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Title: Pressure-Driven Chemical Disorder in Glassy As2S3 up to 14.7 GPa, Postdensification Effects, and Applications in Materials Design

Abstract

A small difference in energy between homopolar and heteropolar bonds and the glass-forming ability of pure chalcogens leads to unexpected trends in densification mechanisms of glassy chalcogenides compared to vitreous oxides. Using high-precision compressibility measurements and in situ high-energy X-ray diffraction up to 14.7 GPa, we show herein a new densification route in a canonical glass As2S3. After the first reversible elastic step with a maximum pressure of 1.3 GPa, characterized by a strong reduction of voids and cavities, a significant bonding or chemical disorder is developed under higher pressure, reaching a saturation of 30% in the population of As-As bonds above 8-9 GPa. The pressure-driven chemical disorder is accompanied by a remarkable structural relaxation and a strongly diminished optical gap and determines structural, vibrational, and optical properties under and after cold compression. The decompressed recovered glass conserves a dark color and exhibits two relaxation processes: (a) fast (a few days) and (b) slow (months/years at room temperature). The enhanced refractive index of the recovered glass is promising for optical applications with improved functionalities. A nearly permanent red shift in optical absorption after decompression can be used in high-impact-force optical sensors.

Authors:
 [1];  [2];  [3];  [4];  [5]; ORCiD logo [2];  [6]; ORCiD logo [5]
  1. Arizona State Univ., Mesa, AZ (United States). The Eyring Materials Center
  2. Russian Academy of Sciences (RAS), Moscow (Russia). Inst. for High Pressure Physics
  3. St. Petersburg State Univ. (Russia). Dept. of Chemistry
  4. European Synchrotron Radiation Facility (ESRF), Grenoble (France)
  5. Univ. du Littoral Côte d’Opale, Dunkerque (France). LPCA
  6. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Région Hauts de France; Ministère de l’Enseignement Supérieur et de la Recherche (CPER Climibio); European Fund for Regional Economic Development; Russian Science Foundation; Saint- Petersburg State University; Grand Equipment National de Calcul Intensif (GENCI)
OSTI Identifier:
1604982
Grant/Contract Number:  
AC02-06CH11357; 19-12-00111; 12.40.1342.2017; 2018-A0050910639
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 124; Journal Issue: 2; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Glass; High pressure; Diseases and disorders; Physical and chemical processes; Amorphous materials; CompressibilityArsenic

Citation Formats

Soignard, Emmanuel, Tsiok, Oleg B., Tverjanovich, Andrey S., Bytchkov, Aleksei, Sokolov, Anton, Brazhkin, Vadim V., Benmore, Chris J., and Bychkov, Eugene. Pressure-Driven Chemical Disorder in Glassy As2S3 up to 14.7 GPa, Postdensification Effects, and Applications in Materials Design. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.jpcb.9b10465.
Soignard, Emmanuel, Tsiok, Oleg B., Tverjanovich, Andrey S., Bytchkov, Aleksei, Sokolov, Anton, Brazhkin, Vadim V., Benmore, Chris J., & Bychkov, Eugene. Pressure-Driven Chemical Disorder in Glassy As2S3 up to 14.7 GPa, Postdensification Effects, and Applications in Materials Design. United States. https://doi.org/10.1021/acs.jpcb.9b10465
Soignard, Emmanuel, Tsiok, Oleg B., Tverjanovich, Andrey S., Bytchkov, Aleksei, Sokolov, Anton, Brazhkin, Vadim V., Benmore, Chris J., and Bychkov, Eugene. Tue . "Pressure-Driven Chemical Disorder in Glassy As2S3 up to 14.7 GPa, Postdensification Effects, and Applications in Materials Design". United States. https://doi.org/10.1021/acs.jpcb.9b10465. https://www.osti.gov/servlets/purl/1604982.
@article{osti_1604982,
title = {Pressure-Driven Chemical Disorder in Glassy As2S3 up to 14.7 GPa, Postdensification Effects, and Applications in Materials Design},
author = {Soignard, Emmanuel and Tsiok, Oleg B. and Tverjanovich, Andrey S. and Bytchkov, Aleksei and Sokolov, Anton and Brazhkin, Vadim V. and Benmore, Chris J. and Bychkov, Eugene},
abstractNote = {A small difference in energy between homopolar and heteropolar bonds and the glass-forming ability of pure chalcogens leads to unexpected trends in densification mechanisms of glassy chalcogenides compared to vitreous oxides. Using high-precision compressibility measurements and in situ high-energy X-ray diffraction up to 14.7 GPa, we show herein a new densification route in a canonical glass As2S3. After the first reversible elastic step with a maximum pressure of 1.3 GPa, characterized by a strong reduction of voids and cavities, a significant bonding or chemical disorder is developed under higher pressure, reaching a saturation of 30% in the population of As-As bonds above 8-9 GPa. The pressure-driven chemical disorder is accompanied by a remarkable structural relaxation and a strongly diminished optical gap and determines structural, vibrational, and optical properties under and after cold compression. The decompressed recovered glass conserves a dark color and exhibits two relaxation processes: (a) fast (a few days) and (b) slow (months/years at room temperature). The enhanced refractive index of the recovered glass is promising for optical applications with improved functionalities. A nearly permanent red shift in optical absorption after decompression can be used in high-impact-force optical sensors.},
doi = {10.1021/acs.jpcb.9b10465},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 2,
volume = 124,
place = {United States},
year = {2019},
month = {12}
}

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