First quaternary A-Pb-Bi-Q (A = K, Rb, Cs; Q = S, Se) compounds

Synthesis, structure, and properties of α-and β-CsPbBi3Se6, APbBi3Se6, (A = K, Rb), and APbBi3S6 (A = Rb, Cs)

Duck Young Chung, Lykourgos Iordanidis, Krishnaswamy Kasthuri Rangan, Paul W. Brazis, Carl R. Kannewurf, Mercouri G Kanatzidis

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Abstract

α-CsPbBi3Se6 (I), β-CsPbBi3Se6 (II), RbPbBi3Se6 (III), KPbBi3Se6 (IV), CsPbBi3S6 (V), and RbPbBi3S6 (VI) were synthesized by the polychalcogenide flux method. α-CsPbBi3Se6 was obtained at 720 °C and crystallizes in the space group Pnma (no. 62) with α = 23.564(6) Å, b = 4.210(2) Å, c = 13.798(3) Å at room temperature. Final R/RW = 3.0/3.6%. In this compound, parallel NaCl-type Pb/Bi/Se columns with rectangularly shaped cross-sections are interconnected by edge sharing to build a 3-D tunnel framework with Cs atoms located inside the tunnels. The hexagonal plates of β-CsPbBi3Se6 were obtained at 400 °C and crystallize in the space group P63/mmc (no. 194) with a = 4.213(2) Å, c = 25.22(1) Å, y = 120° at -100 °C. Final R/RW = 4.2/4.7%. APbBi3Se6 (A = Rb, K) and APbBi3S6 (A = Cs, Rb) are isostructural with β-CsPbBi3Se6 and their hexagonal cell parameters were obtained at room temperature. The structure is composed of negatively charged Bi2Te3-type bilayers separated by alkali metals, which are distributed over two different crystallographic sites. The alkali metal ions are loosely packed in the interlayer space making them mobile. Topotactic ion-exchange reactions of two compounds, β-CsPbBi3Se6 and RbPbBi3Se6, were examined with LiI and NaI in the solid state and in aqueous solution. Prolonged water contact of the hexagonal compounds leads to decomposition and leaching of alkali metal and Pb2+ ions. Electrical conductivity and thermopower measurements for single crystals of I, II, and III show n-type semiconductor behavior with 0.6, 0.3, and 0.3 S/cm and -730, -550, and -560 μV/K at room temperature, respectively. The optical band gaps of all compounds range from 0.27 to 0.89 eV. Thermal properties of the compounds are reported.

Original languageEnglish
Pages (from-to)1352-1362
Number of pages11
JournalChemistry of Materials
Volume11
Issue number5
Publication statusPublished - 1999

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Alkali Metals
Alkali metals
Tunnels
Lead compounds
Thermoelectric power
Optical band gaps
Contacts (fluid mechanics)
Temperature
Leaching
Metal ions
Ion exchange
Thermodynamic properties
Single crystals
Ions
Semiconductor materials
Fluxes
Decomposition
Atoms
Water

ASJC Scopus subject areas

  • Materials Chemistry
  • Materials Science(all)

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First quaternary A-Pb-Bi-Q (A = K, Rb, Cs; Q = S, Se) compounds : Synthesis, structure, and properties of α-and β-CsPbBi3Se6, APbBi3Se6, (A = K, Rb), and APbBi3S6 (A = Rb, Cs). / Chung, Duck Young; Iordanidis, Lykourgos; Rangan, Krishnaswamy Kasthuri; Brazis, Paul W.; Kannewurf, Carl R.; Kanatzidis, Mercouri G.

In: Chemistry of Materials, Vol. 11, No. 5, 1999, p. 1352-1362.

Research output: Contribution to journalArticle

Chung, Duck Young ; Iordanidis, Lykourgos ; Rangan, Krishnaswamy Kasthuri ; Brazis, Paul W. ; Kannewurf, Carl R. ; Kanatzidis, Mercouri G. / First quaternary A-Pb-Bi-Q (A = K, Rb, Cs; Q = S, Se) compounds : Synthesis, structure, and properties of α-and β-CsPbBi3Se6, APbBi3Se6, (A = K, Rb), and APbBi3S6 (A = Rb, Cs). In: Chemistry of Materials. 1999 ; Vol. 11, No. 5. pp. 1352-1362.
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title = "First quaternary A-Pb-Bi-Q (A = K, Rb, Cs; Q = S, Se) compounds: Synthesis, structure, and properties of α-and β-CsPbBi3Se6, APbBi3Se6, (A = K, Rb), and APbBi3S6 (A = Rb, Cs)",
abstract = "α-CsPbBi3Se6 (I), β-CsPbBi3Se6 (II), RbPbBi3Se6 (III), KPbBi3Se6 (IV), CsPbBi3S6 (V), and RbPbBi3S6 (VI) were synthesized by the polychalcogenide flux method. α-CsPbBi3Se6 was obtained at 720 °C and crystallizes in the space group Pnma (no. 62) with α = 23.564(6) {\AA}, b = 4.210(2) {\AA}, c = 13.798(3) {\AA} at room temperature. Final R/RW = 3.0/3.6{\%}. In this compound, parallel NaCl-type Pb/Bi/Se columns with rectangularly shaped cross-sections are interconnected by edge sharing to build a 3-D tunnel framework with Cs atoms located inside the tunnels. The hexagonal plates of β-CsPbBi3Se6 were obtained at 400 °C and crystallize in the space group P63/mmc (no. 194) with a = 4.213(2) {\AA}, c = 25.22(1) {\AA}, y = 120° at -100 °C. Final R/RW = 4.2/4.7{\%}. APbBi3Se6 (A = Rb, K) and APbBi3S6 (A = Cs, Rb) are isostructural with β-CsPbBi3Se6 and their hexagonal cell parameters were obtained at room temperature. The structure is composed of negatively charged Bi2Te3-type bilayers separated by alkali metals, which are distributed over two different crystallographic sites. The alkali metal ions are loosely packed in the interlayer space making them mobile. Topotactic ion-exchange reactions of two compounds, β-CsPbBi3Se6 and RbPbBi3Se6, were examined with LiI and NaI in the solid state and in aqueous solution. Prolonged water contact of the hexagonal compounds leads to decomposition and leaching of alkali metal and Pb2+ ions. Electrical conductivity and thermopower measurements for single crystals of I, II, and III show n-type semiconductor behavior with 0.6, 0.3, and 0.3 S/cm and -730, -550, and -560 μV/K at room temperature, respectively. The optical band gaps of all compounds range from 0.27 to 0.89 eV. Thermal properties of the compounds are reported.",
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T1 - First quaternary A-Pb-Bi-Q (A = K, Rb, Cs; Q = S, Se) compounds

