As a narrow gap, strongly correlated electron semiconductor, FeSb2 single crystals can exhibit a colossal thermopower1 (on the order of −40,000 μV/K or greater) and a relatively high lattice thermal conductivity2 (over 300 W/m-K) at temperatures around 10 K. In this work, a series of FeSb2 polycrystalline samples with different amounts of additional Indium were prepared by a quench-and-anneal method followed by a spark plasma sintering procedure. The x-ray diffraction, scanning electron microscopy, and elemental analysis verified that the Sb/InSb nanoinclusions were formed in situ on the boundaries of coarse FeSb2 grains. The presence of such nanoinclusions and other as-formed multiscale microstructures can scatter phonons and thus dramatically reduce the corresponding lattice thermal conductivity. Furthermore, the electrical properties can be also improved because of the addition of high mobility carriers from the InSb nanoinclusions. Overall, FeSb2-based materials have shown some promising potential for possible thermoelectric cooling applications at cryogenic temperatures.

Phase structures of microscale and nanoscale higher manganese silicides (HMSs) were investigated using in situ energy dispersive x-ray diffraction at high temperatures or/and high pressure. A few phase transformations accompanied with the presence of MnSi phase were observed in different temperature regions, which were associated with the interevolution of several incommensurate HMS phases. It was found that in nanostructured HMS, the interevolution of HMS was remarkable and accelerated compared to that in the micropowders. Meanwhile, high pressure was able to influence these phase transformations due to giant strain in the materials. The phase transformations were discussed from thermodynamic aspects with respect to the different formation enthalpy of Mn–Si system and the large surface energy and structural instability of the nanopowders.

Nowotny chimney-ladder compounds RuAl2 and RuGa2 have been substituted with p- and n-type dopants to study the resistivity, Seebeck and Hall coefficients, and thermal conductivity of resulting compounds in the temperature range of 80–300 K. The resistivity and Seebeck coefficient suggest that these compounds are degenerate semiconductors. Hall measurements reveal that the carrier concentration has indeed been changed by an order of magnitude, particularly in p-type RuGa2 by substituting Cr and Mn. Compared to p-type samples, the resistivity is an order of magnitude larger for n-type samples, for a similar level of carrier concentration. Interestingly, the hole mobility is two to three orders of magnitude larger, reaching the highest value of ∼750 cm2/V·s. The electron mobility is temperature independent and is typically in the range of ∼1–4 cm2/V·s. Thermal conductivity shows characteristics of mixed scattering with impurity scattering contributing appreciably in heavily substituted compositions.

The Y-doped (Hf0.6Zr0.4)1-xYxNiSn (x = 0, 0.01, 0.02, 0.04, 0.06, 0.1, and 0.2) half-Heusler alloys have been prepared by levitation melting and spark plasma sintering. The effect of Y doping on thermoelectric properties of the alloys was investigated in the temperature range of 300–900 K. Y-doped samples had the lower electrical conductivity compared with the parent compound without Y doping. The thermal conductivity had weak dependence on Y doping content. The absolute values of Seebeck coefficient decreased significantly when x < 0.04. The sign of Seebeck coefficient turned from negative to positive at room temperature for x = 0.04 and 0.1, which means that the hole carriers became dominant in these alloys. However, the alloys changed to n-type conduction again at high temperatures. The maximum figure of merit value of about 0.45 was obtained at 780 K for the undoped sample.

Half-Heusler (HH) and especially TiNiSn-based alloys have shown high potential as thermoelectric (TE) materials for power generation applications. The reported transport properties show, however, a significant spread of results, due mainly to the difficulty in fabricating single-phase HH samples in these multicomponent and multiphased systems. In particular, little attention has been paid to the influence of the various minority phases on the TE performance of these compounds. A clear understanding of these issues is mandatory for the design of improved and stable TE HH-based composites. This study examines the structural and compositional influence of the residual metallic (Sn) and intermetallic phases (mainly Ti6Sn5 and the Heusler compound TiNi2Sn) on the TE properties of the TiNiSn HH compounds processed by spark plasma sintering.

