Sascha Populoh

Influence of tungsten substitution and oxygen deficiency on the thermoelectric properties of CaMnO3−δ

Polycrystalline tungsten-substituted CaMn1−xWxO3−δ (0.00 ≤ x ≤ 0.05) powders were synthesized from a polymeric precursor, pressed and sintered to high density. The impact of tungsten substitution on the crystal structure, thermal stability, phase transition, electronic and thermal transport properties is assessed. Tungsten acts as an electron donator and strongly affects high-temperature oxygen stoichiometry. Oxygen vacancies form in the high figure-of-merit (ZT)-region starting from about T = 1000 K and dominate the carrier concentration and electronic transport far more than the tungsten substitution. The analysis of the transport properties yields that in the investigated regime the band filling is sufficiently high to overcome barriers of polaron transport. Therefore, the Cutler-Mott approach describes the electrical transport more accurately than the Mott approach for small polaron transport. The lattice thermal conductivity near room temperature is strongly suppressed with increasing tungsten concen...

Enhancement of thermoelectric performance in strontium titanate by praseodymium substitution

In order to identify the effects of Pr additions on thermoelectric properties of strontium titanate, crystal structure, electrical and thermal conductivity, and Seebeck coefficient of Sr1−xPrxTiO3 (x = 0.02–0.30) materials were studied at 400 < T < 1180 K under highly reducing atmosphere. The mechanism of electronic transport was found to be similar up to 10% of praseodymium content, where generation of the charge carriers upon substitution resulted in significant increase of the electrical conductivity, moderate decrease in Seebeck coefficient, and general improvement of the power factor. Formation of point defects in the course of substitution led to suppression of the lattice thermal conductivity, whilst the contribution from electronic component was increasing with carrier concentration. Possible formation of layered structures and growing distortion of the perovskite lattice resulted in relatively low thermoelectric performance for Sr0.80Pr0.20TiO3 and Sr0.70Pr0.30TiO3. The maximum dimensionless figu...

Invited Article: A round robin test of the uncertainty on the measurement of the thermoelectric dimensionless figure of merit of Co0.97Ni0.03Sb3

A round robin test aiming at measuring the high-temperature thermoelectric properties was carried out by a group of European (mainly French) laboratories (labs). Polycrystalline skutterudite Co0.97Ni0.03Sb3 was characterized by Seebeck coefficient (8 labs), electrical resistivity (9 labs), thermal diffusivity (6 labs), mass volume density (6 labs), and specific heat (6 labs) measurements. These data were statistically processed to determine the uncertainty on all these measured quantities as a function of temperature and combined to obtain an overall uncertainty on the thermal conductivity (product of thermal diffusivity by density and by specific heat) and on the thermoelectric figure of merit ZT. An increase with temperature of all these uncertainties is observed, in agreement with growing difficulties to measure these quantities when temperature increases. The uncertainties on the electrical resistivity and thermal diffusivity are most likely dominated by the uncertainty on the sample dimensions. The temperature-averaged (300-700 K) relative standard uncertainties at the confidence level of 68% amount to 6%, 8%, 11%, and 19% for the Seebeck coefficient, electrical resistivity, thermal conductivity, and figure of merit ZT, respectively. Thermal conductivity measurements appear as the least accurate. The moderate value of the temperature-averaged relative expanded (confidence level of 95%) uncertainty of 17% on the mean of ZT is essential in establishing Co0.97Ni0.03Sb3 as a high temperature standard n-type thermoelectric material.

Half-Heusler (TiZrHf)NiSn Unileg Module with High Powder Density

(TiZrHf)NiSn half-Heusler compounds were prepared by arc melting and their thermoelectric properties characterized in the temperature range between 325 K and 857 K, resulting in a Figure of Merit ZT ≈ 0.45. Furthermore, the prepared samples were used to construct a unileg module. This module was characterized in a homemade thermoelectric module measurement stand and yielded 275 mW/cm2 and a maximum volumetric power density of 700 mW/cm3. This was reached using normal silver paint as a contacting material; from an improved contacting, much higher power yields are to be expected.

Improved thermoelectric performance of (Zr0.3Hf0.7)NiSn half-Heusler compounds by Ta substitution

The thermoelectric performance of Ta substituted (ZrHf)NiSn-based half-Heusler compounds is studied. Here, Ta is used on the Hf site for controlling the charge carrier concentration in contrast to the widely used Sb substitution on the Sn site. The influence of the Ta content on the thermoelectric and transport properties of (Zr0.3Hf0.7-xTax)NiSn (x = 0, 0.01, 0.05) is investigated by means of Seebeck coefficient, electrical resistivity, thermal conductivity, and Hall coefficient measurements. The results are analyzed in context of the single parabolic band model. Ta substitution increases the charge carrier concentration and suppresses the influence of impurity band, which is present in the pristine (Zr0.3Hf0.7)NiSn. Moreover, Ta substitution decouples and simultaneously increases the density-of-states effective mass (m*) and the charge carrier mobility (μ), leading to a larger weighted mobility μ·(m*)3/2. The lattice thermal conductivity is slightly suppressed due to increased point defect scattering. A...

