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

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Environmental challenges, such as global warming, growing demand on energy, and diminishing oil sources have accelerated research on alternative energy conversion methods. Thermoelectric power generation is a promising method to convert wasted heat energy into useful electrical energy form. A temperature gradient imposed on a thermoelectric device produces a Seebeck potential. However, this temperature gradient causes thermal stresses due to differential thermal expansions and mismatching of the bonded components of the device. Thermal stresses are critical for thermoelectric devices since they can generate failures, including dislocations, cracks, fatigue fractures, and even breakdown of the entire device. Decreases in power-generation performance and operation lifetime are major consequences of these failures. In order to minimize thermal stresses in the legs without affecting power-generation capabilities, this study concentrates on structural solutions. Thermoelectric devices with non-segmented and segmented legs were modeled. Specifically, the possible effect of various leg geometries, configurations, and dimensions were evaluated using finite-element and statistical methods. Significant changes in the magnitudes and distributions of thermal stresses occurred. Specifically, the maximum equivalent stresses in the rectangular-prism and cylindrical legs were 49.9 MPa and 43.3 MPa, respectively for the temperature gradient of 100ºC. By using cylindrical legs with modified dimensions, decreases in the maximum stresses in legs reached 21.2% without affecting power-generation performance. Moreover, the effect of leg dimensions and coaxial-leg configurations on power generation was significant; in contrast, various leg geometries and rotated-leg configurations had very limited affect. In particular, it was possible to increase power output from 20 mW to 65 mW by simply modifying leg widths and heights within the defined range. It should be noted, however, this modification also increased stress levels. It is concluded that leg geometries, configurations, and dimensions can be redesigned for improved durability and overall performance of thermoelectric devices.

Thermoelectric (TE) module integration into a notebook computer is experimentally investigated in this thesis for its energy harvesting opportunities. A detailed Finite Element (FE) model was constructed first for thermal simulations. The model outputs were then correlated with the thermal validation results of the selected system. In parallel, a commercial TE micro-module was experimentally characterized to quantify maximum power generation opportunity from the combined system and component data set. Next, suitable &ldquo / warm spots&rdquo / were identified within the mobile computer to extract TE power with minimum or no notable impact to system performance, as measured by thermal changes in the system, in order to avoid unacceptable performance degradation. The prediction was validated by integrating a TE micro-module to the mobile system under test. Measured TE power generation power density in the carefully selected vicinity of the heat pipe was around 1.26 mW/cm3 with high CPU load. The generated power scales down with lower CPU activity and scales up in proportion to the utilized opportunistic space within the system. The technical feasibility of TE energy harvesting in mobile computers was hence experimentally shown for the first time in this thesis.

Thermoelectric devices are capable of providing both localized active cooling and waste heat power generation. This work will explore the possibility of embedding thermoelectric devices within electronic packaging in order to achieve better system performance. Intel and Nextreme, Inc. have produced thin-film superlattice thermoelectric devices that have above average performance for thermoelectrics and are much thinner than most devices on the market currently. This allows them to be packaged inside of the electronic package where the thermoelectric devices can take advantage of the increased temperatures and decreased thermal lag as compared to the devices being planted on the outside of the package. This work uses the numerical CFD solver FLUENT and the analog electronic circuit simulator SPICE to simulate activity of thermoelectric devices within an electronics package.

