PbTe-PbS materials are promising for thermoelectric power generation applications. For the composition of (Pb0.95Sn0.05Te)0.92(PbS)0.08 nanostructuring from nucleation and growth and spinodal decomposition has been reported along with thermal conductivity of approximately 1.1 W/m·K at 650 K [1]. Based on temperature-dependent measurements of electrical conductivity, thermopower, and thermal conductivity, the thermoelectric figure of merit, ZT, are ~1.5 at 650 K for cast ingots.

To develop larger quantities of material for device fabrication, advancement in the synthesis, processing and production of (Pb0.95Sn0.05Te)0.92(PbS)0.08 is necessary. Powder processing of samples is a well-known technique for increasing sample strength, and uniformity. In this presentation, we show sample fabrication and processing details of pulsed electric current sintering (PECS) processed (Pb0.95Sn0.05Te)0.92(PbS)0.08 materials and their thermoelectric properties along with the latest advancements in the preparation of these materials.

The synthesis and properties characterization of several PbS1-xTexx = 0-0.16 samples are presented. Notably it is shown how a local minimum occurs in the thermal diffusivity for the PbS1-xTex samples at x ≈ 0.03. The thermoelectric properties of doped PbS1-xTex with x = 0.03 are reported and the properties are compared to the pure PbS and PbTe end members. The electronic contribution to the total thermal conductivity is analyzed for PbS1-xTexx = 0.03 and it is shown how the lattice thermal conductivity is significantly lowered compared to single crystalline PbS.

We explored the effect of K and K-Na substitution for Pb atoms in the lattice of PbTe, in an effort to test a hypothesis for the development of a resonant state that may enhance the thermoelectric power. At 300K the data can adequately be explained by a combination of a single and two-band model for the valence band of PbTe depending on hole density that varies in the range 1-15 × 1019 cm-3. A change in scattering mechanism was observed in the temperature dependence of the electrical conductivity, σ, for samples concurrently doped with K and Na which results in significantly enhanced σ at elevated temperatures and hence power factors. Thermal conductivity data provide evidence of a strong interaction between the light- and the heavy-hole valence bands at least up to 500K. Figure of merits as high as 1.3 at 700K were measured as a result of the enhanced power factors.

For the material (Pb0.95Sn0.05Te)1-x(PbS)x nanostructuring from nucleation and growth and spinodal decomposition were reported to enhance the thermoelectric figure of merit over bulk PbTe, producing ZT of 1.1 - 1.4 at 650 K for x = 0.08[1]. Thermoelectric modules made from (Pb0.95Sn0.05Te)1-x(PbS)x materials with various hot-side metal electrodes were fabricated and tested. Short circuit current was measured on unicouples of Pb0.95Sn0.05Te – PbS 8% (n-type) legs and Ag0.9Pb9Sn9Sb0.6Te20 (p-type) legs over 10 (A) for a hot side temperature of 870K, and a cold side of 300K. Hot pressed (Pb0.95Sn0.05Te)1-x(PbS)x materials were also investigated for module fabrication. Investigations of the electrical properties of hot-pressed (Pb0.95Sn0.05Te)1-x(PbS)x materials are presented along with the latest advancements in the fabrication and characteristics of modules based on the processing of these materials.

We present the synthesis, crystal structure, spectroscopic properties, and electronic structure of a new member of the Zintl family, Yb5Al2Sb6. The compound crystallizes in the Ba5Al2Bi6 structure type. A preliminary assessment of its thermoelectric properties including electrical conductivity, thermopower, and thermal conductivity are reported. Moreover, investigations of solid solutions of this phase, doping effects and chemical modifications will be presented. The room temperature conductivity, thermopower and thermal conductivity of Yb5Al2Sb6/0.5Ge were 1100 S/cm, 20 μV/K, and 3.8 W/m.K, respectively.

Thermoelectric modules are of great interest for power generation applications where temperature gradients of approximately 500K exist, and hot side temperatures near 800K. The fabrication of such modules requires optimization of the material compositions, low contact resistivities, and low thermal loss.

AgPbmSbTe2+m (LAST) and Ag(Pb1-xSnx)m SbTe2+m (LASTT) compounds are among the best known materials appropriate for this temperature range. Various measurement systems have been developed and used to characterize bulk samples in the LAST and LASTT systems within this operating temperature range. From the characterized data, modeling of modules based on these materials and segmented legs using LAST(T) with Bi2Te3 have been used to identify the optimal geometry for the individual legs, and the length of the Bi2Te3 segments. We have segmented LAST(T) with Bi2Te3 and achieved contact resistivities of less than 10 μΩ•cm2.

