Crystalline and glassy phases in the Cs/Bi/As/S system

Tarun K. Bera, Ratnasabapathy G. Iyer, Christos D. Malliakas, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

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Abstract

The quaternary Cs2S/Bi/As/S system was studied in an attempt to introduce two different asymmetric but isoelectronic building units, namely, [BiIIIxSy] and [AsIII xSy], in a single structure. Reactions with a comparatively lower equivalent of arsenic in the Cs2S/Bi/As/S mixture led to the crystalline compound Cs3Bi(AsS4)2. The structure features tetrahedral [AsVS4]3- connected to BiIII centers to give infinite 1/ [Bi(AsS4)23-] chains. When the basicity was raised in these low arsenic fluxes by increasing the Cs 2S fraction, the crystalline compound Cs9Bi(AsS 4)4, also featuring [AsVS4] 3- anions, was formed. On the other hand, arsenic-rich mixtures of Cs2S/Bi/As/S led to the formation of the glassy phase Cs 2BiAs3S7, which contains AsIII species. X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and pair distribution function (PDF) analysis indicate the presence of As III-containing [AsnS2n+1] fragments in the glass structure. Several glasses in the series Csn-1BiAs nS2n+1 were also prepared using solid-state fusion reactions. The band gaps of the Csn-1BiAsnS2n+1 glasses are in the range of 1.51-1.81 eV, while that of the crystalline compound Cs3Bi(AsS4)2 is ∼2.33 eV. The thermal and optical behaviors of these compounds are correlated with their structures and building units.

Original languageEnglish
Pages (from-to)11370-11376
Number of pages7
JournalInorganic Chemistry
Volume52
Issue number19
DOIs
Publication statusPublished - Oct 7 2013

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Arsenic
arsenic
Crystalline materials
Glass
glass
Alkalinity
Distribution functions
Anions
Raman spectroscopy
Energy gap
Fusion reactions
X ray photoelectron spectroscopy
fusion
distribution functions
fragments
photoelectron spectroscopy
Fluxes
anions
solid state
x rays

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Crystalline and glassy phases in the Cs/Bi/As/S system. / Bera, Tarun K.; Iyer, Ratnasabapathy G.; Malliakas, Christos D.; Kanatzidis, Mercouri G.

In: Inorganic Chemistry, Vol. 52, No. 19, 07.10.2013, p. 11370-11376.

Research output: Contribution to journalArticle

Bera, Tarun K. ; Iyer, Ratnasabapathy G. ; Malliakas, Christos D. ; Kanatzidis, Mercouri G. / Crystalline and glassy phases in the Cs/Bi/As/S system. In: Inorganic Chemistry. 2013 ; Vol. 52, No. 19. pp. 11370-11376.
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abstract = "The quaternary Cs2S/Bi/As/S system was studied in an attempt to introduce two different asymmetric but isoelectronic building units, namely, [BiIIIxSy] and [AsIII xSy], in a single structure. Reactions with a comparatively lower equivalent of arsenic in the Cs2S/Bi/As/S mixture led to the crystalline compound Cs3Bi(AsS4)2. The structure features tetrahedral [AsVS4]3- connected to BiIII centers to give infinite 1/ ∞[Bi(AsS4)23-] chains. When the basicity was raised in these low arsenic fluxes by increasing the Cs 2S fraction, the crystalline compound Cs9Bi(AsS 4)4, also featuring [AsVS4] 3- anions, was formed. On the other hand, arsenic-rich mixtures of Cs2S/Bi/As/S led to the formation of the glassy phase Cs 2BiAs3S7, which contains AsIII species. X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and pair distribution function (PDF) analysis indicate the presence of As III-containing [AsnS2n+1] fragments in the glass structure. Several glasses in the series Csn-1BiAs nS2n+1 were also prepared using solid-state fusion reactions. The band gaps of the Csn-1BiAsnS2n+1 glasses are in the range of 1.51-1.81 eV, while that of the crystalline compound Cs3Bi(AsS4)2 is ∼2.33 eV. The thermal and optical behaviors of these compounds are correlated with their structures and building units.",
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N2 - The quaternary Cs2S/Bi/As/S system was studied in an attempt to introduce two different asymmetric but isoelectronic building units, namely, [BiIIIxSy] and [AsIII xSy], in a single structure. Reactions with a comparatively lower equivalent of arsenic in the Cs2S/Bi/As/S mixture led to the crystalline compound Cs3Bi(AsS4)2. The structure features tetrahedral [AsVS4]3- connected to BiIII centers to give infinite 1/ ∞[Bi(AsS4)23-] chains. When the basicity was raised in these low arsenic fluxes by increasing the Cs 2S fraction, the crystalline compound Cs9Bi(AsS 4)4, also featuring [AsVS4] 3- anions, was formed. On the other hand, arsenic-rich mixtures of Cs2S/Bi/As/S led to the formation of the glassy phase Cs 2BiAs3S7, which contains AsIII species. X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and pair distribution function (PDF) analysis indicate the presence of As III-containing [AsnS2n+1] fragments in the glass structure. Several glasses in the series Csn-1BiAs nS2n+1 were also prepared using solid-state fusion reactions. The band gaps of the Csn-1BiAsnS2n+1 glasses are in the range of 1.51-1.81 eV, while that of the crystalline compound Cs3Bi(AsS4)2 is ∼2.33 eV. The thermal and optical behaviors of these compounds are correlated with their structures and building units.

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