The present study aims to increase understanding of the physical processes that govern thermoelectric efficiency in Na-containing group 14 type II clathrates. This has been achieved through structural characterization and physical property measurements. Local and electronic structures of Si clathrates with the formula NaxSi136, where x = 0, 1.3, 5.5, 7.2, 8.8, 14.1, 20 and 21.5 were studied using x-ray absorption spectroscopy. Thermoelectric properties, namely Seebeck coefficient, electrical conductivity and thermal conductivity were measured from 2.5 K to 400 K. Low Na content samples, x < 8, showed reduced thermal conductivity compared to the empty clathrate, x = 0. For x > 8, increased Na content led to increased charge transfer, increased thermal conductivity and decreased magnitude of Seebeck voltages. The heat capacities of the NaxSi136 materials were measured from 2.5 K to 300 K. Analysis of the heat capacity data showed that the vibrational modes associated with Na in the Si28 cages are of sufficiently low energies to interact with heat transporting acoustic phonons, leading to reduced thermal conductivity as x is increased up to ~ 8. Increasing Na content beyond x = 8 introduces Na into the Si20 cages. This stiffens the lattice, increasing (or maintaining) phononic contributions to thermal conductivity, and increasing electronic contributions. Electronic thermal conductivity is responsible for upwards of 50 % of heat conduction when x = 21.5. Na containing type II Ge clathrates were produced using an ionic liquid reaction medium. Seebeck coefficients observed in Na9Ge136 materials, were negative but larger in magnitude than those of the NaxSi136 materials and thermal conductivities of Na9Ge136 were lower than those of the NaxSi136 materials. While both Si and Ge type II clathrates showed modest figures of merit, with maximum ZT values of 2.5 × 10-6 and 2.8 × 10-5 observed in Na20Si136 and Na¬9Ge136, of the two framework elements, type II Ge clathrates have been shown to have more favourable thermoelectric properties.

Thesis (MDiploma (Mechanical Engineering))--Cape Technikon, 1992. / An investigation into the use of thermoelectric cooling energised by photovoltaic (PV) panels for removing sensible heat from electronic telecommunications equipment. The thermoelectric cooler consists of a solid-state heat pump which operates on the principle of the Peltier effect. The thermoelectric device transfers heat through a cold sink to ambient outside air via a hot sink. A major prerequisite was that the system should be selfsufficient in terms of power because the sites for the microwave transmitters are often remote. Solar power was the only alternative source of energy and the cooler was designed to accept direct current from PV panels which are usually used to power transmitters on distant locations. The cooling device had to be reliable, virtually maintenance-free and simple to repair.

Today many processes generate a lot of waste heat, for example industries or cars. One way to make this thermal energy useful is to transform it into electrical energy with a thermoelectric generator (TEG) or thermoelectric cooler (TEC). This technology is not used in any large scale today, but a lot of research is being done on the subject. The technology is based on the Seebeck effect and uses a temperature difference between two sides of an element to generate an electrical current. The reason that the research has gained more attention in recent years is because of the increasing electricity prices and the diminishing natural resources. Other benefits are that they run quietly and do not demand much maintenance.Another area where this technology could be useful is in off-grid cabins where it is easy to generate a lot of thermal energy by burning wood, but electrical energy is in high demand.In this thesis two different types of TEGs and one type of TEC are tested to investigate how much power they generate at different temperature differences, how well they meet the specified values in their respective data sheet and what their power per euro value is. For this, an experimental setup was made with:- An induction plate to increase the temperature on the hot side.- A CPU-fan, to reduce the temperature on the cold side.- Two temperature sensors (one for measuring the hot temperature and one for the cold one).- An electric circuit featuring a voltmeter, an amperemeter and an adjustable resistor (rheostat).The results show that, for this experiment the highest received power (6,38 W) comes from the medium-priced element but the highest power per euro comes from the lowest priced element (1,16 W/€). A quality problem for the lowest priced element was that parts of the solder melted when the temperature exceeded 225 °C. Another problem was that the induction plate was unable to provide enough heat for the most expensive of the elements to reach the temperature for which the retailer supplies their measured data.

