Quaternary Chalcogenide Semiconductors with 2D Structures: Rb2ZnBi2Se5 and Cs6Cd2Bi8Te17
Abstract
In this work, two new layered compounds Rb2ZnBi2Se5 and Cs6Cd2Bi8Te17 are described. Rb2ZnBi2Se5 crystallizes in the orthorhombic space group Pnma, with lattice parameters of a = 15.6509(17) Å, b = 4.218(8) Å, and c = 18.653(3) Å. Cs6Cd2Bi8Te17 crystallizes in the monoclinic C2/m space group, with a = 28.646(6) Å, b = 4.4634(9) Å, c = 21.164(4) Å, and β = 107.65(3)°. The two structures are different and composed of anionic layers which are formed by inter connecting of BiQ6 octahedra (Q = Se or Te) and MQ4 (M = Zn or Cd) tetrahedra. The space between the layers hosts alkali metal as counter cations. The rubidium atoms of Rb2ZnBi2Se5 structure can be exchanged with other cations (Cd2+, Pb2+ and Zn2+) in aqueous solutions forming new phases. Rb2ZnBi2Se5 is an n-type semiconductor and exhibits an indirect band gap energy of 1.0 eV. Rb2ZnBi2Se5 is a congruently melting compound (mp ~644 °C). The thermal conductivity of this semiconductor is very low with 0.38 W· m-1·K-1 at 873 K. Density functional theory (DFT) calculations suggest that the low lattice thermal conductivity of Rb2ZnBi2Se5 is attributed to heavy Bi atom induced slow phonon velocities and large Gruneisen parameters especially in the a andmore »
- Authors:
-
[1];
[3];
[2];
[2];
[2];
[2]
- Univ. of Science and Technology, Beijing (China); Northwestern Univ., Evanston, IL (United States)
- Northwestern Univ., Evanston, IL (United States)
- Jackson State Univ., Jackson, MS (United States)
- Publication Date:
- Research Org.:
- Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); National Science Foundation (NSF)
- OSTI Identifier:
- 1775444
- Grant/Contract Number:
- SC0014520; 2182080; 2182029; 51702329; DMR-1708254; DMR-1121262; EEC-0118025/003
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 57; Journal Issue: 15; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical structure; Crystal structure; Lattices; Layers; Thermal conductivity
Citation Formats
Zhao, Jing, Hao, Shiqiang, Islam, Saiful M., Chen, Haijie, Ma, Shulan, Wolverton, Chris, and Kanatzidis, Mercouri G. Quaternary Chalcogenide Semiconductors with 2D Structures: Rb2ZnBi2Se5 and Cs6Cd2Bi8Te17. United States: N. p., 2018.
Web. doi:10.1021/acs.inorgchem.8b01383.
Zhao, Jing, Hao, Shiqiang, Islam, Saiful M., Chen, Haijie, Ma, Shulan, Wolverton, Chris, & Kanatzidis, Mercouri G. Quaternary Chalcogenide Semiconductors with 2D Structures: Rb2ZnBi2Se5 and Cs6Cd2Bi8Te17. United States. https://doi.org/10.1021/acs.inorgchem.8b01383
Zhao, Jing, Hao, Shiqiang, Islam, Saiful M., Chen, Haijie, Ma, Shulan, Wolverton, Chris, and Kanatzidis, Mercouri G. Mon .
"Quaternary Chalcogenide Semiconductors with 2D Structures: Rb2ZnBi2Se5 and Cs6Cd2Bi8Te17". United States. https://doi.org/10.1021/acs.inorgchem.8b01383. https://www.osti.gov/servlets/purl/1775444.
