The crystal structure and thermoelectric properties of Type-I clathrate compounds in the Ba-Ge-Ga system (Ba8GaXGe46-X) have been investigated as a function of Ga content. While all ternary compounds containing more than 3 Ga exhibit a crystal structure of normal Type-I clathrates with the space group Pm 3 n, the binary compound possesses a composition Ba8Ge43, which is leaner in Ge than the stoichiometric composition, and has a crystal structure different from that of normal Type-I clathrates because of the ordering of Ge vacancies in 6c sites of the parent normal Type-I clathrate structure. The temperature dependence of electrical resistivity of binary Ba8Ge43 is of semiconductor while that for all the ternary compounds is metallic. The value of Seebeck coefficient increases with the increase in the Ga content. The value of dimensionless figure of merit (ZT) increases with the increase in the Ga content, exhibiting a high value of 0.76 at 700°C for Ba8Ga16Ge30.

Thermal conductivity and other thermoelectric properties were investigated on β-Zn4Sb3 and CoSb3 thin films. They are prepared by co-deposition of the specific sets of Zn, Sb and Co targets by RF magnetron sputtering. Thermal conductivity measurement was performed based on an AC calorimetry method using LaserPIT. The Zn4Sb3 thin films investigated are Zn-rich with respect to the stoichiometric composition. Their thermal conductivity decrement is proportional to the reciprocal film thickness. A nano-scale grain size in a ∼350 nm-thick film specimen gives arise to an almost 50% reduction in its thermal conductivity (∼0.5W/mK) at room temperature. Low electrical resistivity and high Seebeck coefficient can be achieved simultaneously in the film specimen with properly controlled thickness and microstructure. A ZT of 1.2 at ∼460K has been obtained for the ∼350nm thick Zn4Sb3 film specimen. The minimum thermal conductivity of about 1.1 W/mK was obtained in a ∼325 nm-thick CoSb3 film specimen at room temperature.

Solid solution series of the type K2Bi8-xSbxSe13, K2-xRbxBi8Se13 as well as K2Bi8Se13-xSx were prepared and the distribution of the atoms (Bi/Sb, K/Rb and Se/S) on different crystallographic sites, the band gaps and their thermoelectric properties were studied. The distribution Se/S appears to be more uniform than the distribution of the Sb and Rb atoms in the β-K2Bi8Se13 structure that shows preference in specific sites in the lattice. Band gap is mainly affected by Sb and S substitution. Seebeck coefficient measurements showed n-type character for of all Se/S members. In the Bi/Sb series an enhancement of p-type character was observed. The thermoelectric performance as well as preliminary high temperature measurements suggest the potential of these materials for high temperature applications.

A family of metastable [(Bi2Te3)x(TiTe2)y] superlattices (where × and y denote the number of layers of each of the two components) was prepared by annealing modulated elemental reactant precursors at temperatures below 280°C. Structural analysis by traditional XRD shows the superlattice structures are highly aligned to the substrate with many orders of diffraction peaks from the c direction of the superlattice. Off-axis diffraction techniques presented in this paper suggest that the order between the layers in the a-b direction of these superlattice structures is turbostratic. In this type of behavior, the quasi two-dimensional crystals of Bi2Te3 and TiTe2 that comprise the superlattice structure lie like a deck of cards thrown in disarray on a surface. An analysis of the diffraction data leading to this conclusion is given.

Experiments were carried out to determine the cooling power density of SiGe/Si superlattice microcoolers by integrating thin film metal resistor heaters on the cooling surface. By evaluating the maximum cooling of the device under different heat load conditions, the cooling power density was directly measured. Both micro thermocouple probes and the resistance of thin film heaters were used to get an accurate measurement of temperature on top of the device. Superlattice structures were used to enhance the device performance by reducing the thermal conductivity, and by providing selective emission of hot carriers through thermionic emission. Various device sizes were characterized. The maximum cooling and the cooling power density had different dependences on the micro refrigerator size. Net cooling over 4.1 K below ambient and cooling power density of 598 W/cm2 for 40 × 40 μm2 devices were measured at room temperature.

