Exotic filled skutterudite compositions show promise for thermoelectric applications. Current work was undertaken with a nominal composition of Ce(Ru0.67Rh0.33)4Sb12 to experimentally verify its potential as an n-type thermoelectric material. Nominal electroneutrality was expected at 0.89 cerium filling and fully filled materials were expected to be strongly n-type. Filled precursors of the nominal composition were synthesized using straightforward solid state reaction techniques, but standard synthesis routes failed to produce a fully-filled homogenous phase. Instead, the filled thermoelectric Ce(Ru0.67Rh0.33)4Sb12 was synthesized using a combination of solid state reaction of elemental constituents and high pressure hot pressing. A range of pressure-temperature conditions was explored; the upper temperature limit of filled skutterudite in this system decreases with increasing pressure and disappears by 12 GPa. The optimal synthesis was performed in multi-anvil devices at 4–6 GPa pressure and dwell temperatures of 350–700 °C. rutheniumThe result of this work, a Ce(Ru0.67Rh0.33)4Sb12 fully filled skutterudite material, exhibited unexpected p-type conductivity and an electrical resistance of 1.755 mΩ-cm that increased with temperature. Thermal conductivity, Seebeck coefficient, and resistivity were measured on single phase samples. In this paper, we report the details of the synthesis routeand measured thermoelectric properties, speculate on the deviation from expected carrier charge balance, and discuss implications for other filled skutterudite systems.

The known mineral Pavonite AgBi3S5 shows a complex structure composed of NaCl type fragments but has not been studied from the thermoelectric point of view. We present initial results on the synthesis and themoelectric properties of synthetic AgBi3S5, which shows n-type metallic conductivity. In addition, the examination of the solid solutions AgSbxBi3-xS5 (x=0.3) is reported.

To understand thermoelectric properties of multiplayer Bi2Te3/Sb2Te3 superlattices, especially their charge transport properties, electronic structure calculations were carried out using ab-initio gradient corrected density functional theory. The superlattice structures of (1,1) and (1,2) Bi2Te3/Sb2Te3 multilayers were optimized and their band structures were compared with each other. Different lattice relaxation effects are observed for the two structures. The cross-plane and inplane effective masses for both these systems are found to be comparable, consistent with experimental mobility measurements.

An incoherent particle model has been developed to predict the phonon thermal conductivity of nanowires and superlattice nanowires. It is argued that the surface roughness of most real nanowires prevents the formation of idealized confined dispersion relations for typical temperatures and diameters. Instead, the three-dimensional bulk dispersion is used, thus addressing only classical size effects. Four adjustable parameters capture the effects of diameter, superlattice, Umklapp, impurity, and alloy scattering. Predictions are compared with experimental data for nanowires and superlattice nanowires down to 22 nm diameter and 20 K, and are in good agreement above ∼40 nm diameter. The analysis suggests that ideal low thermal conductivity nanowires for thermoelectric applications would have small-diameter, alternating alloy segments that are acoustically dissimilar but electrically similar.

Polycrystalline CoGe1.5Se1.5 was synthesized and characterized. The compound is a member of the class of compounds with the skutterudite crystal structure. Synthesis assuming the above stoichiometry resulted in a n-type semiconductor with composition CoGe1.452Se1.379. The specimen exhibits a large room temperature Seebeck coefficient and resistivity. The electron mobility is very low and the thermal conductivity is lower than that of the binary skutterudite CoSb3. These properties can be attributed to the vacancies in the crystal lattice due to the non-stoichiometric nature of the specimen. The potential for thermoelectric applications of ternary skutterudites is also discussed.

This work reports current efforts in developing experimental techniques applicable for thermoelectric properties characterization at micro and nanoscale. A one-dimensional transport model was used to asses the effects of heat leakage, non-symmetric boundary conditions, and electrical contact resistance, on thermoelectric properties measurements performed by transient Harman method. If the above effects are important, the thermoelectric figure of merit cannot be extracted directly from the ratio between the Seebeck voltage and the resistive voltage drop across the sample. On the other hand, measurements of both thermal conductivity and Seebeck coefficient can be performed if the temperature drop across the sample is acquired simultaneously with the voltage drop. The theoretical model and the experimental technique are validated by measurements performed on bulk calibration samples. Furthermore, this work shows that the spatial resolution of thermoelectric properties characterization methods can be enhanced by using scanning probe based techniques. Preliminary results are presented for Seebeck coefficient measurements of p-type or n-type calibration samples performed using an AFM probe instrumented with a temperature sensor.

