Optimized thermoelectric properties of Mo_3Sb_(7-x)Te_x with significant phonon scattering by electrons

Heavily doped compounds Mo_3Sb_(7−x)Te_x (x = 0, 1.0, 1.4, 1.8) were synthesized by solid state reaction and sintered by spark plasma sintering. Both X-ray diffraction and electron probe microanalysis indicated the maximum solubility of Te was around x = 1.8. The trends in the electrical transport properties can generally be understood using a single parabolic band model, which predicts that the extremely high carrier concentration of Mo_3Sb_7 (~10^(22) cm^(−3)) can be reduced to a nearly optimized level (~2 × 10^(21) cm^(−3)) for thermoelectric figure of merit (zT) by Te-substitution with x = 1.8. The increased lattice thermal conductivity by Te-doping was found to be due to the decreased Umklapp and electron–phonon scattering, according to a Debye model fitting. The thermoelectric figure of merit (zT) monotonously increased with increasing temperature and reached its highest value of about 0.51 at 850 K for the sample with x = 1.8, making these materials competitive with the state-of-the-art thermoelectric SiGe alloys. Evidence of significant electron–phonon scattering is found in the thermal conductivity

Weak electron–phonon coupling contributing to high thermoelectric performance in n-type PbSe

PbSe is a surprisingly good thermoelectric material due, in part, to its low thermal conductivity that had been overestimated in earlier measurements. The thermoelectric figure of merit, zT, can exceed 1 at high temperatures in both p-type and n-type PbSe, similar to that found in PbTe. While the p-type lead chalcogenides (PbSe and PbTe) benefit from the high valley degeneracy (12 or more at high temperature) of the valence band, the n-type versions are limited to a valley degeneracy of 4 in the conduction band. Yet the n-type lead chalcogenides achieve a zT nearly as high as the p-type lead chalcogenides. This effect can be attributed to the weaker electron–phonon coupling (lower deformation potential coefficient) in the conduction band as compared with that in the valence band, which leads to higher mobility of electrons compared to that of holes. This study of PbSe illustrates the importance of the deformation potential coefficient of the charge-carrying band as one of several key parameters to consider for band structure engineering and the search for high performance thermoelectric materials

Combination of large nanostructures and complex band structure for high performance thermoelectric lead telluride

The complexity of the valence band structure in p-type PbTe has been shown to enable a significant enhancement of the average thermoelectric figure of merit (zT) when heavily doped with Na. It has also been shown that when PbTe is nanostructured with large nanometer sized Ag_2Te precipitates there is an enhancement of zT due to phonon scattering at the interfaces. The enhancement in zT resulting from these two mechanisms is of similar magnitude but, in principle, decoupled from one another. This work experimentally demonstrates a successful combination of the complexity in the valence band structure with the addition of nanostructuring to create a high performance thermoelectric material. These effects lead to a high zT over a wide temperature range with peak zT > 1.5 at T > 650 K in Na-doped PbTe/Ag_2Te. This high average zT produces 30% higher efficiency (300–750 K) than pure Na-doped PbTe because of the nanostructures, while the complex valence band structure leads to twice the efficiency as the related n-type La-doped PbTe/Ag_2Te without such band structure complexity

Low effective mass leading to high thermoelectric performance

High Seebeck coefficient by creating large density-of-states effective mass through either electronic structure modification or manipulating nanostructures is commonly considered as a route to advanced thermoelectrics. However, large density-of-state due to flat bands leads to large transport effective mass, which results in a simultaneous decrease of mobility. In fact, the net effect of such a high effective mass is a lower thermoelectric figure of merit, zT, when the carriers are predominantly scattered by phonons according to the deformation potential theory of Bardeen–Shockley. We demonstrate that the beneficial effect of light effective mass contributes to high zT in n-type thermoelectric PbTe, where doping and temperature can be used to tune the effective mass. This clear demonstration of the deformation potential theory to thermoelectrics shows that the guiding principle for band structure engineering should be low effective mass along the transport direction

Reevaluation of PbTe_(1−x)I_x as high performance n-type thermoelectric material

Thermoelectric transport properties of n-type PbTe_(1−x)I_x with carrier concentrations ranging from 5.8 × 10^(18)–1.4 × 10^(20) cm^(−3) are reinvestigated from room temperature to 800 K. The electronic transport properties, resistivity and Seebeck coefficient in this study are effectively consistent with prior reports, however the thermal conductivity has been found to be historically overestimated. The reassessment of the thermal transport properties, in combination with careful control of the carrier density by iodine doping, reveals a significantly larger figure of merit, zT ~ 1.4, than often previously reported for n-type PbTe. The results and analysis of the data from this study lead to a redetermination of zT for this historical thermoelectric material and provide a renewed interest in n-type PbTe based materials

Heavily Doped PBSE with High Thermoelectric Performance

The present invention discloses heavily doped PbSe with high thermoelectric performance. Thermoelectric property measurements disclosed herein indicated that PbSe is high zT material for mid-to-high temperature thermoelectric applications. At 850 K a peak zT (is) greater than 1.3 was observed when n(sub H) approximately 1.0 X 10(exp 20) cm(exp -3). The present invention also discloses that a number of strategies used to improve zT of PbTe, such as alloying with other elements, nanostructuring and band modification may also be used to further improve zT in PbSe

High thermoelectric figure of merit in heavy hole dominated PbTe

Thermoelectric transport properties of p-type PbTe:Na, with high hole concentrations of approximately 10^(20) cm^(−3), are reinvestigated from room temperature to 750 K. The greatly enhanced Seebeck coefficient at these doping levels can be understood by the presence of a sharp increase in the density of states around the Fermi level. As a result, the thermoelectric figure of merit, zT, reaches ~1.4 at 750 K. The influence of these heavy hole carriers may contribute to a similarly high zT observed in related p-type PbTe-based systems such as Tl-doped PbTe and nanostructured composite materials

N-type Doped PbTe and PbSe Alloys for Thermoelectric Applications

The present invention demonstrates that weak scattering of carriers leads to a high mobility and therefore helps achieve low electric resistivity with high Seebeck coefficient for a thermoelectric material. The inventors demonstrate this effect by obtaining a thermoelectric figure of merit, zT, higher than 1.3 at high temperatures in n-type PbSe, because of the weak scattering of carriers in the conduction band as compared with that in the valence band. The invention further demonstrates favorable thermoelectric transport properties of n-type PbTe.sub.1-xI.sub.x with carrier concentrations ranging from 5.8.times.10.sup.18-1.4.times.10.sup.20 cm.sup.-3

Alloying to increase the band gap for improving thermoelectric properties of Ag_(2)Te

Ag_(2)Te simultaneously shows high mobility and low thermal conductivity, however the relatively low band gap of ~0.2 eV prevents it from achieving high thermoelectric figure of merit, zT, in the high temperature phase. In this study, the band gap of Ag_(2)Te has been increased enabling a zT of unity by forming alloys and composites with PbTe, thereby demonstrating the importance of exploiting potentially good thermoelectrics among these small band gap semiconductors and similar materials