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Tin selenide

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Tin selenide
Names
Other names
Tin(II) selenide
Identifiers
ECHA InfoCard 100.013.871 Edit this at Wikidata
Properties
SnSe
Molar mass 197.67 g/mol
Appearance steel gray odorless powder
Density 6.179 g/cm3
Melting point 861 °C (1,582 °F; 1,134 K)
insoluble
Band gap between 1 to 2
Structure
Halite (cubic), cF8
Fm3m, No. 225
Octahedral (Sn2+)
Octahedral (Se2−)
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).
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Tin(II) selenide, also known as stannous selenide, is an inorganic compound with the formula (SnSe), where Tin has a +2 oxidation state. Tin (II) selenide is a narrow band-gap (IV-VI) semiconductor and has received considerable interest for applications including low-cost photovoltaics and memory-switching devices.[1] Tin (II) selenide is a typical layered metal chalcogenide;[2] that is, it includes a Group 16 anion (Se2−) and an electropositive element (Sn2+), and it is arranged in a layered structure.

Tin (II) selenide exhibits low thermal conductivity as well as reasonable electrical conductivity, creating the possibility of it being used in thermoelectric materials.[3]

Structure

Tin (II) selenide (SnSe) has stiff bonds and distorted lattice, crystallizing in the orthorhombic GeSe (Germanium selenide) structure. Thus, SnSe is isomorphous with GeSe because they have similar shapes.[4] In order to be isomorphous, two substances must have the same chemical formulation, and they must contain atoms with corresponding chemical properties and with similar atomic radii. Tin (II) selenide exists in a doubled layered structure that derives from a distorted rock-salt structure. Within these double layers, each tin atom is covalently bonded to three neighboring selenide (Se) atoms, and each selenide atom is covalently bonded to three neighboring tin atoms.[5] The double layers are then held together primarily by van der Waals forces.[6]

Tin (II) selenide’s layered structure bestows both anharmonic and anisotropic bonding to the compound.

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 a CsCl structure.[7]

Synthesis

Tin (II) selenide can be formed by reacting the elements tin and selenium above 350 °C.[8]

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, 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.[9]

However, 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.[10]

Additionally, SnSe nanocrystals have also been synthesized by a gas-phase laser photolysis reaction that used Sn(CH3)4 and Se(CH3)2 (DMS) as precursors.[11]

Chemistry

Tin (II) selenide adopts a layered orthorhombic crystal structure at room temperature, which can be derived from a three-dimensional distortion of the NaCl structure. There are two-atom-thick SnSe slabs (along the b–c plane) with strong Sn–Se bonding within the plane of the slabs, which are then linked with weaker Sn–Se bonding along the a direction. The structure contains highly distorted SnSe7 coordination polyhedra, which have three short and four very long Sn–Se bonds, and a lone pair of the Sn2+ sterically accommodated between the four long Sn–Se bonds. The two-atom-thick SnSe slabs are corrugated, creating a zig-zag accordion-like projection along the b axis. The easy cleavage in this system is along the (100) planes. While cooling from its high-temperature, higher symmetry phase (space group Cmcm, #63), SnSe undergoes a displacive (shear) phase transition at ~750–800 K, resulting in a lower symmetry Pnma (#62) space group. Due to this layered, zig-zag accordion-like structure, SnSe demonstrates low anharmonicity and an intrinsically ultralow lattice thermal conductivity, making SnSe one of the world’s least thermally conductive crystalline materials. Heat cannot travel well through this material because of its very “soft,” accordion-like layered structure, which does not transmit vibrations well.[12]

Use in Energy Harvesting

Tin (II) selenide may be soon used in energy harvesting. Tin (II) selenide has demonstrated the ability to convert waste heat into electrical energy. 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%. In order for this thermoelectric process to work, a thermoelectric generator must take advantage of the temperature difference experienced by two legs of a thermocouple junction. Each leg is composed of a specific material that is optimized at the operating temperature range of interest. SnSe would serve as the p-type semiconductor leg. Such a material needs to have low total thermal conductivity, high electrical conductivity, and high Seebeck coefficient according to the thermoelectric figure of merit ZT. While historically, lead telluride and Silicon-germanium have been used, these materials have suffered from heat conduction through the material.[13]. 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 cool side does not feel the crystal vibrations (also known as phonons). For tin (II) selenide, 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.[14]. 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. [15]. 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 Uses

Tin selenides may be used for optoelectronic devices, solar cells, memory switching devices,[16] and anodes for lithium-ion batteries.[17]

Tin (II) selenide has an additional use as a solid-state lubricant, due to the nature of its interlayer bonding.[18]

