Multiquantum well structures of Bi2Te3 are predicted to show an enhancement of the thermoelectric figure of merit ZT. Electron-conducting Bi2Te3 thin films and superlattices (SL) with a period of 12 nm were epitaxially grown on BaF2 substrates by molecular beam epitaxy. The microstructure was investigated by transmission electron microscopy. The SL could be imaged with strong contrast yielding a period of 12.0±0.5 nm. The SL is slightly bent with an amplitude of 30 nm and a wave length of 400 nm. Threading dislocations were found with a density of 2·109 cm−2. The SL interfaces are strongly bent close to threading dislocations, undisturbed regions have a maximum lateral size of 500 nm. A structural modulation (nns) with a wave length of 10 nm was found in Bi2Te3 thin films, superlattices and bulk materials. The structural modulation is found to be of general character for Bi2Te3 materials and is superimposed to the average structure. It was analysed in detail by stereomicroscopy in bulk material yielding a pure structural modulation with a displacement vector parallel to [5,-5,1] and a wave vector parallel to (1,0,10). The investigations showed the presence of none, one or two (nns). The number of (nns) and thereby the thermoelectric properties might be controlled by the growth parameters. Phonons should be scattered on the sinusoidal strain field of the (nns) yielding (i) a significantly decreased thermal conductivity, (ii) a reduced dimensionality and (iii) anisotropic transport coefficients in the basal plane.

We have prepared polycrystalline bulk samples of various thallium compounds and measured their thermoelectric properties. The most remarkable point of the thermoelectric properties of the thallium compounds is the extremely low thermal conductivity. The state-of-the-art thermoelectric materials such as Bi2Te3 and TAGS materials indicate relatively low the thermal conductivity, around 1.5 W/m/K. However, the thermal conductivity of the thallium compounds is below 0.5 W/m/K; especially that of silver thallium tellurides is around 0.25 W/m/K at room temperature. This extremely low thermal conductivity leads a great advantage for an enhancement of the thermoelectric performance. In this paper, we report on the properties of some thallium compounds selected for study as novel thermoelectric materials. One of these compounds seems to have a thermoelectric figure of merit comparable to those of state-of-the-art materials.

Single crystal NaCo2O4 platelets with sizes up to 6mm were synthesized by the typical high temperature NaCl flux method. The in-plane thermopower α and in-plane resistivity ρ were measured to be ∼100µV/K and 0.3mΩ-cm at 300K, respectively. The in-plane thermal conductivity κ was measured by our custom-designed “PTC” system and found to be ∼5 W-m−1K−1 at 300K, which is 2-3 times larger than the polycrystalline NaCo2O4. The in-plane phonon mean free path lph was estimated to be ∼9.5Å, which is much smaller than the in-plane mean free path of conducting carriers (la∼51Å). A novel low temperature flux method where NaCl/NaOH was used as flux and metallic Co powders as Co source was developed to successfully synthesize Na-deficient NaxCo2O4 crystals with size up to 6mm at low temperature of 550°C. The different temperature dependence in resistivity reveals that two different types of crystals can exist, one is metallic and another is semiconducting. The temperature dependence of the measured k is like that of a disordered solid and the value is found to be ∼7 W-m−1K−1 at 300K.

The thermoelectric properties of Pb9.6SbyTe10−xSex were investigated in the intermediate temperature range of 300 – 700 K. The effect of the variation of Sb content (y) on the electronic properties of the materials is remarkable. Samples with compositions Pb9.6Sb0.2Te10−xSex (y = 0.2) show the best combination of low thermal conductivity with moderate electrical conductivity and thermopower. For Pb9.6Sb0.2Te8Se2 (x = 2) a maximum figure of merit of ZT ∼ 1.1 was obtained around 700 K. This value is nearly 1.4 times higher than that of PbTe at 700 K. This enhancement of the figure of merit of Pb9.6Sb0.2Te8Se2 derives from its extremely low thermal conductivity (∼0.7 at W/m.K at 700 K). High resolution transmission electron microscopy of Pb9.6Sb0.2Te10−xSex samples shows broadly distributed Sb-rich nanocrystals, which may be the key feature responsible for the suppression of the thermal conductivity.

