Unravelling the mechanism of pressure induced polyamorphic transition in an inorganic molecular glass

Kalkan, Bora; Okay, Gokce; Aitken, Bruce G.; Clark, Simon M.; Sen, Sabyasachi

doi:10.1038/s41598-020-61997-x

Title: Unravelling the mechanism of pressure induced polyamorphic transition in an inorganic molecular glass

Journal Article · Mon Mar 23 00:00:00 EDT 2020 · Scientific Reports

DOI:https://doi.org/10.1038/s41598-020-61997-x· OSTI ID:1695722

Kalkan, Bora ^[1]; Okay, Gokce ^[2]; Aitken, Bruce G. ^[3]; Clark, Simon M. ^[4]; Sen, Sabyasachi ^[5]

Univ. of California, Santa Cruz, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Hacettepe Univ., Beytepe (Turkey)
Corning Inc., Corning, NY (United States)
Macquarie Univ., NSW (Australia)
Univ. of California, Davis, CA (United States)

The atomic structure of a germanium doped phosphorous selenide glass of composition Ge_2.8P_57.7Se_39.5 is determined as a function of pressure from ambient to 24 GPa using Monte-Carlo simulations constrained by high energy x-ray scattering data. The ambient pressure structure consists primarily of P₄Se₃ molecules and planar edge shared phosphorus rings, reminiscent of those found in red phosphorous as well as a small fraction of locally clustered corner-sharing GeSe₄ tetrahedra. This low-density amorphous phase transforms into a high-density amorphous phase at ~6.3 GPa. The high-pressure phase is characterized by an extended network structure. The polyamorphic transformation between these two phases involves opening of the P₃ ring at the base of the P₄Se₃ molecules and subsequent reaction with red phosphorus type moieties to produce a cross linked structure. The compression mechanism of the low-density phase involves increased molecular packing, whereas that of the high pressure phase involves an increase in the nearest-neighbor coordination number while the bond angle distributions broaden and shift to smaller angles. The entropy and volume changes associated with this polyamorphic transformation are positive and negative, respectively, and consequently the corresponding Clapeyron slope for this transition would be negative. This result has far reaching implications in our current understanding of the thermodynamics of polyamorphic transitions in glasses and glass-forming liquids.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231; EAR 10–43050; DMR-1855176

OSTI ID:: 1695722

Journal Information:: Scientific Reports, Vol. 10, Issue 1; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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