. Comparable thermal conductivity values were measured for polycrystalline nanowires of varying diameters, suggesting a grain boundary scattering mean free path for all heat carriers in the range of 15 - 40 nm which is smaller than the nanowire diameters. An RTA-based transport model for both charge carriers and phonons was developed which explains the thermal conductivity suppression in the single-crystal nanowire by considering diffuse phonon-surface scattering, partially diffuse surface scattering of electrons and holes, and scattering of phonons and charge carriers by ionized impurities such as oxygen and carbon of a concentration on the order of 10¹⁹ cm⁻³. Using a similar experimental setup, the thermoelectric properties (Seebeck coefficient, electrical conductivity, and thermal conductivity) of higher manganese silicide (HMS) nanostructures were investigated. Bulk HMS is a passable high temperature thermoelectric material which possesses a complex crystal structure that could lead to very interesting and useful nanoscale transport properties. The thermal conductivities of HMS nanowires and nanoribbons were found to be reduced by 50 - 60 % compared to bulk values in the same crystal direction for both nanoribbons and nanowires. The measured Seebeck coefficient data was comparable or below that of bulk, suggesting unintentional doping of the samples either during growth or sample preparation. Difficulty in determining the amorphous oxide layer thickness for nanoribbons samples necessitated using the total, oxide-included cross section in the thermal and electrical conductivity calculation. This in turn led to the determined electrical conductivity values representing the lower bound on the actual electrical conductivity of the HMS core. From this approach, the measured electrical conductivity values were comparable or slightly below the lower end of bulk electrical conductivity values. This oxide thickness issue affects the determination of the HMS nanostructure thermoelectric figure of merit ZT as well, though the lower bound values obtained here were found to still be comparable to or slightly smaller than the expected bulk values in the same crystal direction. Analytical modeling also indicates higher doping than in bulk. Overall, HMS nanostructures appear to have the potential to demonstrate measurable size-induced ZT enhancement, especially if optimal doping and control over the crystallographic growth direction can be achieved. However, experimental methods to achieve reliable electrical contact to quality four-probe samples needs to be improved in order to fully investigate the thermoelectric potential of HMS nanostructures. / text