T2 - Synthesis, structure, and properties of α-and β-CsPbBi3Se6, APbBi3Se6, (A = K, Rb), and APbBi3S6 (A = Rb, Cs)

AU - Chung, Duck Young

AU - Iordanidis, Lykourgos

AU - Rangan, Krishnaswamy Kasthuri

AU - Brazis, Paul W.

AU - Kannewurf, Carl R.

AU - Kanatzidis, Mercouri G

PY - 1999

Y1 - 1999

N2 - α-CsPbBi3Se6 (I), β-CsPbBi3Se6 (II), RbPbBi3Se6 (III), KPbBi3Se6 (IV), CsPbBi3S6 (V), and RbPbBi3S6 (VI) were synthesized by the polychalcogenide flux method. α-CsPbBi3Se6 was obtained at 720 °C and crystallizes in the space group Pnma (no. 62) with α = 23.564(6) Å, b = 4.210(2) Å, c = 13.798(3) Å at room temperature. Final R/RW = 3.0/3.6%. In this compound, parallel NaCl-type Pb/Bi/Se columns with rectangularly shaped cross-sections are interconnected by edge sharing to build a 3-D tunnel framework with Cs atoms located inside the tunnels. The hexagonal plates of β-CsPbBi3Se6 were obtained at 400 °C and crystallize in the space group P63/mmc (no. 194) with a = 4.213(2) Å, c = 25.22(1) Å, y = 120° at -100 °C. Final R/RW = 4.2/4.7%. APbBi3Se6 (A = Rb, K) and APbBi3S6 (A = Cs, Rb) are isostructural with β-CsPbBi3Se6 and their hexagonal cell parameters were obtained at room temperature. The structure is composed of negatively charged Bi2Te3-type bilayers separated by alkali metals, which are distributed over two different crystallographic sites. The alkali metal ions are loosely packed in the interlayer space making them mobile. Topotactic ion-exchange reactions of two compounds, β-CsPbBi3Se6 and RbPbBi3Se6, were examined with LiI and NaI in the solid state and in aqueous solution. Prolonged water contact of the hexagonal compounds leads to decomposition and leaching of alkali metal and Pb2+ ions. Electrical conductivity and thermopower measurements for single crystals of I, II, and III show n-type semiconductor behavior with 0.6, 0.3, and 0.3 S/cm and -730, -550, and -560 μV/K at room temperature, respectively. The optical band gaps of all compounds range from 0.27 to 0.89 eV. Thermal properties of the compounds are reported.

AB - α-CsPbBi3Se6 (I), β-CsPbBi3Se6 (II), RbPbBi3Se6 (III), KPbBi3Se6 (IV), CsPbBi3S6 (V), and RbPbBi3S6 (VI) were synthesized by the polychalcogenide flux method. α-CsPbBi3Se6 was obtained at 720 °C and crystallizes in the space group Pnma (no. 62) with α = 23.564(6) Å, b = 4.210(2) Å, c = 13.798(3) Å at room temperature. Final R/RW = 3.0/3.6%. In this compound, parallel NaCl-type Pb/Bi/Se columns with rectangularly shaped cross-sections are interconnected by edge sharing to build a 3-D tunnel framework with Cs atoms located inside the tunnels. The hexagonal plates of β-CsPbBi3Se6 were obtained at 400 °C and crystallize in the space group P63/mmc (no. 194) with a = 4.213(2) Å, c = 25.22(1) Å, y = 120° at -100 °C. Final R/RW = 4.2/4.7%. APbBi3Se6 (A = Rb, K) and APbBi3S6 (A = Cs, Rb) are isostructural with β-CsPbBi3Se6 and their hexagonal cell parameters were obtained at room temperature. The structure is composed of negatively charged Bi2Te3-type bilayers separated by alkali metals, which are distributed over two different crystallographic sites. The alkali metal ions are loosely packed in the interlayer space making them mobile. Topotactic ion-exchange reactions of two compounds, β-CsPbBi3Se6 and RbPbBi3Se6, were examined with LiI and NaI in the solid state and in aqueous solution. Prolonged water contact of the hexagonal compounds leads to decomposition and leaching of alkali metal and Pb2+ ions. Electrical conductivity and thermopower measurements for single crystals of I, II, and III show n-type semiconductor behavior with 0.6, 0.3, and 0.3 S/cm and -730, -550, and -560 μV/K at room temperature, respectively. The optical band gaps of all compounds range from 0.27 to 0.89 eV. Thermal properties of the compounds are reported.

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