skip to main content


Title: Vacancy defect control of colossal thermopower in FeSb2
Abstract

Iron diantimonide is a material with the highest known thermoelectric power. By combining scanning transmission electron microscopic study with electronic transport neutron, X-ray scattering, and first principle calculation, we identify atomic defects that control colossal thermopower magnitude and nanoprecipitate clusters with Sb vacancy ordering, which induce additional phonon scattering and substantially reduce thermal conductivity. Defects are found to cause rather weak but important monoclinic distortion of the unit cellPnnm → Pm. The absence of Sb along [010] for high defect concentration forms conducting path due to Fedorbital overlap. The connection between atomic defect anisotropy and colossal thermopower in FeSb2paves the way for the understanding and tailoring of giant thermopower in related materials.

 
more » « less
NSF-PAR ID:
10223342
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
npj Quantum Materials
Volume:
6
Issue:
1
ISSN:
2397-4648
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    AMXcompounds with the ZrBeSi structure tolerate a vacancy concentration of up to 50 % on theM‐site in the planarMX‐layers. Here, we investigate the impact of vacancies on the thermal and electronic properties across the full EuCu1−xZn0.5xSb solid solution. The transition from a fully‐occupied honeycomb layer (EuCuSb) to one with a quarter of the atoms missing (EuZn0.5Sb) leads to non‐linear bond expansion in the honeycomb layer, increasing atomic displacement parameters on theMand Sb‐sites, and significant lattice softening. This, combined with a rapid increase in point defect scattering, causes the lattice thermal conductivity to decrease from 3 to 0.5 W mK−1at 300 K. The effect of vacancies on the electronic properties is more nuanced; we see a small increase in effective mass, large increase in band gap, and decrease in carrier concentration. Ultimately, the maximumzTincreases from 0.09 to 0.7 as we go from EuCuSb to EuZn0.5Sb.

     
    more » « less
  2. Abstract

    AMXcompounds with the ZrBeSi structure tolerate a vacancy concentration of up to 50 % on theM‐site in the planarMX‐layers. Here, we investigate the impact of vacancies on the thermal and electronic properties across the full EuCu1−xZn0.5xSb solid solution. The transition from a fully‐occupied honeycomb layer (EuCuSb) to one with a quarter of the atoms missing (EuZn0.5Sb) leads to non‐linear bond expansion in the honeycomb layer, increasing atomic displacement parameters on theMand Sb‐sites, and significant lattice softening. This, combined with a rapid increase in point defect scattering, causes the lattice thermal conductivity to decrease from 3 to 0.5 W mK−1at 300 K. The effect of vacancies on the electronic properties is more nuanced; we see a small increase in effective mass, large increase in band gap, and decrease in carrier concentration. Ultimately, the maximumzTincreases from 0.09 to 0.7 as we go from EuCuSb to EuZn0.5Sb.

     
    more » « less
  3. Abstract

    Sb‐doped and GeTe‐alloyed n‐type thermoelectric materials that show an excellent figure of meritZTin the intermediate temperature range (400–800 K) are reported. The synergistic effect of favorable changes to the band structure resulting in high Seebeck coefficient and enhanced phonon scattering by point defects and nanoscale precipitates resulting in reduction of thermal conductivity are demonstrated. The samples can be tuned as single‐phase solid solution (SS) or two‐phase system with nanoscale precipitates (Nano) based on the annealing processes. The GeTe alloying results in band structure modification by widening the bandgap and increasing the density‐of‐states effective mass of PbTe, resulting in significantly enhanced Seebeck coefficients. The nanoscale precipitates can improve the power factor in the low temperature range and further reduce the lattice thermal conductivity (κlat). Specifically, the Seebeck coefficient of Pb0.988Sb0.012Te–13%GeTe–Nano approaches −280 µV K−1at 673 K with a low κlatof 0.56 W m−1K−1at 573 K. Consequently, a peakZTvalue of 1.38 is achieved at 623 K. Moreover, a high averageZTavgvalue of ≈1.04 is obtained in the temperature range from 300 to 773 K for n‐type Pb0.988Sb0.012Te–13%GeTe–Nano.

     
    more » « less
  4. Abstract

    PbSe is an attractive thermoelectric material due to its favorable electronic structure, high melting point, and lower cost compared to PbTe. Herein, the hitherto unexplored alloys of PbSe with NaSbSe2(NaPbmSbSem+2) are described and the most promising p‐type PbSe‐based thermoelectrics are found among them. Surprisingly, it is observed that below 500 K, NaPbmSbSem+2exhibits unorthodox semiconducting‐like electrical conductivity, despite possessing degenerate carrier densities of ≈1020cm−3. It is shown that the peculiar behavior derives from carrier scattering by the grain boundaries. It is further demonstrated that the high solubility of NaSbSe2in PbSe augments both the thermoelectric properties while maintaining a rock salt structure. Namely, density functional theory calculations and photoemission spectroscopy demonstrate that introduction of NaSbSe2lowers the energy separation between the L‐ and Σ‐valence bands and enhances the power factors under 700 K. The crystallographic disorder of Na+, Pb2+, and Sb3+moreover provides exceptionally strong point defect phonon scattering yielding low lattice thermal conductivities of 1–0.55 W m‐1K‐1between 400 and 873 K without nanostructures. As a consequence, NaPb10SbSe12achieves maximumZT≈1.4 near 900 K when optimally doped. More importantly, NaPb10SbSe12maintains highZTacross a broad temperature range, giving an estimated recordZTavgof ≈0.64 between 400 and 873 K, a significant improvement over existing p‐type PbSe thermoelectrics.

     
    more » « less
  5. Abstract

    Single crystalline BaMnSb2is considered as a 3D Weyl semimetal with the 2D electronic structure containing Dirac cones from the Sb sheet. We report experimental investigation of low-temperature cleaved BaMnSb2surfaces using scanning tunneling microscopy/spectroscopy and low energy electron diffraction. By natural cleavage, we find two terminations: one is Ba (above the orthorhombically distorted Sb sheet) and another Sb2 (at the surface of the Sb/Mn/Sb sandwich layer). Both terminations show the 2 × 1 surface reconstructions, with drastically different morphologies and electronic properties, however. The reconstructed structures, defect types and nature of the electronic structures of the two terminations are extensively studied. The quasiparticle interference (QPI) analysis is conducted at the energy range between −2 V and 2 V, although no interesting states are observed near the Fermi level, the surface-projected electronic band structures strongly depend on the surface termination above 1.6 V. The existence of defects can greatly modify the local density of states to create electronic phase separations on the surface in the order of tens of nm scale. Our observation on the atomic structures of the terminations and the corresponding electronic structures provides critical information towards an understanding of topological properties of BaMnSb2.

     
    more » « less