The Two-Dimensional AxCdxBi4-xQ6 (A = K, Rb, Cs; Q = S, Se): Direct Bandgap Semiconductors and Ion-Exchange Materials

Jing Zhao, Saiful M. Islam, Oleg Y. Kontsevoi, Gangjian Tan, Constantinos C. Stoumpos, Haijie Chen, R. K. Li, Mercouri G Kanatzidis

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Abstract

We report the new layered chalcogenides AxCdxBi4-xQ6 (A = Cs, Rb, K; Q = S and A = Cs; Q = Se). All compounds are isostructural crystallizing in the orthorhombic space group Cmcm, with a = 4.0216(8) Å, b = 6.9537(14) Å, c = 24.203(5) Å for Cs1.43Cd1.43Bi2.57S6 (x = 1.43); a = 3.9968(8) Å, b = 6.9243(14) Å, c = 23.700(5) Å for Rb1.54Cd1.54Bi2.46S6 (x = 1.54); a = 3.9986(8) Å, b = 6.9200(14) Å, c = 23.184(5) Å for K1.83Cd1.83Bi2.17S6 (x = 1.83) and a = 4.1363(8) Å, b = 7.1476(14) Å, c = 25.047(5) Å for Cs1.13Cd1.13Bi2.87Se6 (x = 1.13). These structures are intercalated derivatives of the Bi2Se3 structure by way of replacing some Bi3+ atoms with divalent Cd2+ atoms forming negatively charged Bi2Se3-type quintuple [CdxBi2-xSe3]x- layers. The bandgaps of these compounds are between 1.00 eV for Q = Se and 1.37 eV for Q = S. Electronic band structure calculations at the density functional theory (DFT) level indicate Cs1.13Cd1.13Bi2.87Se6 and Cs1.43Cd1.43Bi2.57S6 to be direct band gap semiconductors. Polycrystalline Cs1.43Cd1.43Bi2.57S6 samples show n-type conduction and an extremely low thermal conductivity of 0.33 W·m-1·K-1 at 773 K. The cesium ions between the layers of Cs1.43Cd1.43Bi2.57S6 are mobile and can be topotactically exchanged with Pb2+, Zn2+, Co2+ and Cd2+ in aqueous solution. The intercalation of metal cations presents a direct "soft chemical" route to create new materials.

Original languageEnglish
Pages (from-to)6978-6987
Number of pages10
JournalJournal of the American Chemical Society
Volume139
Issue number20
DOIs
Publication statusPublished - May 24 2017

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Thermal Conductivity
Cesium
Semiconductors
Ion Exchange
Cations
Ion exchange
Energy gap
Metals
Ions
Semiconductor materials
Chalcogenides
Atoms
Intercalation
Band structure
Density functional theory
Thermal conductivity
Positive ions
Derivatives

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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The Two-Dimensional AxCdxBi4-xQ6 (A = K, Rb, Cs; Q = S, Se) : Direct Bandgap Semiconductors and Ion-Exchange Materials. / Zhao, Jing; Islam, Saiful M.; Kontsevoi, Oleg Y.; Tan, Gangjian; Stoumpos, Constantinos C.; Chen, Haijie; Li, R. K.; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 139, No. 20, 24.05.2017, p. 6978-6987.

Research output: Contribution to journalArticle

Zhao, Jing ; Islam, Saiful M. ; Kontsevoi, Oleg Y. ; Tan, Gangjian ; Stoumpos, Constantinos C. ; Chen, Haijie ; Li, R. K. ; Kanatzidis, Mercouri G. / The Two-Dimensional AxCdxBi4-xQ6 (A = K, Rb, Cs; Q = S, Se) : Direct Bandgap Semiconductors and Ion-Exchange Materials. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 20. pp. 6978-6987.
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title = "The Two-Dimensional AxCdxBi4-xQ6 (A = K, Rb, Cs; Q = S, Se): Direct Bandgap Semiconductors and Ion-Exchange Materials",
abstract = "We report the new layered chalcogenides AxCdxBi4-xQ6 (A = Cs, Rb, K; Q = S and A = Cs; Q = Se). All compounds are isostructural crystallizing in the orthorhombic space group Cmcm, with a = 4.0216(8) {\AA}, b = 6.9537(14) {\AA}, c = 24.203(5) {\AA} for Cs1.43Cd1.43Bi2.57S6 (x = 1.43); a = 3.9968(8) {\AA}, b = 6.9243(14) {\AA}, c = 23.700(5) {\AA} for Rb1.54Cd1.54Bi2.46S6 (x = 1.54); a = 3.9986(8) {\AA}, b = 6.9200(14) {\AA}, c = 23.184(5) {\AA} for K1.83Cd1.83Bi2.17S6 (x = 1.83) and a = 4.1363(8) {\AA}, b = 7.1476(14) {\AA}, c = 25.047(5) {\AA} for Cs1.13Cd1.13Bi2.87Se6 (x = 1.13). These structures are intercalated derivatives of the Bi2Se3 structure by way of replacing some Bi3+ atoms with divalent Cd2+ atoms forming negatively charged Bi2Se3-type quintuple [CdxBi2-xSe3]x- layers. The bandgaps of these compounds are between 1.00 eV for Q = Se and 1.37 eV for Q = S. Electronic band structure calculations at the density functional theory (DFT) level indicate Cs1.13Cd1.13Bi2.87Se6 and Cs1.43Cd1.43Bi2.57S6 to be direct band gap semiconductors. Polycrystalline Cs1.43Cd1.43Bi2.57S6 samples show n-type conduction and an extremely low thermal conductivity of 0.33 W·m-1·K-1 at 773 K. The cesium ions between the layers of Cs1.43Cd1.43Bi2.57S6 are mobile and can be topotactically exchanged with Pb2+, Zn2+, Co2+ and Cd2+ in aqueous solution. The intercalation of metal cations presents a direct {"}soft chemical{"} route to create new materials.",
author = "Jing Zhao and Islam, {Saiful M.} and Kontsevoi, {Oleg Y.} and Gangjian Tan and Stoumpos, {Constantinos C.} and Haijie Chen and Li, {R. K.} and Kanatzidis, {Mercouri G}",
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T1 - The Two-Dimensional AxCdxBi4-xQ6 (A = K, Rb, Cs; Q = S, Se)

