Tin selenide

Last updated
Tin selenide
Crystal structure of orthorhombic SnSe and GeSe.png
Names
Other names
Tin(II) selenide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.871 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 215-257-6
PubChem CID
UNII
  • InChI=1S/Se.Sn
    Key: MFIWAIVSOUGHLI-UHFFFAOYSA-N
  • InChI=1S/Se.Sn
  • [Se]=[Sn]
Properties
SnSe
Molar mass 197.67 g/mol
Appearancesteel gray odorless powder
Density 5.75 g/cm3 [1]
Melting point 861 °C (1,582 °F; 1,134 K)
negligible
Band gap 0.9 eV (indirect), 1.3 eV (direct) [2]
Structure
Orthorhombic, oP8 [2]
Pnma, No. 62 [2]
a = 4.4 Å, b = 4.2 Å, c = 11.5 Å [3]
Thermochemistry
-88.7 kJ/mol
Hazards
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Danger
H301, H331, H373, H410
P260, P261, P264, P270, P271, P273, P301+P310, P304+P340, P311, P314, P321, P330, P391, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
2
1
1
Safety data sheet (SDS) https://www.ltschem.com/msds/SnSe.pdf
Related compounds
Other anions
Tin(II) oxide
Tin(II) sulfide
Tin telluride
Other cations
Carbon monoselenide
Silicon monoselenide
Germanium selenide
Lead selenide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Tin selenide, also known as stannous selenide, is an inorganic compound with the formula Sn Se. Tin(II) selenide is a narrow band-gap (IV-VI) semiconductor structurally analogous to black phosphorus. It has received considerable interest for possible applications including low-cost photovoltaics, and memory-switching devices. Because of its low thermal conductivity as well as reasonable electrical conductivity, tin selenide is one of the most efficient thermoelectric materials. [4] [5]

Contents

Structure

α-SnSe is classified as a layered metal chalcogenide. [6] It includes a group 16 anion (Se2−) and an electropositive element (Sn2+), and is arranged in a layered structure. Tin(II) selenide (SnSe) crystallizes in the orthorhombic structure that is related to the rock-salt structure. It is isomorphous to germanium selenide (GeSe). [7] The unit cell encompasses two inverted layers. Each tin atom is covalently bonded to three neighboring selenium atoms, and each selenium atom is covalently bonded to three neighboring tin atoms. [8] The layers are held together primarily by van der Waals forces. [9] At temperatures above 800 K its structure changes to rock-salt structure. [4]

At pressures above 58 GPa, SnSe acts as a superconductor; this change of conductivity is likely due to a change in the structure to that of CsCl. [10] Another polymorph is based upon the cubic and orthorhombic crystal system is known as π-SnSe (space group: P213, No. 198). [11] A γ-SnSe phase has also been reported (space group: Pnma, No. 62). [12]

Synthesis

Tin(II) selenide can be formed by combining the elements tin and selenium above 350 °C. [13]

Problems with the composition are encountered during synthesis. Two phases exist—the hexagonal SnSe2 phase and the orthorhombic SnSe phase. Specific nanostructures can be synthesized, [14] but few 2D nanostructures have been prepared. Both square SnSe nanostructures and single-layer SnSe nanostructures have been prepared. Historically, phase-controlled synthesis of 2D tin selenide nanostructures is quite difficult. [6]

Sheet-like nanocrystalline SnSe with an orthorhombic phase has been prepared with good purity and crystallization via a reaction between a selenium alkaline aqueous solution and tin(II) complex at room temperature under atmospheric pressure. [15] A few-atom-thick SnSe nanowires can be grown inside narrow (~1 nm diameter) single-wall carbon nanotubes by heating the nanotubes with SnSe powder in vacuum at 960 °C. Contrary to the bulk SnSe, they have the cubic crystal structure. [2]

