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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

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:
; ;
Publication Date:
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

Citation Formats

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.
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
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.
@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}
}