| Citation: |
Archana K. Munirathnappa, Hyungseok Lee, In Chung. Recent advances in ultrahigh thermoelectric performance material SnSe[J]. Materials Lab, 2023, 2(1): 220056. doi: 10.54227/mlab.20220056
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Recent advances in ultrahigh thermoelectric performance material SnSe
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Abstract
This perspective discusses the surprising discovery and development of SnSe thermoelectrics. Undoped, hole-doped, and electron-doped SnSe single crystals have successively represented an extraordinarily high thermoelectric figure of merit (
ZT ) ranging from 2.6 to 2.9, revitalizing efforts on finding new high-performance thermoelectric systems. Their unprecedented performance is mainly attributed to ultralow thermal conductivity arising from the uniquely anisotropic and anharmonic crystal chemistry of SnSe. Soon after the publications on SnSe single crystals, substantial debates were raised on their thermoelectric performance, especially on truth in ultralow thermal conductivity. Very recently, polycrystalline SnSe samples were synthesized, exhibiting lower lattice thermal conductivity and higherZT than the single crystal samples. This work clearly addressed many questions that have arisen on the intrinsic thermal and charge transport properties of SnSe-based materials. It shows a peakZT of ~3.1 at 783 K and an averageZT of ~2.0 from 400 to 783 K, which are the record-breaking performances of all bulk thermoelectric materials in any form ever reported. -
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Author Biographies
Dr. Archana K. Munirathnappa holds a M.Sc. degree in Inorganic Chemistry from Central College, Bengaluru, and a Ph.D. degree in Chemistry from the Manipal Academy of Higher Education, with Dr. Nalini G. Sundaram through Poornaprajna Institute of Scientific Research, India. She was a postdoctoral researcher with Prof. Kanishka Biswas at Jawaharlal Nehru Centre for Advanced Scientific Research, India. Currently, she is a postdoctoral researcher at the School of Chemical and Biological Engineering, Seoul National University with Prof. In Chung. Her research area is the design and development of high-performance polycrystalline SnSe materials for waste heat recovery applications. 
Hyungseok Lee is currently a Ph.D. candidate at the School of Chemical and Biological Engineering, Seoul National University, Korea. His research interests include the synthesis of new inorganic materials for energy and electronic applications and exotic strongly correlated electron systems. 
Dr. In Chung holds a B.Sc. and M.Sc. from Seoul National University, Korea, and a Ph.D. in chemistry from Michigan State University with Prof. Mercouri G. Kanatzidis. He was a postdoctoral research fellow at Northwestern University. He joined the Korea Advanced Institute of Science and Technology as an assistant professor in 2013. He moved to Seoul National University in 2015 and is currently an associate professor. His research interests include material design and synthesis mainly focusing on energy harvesting and storage materials regarding thermoelectrics, all-solid-state secondary batteries and photovoltaics, and metamaterials with extraordinary properties such as negative refraction and guiding thermal radiation. -
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Archana K. Munirathnappa, Hyungseok Lee, In Chung. Recent advances in ultrahigh thermoelectric performance material SnSe[J]. Materials Lab, 2023, 2(1): 220056. doi: 10.54227/mlab.20220056
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Figure 1.
a Crystal structure of orthorhombic SnSe (Pnma) along the b-axis. b Highly distorted SnSe7 polyhedron with three short (solid lines) and four long Sn-Se bonds (dashed lines). c Experimental ZT values of undoped and doped SnSe single crystals. Open black squares, filled black circles and open black triangles represent undoped SnSe along the a-, b-, and c-axis, respectively.[8] Blue diamonds, Br-doped SnSe with carrier concentration of ~1.2 × 1019 cm-3.[33] Red pentagons, 3% Br-doped SnSe with 12% PbSe alloying.[34]
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Figure 2.
Temperature-dependent a electrical conductivity, b Seebeck coefficient of undoped SnSe[8] and hole-doped SnSe[32] along the a-, b- and c-axes. c Schematic illustration of the multi-valence bands of SnSe. d The comparison of power factor of undoped SnSe crystal,[8] hole-doped SnSe crystal,[32] Bi2-xSbxTe3,[63] and PbTe alloyed with 4 mol% SrTe and doped with 2 mol% Na.[46] e Thermal diffusivities of polycrystalline SnSe with and without SnO2 with respect to temperature. For comparison, thermal diffusivities of single crystal SnSe along the three different axial directions are also given.[7] Copyright 2016, Royal Society of Chemistry.
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Figure 3.
A schematic illustration of the SnOx-removal process involving ball milling and H2-reduction and its effects on thermoelectric properties of the polycrystalline SnSe-based materials.[62] Copyright 2019, Elsevier.
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Figure 4.
a Typical image of Sn ingot after H2-chemical reduction and subsequent melting-purification for 6 h at
1273 K. 99.999% Sn chunk (American Element) was used. The ash-like black residues evolved on the top and the entire surface of the ingot. b Sn ingot after the multiple melting-purification processes showing no ash-like residues. c The SnOH+ image of the untreated SnSe by time-of-flight-secondary ion mass spectroscopy in scale bar 10 μm (the red spots correspond to SnOx and the white dotted line indicates GBs, which are defined by the optical images collected on the corresponding areas. d The SnOH+ image of the purified SnSe sample (scale bar 10 μm). e The high-angle annular dark-field (HAADF) image (scale bar 20 nm) of the untreated SnSe sample reveals SnOx precipitates (white arrows) at the GBs indicated by orange dashed lines. f The corresponding three-dimensional atom probe tomography (APT) reconstruction showing the spatial distribution of Sn, O, and Se atoms (scale bar 50 nm). g The HAADF image of the purified SnSe sample. h The corresponding APT image shows negligible existence of oxygen concentration by the purification process.[35] Copyright 2021, Springer Nature. -
Figure 5.
A schematic illustration of the two-step purification process for the surface SnOx removal in the polycrystalline SnSe to achieve high TE performance.[35] Copyright 2021, Springer Nature.
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Figure 6.
a The κlat for the untreated SnSe, H2-reduced SnSe with no Sn purification, and purified SnSe samples. b The κlat of the purified NaxSn0.995-xSe (x = 0.01, 0.02, and 0.03) samples in comparison with that of the untreated and purified SnSe samples. The κlat of single crystal SnSe along the a-axis is shown for comparison. c The κtot of the purified Na0.03Sn0.965Se calculated by the experimental Cp by DSC and the derived Cp values from the literature.[32] d ZT values of the purified Na0.03Sn0.965Se (filled red) polycrystalline sample taken parallel to the SPS pressing direction and the current state-of-the-art polycrystalline materials such as 2% Na doped PbTe-8%SrTe (filled pink),[10] SnSe-5% PbSe (filled green)[62] as well as undoped single crystal SnSe (p-type, open orange),[8] Na-doped single crystal SnSe (p-type, open blue)[32] and Br-doped single crystal SnSe (open black).[33] Copyright 2021, Springer Nature.[35]