Use in energy harvesting

Tin(II) selenide has been considered for thermoelectric applications. [16] SnSe has exhibited the highest thermoelectric material efficiency, measured by the unitless ZT parameter, of any known material (~2.62 at 923 K along the b axis and ~2.3 along the c axis). When coupled with the Carnot efficiency for heat conversion, the overall energy conversion efficiency of approximately 25%. Its high efficiency is most likely due to low thermal conductivity of the crystal, the electronic structure may have as important role: SnSe has highly anisotropic valence band structure, which consists of multiple valleys that act as independent channels for very mobile, low effective-mass charge transport within, and heavy-carrier conductivity perpendicular to the layers. [17] While, historically, lead telluride and silicon-germanium have been used, these materials suffer from high thermal conductivity. [18]

At room temperature, the crystal structure of SnSe is Pnma. However, at ~750 K, it undergoes a phase transition that results in a higher symmetry Cmcm structure. This phase transition preserves many of the advantageous transport properties of SnSe. The dynamic structural behavior of SnSe involving the reversible phase transition helps to preserve the high power factor. The Cmcm phase, which is structurally related to the low temperature Pnma phase, exhibits a substantially reduced energy gap and enhanced carrier mobilities while maintaining the ultralow thermal conductivity thus yielding the record ZT. Because of SnSe's layered structure, which does not conduct heat well, one end of the SnSe single crystal can get hot while the other remains cool. This idea can be paralleled with the idea of a posture-pedic mattress that does not transfer vibrations laterally. In SnSe, the ability of crystal vibrations (also known as phonons) to propagate through the material is significantly hampered. This means heat can only travel due to hot carriers (an effect that can be approximated by the Wiedemann–Franz law), a heat transport mechanism that is much less significant to the total thermal conductivity. Thus the hot end can stay hot while the cold end remains cold, maintaining the temperature gradient needed for thermoelectric device operation. The poor ability to carry heat through its lattice enables the resulting record high thermoelectric conversion efficiency. [19] The previously reported nanostructured all-scale hierarchical PbTe-4SrTe-2Na (with a ZT of 2.2) exhibits a lattice thermal conductivity of 0.5 W m−1 K−1. The unprecedentedly high ZT ~2.6 of SnSe arises primarily from an even lower lattice thermal conductivity of 0.23 W m−1 K−1. [20] However, in order to take advantage of this ultralow lattice thermal conductivity, the synthesis method must result in macroscale single crystals as p-type polycrystalline SnSe has been shown to have a significantly reduced ZT. [21] Enhancement in the figure of merit above a relatively high value of 2.5 can have sweeping ramifications for commercial applications especially for materials using less expensive, more Earth-abundant elements that are devoid of lead and tellurium (two materials that have been prevalent in the thermoelectric materials industry for the past couple decades).

Other possible uses

Tin selenides may be used for optoelectronic devices, solar cells, memory switching devices, [7] and anodes for lithium-ion batteries. [6]

Tin(II) selenide has potential as a solid-state lubricant, due to the nature of its interlayer bonding. [22] It is not the most stable of the chalcogenide solid-state lubricants, as tungsten diselenide has much weaker interplanar bonding, is highly chemically inert and has high stability in high-temperature, high-vacuum environments.

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<span class="mw-page-title-main">Thermoelectric cooling</span> Electrically powered heat-transfer

Thermoelectric cooling uses the Peltier effect to create a heat flux at the junction of two different types of materials. A Peltier cooler, heater, or thermoelectric heat pump is a solid-state active heat pump which transfers heat from one side of the device to the other, with consumption of electrical energy, depending on the direction of the current. Such an instrument is also called a Peltier device, Peltier heat pump, solid state refrigerator, or thermoelectric cooler (TEC) and occasionally a thermoelectric battery. It can be used either for heating or for cooling, although in practice the main application is cooling since heating can be achieved more efficiently with simpler devices. It can also be used as a temperature controller that either heats or cools.

<span class="mw-page-title-main">Thermoelectric materials</span> Materials whose temperature variance leads to voltage change

Thermoelectric materials show the thermoelectric effect in a strong or convenient form.