The thermoelectric power of bismuth nanowires is theoretically calculated to be greatly enhanced over that of bulk Bi. This is a result of the size-quantization of the electron wavefunction in nanowires with diameters below 50 nm. The effect is expected to lead to the development of high figure of merit thermoelectric materials. We review here the experimental observation of such enhancement in composites containing nanowires with diameters down to 9 nm. When the wire diameter is further decreased, localization effects take over and limit the thermopower. The theory further predicts the appearance of an energy gap in bismuth nanowires with diameters below 50 nm. We observe such a gap in the temperature dependence of the resistivity. The dependence of the gap on nanowire diameter is consistent with theory. Comparisons of the transport properties of Bi nanowires with those in other nanowire systems show the influence of localization effects.

K2Bi8Se13 belongs to a class of complex chalcogenides which show potential for superior thermoelectric performance. This compound forms in two distinct phases, α and β. The β-phase, which has several sites with mixed K/Bi occupancy is a better thermoelectric. To understand the origin of this difference we have carried out electronic structure calculations within ab initio density functional theory using full potential linearized augmented plane wave (FLAPW) method. The generalized gradient approximation was used to treat the exchange and correlation potential. Spin-orbit interaction (SOI) was incorporated using a second variational procedure. The α-phase is found to be a semiconductor with an indirect band gap of 0.47eV compared to 0.76eV for the observed direct optical gap. For the β-phase we have chosen two different ordered structures with full occupancies of K and Bi atoms at the “mixed sites”. The system is a semi-metal for both the ordered structures. To incorporate the effect of mixed occupancy we have chosen a 1x1x2 supercell with an alternative K/Bi occupancy at the “mixed sites”. The superlattice ordering gives a semiconductor with an indirect gap of 0.38eV. Mixed occupancy is crucial for the system to be a semiconductor because the Bi atoms at the “mixed sites” stabilize the p orbitals of the neighboring Se atoms by lowering their energy, and opening up a gap at the chemical potential.

In the field of thermoelectrics, the figure of merit of new materials is based on the electrical conductivity, thermoelectric power, and thermal conductivity of the sample, however additional insight is gained through knowledge of the carrier concentrations and mobility in the materials. The figure of merit is commonly related to the material properties through the B factor which is directly dependent on the mobility of the carriers as well as the effective mass.

To gain additional insight on the new materials of interest for thermoelectric applications, a Hall Effect system has been developed for measuring the temperature dependent carrier concentrations and mobilities. In this paper, the measurement system will be described, and recent results for several new materials will be presented.

Thermolectric devices have been constructed using Bi2Te3/Sb2Te3 and Bi2Te3/Bi2Te2-xSex superlattice thin films. Since these devices are intended for use in systems that will operate at elevated temperatures over their lifetime as in many power conversion applications, thermal stability of the thermoelectric figure of merit is an important consideration. The ZTe of p-type and n-type superlattice thin film elements was evaluated at specific intervals during exposure to elevated temperatures of 150°C for up to 60 hrs. Results indicate that the figure of merit for p- and n-type superlattice films is not compromised over time when exposed to these operating temperatures. In fact, both p- and n-type superlattice thin film ZTe remains very constant or improves slightly when subjected to continuous exposure to elevated temperatures. Evaluation of these thin film thermoelements is reported and implications of these results are considered for thin film thermoelectric modules.

An attempt was made to obtain bulk III-nitride semiconductors such as InN, GaN and InxGa1−xN alloy using hot-press method in order to test their high temperature thermoelectric properties. The Seebeck coefficient and the resistivity were –10μV/K and 1.8×10−6 Ωm for InN, and –50μV/K and 1.9×10−4 Ωm for GaN at 300K, respectively. Thermal conductivity determined by laser flash method with porosity correction was 17W/mK for InN and 2.6W/mK for GaN. For InN the Seebeck coefficient and the resistivity increased monotonously with increasing temperature, which indicates that InN is a metal or a degenerately doped semiconductor. The power factor and the figure of merit were 2.1 × 10−4 W/mK2 and 1.5×10−5 K−1 for InN and 6.9 × 10−5 W/mK2 and 2.6×10−5 K−1 for GaN at 650K, respectively.