In the filled gallium-germanium clathrates, R8Ga16Ge30, where R is Ba, Sr, or Eu, the guests are located in two large cages and are weakly bound to the crystalline clathrate framework. The caged guests exhibit a localized “rattling” vibrational mode that provides an efficient mechanism for reducing the thermal conductivity. Inelastic neutron scattering and nuclear inelastic scattering measurements have yielded the phonon density of states in R8Ga16Ge30; the line width of the localized vibrational modes is found to be an important parameter in determining the lattice thermal conductivity. Neutron diffraction studies on R8Ga16Ge30 have shown that the guests in the larger cage are located off-center, and it was proposed that their jumping about the four off-center locations is responsible for the observed glass-like thermal conductivity at temperatures below 10 K. The detection of such slow guest motion is challenging because the typical time and energy scales involved are ca. 4 ns and 1 µeV, respectively. We have studied the slow europium tunneling dynamics in Eu4Sr4Ga16Ge30 by both Mössbauer and microwave absorption spectroscopy.

We have succeeded to grow almost single-phase of Half-Heusler intermetallic compounds MNiSn, where M = (Hfx,Zr1−x) and x varies from 0 to 1, for the first time by directional solidification using optical floating zone melting (OFZ). Thermoelectric power and electrical resistivity can be dramatically improved since OFZ process effectively reduces solidification defects such as micro-cracks and cavities as well as unfavorable coexisting phases. Dimensionless thermoelectric figure of merit, ZT, of OFZ (Hf,Zr)NiSn alloys can be improved effectively by lowering the lattice thermal conductivity through the solid solution effects due to the substitution of Hf and Zr with each other. The maximum ZT value of 0.9 is achieved in (Hf0.5Zr0.5)NiSn at 963 K.

Novel rare earth boron icosahedral compounds are investigated as potential high temperature thermoelectric materials. REB50-type compounds and a homologous series of RE-B-C(N) compounds were synthesized and the thermal conductivity and thermoelectric properties measured. Seebeck coefficients in excess of 200 μV/K are observed at temperatures above 1000 K for the REB50-type compounds. Strikingly, n-type behavior was observed for REB22C2N and REB17CN. Up to now, non-doped B12 icosahedral compounds like boron carbide have all been p-type. The discovery of an n-type compound is extremely important in terms of the potential development of this class of compounds as viable thermoelectric materials. Low thermal conductivities of κ < 0.03 W/cm/K at room temperature was observed for these rare earth boron cluster compounds. In comparison among the homologous series in which there are rare earth and B6 octahedra layers separated by an increasing number of B12 icosahedra layers, we observe that the thermal conductivity actually increases as the number of boron cluster layers increases. We find that the rare earth B12 icosahedral cluster compounds in which RE atoms occupy voids among the clusters generally appear to have lower thermal conductivity than boron cluster compounds which do not contain RE atoms.

Quantum-dot superlattices (QDSLs) have demonstrated thermoelectric figure of merit (ZT) values double those of classical bulk materials, providing the proof that nanoscale materials can address this age-old limitation on thermoelectric technology. Since QDSL materials can only be obtained in thin-film form, the development of bulk materials with nanoscale inclusions would be useful for many large-scale applications. Nanometer-scale inclusions in lead chalcogenides are known to improve the thermoelectric figure of merit through a combination of two factors: a strong decrease in lattice thermal conductivity, and an increase in the Seebeck coefficient over that of bulk PbTe for a given carrier concentration. This paper focuses on experimental results obtained on two types of PbTe nanocomposites, namely samples prepared by sintering powders with nanometer-sized grains, and samples prepared with nanoprecipitates of metallic Pb. The results are analyzed using the “method of four coefficients.” At each measurement temperature there are four unknowns. These are the carrier concentration, the mobility, the carrier effective mass, and the energy dependence of the relaxation time Tau, which is modeled by a power law: Tau proportional to energy to power Lamda. Therefore, at each temperature, four measurements are taken: the electrical conductivity, and the Hall, Seebeck and transverse Nernst-Ettingshausen coefficients. This analysis concludes that the effect of the nanoscale inclusions on the power factor is due to an increase in the scattering parameter λ, and that the nanoscale inclusions affect the electron scattering in such a way as to increase the Seebeck coefficient.

