Redox-Mediated Stabilization in Zinc Molybdenum Nitrides

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

doi:10.1021/jacs.7b12861

Title: Redox-Mediated Stabilization in Zinc Molybdenum Nitrides

Journal Article · 01 March 2018 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.7b12861 · OSTI ID:1429974

^[1]; Lany, Stephan ^[1]; Perkins, John D. ^[1]; Bartel, Christopher ^[2]; Mangum, John ^[3]; Sun, Wenhao ^[4]; Holder, Aaron ^[5]; Ceder, Gerbrand ^[6]; Gorman, Brian ^[3]; Teeter, Glenn ^[1]; Tumas, William ^[1];

^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
Univ. of Colorado, Boulder, CO (United States)
Colorado School of Mines, Golden, CO (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

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.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1429974

Report Number(s):: NREL/JA--5K00-70614

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 12 Vol. 140; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (53)

Li-Doped Cr ₂ MnO ₄ : A New p-Type Transparent Conducting Oxide by Computational Materials Design Peng, Haowei; Zakutayev, Andriy; Lany, Stephan Advanced Functional Materials, Vol. 23, Issue 42 https://doi.org/10.1002/adfm.201300807	journal	May 2013
Band Gap Dependence on Cation Disorder in ZnSnN ₂ Solar Absorber Veal, Tim D.; Feldberg, Nathaniel; Quackenbush, Nicholas F. Advanced Energy Materials, Vol. 5, Issue 24 https://doi.org/10.1002/aenm.201501462	journal	October 2015
3D Porous Hierarchical Nickel-Molybdenum Nitrides Synthesized by RF Plasma as Highly Active and Stable Hydrogen-Evolution-Reaction Electrocatalysts Zhang, Yongqi; Ouyang, Bo; Xu, Jing Advanced Energy Materials, Vol. 6, Issue 11 https://doi.org/10.1002/aenm.201600221	journal	April 2016
LOBSTER: A tool to extract chemical bonding from plane-wave based DFT: Tool to Extract Chemical Bonding Maintz, Stefan; Deringer, Volker L.; Tchougréeff, Andrei L. Journal of Computational Chemistry, Vol. 37, Issue 11 https://doi.org/10.1002/jcc.24300	journal	February 2016
Sr10[Mo2N6][MoN4]2 and ?-Sr3MoN4 Bailey, Mark S.; McGuire, Michael A.; DiSalvo, Francis J. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 630, Issue 13-14 https://doi.org/10.1002/zaac.200400081	journal	November 2004
From the computer to the laboratory: materials discovery and design using first-principles calculations Hautier, Geoffroy; Jain, Anubhav; Ong, Shyue Ping Journal of Materials Science, Vol. 47, Issue 21 https://doi.org/10.1007/s10853-012-6424-0	journal	May 2012
Synthesis, characterisation and hydrogenation performance of ternary nitride catalysts Perret, Noémie; Alexander, Anne-Marie; Hunter, Stuart M. Applied Catalysis A: General, Vol. 488 https://doi.org/10.1016/j.apcata.2014.09.026	journal	November 2014
Prediction of Stable Nitride Perovskites Sarmiento-Pérez, Rafael; Cerqueira, Tiago F. T.; Körbel, Sabine Chemistry of Materials, Vol. 27, Issue 17 https://doi.org/10.1021/acs.chemmater.5b02026	journal	August 2015
High-Pressure Synthesis and Characterization of Incompressible Titanium Pernitride Bhadram, Venkata S.; Kim, Duck Young; Strobel, Timothy A. Chemistry of Materials, Vol. 28, Issue 6 https://doi.org/10.1021/acs.chemmater.6b00042	journal	February 2016
Exploring the PbS–Bi ₂ S ₃ Series for Next Generation Energy Conversion Materials Savory, Christopher N.; Ganose, Alex M.; Scanlon, David O. Chemistry of Materials, Vol. 29, Issue 12 https://doi.org/10.1021/acs.chemmater.7b00628	journal	May 2017
Design of Metastable Tin Titanium Nitride Semiconductor Alloys Bikowski, Andre; Siol, Sebastian; Gu, Jing Chemistry of Materials, Vol. 29, Issue 15 https://doi.org/10.1021/acs.chemmater.7b02122	journal	July 2017
Thermodynamic Routes to Novel Metastable Nitrogen-Rich Nitrides Sun, Wenhao; Holder, Aaron; Orvañanos, Bernardo Chemistry of Materials, Vol. 29, Issue 16 https://doi.org/10.1021/acs.chemmater.7b02399	journal	August 2017