At JPL, it is our desire to fabricate thermoelectric micro-devices for power generation and cooling applications using an electrochemical deposition (ECD) technique. We believe that the performance of our current micro-device developed is limited by the properties of the ECD materials. Therefore, the objective of this study is to develop ECD methods for obtaining n-type Bi2Te3 and p-type Bi2-xSbxTe3 thermoelectric materials with near bulk properties, as well as optimizing morphology and transport properties. The films of Bi2Te3 and Bi2-xSbxTe3 were initially obtained under various ECD conditions. Seebeck coefficients and transport properties were then measured along the direction parallel to the substrates before and after annealing at 250°C for 2hrs. From the data obtained, ECD n-Bi2Te3 material can achieve a high Seebeck coefficient (-189 μV/K) when it is deposited at –200 mV vs. SCE. The in-plane resistivity, in-plane mobility, and carrier concentration are 3.0 mohm-cm, 31 cm2 V−1 S−1, and 6.79 × 1019 cm−3, respectively. As for the p-type Bi2-xSbxTe3, it is possible to achieve a high Seebeck coefficient (+295 μV/K) when it is deposited at 0.3 mA/cm2. The in-plane resistivity, in-plane mobility, and carrier concentration are 9.8374 mohm-cm, 66.58 cm2 V−1 S−1, and 9.54 × 1018 cm−3, respectively. From the results of our preliminary study, we have found the conditions for depositing high quality Bi2Te3 and Bi2-xSbxTe3 materials with thermoelectric properties comparable to those of their state-of-the-art bulk samples.

Thermoelectrics is a multidiscipline area of study, rich in condensed matter physics, chemistry, engineering, and material science. The figure of merit used for evaluating individual materials consists of three interdependent material properties. The measurement of these properties should be taken on the same sample for all three measurements, preferably simultaneously. Each of these measurements requires close attention to potential sources of losses for accurate analysis of the materials and testing of theoretical models. For example, relatively simple scanning measurement techniques can be used to gain insight into accurate geometry measurements and influences of contact dimensions. In addition, the field of thermoelectrics spans a wide temperature range, from cryogenic temperatures to > 1000 °C. This requires systems capable of large temperature variations, and/or multiple measurement systems for various ranges of interest. Additional measurements, such as Hall effect, help to gain further insight into the material properties and their optimization. The number and importance of measurements is further extended as the development of devices from these new materials is initiated, where studies of contact resistance and overall device performance must be evaluated. For mechanical robustness of fabricated modules, properties such as the coefficient of thermal expansion, and grain size for the new materials are of interest. Models for device behavior are useful in evaluating the measured results and further extracting material and device properties. In this paper, we review measurements used in evaluating bulk thermoelectric materials some of the information that can be extracted from these measurements, along with a model that can be used in conjunction with these measurements for module design.

Sedov-Taylor theory is modified to describe plasma shock waves generated in a pulsed laser ablating process. Under the reasonable asymptotic behavior and boundary conditions, the propagating rules in the global free space (including close areas and mid-far areas) of pulsed-laser-induced shock waves are established for the first time. In particular, the temporal behavior of energy causing the difference of the propagation characteristics between the practical plasma shock wave and the ideal shock wave in point explosion model is discussed in detail.

We report transport properties of polycrystalline TMGa3 (TM = Fe and Ru) compounds in the temperature range 313K<T<973K. These compounds exhibit semiconductorlike behavior with relatively high Seebeck coefficient, electrical resistivity, and Hall carrier concentrations at room temperature in the range of 1017 - 1018cm−3. Seebeck coefficient measurements reveal that FeGa3 is n -type material, while the Seebeck coefficient of RuGa3 changes signs rapidly from large positive values to large negative values around 450K. The thermal conductivity of these compounds is estimated to be 3.5Wm−1K−1 at room temperature and decreased to 2.5Wm−1K−1 for FeGa3 and 2.0Wm−1K−1 for RuGa3 at high temperature. The resulting thermoelectric figure of merit, ZT, at 945K for RuGa3 reaches 0.18.