<span class="mw-page-title-main">Semimetal</span> Metal with a small negative indirect band-gap

A semimetal is a material with a small energy overlap between the bottom of the conduction band and the top of the valence band, but they do not overlap in momentum space. According to electronic band theory, solids can be classified as insulators, semiconductors, semimetals, or metals. In insulators and semiconductors the filled valence band is separated from an empty conduction band by a band gap. For insulators, the magnitude of the band gap is larger than that of a semiconductor. Because of the slight overlap between the conduction and valence bands, semimetals have no band gap and a small density of states at the Fermi level. A metal, by contrast, has an appreciable density of states at the Fermi level because the conduction band is partially filled.

<span class="mw-page-title-main">Cadmium selenide</span> Chemical compound

Cadmium selenide is an inorganic compound with the formula CdSe. It is a black to red-black solid that is classified as a II-VI semiconductor of the n-type. It is a pigment, but applications are declining because of environmental concerns.

Lead selenide (PbSe), or lead(II) selenide, a selenide of lead, is a semiconductor material. It forms cubic crystals of the NaCl structure; it has a direct bandgap of 0.27 eV at room temperature. A grey solid, it is used for manufacture of infrared detectors for thermal imaging. The mineral clausthalite is a naturally occurring lead selenide.

<span class="mw-page-title-main">Lead telluride</span> Chemical compound

Lead telluride is a compound of lead and tellurium (PbTe). It crystallizes in the NaCl crystal structure with Pb atoms occupying the cation and Te forming the anionic lattice. It is a narrow gap semiconductor with a band gap of 0.32 eV. It occurs naturally as the mineral altaite.

<span class="mw-page-title-main">Tin telluride</span> Chemical compound

Tin telluride is a compound of tin and tellurium (SnTe); is a IV-VI narrow band gap semiconductor and has direct band gap of 0.18 eV. It is often alloyed with lead to make lead tin telluride, which is used as an infrared detector material.

<span class="mw-page-title-main">Silver(I) selenide</span> Chemical compound

Silver selenide (Ag2Se) is the reaction product formed when selenium toning analog silver gelatine photo papers in photographic print toning. The selenium toner contains sodium selenite (Na2SeO3) as one of its active ingredients, which is the source of the selenide (Se2−) anion combining with the silver in the toning process.

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Tin(II) sulfide is an inorganic compound with the chemical formula is SnS. A black or brown solid, it occurs as the rare mineral herzenbergite (α-SnS).It is insoluble in water but dissolves with degradation in concentrated hydrochloric acid. Tin(II) sulfide is insoluble in ammonium sulfide.

Bismuth selenide is a gray compound of bismuth and selenium also known as bismuth(III) selenide.

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Oxyselenides are a group of chemical compounds that contain oxygen and selenium atoms. Oxyselenides can form a wide range of structures in compounds containing various transition metals, and thus can exhibit a wide range of properties. Most importantly, oxyselenides have a wide range of thermal conductivity, which can be controlled with changes in temperature in order to adjust their thermoelectric performance. Current research on oxyselenides indicates their potential for significant application in electronic materials.

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Indium(II) selenide (InSe) is an inorganic compound composed of indium and selenium. It is a III-VI layered semiconductor. The solid has a structure consisting of two-dimensional layers bonded together only by van der Waals forces. Each layer has the atoms in the order Se-In-In-Se.

Selenogallates are chemical compounds which contain anionic units of selenium connected to gallium. They can be considered as gallates where selenium substitutes for oxygen. Similar compounds include the thiogallates and selenostannates. They are in the category of chalcogenotrielates or more broadly chalcogenometallates.

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Strontium selenide is an inorganic compound with the chemical formula SrSe.

Jong-Soo Rhyee is a South Korean physicist and materials scientist. He is a professor in the Department of Applied Physics at the Applied Science College of Kyung Hee University and serves as the Outside Director at KPT, the Representative CEO of V-memory, and the CTO of R-Materials in South Korea.