T2 - Direct Bandgap Semiconductors and Ion-Exchange Materials

AU - Zhao, Jing

AU - Islam, Saiful M.

AU - Kontsevoi, Oleg Y.

AU - Tan, Gangjian

AU - Stoumpos, Constantinos C.

AU - Chen, Haijie

AU - Li, R. K.

AU - Kanatzidis, Mercouri G

PY - 2017/5/24

Y1 - 2017/5/24

N2 - We report the new layered chalcogenides AxCdxBi4-xQ6 (A = Cs, Rb, K; Q = S and A = Cs; Q = Se). All compounds are isostructural crystallizing in the orthorhombic space group Cmcm, with a = 4.0216(8) Å, b = 6.9537(14) Å, c = 24.203(5) Å for Cs1.43Cd1.43Bi2.57S6 (x = 1.43); a = 3.9968(8) Å, b = 6.9243(14) Å, c = 23.700(5) Å for Rb1.54Cd1.54Bi2.46S6 (x = 1.54); a = 3.9986(8) Å, b = 6.9200(14) Å, c = 23.184(5) Å for K1.83Cd1.83Bi2.17S6 (x = 1.83) and a = 4.1363(8) Å, b = 7.1476(14) Å, c = 25.047(5) Å for Cs1.13Cd1.13Bi2.87Se6 (x = 1.13). These structures are intercalated derivatives of the Bi2Se3 structure by way of replacing some Bi3+ atoms with divalent Cd2+ atoms forming negatively charged Bi2Se3-type quintuple [CdxBi2-xSe3]x- layers. The bandgaps of these compounds are between 1.00 eV for Q = Se and 1.37 eV for Q = S. Electronic band structure calculations at the density functional theory (DFT) level indicate Cs1.13Cd1.13Bi2.87Se6 and Cs1.43Cd1.43Bi2.57S6 to be direct band gap semiconductors. Polycrystalline Cs1.43Cd1.43Bi2.57S6 samples show n-type conduction and an extremely low thermal conductivity of 0.33 W·m-1·K-1 at 773 K. The cesium ions between the layers of Cs1.43Cd1.43Bi2.57S6 are mobile and can be topotactically exchanged with Pb2+, Zn2+, Co2+ and Cd2+ in aqueous solution. The intercalation of metal cations presents a direct "soft chemical" route to create new materials.

AB - We report the new layered chalcogenides AxCdxBi4-xQ6 (A = Cs, Rb, K; Q = S and A = Cs; Q = Se). All compounds are isostructural crystallizing in the orthorhombic space group Cmcm, with a = 4.0216(8) Å, b = 6.9537(14) Å, c = 24.203(5) Å for Cs1.43Cd1.43Bi2.57S6 (x = 1.43); a = 3.9968(8) Å, b = 6.9243(14) Å, c = 23.700(5) Å for Rb1.54Cd1.54Bi2.46S6 (x = 1.54); a = 3.9986(8) Å, b = 6.9200(14) Å, c = 23.184(5) Å for K1.83Cd1.83Bi2.17S6 (x = 1.83) and a = 4.1363(8) Å, b = 7.1476(14) Å, c = 25.047(5) Å for Cs1.13Cd1.13Bi2.87Se6 (x = 1.13). These structures are intercalated derivatives of the Bi2Se3 structure by way of replacing some Bi3+ atoms with divalent Cd2+ atoms forming negatively charged Bi2Se3-type quintuple [CdxBi2-xSe3]x- layers. The bandgaps of these compounds are between 1.00 eV for Q = Se and 1.37 eV for Q = S. Electronic band structure calculations at the density functional theory (DFT) level indicate Cs1.13Cd1.13Bi2.87Se6 and Cs1.43Cd1.43Bi2.57S6 to be direct band gap semiconductors. Polycrystalline Cs1.43Cd1.43Bi2.57S6 samples show n-type conduction and an extremely low thermal conductivity of 0.33 W·m-1·K-1 at 773 K. The cesium ions between the layers of Cs1.43Cd1.43Bi2.57S6 are mobile and can be topotactically exchanged with Pb2+, Zn2+, Co2+ and Cd2+ in aqueous solution. The intercalation of metal cations presents a direct "soft chemical" route to create new materials.

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