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Title: Negative-pressure polymorphs made by heterostructural alloying

Abstract

The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material's structure by applying tension under negative pressure is much more difficult. We show how negative-pressure polymorphs can be synthesized by mixing materials with different crystal structures - a general approach that should be applicable to many materials. Theoretical calculations suggest that it costs less energy to mix low-density structures than high-density structures, due to less competition for space between the atoms. Proof-of-concept experiments confirm that mixing two different high-density forms of MnSe and MnTe stabilizes a Mn(Se,Te) alloy with a low-density wurtzite structure. This Mn(Se,Te) negative-pressure polymorph has 2x to 4x lower electron effective mass compared to MnSe and MnTe parent compounds and has a piezoelectric response that none of the parent compounds have. Lastly, this example shows how heterostructural alloying can lead to negative-pressure polymorphs with useful properties - materials that are otherwise nearly impossible to make.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
  3. Univ. of Connecticut, Storrs, CT (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE) USDOE Laboratory Directed Research and Development (LDRD)
OSTI Identifier:
1437565
Alternate Identifier(s):
OSTI ID: 1438818
Report Number(s):
NREL/JA-5K00-68342
Journal ID: ISSN 2375-2548
Grant/Contract Number:  
AC36-08GO28308; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 4; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; polymorphism; synthesis; crystal structure

Citation Formats

Siol, Sebastian, Holder, Aaron, Steffes, James, Schelhas, Laura T., Stone, Kevin H., Garten, Lauren, Perkins, John D., Parilla, Philip A., Toney, Michael F., Huey, Bryan D., Tumas, William, Lany, Stephan, and Zakutayev, Andriy. Negative-pressure polymorphs made by heterostructural alloying. United States: N. p., 2018. Web. doi:10.1126/sciadv.aaq1442.
Siol, Sebastian, Holder, Aaron, Steffes, James, Schelhas, Laura T., Stone, Kevin H., Garten, Lauren, Perkins, John D., Parilla, Philip A., Toney, Michael F., Huey, Bryan D., Tumas, William, Lany, Stephan, & Zakutayev, Andriy. Negative-pressure polymorphs made by heterostructural alloying. United States. doi:10.1126/sciadv.aaq1442.
Siol, Sebastian, Holder, Aaron, Steffes, James, Schelhas, Laura T., Stone, Kevin H., Garten, Lauren, Perkins, John D., Parilla, Philip A., Toney, Michael F., Huey, Bryan D., Tumas, William, Lany, Stephan, and Zakutayev, Andriy. Fri . "Negative-pressure polymorphs made by heterostructural alloying". United States. doi:10.1126/sciadv.aaq1442. https://www.osti.gov/servlets/purl/1437565.
@article{osti_1437565,
title = {Negative-pressure polymorphs made by heterostructural alloying},
author = {Siol, Sebastian and Holder, Aaron and Steffes, James and Schelhas, Laura T. and Stone, Kevin H. and Garten, Lauren and Perkins, John D. and Parilla, Philip A. and Toney, Michael F. and Huey, Bryan D. and Tumas, William and Lany, Stephan and Zakutayev, Andriy},
abstractNote = {The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material's structure by applying tension under negative pressure is much more difficult. We show how negative-pressure polymorphs can be synthesized by mixing materials with different crystal structures - a general approach that should be applicable to many materials. Theoretical calculations suggest that it costs less energy to mix low-density structures than high-density structures, due to less competition for space between the atoms. Proof-of-concept experiments confirm that mixing two different high-density forms of MnSe and MnTe stabilizes a Mn(Se,Te) alloy with a low-density wurtzite structure. This Mn(Se,Te) negative-pressure polymorph has 2x to 4x lower electron effective mass compared to MnSe and MnTe parent compounds and has a piezoelectric response that none of the parent compounds have. Lastly, this example shows how heterostructural alloying can lead to negative-pressure polymorphs with useful properties - materials that are otherwise nearly impossible to make.},
doi = {10.1126/sciadv.aaq1442},
journal = {Science Advances},
number = 4,
volume = 4,
place = {United States},
year = {2018},
month = {4}
}

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