@article{osti_1775444,
title = {Quaternary Chalcogenide Semiconductors with 2D Structures: Rb2ZnBi2Se5 and Cs6Cd2Bi8Te17},
author = {Zhao, Jing and Hao, Shiqiang and Islam, Saiful M. and Chen, Haijie and Ma, Shulan and Wolverton, Chris and Kanatzidis, Mercouri G.},
abstractNote = {In this work, two new layered compounds Rb2ZnBi2Se5 and Cs6Cd2Bi8Te17 are described. Rb2ZnBi2Se5 crystallizes in the orthorhombic space group Pnma, with lattice parameters of a = 15.6509(17) Å, b = 4.218(8) Å, and c = 18.653(3) Å. Cs6Cd2Bi8Te17 crystallizes in the monoclinic C2/m space group, with a = 28.646(6) Å, b = 4.4634(9) Å, c = 21.164(4) Å, and β = 107.65(3)°. The two structures are different and composed of anionic layers which are formed by inter connecting of BiQ6 octahedra (Q = Se or Te) and MQ4 (M = Zn or Cd) tetrahedra. The space between the layers hosts alkali metal as counter cations. The rubidium atoms of Rb2ZnBi2Se5 structure can be exchanged with other cations (Cd2+, Pb2+ and Zn2+) in aqueous solutions forming new phases. Rb2ZnBi2Se5 is an n-type semiconductor and exhibits an indirect band gap energy of 1.0 eV. Rb2ZnBi2Se5 is a congruently melting compound (mp ~644 °C). The thermal conductivity of this semiconductor is very low with 0.38 W· m-1·K-1 at 873 K. Density functional theory (DFT) calculations suggest that the low lattice thermal conductivity of Rb2ZnBi2Se5 is attributed to heavy Bi atom induced slow phonon velocities and large Gruneisen parameters especially in the a and c directions. The thermoelectric properties of Rb2ZnBi2Se5 were characterized with the highest ZT value of ~0.25 at 839 K.},
doi = {10.1021/acs.inorgchem.8b01383},
journal = {Inorganic Chemistry},
number = 15,
volume = 57,
place = {United States},
year = {Mon Jul 16 00:00:00 EDT 2018},
month = {Mon Jul 16 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 8 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Concerted Rattling in CsAg 5 Te 3 Leading to Ultralow Thermal Conductivity and High Thermoelectric Performance
journal, August 2016
- Lin, Hua; Tan, Gangjian; Shen, Jin-Ni
- Angewandte Chemie International Edition, Vol. 55, Issue 38
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Visualizing the Role of Bi 6s “Lone Pairs” in the Off-Center Distortion in Ferromagnetic BiMnO 3
journal, September 2001
- Seshadri, Ram; Hill, Nicola A.
- Chemistry of Materials, Vol. 13, Issue 9
Flexible Polar Nanowires of Cs 5 BiP 4 Se 12 from Weak Interactions between Coordination Complexes: Strong Nonlinear Optical Second Harmonic Generation
journal, January 2009
- Chung, In; Song, Jung-Hwan; Jang, Joon I.
- Journal of the American Chemical Society, Vol. 131, Issue 7
Structure and Thermoelectric Properties of the New Quaternary Bismuth Selenides A1−xM4−xBi11+xSe21 (A=K and Rb and Cs; M=Sn and Pb)—Members of the Grand Homologous Series Km(M6Se8)m(M5+nSe9+n)
journal, May 2001
- Mrotzek, Antje; Chung, Duck-Young; Ghelani, Nishant
- Chemistry, Vol. 7, Issue 9
Molten salt synthesis and properties of three new solid-state ternary bismuth chalcogenides, .beta.-CsBiS2, .gamma.-CsBiS2, and K2Bi8Se13
journal, March 1993
- McCarthy, Timothy J.; Ngeyi, Stanley Pierre; Liao, Ju Hsiou
- Chemistry of Materials, Vol. 5, Issue 3
An argyrodite-type Ag 9 GaSe 6 liquid-like material with ultralow thermal conductivity and high thermoelectric performance
journal, January 2017
- Jiang, Binbin; Qiu, Pengfei; Chen, Hongyi
- Chem. Commun., Vol. 53, Issue 85
Solution-Based Synthesis of Layered Intergrowth Compounds of the Homologous Pb m Bi 2 n Te 3 n + m Series as Nanosheets
journal, March 2015
- Chatterjee, Arindom; Biswas, Kanishka
- Angewandte Chemie International Edition, Vol. 54, Issue 19
High thermoelectric performance in tellurium free p-type AgSbSe2
journal, January 2013
- Guin, Satya N.; Chatterjee, Arindom; Negi, Devendra Singh
- Energy & Environmental Science, Vol. 6, Issue 9
Thermoelectric transport and microstructure of optimized Mg 2 Si 0.8 Sn 0.2
journal, January 2015
- de Boor, J.; Gupta, S.; Kolb, H.