Thermoelectric study of crossroads material MnTe via sulfur doping

Here, we report thermoelectric study of crossroads material MnTe via iso-electronic doping S on the Te-site. MnTe1-xSx samples with nominal S content of x = 0.00, 0.05, and 0.10 were prepared using a melt-quench method followed by pulverization and spark plasma sintering. The X-ray powder diffraction, scanning electron microscopy, and ZAF-corrected compositional analysis confirmed that S uniformly substitutes Te up to slightly over 2%. A higher content of S in the starting materials led to the formation of secondary phases. The thermoelectric properties of MnTe1-xSx samples were characterized by means of Seebeck coefficient, electrical conductivity, and thermal conductivity measurements from 300 K to 773 K. Furthermore, Hall coefficient measurements and a single parabolic band model were used to help gain insights on the effects of S-doping on the scattering mechanism and the carrier effective mass. As expected, S doping not only introduced hole charge carriers but also created short-range defects that ef...

Laser deposition and direct-writing of thermoelectric misfit cobaltite thin films

A two-step process combining pulsed laser deposition of calcium cobaltite thin films and a subsequent laser induced forward transfer as micro-pixel is demonstrated as a direct writing approach of micro-scale thin film structures for potential applications in thermoelectric micro-devices. To achieve the desired thermo-electric properties of the cobaltite thin film, the laser induced plasma properties have been characterized utilizing plasma mass spectrometry establishing a direct correlation to the corresponding film composition and structure. The introduction of a platinum sacrificial layer when growing the oxide thin film enables a damage-free laser transfer of calcium cobaltite thereby preserving the film composition and crystallinity as well as the shape integrity of the as-transferred pixels. The demonstrated direct writing approach simplifies the fabrication of micro-devices and provides a large degree of flexibility in designing and fabricating fully functional thermoelectric micro-devices.

Electronic structure and thermoelectric properties of nanostructured EuTi1−xNbxO3−δ (x = 0.00; 0.02)

The thermoelectric properties of polycrystalline nanostructured EuTiO3−δ samples are improved by a substitution of 2% Nb for Ti. The figure of merit (ZT) was measured to reach ZT(EuTi0.98Nb0.02O3−δ) ≈ 0.4 at T = 1040 K while ZT(EuTiO3−δ) ≈ 0.3 at the same temperature. X-ray photoelectron spectra reveal that the in-gap states at the Fermi level are more pronounced for the Nb-substituted samples, resulting in an improved power factor. The valence band peak below the Fermi level is sharply shaped, therefore fulfilling the condition for a large Seebeck coefficient. The specific porosity of the samples reduces the lattice thermal conductivity with a minor effect on the electron transport.

Structure and thermoelectric properties of EuTi(O,N)3 ± δ

After partial substitution of nitrogen for oxygen in EuTiO3, the crystal structure, thermoelectric properties, morphology, and electronic structure of the products were analyzed and compared with pristine EuTiO3. The space group of EuTi(O,N)3 ± δ was orthorhombic Pnma due to the tilt and rotation of the anion octahedra, compared to cubic Pm3¯m of EuTiO3 (at room temperature). The thermoelectric properties of oxynitride polycrystalline bodies sintered in three different ways were investigated in the temperature range of 300 K < T < 950 K. The Seebeck coefficients (S) of the oxynitrides were lower compared with the oxide, and the electrical resistivities (ρ) were increased about one order of magnitude. The activation energies (EA) indicated a larger band gap of EuTi(O,N)3 ± δ when compared to the pristine EuTiO3 (∼1.3 eV compared to 0.98 eV). A morphological characterization by transmission electron microscopy and scanning electron microscopy illustrated intrinsic nanopores within the individual particles a...

Designing strontium titanate-based thermoelectrics: insight into defect chemistry mechanisms

Driven by a need to develop low-cost and thermally stable materials for thermoelectric applications, donor-substituted strontium titanate is considered as a promising alternative to traditional thermoelectrics. The complex defect chemistry of SrTiO3-based materials imposes various limitations on identifying the relevant effects exerted on the electronic band structure and heat transfer, being a subject of debate and intensive research. Based on combined XRD, SEM/EDS, HRTEM, XPS, and TGA studies and measurements of thermoelectric properties, this work uncovers the particular role of various structural defects in electrical and thermal transport in Sr1±yTi0.9Nb0.1O3±δ, selected as a model system. Introduction of A-site cation vacancies provides a synergistic effect of combining fast charge transport in the perovskite lattice and suppressing the thermal conductivity mostly due to simultaneous generation of oxygen vacancies. The presence of oxygen vacancies promotes more efficient phonon scattering compared to Ruddlesden–Popper-type layers. These findings provide a link between structural and thermoelectric properties, offering further prospects for seeking highly performing SrTiO3-based thermoelectrics by tailoring the defect chemistry mechanisms.