References

  1. ↑ "Supplementary Information - Facile chemical synthesis and enhanced thermoelectric properties of Ag doped SnSe nanocrystals" (PDF). www.rsc.org.
  2. 1 2 3 4 Carter, Robin; Suyetin, Mikhail; Lister, Samantha; Dyson, M. Adam; Trewhitt, Harrison; Goel, Sanam; Liu, Zheng; Suenaga, Kazu; Giusca, Cristina; Kashtiban, Reza J.; Hutchison, John L.; Dore, John C.; Bell, Gavin R.; Bichoutskaia, Elena; Sloan, Jeremy (2014). "Band gap expansion, shear inversion phase change behaviour and low-voltage induced crystal oscillation in low-dimensional tin selenide crystals". Dalton Trans. 43 (20): 7391–9. doi: 10.1039/C4DT00185K . PMID   24637546.
  3. ↑ Persson, Kristin (2014). "Materials Data on SnSe (SG:62) by Materials Project". LBNL Materials Project; Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). doi:10.17188/1284598 . Retrieved 2020-08-07.
  4. 1 2 Zhao, L. D.; Lo, S. H.; Zhang, Y; Sun, H; Tan, G; Uher, C; Wolverton, C; Dravid, V. P.; Kanatzidis, M. G. (2014). "Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals". Nature. 508 (7496): 373–7. Bibcode:2014Natur.508..373Z. doi:10.1038/nature13184. PMID   24740068. S2CID   205238132.
  5. ↑ Kang, Joon Sang; Wu, Huan; Li, Man; Hu, Yongjie (2019). "Intrinsic Low Thermal Conductivity and Phonon Renormalization Due to Strong Anharmonicity of Single-Crystal Tin Selenide". Nano Letters. 19 (8): 4941–4948. Bibcode:2019NanoL..19.4941K. doi:10.1021/acs.nanolett.9b01056. PMID   31265307. S2CID   206750455.
  6. 1 2 3 Zhang, Chunli; Yin, Huanhuan; Han, Min; Dai, Zhihui; Pang, Huan; Zheng, Yulin; Lan, Ya-Qian; Bao, Jianchun; Zhu, Jianmin (2014). "Two-Dimensional Tin Selenide Nanostructures for Flexible All-Solid-State Supercapacitors". ACS Nano. 8 (4): 3761–70. doi:10.1021/nn5004315. PMID   24601530.
  7. 1 2 Boudjouk, Philip; Seidler, Dean J.; Grier, Dean; McCarthy, Gregory J. (1996). "Benzyl-Substituted Tin Chalcogenides. Efficient Single-Source Precursors for Tin Sulfide, Tin Selenide, and Sn(SxSe1−x) Solid Solutions". Chemistry of Materials. 8 (6): 1189. doi:10.1021/cm9504347.
  8. ↑ Wiedemeier, Heribert; von Schnering, Hans Georg (1978). "Refinement of the structures of GeS, Ge Se, SnS and Sn Se". Zeitschrift für Kristallographie. 148 (3–4): 295. Bibcode:1978ZK....148..295W. doi:10.1524/zkri.1978.148.3-4.295. S2CID   53314748.
  9. ↑ Taniguchi, M.; Johnson, R. L.; Ghijsen, J.; Cardona, M. (1990). "Core excitons and conduction-band structures in orthorhombic GeS, Ge Se, SnS, and Sn Se single crystals" (PDF). Physical Review B. 42 (6): 3634–3643. Bibcode:1990PhRvB..42.3634T. doi:10.1103/PhysRevB.42.3634. PMID   9995878.
  10. ↑ Timofeev, Yu. A.; Vinogradov, B. V.; Begoulev, V. B. (1997). "Superconductivity of tin selenide at pressures up to 70 GPa". Physics of the Solid State. 39 (2): 207. Bibcode:1997PhSS...39..207T. doi:10.1134/1.1130136. S2CID   120770417.