The extremely low thermal conductivity (κ) coupled with suitable Seebeck (S) and electrical conductivity (σ) values makes β-Zn4Sb3 a promising candidate for intermediate temperature (200–400 °C) thermogenerator applications. However, the poor thermal stability makes it difficult to reproduce the high thermoelectric figure of merit originally reported for this material.1 Using a combination of surface scanning techniques (Potential Seebeck microprobe, electron backscatter diffraction, and x-ray diffraction), we investigate specimens of β-Zn4Sb3 prepared under different synthesis conditions. Our results indicate the presence of multiple phases of Zn4Sb3 with distinct room temperature S values ranging from 70 to 140 μV/K. Though crystallographically similar, these phases have very different lattice contribution to the thermal conductivity (κL), which vary between 0.45 and 1.0 W/mK and might predominantly reflect the degree of Zn disorder among the different phases.

Within the framework of a new optimization strategy based on self-compatible thermoelectric elements, the ability to reach maximum performance is discussed. For the efficiency of a thermogenerator and the coefficient of performance of a Peltier cooler, the constraint z T = ko = const. turned out to provide a suitable criterion for judging maximum performance. In this paper ko is calculated as an average of the temperature dependent figure of merit z T.

In this article, we report the use of a microwave plasma in a microwave plasma–assisted spray (MPAS) technique to grow crystalline nanoparticles of the oxide thermoelectric material Ca3Co4O9. This unique growth process allows the formation of nanoparticle coatings on substrates from an aqueous precursor of Ca and Co salts. The particle size is controlled from few tens to few hundred nanometers by varying the concentration of the precursor. The resistivity, Seebeck coefficient, and the power factor (PF) measured in the temperature range of 300–700 K for films grown by MPAS process with varying concentrations of calcium and cobalt chlorides are presented. Films with larger nanoparticles showed a trend toward higher PFs than those with smaller nanoparticles. Films with PFs as high as 220 μW/mK2 were observed to contain larger nanoparticles.

One way to further optimize the thermoelectric properties toward a higher ZT is a temperature stable nanoengineering of materials, where the thermal conductivity is reduced by increasing the phonon scattering at the grain boundaries. To study this, Nb-substituted CaMnO3 perovskite-type material was synthesized by ultrasonic spray combustion (USC). The grain growth has been characterized by x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Finally, the thermoelectric properties of compacted and sintered bulk samples from powder prepared by a continuous scalable USC process were measured up to 1050 K. The thermoelectric legs were prepared by an adapted sintering process. Here, a compromise between enhanced porosity to reduce the thermal conductivity and securing of mechanical stability and low resistivity should be obtained. Based on the grain growth mechanisms, an advanced sintering process for additional interconnection of the particles without particle growth is needed to further increase the thermoelectric performance.

Effect of the seed layer on Seebeck coefficient measurement of electroplated thermoelectric films was quantitatively analyzed. It is found that sheet, rather than bulk resistance of the seed layer, or more precisely its relative comparison to sheet resistance of the film, determines the effects. The analysis reveals that the seed layer’s effect can be neglected (within 1% error) only if the sheet resistance ratio [R□2(film)/R□1(seed)] is smaller than 0.01. This condition commonly requires film thicknesses of 100 μm or more, which is not practically relevant. Based on the analysis we proposed a new method that is applicable for 10 times thinner films. This approach for determining Seebeck coefficient is simple, and more importantly, electroplated films can be characterized in their statu nascendi. Finite element simulation and experiments verified the analysis.

Arrays of vertically aligned silicon wires of 250 nm–4 μm in diameter were fabricated in a top–down process using photolithography and deep reactive ion etching at cryogenic temperatures. Using the 3-omega method, thermal conductance of vertical silicon nanowires, i.e., nanopillars, was measured immediately on-chip without the need of breaking off single wires and mounting them into a special testing device. The Seebeck coefficient was measured with 2-mm2 arrays of pillars of 260 nm in diameter, which were pressure-joined with bulk chips for testing. Testing was performed in the temperature range between 50 and 470 °C at applied temperature gradients of up to 190 °C. We found a reduction of the thermal conductivity to less than 30% of the bulk silicon, confirming that arrayed vertical nanowires fabricated in an economical top–down process can strongly promote silicon as a thermoelectric material.