Here we give a detailed presentation on the procedures used in the fabrication of thermoelectric generators based on LAST, LASTT, and segmented with Bi2Te3 materials. We also present the output data on these generators.

Solid solutions of β-K2Bi8-xSbxSe13 are an interesting series of materials for thermoelectric investigations due to their very low thermal conductivity and highly anisotropic electrical properties. In this work, we aimed to synthesize solid solutions of β-K2Bi8-xSbxSe13 type materials using powder techniques. The synthesis was based on mechanical alloying as well as sintering procedures. The products were studied in terms of structural features, composition and purity with powder x-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Preliminary results on thermoelectric properties as well as IR reflectivity measurements are presented.

Low electrical contact resistance is essential for the fabrication of high efficiency thermoelectric generators in order to convert heat to electricity. These contacts must be stable to high temperatures and through thermal cycling. A ratio of the contact resistance to the leg resistance below 0.1 is the goal for fabrication of a high efficiency thermoelectric power generation device. Here we present the fabrication procedures and characterization of contacts of metal alloys to Pb-Sb-Ag-Te (LAST) and Pb-Sb-Ag-Sn-Te (LASTT) compounds. Contacts were fabricated and measured for both ingot and hot pressed materials. Stainless steel 316 has shown a low resistance contact to these thermoelectric materials when the proper bonding conditions are used. Different time-temperature-pressure conditions for bonding to n-type and to p-type legs are presented. Contact resistances below 10μΩcm2 have been measured. In addition, break tests have shown bond strengths exceeding the semiconductor fracture strength. One of the considerations used in selecting iron alloys for electrical interconnects is the similarity in the coefficient of thermal expansion to the LAST and LASTT materials which is 18 ppm/°C and relatively temperature insensitive. Contacts to the thermoelectric materials were accomplished by diffusion bonding in a furnace developed in our lab at Michigan State University. The furnace is capable of reaching temperatures of up to 1000°C with a controlled atmosphere of a reducing gas. Fabrication procedures and contact data are presented in this paper.

Investigation of a family of bulk cubic compounds with general formula AgPbmMS2+m (M = Sb, Bi) is reported. These PbS-based cubic structured quaternary systems combine a set of desirable features for efficient ZT thermoelectric materials for solar thermal power generation. AgPbmMS2+m (M = Sb, Bi) possess an average NaCl structure (Fm-3m symmetry), high melting point (991 - 1095 °C for M = Sb; 865 - 1091 °C for M = Bi), relatively wide energy gap (0.7 > Eg (eV) > 0.39 for both Sb and Bi). The systematic variation of lattice parameters, energy gap and melting point is reported. Preliminary charge transport properties are reported along with variable temperature thermal conductivity data of selected members.

Low electrical contact resistance is essential for the fabrication of high efficiency thermoelectric generators. These contacts must be stable to high temperatures and through thermal cycling. Here we present the fabrication procedure and characterization of several contacts to Pb-Sb-Ag-Te (LAST) compounds. Contact materials investigated include tungsten, antimony, tin, nickel, and bismuth antimony based solder. The contacts were typically deposited by an electron beam evaporation method after careful preparation of the sample surface. The resistances were measured by using the transmission line model, and ohmic behavior was verified through current vs. voltage measurements. The best contact resistivities of less than 20 µΩ·cm2 have been measured for annealed antimony to n-type LAST samples. We present these procedures for fabricating low resistance contacts and the use of these procedures towards the fabrication of high efficiency thermoelectric generator modules.

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.

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.

New thermoelectric bulk materials such as CsBi4Te6 have shown superior properties to traditional materials, however, optimal performance requires continuing investigations of doping and alloying trends. A recently modified high throughput measurement system is presented for doping and alloying investigations in several new thermoelectric materials. The modification includes a four-probe configuration for more accurate measurements while maintaining a relatively short sample preparation time. The system is fully computer controlled and provides flexible contacts to accommodate various sample dimensions. Optimal compositions are then identified for further investigations in thermoelectric prototype modules. The most promising materials will be further characterized for electrical conductivity, thermoelectric power, thermal conductivity, and Hall effect measurements as a function of temperature.