- Journal of Materials Chemistry C, Vol. 3, Issue 40
Superconductivity in the 2-Dimensional Homologous Series AM m Bi 3 Q 5+ m ( m =1, 2) (A=Rb, Cs; M=Pb, Sn; Q=Se, Te)
journal, April 2018
- Malliakas, Christos D.; Chung, Duck Young; Claus, Helmut
- Chemistry - A European Journal, Vol. 24, Issue 28
First-Principles Determination of Multicomponent Hydride Phase Diagrams: Application to the Li-Mg-N-H System
journal, September 2007
- R. Akbarzadeh, A.; Ozoliņš, V.; Wolverton, C.
- Advanced Materials, Vol. 19, Issue 20
Homologous Series of 2D Chalcogenides Cs–Ag–Bi–Q (Q = S, Se) with Ion-Exchange Properties
journal, August 2017
- Zhao, Jing; Islam, Saiful M.; Hao, Shiqiang
- Journal of the American Chemical Society, Vol. 139, Issue 36
Measuring thermoelectric transport properties of materials
journal, January 2015
- Borup, Kasper A.; de Boor, Johannes; Wang, Heng
- Energy & Environmental Science, Vol. 8, Issue 2
A New Thermoelectric Material: CsBi 4 Te 6
journal, May 2004
- Chung, Duck-Young; Hogan, Tim P.; Rocci-Lane, Melissa
- Journal of the American Chemical Society, Vol. 126, Issue 20
Thermal conductivity of germanium crystals with different isotopic compositions
journal, October 1997
- Asen-Palmer, M.; Bartkowski, K.; Gmelin, E.
- Physical Review B, Vol. 56, Issue 15
Structural Evolution and Phase Homologies for “Design” and Prediction of Solid-State Compounds
journal, April 2005
- Kanatzidis, Mercouri G.
- Accounts of Chemical Research, Vol. 38, Issue 4
A 2 CuP 3 S 9 (A = K, Rb), Cs 2 Cu 2 P 2 S 6 , and K 3 CuP 2 S 7 : New Phases from the Dissolution of Copper in Molten Polythiophosphate Fluxes
journal, October 1998
- Hanko, Jason A.; Sayettat, Julien; Jobic, Stéphane
- Chemistry of Materials, Vol. 10, Issue 10
High-performance bulk thermoelectrics with all-scale hierarchical architectures
journal, September 2012
- Biswas, Kanishka; He, Jiaqing; Blum, Ivan D.
- Nature, Vol. 489, Issue 7416, p. 414-418
A 2 Bi 8 Se 13 (A = Rb, Cs), CsBi 3.67 Se 6 , and BaBi 2 Se 4 : New Ternary Semiconducting Bismuth Selenides
journal, January 2001
- Iordanidis, Lykourgos; Brazis, Paul W.; Kyratsi, Theodora
- Chemistry of Materials, Vol. 13, Issue 2
The Two-Dimensional A x Cd x Bi 4– x Q 6 (A = K, Rb, Cs; Q = S, Se): Direct Bandgap Semiconductors and Ion-Exchange Materials
journal, May 2017
- Zhao, Jing; Islam, Saiful M.; Kontsevoi, Oleg Y.
- Journal of the American Chemical Society, Vol. 139, Issue 20
Syntheses and structures of the quaternary alkali-metal bismuth coinage-metal chalcogenides K3Bi5Cu2S10, CsBi2CuS4, RbBi2.66CuSe5, and CsBiAg2S3
journal, July 2001
- Huang, Fu Qiang; Mitchell, Kwasi; Ibers, James A.
- Journal of Alloys and Compounds, Vol. 325, Issue 1-2
Cs 2 Bi 2 ZnSe 5
journal, August 2004
- Yao, Jiyong; Ibers, James A.
- Acta Crystallographica Section E Structure Reports Online, Vol. 60, Issue 9
The New Semiconductor Cs 4 Cu 3 Bi 9 S 17
journal, February 2017
- Zhao, Jing; Islam, Saiful M.; Tan, Gangjian
- Chemistry of Materials, Vol. 29, Issue 4
Modular Construction of A 1+ x M 4 - 2 x M‘ 7+ x Se 15 (A = K, Rb; M = Pb, Sn; M‘ = Bi, Sb): A New Class of Solid State Quaternary Thermoelectric Compounds
journal, March 2001
- Choi, Kyoung-Shin; Chung, Duck-Young; Mrotzek, Antje
- Chemistry of Materials, Vol. 13, Issue 3
High Thermoelectric Performance in Non-Toxic Earth-Abundant Copper Sulfide
journal, March 2014
- He, Ying; Day, Tristan; Zhang, Tiansong
- Advanced Materials, Vol. 26, Issue 23
New Quaternary Bismuth Sulfides: Syntheses, Structures, and Band Structures of AMBiS 4 (A = Rb, Cs; M = Si, Ge)
journal, December 2002
- Yao, Jiyong; Deng, Bin; Ellis, Donald E.