Graded and segmented thermoelectric elements are studied in order to improve the performance of thermogenerators that are exposed to a large temperature difference. The linear thermodynamics of irreversible processes is extended by assuming spatially dependent material parameters like the Seebeck coefficient, the electrical and thermal conductivities. For the particular case in which these transport coefficients exhibit a constant gradient, we present an analytical solution of the one-dimensional thermal energy balance in terms of Bessel functions. Given linear spatial material profiles, we discuss the optimization of performance parameters like the electrical power Pel and the efficiency η of a graded thermogenerator element of fixed length and fixed boundary temperatures. The results are compared with the constant properties model, i.e., physically and chemically homogeneous material, as a suitable reference for performance evaluation.

Four-leg thermoelectric oxide modules (TOMs) consisting of two p-type (La1.98Sr0.02CuO4) and two n-type (CaMn0.98Nb0.02O3) thermoelectric (TE) legs were produced with a manufacturing quality factor between 30 and 60%. The pressed sintered TE legs revealed 90% of the theoretical density to ensure a sufficient mechanical stability of the TE modules. The legs were connected electrically in series and sandwiched thermally in parallel between two Al2O3 plates serving as absorber and cooler, respectively. A solar cavity-receiver packed with an array of TOMs was subjected to concentrated thermal radiation with peak solar radiative flux intensities exceeding 600 kW/m2. Temperature distributions in the cavity, open-circuit voltage (VOC), and maximum output power (Pmax) were measured for different external loads and solar radiative fluxes (qin). Finally, the solar-to-electricity conversion efficiency (η) was calculated.

We have successfully developed a Seebeck coefficient Standard Reference Material (SRM™), Bi2Te3, that is essential for interlaboratory data comparison and for instrument calibration. Certification measurements were performed using a differential steady-state technique on 10 samples (15 measurements) randomly selected from a batch of 390 bars. The certified Seebeck coefficient values are provided from 10 to 390 K, and they are further supported by transient measurements. The availability of this SRM will validate measurement results, leading to a better understanding of the structure/property relationships and underlying physics of potential high-efficiency thermoelectric materials.

Variably spaced semiconductor superlattices (VSSLs) exhibited superior electron mobility and rectification because of electronic level alignment. We investigated the thermoelectric properties of VSSL structures using a self-consistent nonequilibrium Green’s function quantum model to capture the ballistic electron transport and anatomistic nonequilibrium Green’s function model to capture the phonon transport. A figure of merit was calculated as a function of temperature for two VSSL strain silicon–germanium materials and a non-VSSL material. Calculation of the figure of merit (ZT) versus temperature for a VSSL demonstrated a 17 times increase in power factor at the expense of a 4 times increase in thermal conductivity at room temperature compared to a comparable uniform superlattice. Calculation determined a ZT of 0.20 for a VSSL compared to a ZT of 0.04 for non-VSSL material at 400 K. VSSLs proved to be a candidate material to further increased ZT near room temperature for superlattice materials.

We report the results of an investigation on the structural evolution of a potential new thermoelectric material, Cu3SbSe3, as a function of temperature from 25 to 390 °C. From high-temperature x-ray diffraction data, the refined lattice parameters were seen to change nonlinearly, but continuously, with temperature, with an increased rate of thermal expansion in the a and b lattice parameters from around 125 °C to 175 °C and negative thermal expansion in the c axis from around 100 °C to 175 °C. Crystallographic charge flipping analysis indicated an increase in the disorder of the copper cations with temperature. This reversible order/disorder phase transition in Cu3SbSe3 affects the transport properties, as evidenced by thermal conductivity measurements, which change from negative to positive slope at the transition temperature. This structural change in Cu3SbSe3 has implications for its potential use in thermoelectric generators.