  11. ↑ Abutbul, Ran Eitan; Segev, Elad; Samuha, Shmuel; Zeiri, Leila; Ezersky, Vladimir; Makov, Guy; Golan, Yuval (2016). "A new nanocrystalline binary phase: synthesis and properties of cubic tin monoselenide". CrystEngComm. 18 (11): 1918–1923. doi: 10.1039/c5ce02437d .
  12. ↑ Koren, Bar; Abutbul, Ran Eitan; Ezersky, Vladimir; Maman, Nitzan; Golan, Yuval (2021). "A new binary phase in the tin monoselenide system: chemical epitaxy of orthorhombic γ-SnSe thin films". Materials Chemistry Frontiers. 5 (13): 5004–5011. doi:10.1039/d1qm00410g. S2CID   235849184.
  13. ↑ Greenwood, Norman N.; Earnshaw, Alan (1984). Chemistry of the Elements. Oxford: Pergamon Press. p. 453. ISBN   978-0-08-022057-4.
  14. ↑ Liu, Shuhao; Sun, Naikun; Liu, Mei; Sucharitakul, Sukrit; Gao, Xuan (20 March 2018). "Nanostructured SnSe: Synthesis, doping, and thermoelectric properties". Journal of Applied Physics. 123 (11). American Institute of Physics: 115109. Bibcode:2018JAP...123k5109L. doi:10.1063/1.5018860.
  15. ↑ Zhang, Weixin; Yang, Zeheng; Liu, Juewen; Zhang, Lei; Hui, Zehua; Yu, Weichao; Qian, Yitai; Chen, Lin; Liu, Xianming (2000). "Room temperature growth of nanocrystalline tin (II) selenide from aqueous solution". Journal of Crystal Growth. 217 (1–2): 157–160. Bibcode:2000JCrGr.217..157Z. doi:10.1016/S0022-0248(00)00462-0.
  16. ↑ Rongione, N. (2019). "High-performance solution-processable flexible SnSe nanosheet films for lower grade waste heat recovery". Advanced Electronic Materials. 5 (3): 1800774. doi:10.1002/aelm.201800774. S2CID   139199322.
  17. ↑ Pletikosić, Ivo; von Rohr, Fabian S.; Pervan, Petar; Das, Pranab K.; Cava, Robert (2018). "Band structure of a IV-VI black phosphorus analogue, the thermoelectric SnSe". Physical Review Letters. 120 (15): 156403. arXiv: 1707.04289 . doi:10.1103/PhysRevLett.120.156403. PMID   29756873. S2CID   21734023.
  18. ↑ Snyder, G. Jeffrey; Toberer, Eric S. (2008). "Complex thermoelectric materials". Nature Materials. 7 (2): 105–14. Bibcode:2008NatMa...7..105S. doi:10.1038/nmat2090. PMID   18219332.
  19. ↑ Researchers find tin selenide shows promise for efficiently converting waste heat into electrical energy. phys.org (April 17, 2014)
  20. ↑ Zhao, L. D.; Lo, S. H.; Zhang, Y; Sun, H; Tan, G; Uher, C; Wolverton, C; Dravid, V. P.; Kanatzidis, M. G. (2014). "Ultralow thermal conductivity and high thermoelectric figure of merit in Sn Se crystals". Nature. 508 (7496): 373–7. Bibcode:2014Natur.508..373Z. doi:10.1038/nature13184. PMID   24740068. S2CID   205238132.
  21. ↑ Chen, Cheng-Lung; Wang, Heng; Chen, Yang-Yuan; Day, Tristan; Snyder, G. Jeffrey (2014). "Thermoelectric properties of p-type polycrystalline Sn Se doped with Ag" (PDF). Journal of Materials Chemistry A. 2 (29): 11171. doi:10.1039/C4TA01643B.
  22. ↑ Erdemir, Ali (2008). "Crystal Chemistry and Solid Lubricating Properties of the Monochalcogenides Gallium Selenide and Tin Selenide". Tribology Transactions. 37 (3): 471–478. doi:10.1080/10402009408983319.
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