By introducing of various equivalents of PbTe into the layered framework of CsBi4Te6, the four new compounds CsPbBi3Te6 (1), CsPb2Bi3Te7 (2), CsPb3Bi3Te8 (3) and CsPb4Bi3Te9 (4), were discovered. The compounds adopt layered structures built up of anionic slabs of progressively increasing thickness. The [PbmBi3Te5+m]- (m = 1, 2, 3, 4) slabs in the four structures can be viewed as fragments excised from the PbTe-type structures with 4-, 5-, 6- and 7-monolayers, respectively. As prepared, these materials are off-stoichiometric and n-type conductors. We present preliminary results of the crystal structures and thermoelectric properties of these materials and classify them as members of the new homologous series CsPbmBi3Te5+m (m = 1 to 4).

The possibility of a prototype thermoelectric cooling device for operation near liquid nitrogen temperatures has been explored. In these devices, the figure of merit involves a combination of the properties of the two branches of the module. Here, we investigate the fabrication of a module with a new low temperature material, CsBi4Te6 (p-type), and the best known low temperature n-type materials Bi85Sb15. Transport measurements for each of these materials show high performance at low temperatures. Known values for the figure of merit Zmax of CsBi4Te6 is 3.5 × 10−3 K−1 at 225K and for Bi85Sb15 is 6.5 × 10−3 K−1 at 77K. At 100K these values drop to 2.0×10−3 K−1 for CsBi4Te6 and 6.0×10−3 K−1 for Bi85Sb15. Theoretical simulations based on these data show a cooling of δT = 12K at 100K, which is almost three times the efficiency of a Bi2Te3 module at that temperature. We present transport measurements of elements used in the fabrication of a low temperature thermoelectric module and properties of the resulting module.

Our efforts to improve the thermoelectric properties of β-K2Bi8Se13, led to systematic studies of solid solutions of the type β-K2Bi8−xSbxSe13. The charge transport properties and thermal conductivities were studied for selected members of the series. Lattice thermal conductivity decreases due to the mass fluctuation generated in the lattice by the mixed occupation of Sb and Bi atoms. Se excess as a dopant was found to increase the figure-of merit of the solid solutions.

We have previously reported the successful p-type doping of CsBi4Te6 which had a high figure of merit at temperatures below 300 K. In this study, several dopants were explored to make n-type CsBi4Te6. A program of measurements was performed to identify the optimum doping concentration for several series of dopants. The highest power factors occurred around 125 K for the 0.5% Sn doped CsBi4Te6 sample which had a power factor of 21.9 μW/cm•K2 and 1.0% Te doped CsBi4Te6 which had a power factor of 21.7 μW/cm•K2.

Our exploratory research in new thermoelectric materials has identified the ternary and quaternary bismuth chalcogenides β-K2Bi8Se13, K2.5Bi8.5Se14 and K1+xPb4-2xBi7+xSe15, to have promising properties for thermoelectric applications. These materials have needlelike morphology so they are highly anisotropic in their electrical and thermal properties. In order to achieve long and well-oriented needles for which, consequently, the best thermoelectric performance is expected, we developed a modified Bridgman technique for their bulk crystal growth. The preliminary results of our crystal growth experiments as well as electrical conductivity, Seebeck coefficient and thermal conductivity for the compounds obtained from this technique are presented.

Based on the versatile combination of PbQ- and Bi2Q3-type (Q = S, Se, Te) fragments, we explored new compounds in the Pb/Bi/Se ternary system. The new class of compounds, Pb5Bi6Se14, Pb5Pb12Se23, and PbBi8Se13 are homologues with different combination of alternating Bi2Se3- and PbSe-type layers. α- and β-Pb6Bi2Se9 were obtained in different synthetic conditions and the former is isostructural to heyrovskyite (Pb6Bi2S9) while the latter is a NaCl-type cubic phase. Pb5Bi6Se14 shows a power factor of 11.2 μW/cm·K2 with electrical conductivity of 657 S/cm and thermopower of -131 μV/K at 271 K. The most significant characteristic of this material is the extremely low thermal conductivity of less than 1.0 W/m·K at room temperature. On the basis of these properties, a preliminary doping study for Pb5Bi6Se14 with Sn, Sb, and SbBr3 as dopants was undertaken and the results are presented in this report.