Polycrystalline alkaline-earth hexaborides (MB6: M =Ca, Sr, Ba) were synthesized and their thermoelectric and transport properties were examined to discuss their possibility as high temperature thermoelectric materials. Hall measurements showed that carrier concentration of the BaB6 was the highest among the three hexaborides and that of CaB6 was the lowest. Substitution of part of the alkaline earth metals with one of the others changed the carrier concentration of the hexaboride. As the carrier concentration increased, Seebeck coefficient increased and electrical conductivity decreased. These results suggest that the thermoelectric properties of the divalent hexaborides depend largely on the carrier concentration, and optimum carrier concentration which gives maximum power factor was estimated to be approximately 2x1026 m−3. Consequently, such a substitution enables us to control Seebeck coefficient and electrical conductivity of the hexaborides, and will also be effective to reduce the lattice heat conduction due to the alloying effect. A thermoelectric device was fabricated using SrB6 and boron carbide thin films as n-type and p-type elements, respectively. To the best of our knowledge, this is the first demonstration of a thermoelectric device composed of only boron-rich solids.

The electrical and thermal transport properties (electrical resistivity, thermopower, heat capacity and thermal conductivity) of the crystalline phase of the binary Cd6Yb system has been measured over a temperature range from 10 K to 300 K. Evidence for a phase transition in Cd6Yb is observed in the electrical transport properties with distinct changes in the temperature dependence of the resistivity and thermopower around T ≈ 110K. An anomaly in the heat capacity and a thermal conductivity is also observed at this same temperature. Hysteretic behavior is not evident in the temperature dependence of any of the electrical and thermal transport properties. In addition, the elastic properties using resonant ultrasound (RUS) techniques have been investigated over a similar temperature range. A large “resonance dip” is observed in the RUS data at T ≈ 110K, which is indicative of some type of structural change in the crystalline material at this temperature. These data will be presented and discussed in context of the undergoes reversible order-disorder transition in the 1/1 cubic approximant at about 110 K, which makes the system very interesting compared to the quasicrystal phase Cd5.7Yb

We have developed thin film heaters/sensors that can be integrated on top of superlattice microcoolers to measure the Seebeck coefficient perpendicular to the layer. In this paper, we discuss the Seebeck coefficients of InGaAs/InAlAs superlattices grown with Molecular Beam Epitaxy (MBE) that have different doping concentrations, varying between 2e18, 4e18, and 8e18 to 3e19 cm−3. It was interesting to find out that – contrary to the behavior in bulk material – the Seebeck coefficient did not decrease monotonically with doping concentration. A preliminary theory of thermoelectric transport in superlattices in the regime of miniband formation has been developed to fit the experimental results. The miniband formation could enhance the thermoelectric power factor (Seebeck coefficient square times electrical conductivity) and thereby improve the Figure of merit, ZT. With this improvement, InGaAs/InAlAs superlattice microcooler become a promising candidate for on-chip temperature control.

High figure of merit has been reported in superlattice structures in recent years mainly due to a large reduction in thermal conductivity, while maintaining or even enhancing the power factor. These findings suggest the possibility of using nanocomposites to reduce a material's thermal conductivity and thereby increasing the thermoelectric figure of merit. The current work reports on the thermal conductivity of various Si-Ge nanocomposites synthesized in a simple and straightforward process that allows one to exploit nanoscale physics while rapidly producing macroscale devices. Composite synthesis consisted of combining Si nanoparticles approximately 70 nm in diameter with micron-sized Ge particles in various atomic ratios via hotpressing to form macroscale samples. Room-temperature thermal conductivity was measured for each of the nanocomposite samples and compared with the values of SiGe bulk alloys. In this preliminary work, we observed a significant reduction in bulk thermal conductivity in such materials.

The improving performance of microprocessors is increasing the Thermal Design Power [TDP] and cause localized power densities commonly referred to as “Hot-spots”, which reach in excess of 200 W/cm2. The focus of this work is to present Thin-film Superlattice Thermoelectric materials [TFST] as a solution for microprocessor die hot spot cooling. TFST have measured ZT values of ∼2 at 300K, response times of the order of 15μs and potential to pump heat flux of several hundred Watts/cm2. TFST devices appear suitable for managing the junction temperatures at such hot spots such that the recommended maximum operational temperature, Tjmax, is not exceeded. This promotes stable processor performance and increased reliability. To test this theory, hot spots were identified on the microprocessor die by infrared (IR) imaging during operation and a suitable TFST module was mounted onto the processor. Thermal transients at the hot spot show that active heat pumping and spreading by TFST significantly reduces the constraints on the thermal design. This investigation suggests that in the future, with the transition of Superlattice material performance into higher module ZT values; these hot spots may be effectively removed.