We have grown single crystals of Bi-substituted Ca3Co4O9 by a solution method. The cationic ratio (Ca, Bi)/Co of the grown crystals measured by an energy dispersive X-ray spectrometer tended to exceed that of the starting ratio (Ca, Bi)/Co=3/4. For instance, the average cationic composition of the grown crystals was Ca:Bi:Co=3.3:0.3:4, while that of the starting material was Ca:Bi:Co=2.7:0.3:4. So, the crystallographic structure of the obtained crystals may correspond to the Ca2Co2O5 phase rather than the Ca3Co4O9 phase. Thermoelectric properties in the direction of ab-axis were measured at various temperatures. Seebeck coefficient (S) of Ca3.3Bi0.3Co4O9+δ is positive and increases with increasing temperature from 130 to 200 μV/K in a temperature region of 300–973 K. The electrical resistivity (ρ) of the sample is about 1.5 mΩcm at whole temperature region of 300–973 K. This value is lower than that of non-substituted Ca3Co4O9. The thermoelectric power factor (S2/ρ) is improved by the Bi-substitution, resulting from the reduction of resistivity.

PbTe-based thin films were deposited by thermal evaporation at temperatures ranging from ambient temperature to 430°C on different vicinal GaAs (100) substrates and BaF2 (111). This materials system is being evaluated as a potential candidate thermoelectric material for a mid-temperature stage in a cascade power generation module. Pure PbTe, PbSe, and multilayer PbTe/PbSe films were investigated. All films deposited on different vicinal GaAs (100) substrates were found to be polycrystalline when deposited at 250°C or lower. A subtle effect of substrate orientation and multilayer periodicity appears to contribute to the more randomly oriented polycrystallinity, which also lowers the thermal conductivity. These results are compared with PbTe epitaxial results on BaF2 (111).

Towards fabricating a thermoelectric power device using III-nitrides and III-oxynitrides, we studied their thermal and thermoelectric properties and, in particular, we have focused on their thermal conductivity. AInN and AlInON were prepared by reactive radio-frequency sputtering method. We measured the thermal diffusivity and specific heat using the ac calorimetric method, and we estimated values of the thermal conductivity to be 2.2 W/mK (at 773 K) for AlInN and 3.3 W/mK (at 673 K) for AlInON. These values are much smaller than expected considering the large thermal conductivity of nitrides. As for a device composed of 20-pair Chromel-AlInN films, the maximum output power was 0.36 μW at the temperature difference of 180 K, and the open voltage was 0.10 V.

Low dimensionality provides opportunities to modify the properties of bulk materials dramatically and to control materials properties independently in a manner that is not possible for bulk materials. The special characteristics of low dimensional materials to enhance thermoelectric performance have already been demonstrated in quantum wells, quantum wires and quantum dots. The main focus of this review is a summary of advances made in the modeling of quantum dot superlattice nanowires. Several new research directions for low dimensional thermoelectricity or inspired by this research are briefly mentioned.

We present here a simplified approach to the synthesis of bismuth sulfide and bismuth telluride nanorods and their polyaniline(PAN)-coated nanocomposites. The present method gives highly crystalline nanorods of bismuth sulfide of varying aspect ratio depending on the capping ligand employed, and involves reacting bismuth(III) trioleate with thioacetamide in phenyl ether at elevated temperatures in the presence of excess capping ligand. Bismuth telluride was obtained in high yields by reacting bismuth(III) trioleate with trioctylphosphine telluride at relatively low temperature. Oleic acid, sodium dodecylsulfonate and sodium dodecylbenzene sulfonate, used as capping ligands, did not have significant effect on the aspect ratio of Bi2Te3 nanorods. The nanostructured materials obtained this way were then coated with polyaniline (PAN) by heating a specific amount of material with half as much PAN in toluene close to reflux temperature for 6–8 h. It was necessary to keep the mixture thoroughly stirred and intermittently sonicated in order to ensure that the particles remain dispersed at all times. Bismuth chalcogenide nanoparticles as well as their composites were characterized using transmission electron microscopy and X-ray powder diffraction.