We report the preparation of grain-aligned [Ca2CoO3−δ]0.62CoO2 (Ca349) thick films and the conversion of the easy axis of magnetization from the a-axis to the c-axis. The thick films were fabricated by a simultaneous usage of electrophoretic deposition and magnetic alignment methods (MEPD) at high deposition rate with the order of 10 mm/min. Moreover, a multi-layered thick film of Al2O3/Ca349/Al2O3/Ca0.9La0.1MnO3/Al2O3 was also fabricated by the MEPD method by the optimization of condition of each suspension. The conversion of the easy axis was performed crystallochemically for a [Bi2Sr2O4]0.55CoO2 (BiSr222) compound with the easy axis parallel to the a-axis in order to fabricate c-axis grain-oriented bulks by the magnetic alignment method. The substitution of Ca for Sr in the [(Bi0.5Pb0.5)2Sr2O4] block layer induced the change of the easy axis into the c-axis direction, and the magnetic anisotropy was increased by the partial substitution of rare earth elements of Pr, Nd, Tb and Dy for Ca. Using a compound of [(Bi0.5Pb0.5)2(Ca0.8Pr0.2)2O4]0.55CoO2, we have successfully prepared the c-axis grain-aligned bulk by the magneto-scientific method. Our present results indicate that the magneto-scientific method is one of the useful and realistic processes for production of thermoelectric modules.

Ishikawajima–Harima Heavy Industries Co., Ltd. (IHI) is currently investigating applications of thermoelectric conversion systems based on the usage of radiant heat for industrial furnaces. The thermoelectric module units, which have been connected to a water-cooled jacket wall inside an electric resistance-heating-type industrial furnace, receive the heat originating from the in-furnace heat insulator by means of radiation, and collect the electric power based on the temperature difference. In this work, experimental results are presented, concerning the mechanical characteristics of a two-step cascade connection type module based on the heat transmission and thermoelectric conversion characteristic.

The module performance analytic result, which turned character of several physical properties of the thermal radiation receiver of the upper part of modules, heat transmission characteristic, and the result, which performed the foundation examination for industrial furnace application, is reported.

The synthesis of a number of (Bi2Te3)x(HfTe2)y superlattices was accomplished using the modulated elemental reactants (MER) method. The samples were characterized using X-ray reflectivity and X-ray diffraction in the as deposited (amorphous) state and as a function of annealing temperature and time.

The recent material research of mixed cobalt oxides is strongly motivated by the potential of some of them to be used as chemically stable high temperature thermoelectric material. This fact together with both the theoretical and experimental ambitions to fulfill the severe criteria needed for efficient thermoelectric conversion intensified both their theoretical and experimental research. Nonetheless, despite the investigations of the prototype materials represented by 3D perovskites Ln1−xAxCoO3 (Ln = La, Y, rare-earth, A = alkaline-earth) and 2D cobaltites of NaxCoO2 type, the concise physical background of their transport and magnetic properties remain still a matter of debate. This is likely due to a fact that cobalt ions can be stabilized either in low-spin state (diamagnetic for “pure” Co3+), with filled t2g levels and empty eg states, or magnetic ones, with filled eg states. As the energy difference between respective states is due to comparable strength of crystal field and Hund's energies rather small, the thermodynamically most stable ground-state, with eventually different character of charge carriers, can be critically influenced by an interplay of additional degrees of freedom - orbital and charge. The challenge for unequivocal theoretical model represents the thermoelectric power of mixed cobaltites where, up to now, somewhat ambiguous models based either on “classical” approach, associated with diffusion of itinerant charge carriers, or more exotic - based on configurational entropy of quasi-itinerant carriers - are often used for similar materials. Simultaneously, the open question remains the assessment of the dominant mechanism of phonon scattering in 2D cobaltites.

High efficiency thermoelectric modules are of great interest for power generation applications where hot side temperatures of approximately 800K exist. The fabrication of such modules requires a multidisciplinary effort for the optimization of the material compositions, the engineering of the module systems, modeling and fabrication of the devices, and constant feedback from characterization. Pb-Sb-Ag-Te (LAST) and Pb-Sb-Ag-Sn-Te (LASTT) compounds are among the best known materials for this temperature range. Modeling of these materials and possible cascaded structures shows efficiencies of 14% can be achieved for low resistance contacts. Using antimony we have achieved contact resistivities less than 20 µΩ·cm2. Here we give a detailed presentation on the procedures used in the fabrication of thermoelectric generators based on these new materials. We also present the characterization systems and measurements on these generators.

The structural and thermoelectric properties of the AgSbTe2-SnTe quaternary system were studied. Powder averaged x-ray diffraction of Ag0.85SnSb1.15Te3 indicates a cubic NaCl-type structure in contrast with the single crystal refinements, which point towards tetragonal symmetry. Furthermore, high-resolution electron microscopy imaging revealed the system to be a nano-composite formed by thermodynamically driven compositional fluctuations rather than a solid solution as it was viewed in the past. The lattice thermal conductivity attains very low values, which is in accord with recent theories on thermal transport in heterogeneous systems. The charge transport properties of the system exhibit a rich physical behavior highlighted in the coexistence of an almost metallic carrier concentration (∼5×1021 cm−3) with a large thermoelectric power response of ∼160 μV/K at 650 K. This is attributed to a heavy hole effective mass that is almost six times that of the electron rest mass.