- Inorganic Chemistry, Vol. 41, Issue 26
Synthesis and Thermoelectric Properties of Cs 2 Bi 7.33 Se 12 , A 2 Bi 8 Se 13 (A = Rb, Cs), Ba 4-x Bi 6+2/3x Se 13 , and Ba 3±x Pb 3±x Bi 6 Se 15
journal, January 1998
- Iordanidis, Lykourgos; Brazis, Paul W.; Kannewurf, Carl R.
- MRS Proceedings, Vol. 545
Structures and Conductivities of the Quaternary A/Bi/Cu/S Phases KBi2CuS4 and A3Bi5Cu2S10 (A=Rb, Cs)
journal, November 2000
- Yang, Yuting; Brazis, Paul; Kannewurf, Carl R.
- Journal of Solid State Chemistry, Vol. 155, Issue 1
Quaternary rubidium copper tin sulfides (Rb2Cu2SnS4, A2Cu2Sn2S6 (A = Na, K, Rb, Cs), A2Cu2Sn2Se6 (A = K, Rb), potassium gold tin sulfides, K2Au2SnS4, and K2Au2Sn2S6. Syntheses, structures, and properties of new solid-state chalcogenides based on tetrahedral [SnS4]4- units
journal, October 1993
- Liao, Ju Hsiou; Kanatzidis, Mercouri G.
- Chemistry of Materials, Vol. 5, Issue 10
“Design” in Solid-State Chemistry Based on Phase Homologies. The Concept of Structural Evolution and the New Megaseries Am[M1+lSe2+l]2m[M2l+nSe2+3l+n]
journal, January 2003
- Mrotzek, Antje; Kanatzidis, Mercouri G.
- Accounts of Chemical Research, Vol. 36, Issue 2
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
CsBi4Te6: A High-Performance Thermoelectric Material for Low-Temperature Applications
journal, February 2000
- Chung, D.
- Science, Vol. 287, Issue 5455
High Thermoelectric Performance in Electron-Doped AgBi 3 S 5 with Ultralow Thermal Conductivity
journal, May 2017
- Tan, Gangjian; Hao, Shiqiang; Zhao, Jing
- Journal of the American Chemical Society, Vol. 139, Issue 18
Novel Quaternary Lanthanum Bismuth Sulfides Pb 2 La x Bi 8- x S 14 , Sr 2 La x Bi 8- x S 14 , and Cs 2 La x Bi 10- x S 16 with Complex Structures
journal, April 2001
- Iordanidis, Lykourgos; Kanatzidis, Mercouri G.
- Inorganic Chemistry, Vol. 40, Issue 8
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Chemistry in Molten Alkali Metal Polyselenophosphate Fluxes. Influence of Flux Composition on Dimensionality. Layers and Chains in APbPSe4, A4Pb(PSe4)2 (A = Rb, Cs), and K4Eu(PSe4)2
journal, January 1996
- Chondroudis, Konstantinos; McCarthy, Timothy J.; Kanatzidis, Mercouri G.
- Inorganic Chemistry, Vol. 35, Issue 4
Superconductivity with Topological Surface State in Sr x Bi 2 Se 3
journal, August 2015
- Liu, Zhongheng; Yao, Xiong; Shao, Jifeng
- Journal of the American Chemical Society, Vol. 137, Issue 33
Highly Porous Thermoelectric Nanocomposites with Low Thermal Conductivity and High Figure of Merit from Large-Scale Solution-Synthesized Bi 2 Te 2.5 Se 0.5 Hollow Nanostructures
journal, January 2017
- Xu, Biao; Feng, Tianli; Agne, Matthias T.
- Angewandte Chemie, Vol. 129, Issue 13
Topological insulators in Bi2Se3, Bi2Te3 and Sb2Te3 with a single Dirac cone on the surface
journal, May 2009
- Zhang, Haijun; Liu, Chao-Xing; Qi, Xiao-Liang
- Nature Physics, Vol. 5, Issue 6, p. 438-442
Sb and Se Substitution in CsBi 4 Te 6 : The Semiconductors CsM 4 Q 6 (M = Bi, Sb; Q = Te, Se), Cs 2 Bi 10 Q 15 , and CsBi 5 Q 8
journal, May 2012
- Chung, Duck Young; Uher, Ctirad; Kanatzidis, Mercouri G.