Recent interest in thermoelectric materials for power generation applications has initiated the development of a measurement system in our laboratory for characterization of materials in the 80K to 800K temperature range. This system has been specifically designed for measuring thermoelectric power and electrical conductivity as needed for determining the power factor of the measured samples. This is a single sample measurement system based on a continuous flow cryostat. Significant effort has gone into the computer controlled data acquisition and PID controlled temperature stabilization. Investigation of the influence of temperature stability on the measured data will be presented along with important aspects of the system design, development, and testing. Data collected on reference materials and new thermoelectric materials of interest will be presented.

Crystallographic features of Rhenium disilicide have been examined by powder and single-crystal X-ray diffractometry with a synchrotron radiation. The chemical composition of the compound is determined as Re4Si7 (ReSi2-x, x = 0.25) from lattice constants and specific density determined. The structure is defined as a vacancy ordered structure with the space group of Cm. The positions of the constituent atoms in the structure have been refined. The positions of silicon atoms apparently shift from the ideal positions of the C11b structure which is the structure without containing structural vacancies.

A novel computational scheme has been used to predict the electric potentials generated by arbitrary temperature gradients in semiconductor materials. Written in object-oriented code, the Discrete State Simulation (DSS) is a coupled cellular automata simulator that builds upon the objects and rules of quantum mechanics. The DSS represents global non-equilibrium processes as patterns that emerge through an ensemble of scattering events that are localized at vibronic nodes. By tracking the energy-momentum-position coordinates of the individual particles that define the vibronic state at a node, the DSS undercuts equilibrium concepts such as temperature. Consequently, the DSS can represent physical systems that are described by more than one temperature or that contain physical features that defy definitions of temperature. Using modified bootstrap sampling algorithms, the DSS depicted (1) shifts in distribution functions induced by external fields and temperature gradients, (2) field-dependent transitions from linear mobility to non-linear mobility, (3) saturation velocities, (4) non-exponential decay functions generated by multiple phonon scattering modes, and (5) charge separations and electric potentials generated by temperature gradients. Ensemble averages were sensitive to the structure of dispersion relations, to the energy of the system, and to quantum coupling strengths. Seebeck coefficients were sensitive to the features of the electronic and the vibrational band structures, and their associated coupling coefficients.

We report the electrical resistivity and the Seebeck coefficient of AZn13 (A = Sr, Ba, and La) and LaCo13 measured over a wide temperature range and their thermal conductivity measured at room temperature. The electrical measurements of AZn13 and LaCo13 above room temperature reveal that the compounds show good metallic behavior. We find that the absolute value of Seebeck coefficient for AZn13 (A = Sr, Ba, and La) increases with increasing temperature, which is a typical metallic behavior and the absolute value is less than 3μVK−1 at room temperature. Accordingly, the power factor of AZn13 is quite low. Temperature dependence of the Seebeck coefficient for LaCo13 is similar to that of Co. The absolute value of the Seebeck coefficient for LaCo13 is high as a metallic conductor and approaches -30μVK−1 at 500K, which leads LaCo13 to large power factor of 1.8 × 10−3Wm−1K−2. We obtained lattice components of the thermal conductivity by subtracting electronic contributions from the total thermal conductivity. The electronic components of the thermal conductivity were estimated using Wiedemann-Frantz law assuming L (Lorentz number) is 2.45 × 10−8 V2K−2. The thermal conductivities of the lattice components for AZn13 (A = Sr, Ba, and La) and LaCo13 with NaZn13 type structure are about 10 Wm−1K−1, respectively. These values are high as compared with other thermoelectric materials.

