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Title: Redox-Mediated Stabilization in Zinc Molybdenum Nitrides

Abstract

We report on the theoretical prediction and experimental realization of new ternary zinc molybdenum nitride compounds. We used theory to identify previously unknown ternary compounds in the Zn-Mo-N systems, Zn3MoN4 and ZnMoN2, and to analyze their bonding environment. Experiments show that Zn-Mo-N alloys can form in broad composition range from Zn3MoN4 to ZnMoN2 in the wurtzite-derived structure, accommodating very large off-stoichiometry. Interestingly, the measured wurtzite-derived structure of the alloys is metastable for the ZnMoN2 stoichiometry, in contrast to the Zn3MoN4 stoichiometry, where ordered wurtzite is predicted to be the ground state. The formation of Zn3MoN4-ZnMoN2 alloy with wurtzite-derived crystal structure is enabled by the concomitant ability of Mo to change oxidation state from +VI in Zn3MoN4 to +IV in ZnMoN2, and the capability of Zn to contribute to the bonding states of both compounds, an effect that we define as "redox-mediated stabilization". The stabilization of Mo in both the +VI and +IV oxidation states is due to the intermediate electronegativity of Zn, which enables significant polar covalent bonding in both Zn3MoN4 and ZnMoN2 compounds. The smooth change in the Mo oxidation state between Zn3MoN4 and ZnMoN2 stoichiometries leads to a continuous change in optoelectronic properties - from resistive and semitransparentmore » Zn3MoN4 to conductive and absorptive ZnMoN2. The reported redox-mediated stabilization in zinc molybdenum nitrides suggests there might be many undiscovered ternary compounds with one metal having an intermediate electronegativity, enabling significant covalent bonding, and another metal capable of accommodating multiple oxidation states, enabling stoichiometric flexibility.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [3];  [4];  [5];  [6];  [3];  [1];  [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Univ. of Colorado, Boulder, CO (United States)
  3. Colorado School of Mines, Golden, CO (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, 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); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1429974
Alternate Identifier(s):
OSTI ID: 1530347
Report Number(s):
NREL/JA-5K00-70614
Journal ID: ISSN 0002-7863; TRN: US1802486
Grant/Contract Number:  
AC36-08GO28308; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 12; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; zinc molybdenum nitrides; ternary compounds; composition

Citation Formats

Arca, Elisabetta, Lany, Stephan, Perkins, John D., Bartel, Christopher, Mangum, John, Sun, Wenhao, Holder, Aaron, Ceder, Gerbrand, Gorman, Brian, Teeter, Glenn, Tumas, William, and Zakutayev, Andriy. Redox-Mediated Stabilization in Zinc Molybdenum Nitrides. United States: N. p., 2018. Web. doi:10.1021/jacs.7b12861.
Arca, Elisabetta, Lany, Stephan, Perkins, John D., Bartel, Christopher, Mangum, John, Sun, Wenhao, Holder, Aaron, Ceder, Gerbrand, Gorman, Brian, Teeter, Glenn, Tumas, William, & Zakutayev, Andriy. Redox-Mediated Stabilization in Zinc Molybdenum Nitrides. United States. https://doi.org/10.1021/jacs.7b12861
Arca, Elisabetta, Lany, Stephan, Perkins, John D., Bartel, Christopher, Mangum, John, Sun, Wenhao, Holder, Aaron, Ceder, Gerbrand, Gorman, Brian, Teeter, Glenn, Tumas, William, and Zakutayev, Andriy. Thu . "Redox-Mediated Stabilization in Zinc Molybdenum Nitrides". United States. https://doi.org/10.1021/jacs.7b12861. https://www.osti.gov/servlets/purl/1429974.
@article{osti_1429974,
title = {Redox-Mediated Stabilization in Zinc Molybdenum Nitrides},
author = {Arca, Elisabetta and Lany, Stephan and Perkins, John D. and Bartel, Christopher and Mangum, John and Sun, Wenhao and Holder, Aaron and Ceder, Gerbrand and Gorman, Brian and Teeter, Glenn and Tumas, William and Zakutayev, Andriy},
abstractNote = {We report on the theoretical prediction and experimental realization of new ternary zinc molybdenum nitride compounds. We used theory to identify previously unknown ternary compounds in the Zn-Mo-N systems, Zn3MoN4 and ZnMoN2, and to analyze their bonding environment. Experiments show that Zn-Mo-N alloys can form in broad composition range from Zn3MoN4 to ZnMoN2 in the wurtzite-derived structure, accommodating very large off-stoichiometry. Interestingly, the measured wurtzite-derived structure of the alloys is metastable for the ZnMoN2 stoichiometry, in contrast to the Zn3MoN4 stoichiometry, where ordered wurtzite is predicted to be the ground state. The formation of Zn3MoN4-ZnMoN2 alloy with wurtzite-derived crystal structure is enabled by the concomitant ability of Mo to change oxidation state from +VI in Zn3MoN4 to +IV in ZnMoN2, and the capability of Zn to contribute to the bonding states of both compounds, an effect that we define as "redox-mediated stabilization". The stabilization of Mo in both the +VI and +IV oxidation states is due to the intermediate electronegativity of Zn, which enables significant polar covalent bonding in both Zn3MoN4 and ZnMoN2 compounds. The smooth change in the Mo oxidation state between Zn3MoN4 and ZnMoN2 stoichiometries leads to a continuous change in optoelectronic properties - from resistive and semitransparent Zn3MoN4 to conductive and absorptive ZnMoN2. The reported redox-mediated stabilization in zinc molybdenum nitrides suggests there might be many undiscovered ternary compounds with one metal having an intermediate electronegativity, enabling significant covalent bonding, and another metal capable of accommodating multiple oxidation states, enabling stoichiometric flexibility.},
doi = {10.1021/jacs.7b12861},
journal = {Journal of the American Chemical Society},
number = 12,
volume = 140,
place = {United States},
year = {2018},
month = {3}
}

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Cited by: 14 works
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Figures / Tables:

Figure 1 Figure 1: Predicted crystal structures of the (A) ZnMoN2 with Mo in 6-fold coordination and (B) Zn3MoN4 compounds with Mo in 4-fold coordination. For Zn, 4-fold coordination is observed in both structures. The Mo coordination polyhedrons are magenta, and the Zn coordination polyhedrons are gray.

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