References

  1. ^ http://www.sigmaaldrich.com/catalog/product/aldrich/751448?lang=en&region=US
  2. ^ Two-Dimensional Tin Selenide Nanostructures for Flexible All-Solid-State Supercapacitors Chunli Zhang, Huanhuan Yin, Min Han, Zhihui Dai, Huan Pang, Yulin Zheng, Ya-Qian Lan, Jianchun Bao, and Jianmin Zhu ACS Nano 2014 8 (4), 3761-3770. http://dx.doi.org/10.1021/nn5004315
  3. ^ Northwestern University. "Surprising material could play huge role in saving energy: Tin selenide is best at converting waste heat to electricity." ScienceDaily. ScienceDaily, 17 April 2014. <www.sciencedaily.com/releases/2014/04/140417124519.htm>.
  4. ^ Benzyl-Substituted Tin Chalcogenides. Efficient Single-Source Precursors for Tin Sulfide, Tin Selenide, and Sn(SxSe1-x) Solid Solutions Philip Boudjouk,*, Dean J. Seidler,Dean Grier, and, and Gregory J. McCarthy Chemistry of Materials 1996 8 (6), 1189-1196. http://dx.doi.org/10.1021/cm9504347
  5. ^ Wiedemeier,H.;vonSchnering,H.G.Z.Kristallogr.1978,148, 295.
  6. ^ Taniguchi, M.; Johnson, P. L.; Ghijsen, J.; Cardona, M. Phys. Rev. B 1990, 42, 3634. http://dx.doi.org/10.1103/PhysRevB.42.3634
  7. ^ Timofeev, Yu. A., B. V. Vinogradov, and V. B. Begoulev. "Superconductivity Of Tin Selenide At Pressures Up To 70 Gpa." Physics Of The Solid State 39.2 (1997): 207. Academic Search Elite. Web. 28 Nov. 2014. http://search.ebscohost.com.ezproxy.dordt.edu:8080/login.aspx?direct=true&db=afh&AN=7322893&site=ehost-live
  8. ^ Greenwood, Norman N.; Earnshaw, Alan (1984). Chemistry of the Elements. Oxford: Pergamon Press. p. 453. ISBN 978-0-08-022057-4.
  9. ^ Two-Dimensional Tin Selenide Nanostructures for Flexible All-Solid-State Supercapacitors Chunli Zhang, Huanhuan Yin, Min Han, Zhihui Dai, Huan Pang, Yulin Zheng, Ya-Qian Lan, Jianchun Bao, and Jianmin Zhu ACS Nano 2014 8 (4), 3761-3770. http://dx.doi.org/10.1021/nn5004315
  10. ^ Room temperature growth of nanocrystalline tin (II) selenide from aqueous solution. Weixin Zhang, Zeheng Yang, Juewen Liu, Lei Zhang, Zehua Hui, Weichao Yu Yitai Qian, Lin Chen, Xianming Liu. Journal of Crystal Growth. Volume 217, Issues 1–2, 11 July 2000, Pages 157–160. http://dx.doi.org/10.1016/S0022-0248(00)00462-0
  11. ^ Im, H.S, Y.R Lim, Y.J Cho, J Park, E.H Cha, and H.S Kang. "Germanium and Tin Selenide Nanocrystals for High-Capacity Lithium Ion Batteries: Comparative Phase Conversion of Germanium and Tin." Journal of Physical Chemistry C. 118.38 (2014): 21884-21888. http://dx.doi.org.ezproxy.dordt.edu:8080/10.1021/jp507337c
  12. ^ Researchers find tin selenide shows promise for efficiently converting waste heat into electrical energy (2014, April 17) retrieved 11 November 2014 from http://phys.org/news/2014-04-tin-selenide-efficiently-electrical-energy.html
  13. ^ Snyder, G. J. & Toberer, E. S. Complex thermoelectric materials. Nature Mater. 7, 105–114 (2008)
  14. ^ Researchers find tin selenide shows promise for efficiently converting waste heat into electrical energy (2014, April 17) retrieved 11 November 2014 from http://phys.org/news/2014-04-tin-selenide-efficiently-electrical-energy.html
  15. ^ Zhao, L.D. et al. Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals. Nature 508, 373-377 (2014)
  16. ^ Benzyl-Substituted Tin Chalcogenides. Efficient Single-Source Precursors for Tin Sulfide, Tin Selenide, and Sn(SxSe1-x) Solid Solutions Philip Boudjouk,*, Dean J. Seidler,Dean Grier, and, and Gregory J. McCarthy Chemistry of Materials 1996 8 (6), 1189-1196 http://dx.doi.org/10.1021/cm9504347
  17. ^ Two-Dimensional Tin Selenide Nanostructures for Flexible All-Solid-State Supercapacitors Chunli Zhang, Huanhuan Yin, Min Han, Zhihui Dai, Huan Pang, Yulin Zheng, Ya-Qian Lan, Jianchun Bao, and Jianmin Zhu ACS Nano 2014 8 (4), 3761-3770 http://dx.doi.org/10.1021/nn5004315
  18. ^ Erdemir, A. "Crystal Chemistry and Solid Lubricating Properties of the Monochalcogenides Gallium Selenide and Tin Selenide." Asle Transactions. 37.3 (1994): 471. http://dx.doi.org/10.1080/10402009408983319
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