- Chemistry of Materials, Vol. 24, Issue 10
Materials Design and Discovery with High-Throughput Density Functional Theory: The Open Quantum Materials Database (OQMD)
journal, September 2013
- Saal, James E.; Kirklin, Scott; Aykol, Muratahan
- JOM, Vol. 65, Issue 11
Superconductivity in the Narrow Gap Semiconductor RbBi 11/3 Te 6
journal, October 2016
- Malliakas, Christos D.; Chung, Duck Young; Claus, Helmut
- Journal of the American Chemical Society, Vol. 138, Issue 44
Semiconducting Pavonites CdMBi 4 Se 8 (M = Sn and Pb) and Their Thermoelectric Properties
journal, September 2017
- Zhao, Jing; Islam, Saiful M.; Hao, Shiqiang
- Chemistry of Materials, Vol. 29, Issue 19
Syntheses, structures, optical properties, and theoretical calculations of Cs2Bi2ZnS5, Cs2Bi2CdS5, and Cs2Bi2MnS5
journal, September 2003
- Huang, Fu Qiang; Somers, Rebecca C.; McFarland, Adam D.
- Journal of Solid State Chemistry, Vol. 174, Issue 2
Estimation of the isotope effect on the lattice thermal conductivity of group IV and group III-V semiconductors
journal, November 2002
- Morelli, D. T.; Heremans, J. P.; Slack, G. A.
- Physical Review B, Vol. 66, Issue 19
A new chalcogenide homologous series A2[M5+nSe9+n] (A = Rb, Cs; M = Bi, Ag, Cd)
journal, January 2006
- Kim, Jun-Ho; Chung, Duck-Young; Kanatzidis, Mercouri G.
- Chemical Communications, Issue 15
Synthesis, Crystal Structure and Thermoelectric Properties of β-K 2 Bi 8 Se 13 Solid Solutions
journal, January 2003
- Kyratsi, Theodora; Chung, Duck Young; Dyck, Jeff S.
- MRS Proceedings, Vol. 793
KBiMS4 (M=Si, Ge): Synthesis, structure, and electronic structure
journal, July 2010
- Mei, Dajiang; Lin, Zheshuai; Bai, Lei
- Journal of Solid State Chemistry, Vol. 183, Issue 7
CsMBi 3 Te 6 and CsM 2 Bi 3 Te 7 (M = Pb, Sn): New Thermoelectric Compounds with Low-Dimensional Structures
journal, March 2002
- Hsu, Kuei-Fang; Chung, Duck-Young; Lal, Sangeeta
- Journal of the American Chemical Society, Vol. 124, Issue 11
Solution-Based Synthesis and Low-Temperature Transport Properties of CsBi 4 Te 6
journal, January 2012
- Datta, Anuja; Nolas, George S.
- ACS Applied Materials & Interfaces, Vol. 4, Issue 2
Role of ion exchange in solid-state chemistry
journal, January 1988
- Clearfield, Abraham
- Chemical Reviews, Vol. 88, Issue 1
Lone pair electrons minimize lattice thermal conductivity
journal, January 2013
- Nielsen, Michele D.; Ozolins, Vidvuds; Heremans, Joseph P.
- Energy Environ. Sci., Vol. 6, Issue 2
Copper ion liquid-like thermoelectrics
journal, March 2012
- Liu, Huili; Shi, Xun; Xu, Fangfang
- Nature Materials, Vol. 11, Issue 5, p. 422-425
Substitutions in the Homologous Family CsPb m Bi 3 Te 5+m and Preliminary Thermoelectric Results
journal, January 2005
- Guéguen, Aurélie; Quarez, Eric; Kanatzidis, Mercouri G.
- MRS Proceedings, Vol. 886
CsPb3Bi3Te8 and CsPb4Bi3Te9: low-dimensional compounds and the homologous series CsPbmBi3Te5 + m
journal, May 2002
- Hsu, Kuei-Fang; Lal, Sangeeta; Hogan, Tim
- Chemical Communications, Issue 13
Works referencing / citing this record:
Discordant nature of Cd in PbSe: off-centering and core–shell nanoscale CdSe precipitates lead to high thermoelectric performance
journal, January 2020
- Cai, Songting; Hao, Shiqiang; Luo, Zhong-Zhen
- Energy & Environmental Science, Vol. 13, Issue 1