Prevalence of pretransition disordering in the rutile-to- CaCl 2 phase transition of GeO 2
Abstract
WE report the ability to tailor a material's electronic properties using density driven disordering has emerged as a powerful route to materials design. The observation of anomalous structural and electronic behavior in the rutile to CaCl2 phase transition in SnO2 led to the prediction that such behavior is inherent to all oxides experiencing such a phase transition sequence [Smith et al., J. Phys. Chem. Lett. 10, 5351 (2019)]. Here, the ultrawide band gap semiconductor GeO2 is confirmed to exhibit anomalous behavior during the rutile to CaCl2 phase transition. A phase pure rutile GeO2 sample synthesized under high-pressure, high-temperature conditions is probed using synchrotron diffraction and x-ray and optical spectroscopy under high pressure conditions. Density functional theory calculations show that the enthalpic barrier to displacing an oxygen along the B1g librational mode decreases with pressure leading up to the rutile to CaCl2 phase transition. The band structure of the distorted state shows that such oxygen displacements form small polarons.
- Authors:
-
[1];
[1];
[1];
[2];
[3];
[1]
- Univ. of Nevada, Las Vegas, NV (United States)
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Eidgenoessische Technische Hochschule (ETH), Zurich (Switzerland)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1897902
- Alternate Identifier(s):
- OSTI ID: 1871784
- Report Number(s):
- LLNL-JRNL-836003
Journal ID: ISSN 2469-9950; 171963; TRN: US2310842
- Grant/Contract Number:
- AC02-06CH11357; FA9550-21-1-0097; AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review. B
- Additional Journal Information:
- Journal Volume: 104; Journal Issue: 13; Journal ID: ISSN 2469-9950
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; electronic structure; phase transitions; crystalline systems; oxides; density functional theory; pressure techniques
Citation Formats
Smith, G. Alexander, Schacher, Daniel, Hinton, Jasmine K., Sneed, Daniel, Park, Changyong, Petitgirard, Sylvain, Lawler, Keith V., and Salamat, Ashkan. Prevalence of pretransition disordering in the rutile-to- CaCl2 phase transition of GeO2. United States: N. p., 2021.
Web. doi:10.1103/physrevb.104.134107.
Smith, G. Alexander, Schacher, Daniel, Hinton, Jasmine K., Sneed, Daniel, Park, Changyong, Petitgirard, Sylvain, Lawler, Keith V., & Salamat, Ashkan. Prevalence of pretransition disordering in the rutile-to- CaCl2 phase transition of GeO2. United States. https://doi.org/10.1103/physrevb.104.134107
Smith, G. Alexander, Schacher, Daniel, Hinton, Jasmine K., Sneed, Daniel, Park, Changyong, Petitgirard, Sylvain, Lawler, Keith V., and Salamat, Ashkan. Mon .
"Prevalence of pretransition disordering in the rutile-to- CaCl2 phase transition of GeO2". United States. https://doi.org/10.1103/physrevb.104.134107. https://www.osti.gov/servlets/purl/1897902.
@article{osti_1897902,
title = {Prevalence of pretransition disordering in the rutile-to- CaCl2 phase transition of GeO2},
author = {Smith, G. Alexander and Schacher, Daniel and Hinton, Jasmine K. and Sneed, Daniel and Park, Changyong and Petitgirard, Sylvain and Lawler, Keith V. and Salamat, Ashkan},
abstractNote = {WE report the ability to tailor a material's electronic properties using density driven disordering has emerged as a powerful route to materials design. The observation of anomalous structural and electronic behavior in the rutile to CaCl2 phase transition in SnO2 led to the prediction that such behavior is inherent to all oxides experiencing such a phase transition sequence [Smith et al., J. Phys. Chem. Lett. 10, 5351 (2019)]. Here, the ultrawide band gap semiconductor GeO2 is confirmed to exhibit anomalous behavior during the rutile to CaCl2 phase transition. A phase pure rutile GeO2 sample synthesized under high-pressure, high-temperature conditions is probed using synchrotron diffraction and x-ray and optical spectroscopy under high pressure conditions. Density functional theory calculations show that the enthalpic barrier to displacing an oxygen along the B1g librational mode decreases with pressure leading up to the rutile to CaCl2 phase transition. The band structure of the distorted state shows that such oxygen displacements form small polarons.},
doi = {10.1103/physrevb.104.134107},
journal = {Physical Review. B},
number = 13,
volume = 104,
place = {United States},
year = {Mon Oct 25 00:00:00 EDT 2021},
month = {Mon Oct 25 00:00:00 EDT 2021}
}
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