Measurements of assembled thermoelectric modules commonly include investigations of the module output power versus load resistance. Such measurements include non-ideal effects such as electrical and thermal contact resistances. Using an AC electrical measurement, two models for a thermoelectric module have been developed utilizing electrical circuits for both the thermal and electrical characteristics of the module.

Measurements were taken over the frequency range of 1mHz to 500Hz using lock-in amplifiers. We present data showing the extraction of ZT from such measurements on commercially available modules utilizing both the magnitude and phase of the measured impedance. Here we extend upon a simple RC equivalent circuit model by utilizing transmission line theory in electrical circuits to explain the thermal activity in a thermoelectric module. This model includes all components of a module such as nickel traces and ceramic end caps, and makes use of their corresponding thermal conductivities, thermal capacitance, and density. This model can then be applied to pn unicouples in either a standard or inline configuration, and to individual p or n legs of the module. Data is presented showing the advantages of both models. Measurements on new thermoelectric materials and modules are also presented.

The otherorhombic distorted perovskite La1−xSrxRuO3 (0.1<x<0.9) polycrystalline samples have been prepared using conventional solid state chemistry reaction. The phase constituent, compositional homogeneity and micro-morphology were checked by X-ray powder diffraction, Energy Disperse X-ray spectroscopy and scanning electron microscopy before characterized by means of the electrical resistivity, thermal conductivity and thermal power measurements. Particularly, the compositional dependence of Seebeck coefficient of present compound was studied in light of the comparison with the strongly correlated system NaxCoO4 and the relevant model proposed by W. Koshibae. Finally, the potential of using La1−xSrxRuO3 as a practical thermoelectric material has been also discussed.

Multicrystalline Mg2Si crystals were grown using a Brigdman method combined with a die-casting growth technique. Although molten and/or vapor-phase Mg at elevated growth temperatures exhibit high chemical reactivity with the surrounding crucible materials, the use of an alumina crucible with a BN coating allowed single phase crystal growth and Mg2Si of good crystalline quality. Incorporation of carbon into the Mg2Si was observed to form Mg2Si1−xCx. For x=0.01 and 0.03, a lower thermal conductivity and higher figure of merit than those of Mg2Si were observed in the temperature range from room temperature to 773 K. The maximum figure of merit was 0.62 at 773 K for a Mg2Si0.99C0.01 sample.

CeOs4Sb12 is a very interesting material due to the diversity of physical properties which could be dedicated to industrial applications. With this goal in mind, electronic structural calculations were performed in order to provide information regarding its properties. The energy bands yielded information regarding its semiconductor behavior as well as a mini gap of the order of 0.45 eV between the valence and conduction bands. Moreover, total and projected density of states yielded information of a possible hybridization between Ce f-, Os d- and p-, with Sb p-orbitals. Hence, this compound could be considered a likely candidate as a thermoelectic material

Bulk bismuth telluride (Bi2Te3) is one of the best known thermoelectric materials with a figure of merit ZT ∼1 at room temperature. Theoretical studies have suggested that low-dimensional materials may exhibit ZT values that exceed 1. In this study, we used the pulsed laser vaporization (PLV) method to prepare Bi2Te3 nanowires on silicon and quartz substrates by ablating Bi2Te3 targets in an inert atmosphere. Nano-sized gold or iron catalyst particles were used to seed the growth of the Bi2Te3 nanowires. Results from electron microscopy and Raman spectroscopy are discussed.

Solid solutions of K2Bi8−XSbXSe13 is an interesting series of complex bismuth-chalcogenide compounds, which are attractive for thermoelectric investigations. The highly anisotropic structure in these compounds results in needle-like morphology along the b- crystallographic axis, leaving structural tunnels where K+ ions reside. The complex electronic structure that arises from a large and low symmetry unit cell and the weakly bound K+ ions, lead to high Seebeck coefficient, highly anisotropic electrical properties and very low thermal conductivity.

Reflectivity spectra in the FIR region are presented for several members in the Sb-rich (x≥6) side. Optical investigations are carried out on crystalline and pelletized samples. The received spectra are analyzed, examined comparatively and discussed. Results indicate that upon Bi/Sb substitution in the Sb-rich region, phonons develop a mixed-mode behavior in the FIR spectral region.