Mo3Sb7 may be chemically modified to become semiconducting by replacing two Sb atoms with two Te atoms (per formula unit). This material may be an attractive candidate for the thermoelectric energy conversion, as its thermal conductivity may be lowered by creating the rattling effect upon intercalation of small cations, and its band structure may be tailored, i.e. the band gap size modified. The higher the Te content and the higher the cation amount, the smaller is the band gap, which can virtually reach any value below 0.5 eV.

The transport properties of the partially filled CaxCo4-yNiySb12 skutterudite compounds have been investigated in the 300 – 800 K temperature range. We underline the positive influence of the Ni substitution on the electrical resistivity and thermopower while the thermal properties – thermal conductivity – remains almost unaffected. These results suggest again a beneficial effect of Ni atoms on the dimensionless figure of merit in CoSb3 based compounds.

[Abstract] Bi2Te 3 nanoparticles of 15∼25nm were prepared via solvothermal processes in which pyridine, absolute ethanol and distilled water were used as reaction medium respectively. The XRD and TEM have been applied to analyze the samples, and the grain sizes have also been calculated by Scherrer Equation. The results showed that in these experiments, all of the reaction products' purity, crystallization, grain size and tropism increased with dielectric constant and polarity of the solvent. A novel Bi2Te3 nanowires with several tens to a hundred nanometers diameter and up to more than ten microns length have been prepared when distilled water was used as reaction medium.

CsBi4Te6 (ZT ∼ 0.8 at 225 K) shows highly anisotropic features in its crystal morphology and structure as expressed by the parallel infinite [Bi4Te6] rods which are linked via Bi-Bi bonds. Band calculations also point to a significant anisotropy in the carrier effective masses, and for this reason we examined the anisotropic thermoelectric properties of CsBi4Te6. The electrical conductivity, thermopower and thermal conductivity were measured along the three different crystallographic directions of the monoclinic structure of CsBi4Te6. These measurements were performed on samples with different degrees of doping. The strong charge transport anisotropy of these samples was confirmed and also observed that the thermopower values along the c-axis direction (which is perpendicular to the layer of Cs atoms) was negative (-80 μV/K) while those along the needle direction (b-axis) and parallel to the [Bi4Te6] layers (a-axis) were p-type (50–100 μV/K at room temperature. Other anisotropic features in the crystal growth habit, electronic band structure, and electrical and thermal conductivities are also presented.

We study Raman phonon vibrations and relate them to thermal conductivity for empty and filled skutterudites designed for thermoelectric applications, where low thermal conduction is critical. Polarized Raman scattering spectra of crystallite and polycrystalline samples are compared with theoretical predictions and analyzed in comparison to the thermal conduction properties. Our emphasis is on the CoSb3 skutterudite and its filled derivatives, including materials with Ge, Sn, and La in the cages. We observe a strong correlation between aspects of the Raman spectrum and low thermal conductivity. This presents Raman spectroscopy as a characteristic screening tool for potential thermoelectrics and is a crucial step toward predicting lattice thermal conductivities.

We report the synthesis and thermoelectric properties of high valence metal-doped [Ca2Co1-xMxO3-δ]0.62CoO2 (M = Re, Mo or Nb) compounds. Approximately 10% M-doping for Co sites in block layer was found to be effective for dramatic suppression of oxygen nonstoichiometries. Seebeck coefficients were systematically enhanced with M-doping levels (x), and however, electrical resistivities also increased with x for conventionally sintered bulk samples. On the other hand, magnetic alignment and/or densification were remarkably effective for reduction of the resistivity. In the case of Mo-doped (x = 0.1) sample, a highly c-axis aligned and densified sample showed 1–3 times larger power factor at 1100K (5.3 μ WK−2cm−1) than the non-doped one. Moreover, these high valence metal doped Ca349 compounds exhibited the oxygen nonstoichiometry suppressed dramatically.