In recent decades the development of technologies capable to offer highly localized and precise temperature control has received increasing attention due to their relevance and applicability in numerous engineering fields. Multiple scientific papers have been written that focus on the enhancement of the performance of thermoelectric materials and micro-devices. This Ph.D. thesis in the field of Mechanical Engineering pursues three main research goals regarding electrothermal phenomena: (1) To provide an optimization design strategy for micro-thermoelectric coolers by analyzing the interplay between electrical and thermal fluxes during device operation. (2) To analyze the suitability of a device, based on micro-thermoelectric coolers, for controlling the thermal environment in microbiological systems. (3) To develop an experimental technique, based on optical pump-probe thermal imaging, to extract the thermal conductivity anisotropy of thin films. For this purpose, numerical simulations and experiments were carried out. The results show, that the design of micro-thermoelectric devices must take into account the impact of parameters that are typically neglected in the construction of macro scale devices. Poorly designed parameters, such as the metallic contacts, the distance between thermoelectric elements and their interaction with the substrate, carry severe reductions of the performance of micro-thermoelectric devices. It is demonstrated that the optimal performance is achieved when the thermoelectric legs are properly dimensioned, so that a balance of the Fourier and Joule fluxes is reached. Numerical analyses prove that micro-thermoelectric coolers offer a feasible alternative to overcome the current spatial and temperature limitations of conventional technologies and therefore enable to investigate the thermal environment of biological systems at the micro-scale. Guidelines for the implementation of the experimental platform are provided. The evaluation of the numerical and experimental data proves that optical pump-probe thermal imaging is suitable to characterize both the in-plane and the through-plane thermal conductivity of thin films. The experimental conditions to extract the anisotropy of the sample under study are determined. The outcome of this work yields new insights into electrothermal phenomena at the micro-scale and thus creates new routes in the design, fabrication and characterization of micro- thermoelectric materials and devices.:Acknowledgements IV Erklärung der Urheberschaft VI Summary VII Zusammenfassung VIII Table of content IX List of figures XI List of tables XIV Abbreviations and symbols XV 1 Introduction 1 1.1 Motivation 1 1.2 Outline of the thesis 4 1.2.1 Chapter 2 - Fundamentals 4 1.2.2 Chapter 3 - Design guidelines of micro-thermoelectric coolers 4 1.2.3 Chapter 4 - Development of a platform for biological systems experimentation 4 1.2.4 Chapter 5 - Development of a technique for thermal transport characterization in thin films 5 1.2.5 Chapter 6 - Main conclusion and future research 5 1.3 Main research objectives 5 2 Fundamentals 7 2.1 Thermoelectric phenomena 7 2.2 Performance estimation of micro-thermoelectric coolers 10 2.3 Finite element modelling 12 2.3.1 Introduction to finite element modelling 12 2.3.2 Finite element modelling of thermoelectric phenomena 17 2.4 Thermoreflectance imaging microscopy 19 3 Design guidelines of micro-thermoelectric coolers 26 3.1 Introduction 26 3.2 Micro-thermoelectric coolers: an alternative for thermal management 28 3.3 Analysis approach 29 3.3.1 Input current optimization 31 3.3.2 Metallic contacts 32 3.3.3 Leg pair geometry 35 3.3.4 Fill factor 38 3.3.5 Experimental characterization of µTECs 41 3.4 Summary 44 4 Development of a platform for biological systems experimentation 46 4.1 Introduction 46 4.2 Thermal analysis on biological systems 48 4.3 Platform conceptual proposal 50 4.4 Analysis approach 52 4.4.1 Input current optimization 52 4.4.2 Fill material 54 4.4.3 Thermotaxis 55 4.4.4 Top material 56 4.4.5 Cold spot optimization 58 4.5 Experimental platform construction 59 4.6 Summary 62 5 Development of a technique for thermal transport characterization in thin films 64 5.1 Introduction 64 5.2 Thermal anisotropy characterization in thin films 65 5.3 Experimental apparatus 66 5.4 Experimental measurements 69 5.5 Analysis approach 72 5.5.1 Thermal conductivity anisotropy analysis 76 5.5.2 Effect of the laser power on the temperature distribution 79 5.5.3 Enhancement of the system sensitivity 80 5.6 Summary 83 6 Main conclusion and future research 85 6.1 Main conclusion 85 6.2 Outlook 88 7 References 89 8 Scientific output 97 8.1 Publications in peer review journals 97 8.2 Selected conference abstracts 98 9 Curriculum vitae 99

The thermoelectric properties of bismuth telluride based thermoelectric (TE) materials are well-characterized, but comparatively little has been published on the thermomechanical properties. In this paper, dynamic mechanical analysis (DMA) and differential scanning calorimetry data for bismuth telluride based TE materials is presented. The TE materials' tan delta values, indicative of viscoelastic energy dissipation modes, approached that of glassy or crystalline polymers, were greater than ten times the tan delta of structural metals, and reflected the anisotropic nature of TE materials. DMA thermal scans showed changes in mechanical properties versus temperature with clear hysteresis effects. These results showed that the application of DMA techniques are useful for evaluation of thermophysical and thermomechanical properties of these TE materials.