Network vs Molecular Structural Characteristics of Ge-Doped Arsenic Sulfide Glasses: A Combined Neutron/X-ray Diffraction, Extended X-ray Absorption Fine Structure, and Raman Spectroscopic Study

doi:https://doi.org/10.1021/jp810446g

Title: Network vs Molecular Structural Characteristics of Ge-Doped Arsenic Sulfide Glasses: A Combined Neutron/X-ray Diffraction, Extended X-ray Absorption Fine Structure, and Raman Spectroscopic Study

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Abstract

Combined neutron/X-ray diffraction, Ge and As K-edge extended X-ray absorption fine structure analysis, and Raman spectroscopy are employed to study the compositional dependence of the short- and intermediate-range structures of As-rich GexAsyS100-x-y glasses with a constant Ge:As atomic ratio of 1:17.3. The structures of glasses with compositions near stoichiometry (35 ? x + y ? 43) are dominated by the presence of a predominantly heteropolar-bonded As2S3 network. However, an increasing metal content (x + y = 55) results in a novel glass consisting predominantly of As4S3 molecules, held together by van der Waals forces. The formation of this 'molecular' glass implies an apparently anomalous situation of near-zero connectivity and dimensionality with increasing average coordination number. A further increase in metal content (60 ? x + y ? 65) results in the formation of As-As homopolar-bonded structural regions that coexist with As4S3 molecules. Such unusual evolution of intermediate-range order is shown to be closely related to the compositional variation of thermophysical properties and density fluctuation in these glasses

Authors:: Soyer-Uzun, S; Sen, S; Aitken, B

Publication Date:: 2009-01-01

Research Org.:: Brookhaven National Laboratory (BNL) National Synchrotron Light Source

Sponsoring Org.:: Doe - Office Of Science

OSTI Identifier:: 980361

Report Number(s):: BNL-93279-2010-JA
Journal ID: ISSN 1932-7447; TRN: US201015%%1746

DOE Contract Number:: DE-AC02-98CH10886

Resource Type:: Journal Article

Journal Name:: Journal of Physical Chemistry C

Additional Journal Information:: Journal Volume: 113; Journal ID: ISSN 1932-7447

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; ARSENIC; ARSENIC SULFIDES; COORDINATION NUMBER; DENSITY; DIFFRACTION; FINE STRUCTURE; FLUCTUATIONS; GERMANIUM; GLASS; METALS; MOLECULES; RAMAN SPECTROSCOPY; STOICHIOMETRY; VAN DER WAALS FORCES; VARIATIONS; national synchrotron light source

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                    Soyer-Uzun, S, Sen, S, and Aitken, B. Network vs Molecular Structural Characteristics of Ge-Doped Arsenic Sulfide Glasses: A Combined Neutron/X-ray Diffraction, Extended X-ray Absorption Fine Structure, and Raman Spectroscopic Study.  United States: N. p., 2009. 
        Web.  doi:10.1021/jp810446g.

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                    Soyer-Uzun, S, Sen, S, & Aitken, B. Network vs Molecular Structural Characteristics of Ge-Doped Arsenic Sulfide Glasses: A Combined Neutron/X-ray Diffraction, Extended X-ray Absorption Fine Structure, and Raman Spectroscopic Study.  United States.  https://doi.org/10.1021/jp810446g

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                    Soyer-Uzun, S, Sen, S, and Aitken, B. Thu .  
        "Network vs Molecular Structural Characteristics of Ge-Doped Arsenic Sulfide Glasses: A Combined Neutron/X-ray Diffraction, Extended X-ray Absorption Fine Structure, and Raman Spectroscopic Study".  United States.  https://doi.org/10.1021/jp810446g.

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@article{osti_980361,

  title        = {Network vs Molecular Structural Characteristics of Ge-Doped Arsenic Sulfide Glasses: A Combined Neutron/X-ray Diffraction, Extended X-ray Absorption Fine Structure, and Raman Spectroscopic Study},

  author       = {Soyer-Uzun, S and Sen, S and Aitken, B},

  abstractNote = {Combined neutron/X-ray diffraction, Ge and As K-edge extended X-ray absorption fine structure analysis, and Raman spectroscopy are employed to study the compositional dependence of the short- and intermediate-range structures of As-rich GexAsyS100-x-y glasses with a constant Ge:As atomic ratio of 1:17.3. The structures of glasses with compositions near stoichiometry (35 ? x + y ? 43) are dominated by the presence of a predominantly heteropolar-bonded As2S3 network. However, an increasing metal content (x + y = 55) results in a novel glass consisting predominantly of As4S3 molecules, held together by van der Waals forces. The formation of this 'molecular' glass implies an apparently anomalous situation of near-zero connectivity and dimensionality with increasing average coordination number. A further increase in metal content (60 ? x + y ? 65) results in the formation of As-As homopolar-bonded structural regions that coexist with As4S3 molecules. Such unusual evolution of intermediate-range order is shown to be closely related to the compositional variation of thermophysical properties and density fluctuation in these glasses},

  doi          = {10.1021/jp810446g},

  url          = {https://www.osti.gov/biblio/980361},
  journal      = {Journal of Physical Chemistry C},

  issn         = {1932-7447},

  number       = ,

  volume       = 113,

  place        = {United States},

  year         = {2009},

  month        = {1}

}

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