Exploring the Real Ground-State Structures of Molybdenum Dinitride Yu, Shuyin; Huang, Bowen; Jia, Xiaojing The Journal of Physical Chemistry C, Vol. 120, Issue 20 https://doi.org/10.1021/acs.jpcc.6b00665	journal	May 2016
Infrared Plasmonics with Conductive Ternary Nitrides Metaxa, C.; Kassavetis, S.; Pierson, J. F. ACS Applied Materials & Interfaces, Vol. 9, Issue 12 https://doi.org/10.1021/acsami.6b16343	journal	March 2017
Salt-Templated Synthesis of 2D Metallic MoN and Other Nitrides Xiao, Xu; Yu, Huimin; Jin, Huanyu ACS Nano, Vol. 11, Issue 2 https://doi.org/10.1021/acsnano.6b08534	journal	February 2017
Finding Nature’s Missing Ternary Oxide Compounds Using Machine Learning and Density Functional Theory Hautier, Geoffroy; Fischer, Christopher C.; Jain, Anubhav Chemistry of Materials, Vol. 22, Issue 12 https://doi.org/10.1021/cm100795d	journal	June 2010
Two-Dimensional Layered Complex Nitrides as a New Class of Thermoelectric Materials Ohkubo, Isao; Mori, Takao Chemistry of Materials, Vol. 26, Issue 8 https://doi.org/10.1021/cm403840e	journal	April 2014
Control of Doping in Cu ₂ SnS ₃ through Defects and Alloying Baranowski, Lauryn L.; Zawadzki, Pawel; Christensen, Steven Chemistry of Materials, Vol. 26, Issue 17 https://doi.org/10.1021/cm501339v	journal	August 2014
Group V and VI Alkali Nitridometalates: A Growing Class of Compounds with Structures Related to Silicate Chemistry Niewa, Rainer; Jacobs, Herbert Chemical Reviews, Vol. 96, Issue 6 https://doi.org/10.1021/cr9405157	journal	January 1996
Molybdenum enzymes, cofactors, and systems: The chemical uniqueness of molybdenum Burgmayer, S. J. N.; Stiefel, E. I. Journal of Chemical Education, Vol. 62, Issue 11 https://doi.org/10.1021/ed062p943	journal	November 1985
Synthesis and Structure of Two New Ternary Nitrides: FeWN ₂ and MnMoN ₂ Bem, David S.; Lampe-Önnerud, Christina M.; Olsen, Hans P. Inorganic Chemistry, Vol. 35, Issue 3 https://doi.org/10.1021/ic9512338	journal	January 1996
Mixed Close-Packed Cobalt Molybdenum Nitrides as Non-noble Metal Electrocatalysts for the Hydrogen Evolution Reaction Cao, Bingfei; Veith, Gabriel M.; Neuefeind, Joerg C. Journal of the American Chemical Society, Vol. 135, Issue 51 https://doi.org/10.1021/ja4081056	journal	December 2013
Metal Nitrides Grown from Ca/Li Flux: Ca ₆ Te ₃ N ₂ and New Nitridoferrate(I) Ca ₆ (Li _x Fe _{1– x} )Te ₂ N ₃ Dickman, Matthew J.; Latturner, Susan E. Journal of the American Chemical Society, Vol. 138, Issue 33 https://doi.org/10.1021/jacs.6b06024	journal	August 2016
Oxidation-State-Dependent Binding Properties of the Active Site in a Mo-Containing Formate Dehydrogenase Robinson, William E.; Bassegoda, Arnau; Reisner, Erwin Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b03958	journal	July 2017
Theoretical and Experimental Study of the Electronic Structures of MoO ₃ and MoO ₂ Scanlon, David O.; Watson, Graeme W.; Payne, D. J. The Journal of Physical Chemistry C, Vol. 114, Issue 10 https://doi.org/10.1021/jp9093172	journal	March 2010
Discovery of earth-abundant nitride semiconductors by computational screening and high-pressure synthesis Hinuma, Yoyo; Hatakeyama, Taisuke; Kumagai, Yu Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11962	journal	June 2016
Synthesis and characterization of a binary noble metal nitride Gregoryanz, Eugene; Sanloup, Chrystele; Somayazulu, M. Nature Materials, Vol. 3, Issue 5 https://doi.org/10.1038/nmat1115	journal	April 2004
The high-throughput highway to computational materials design Curtarolo, Stefano; Hart, Gus L. W.; Nardelli, Marco Buongiorno Nature Materials, Vol. 12, Issue 3 https://doi.org/10.1038/nmat3568	journal	February 2013
Thin film synthesis and properties of copper nitride, a metastable semiconductor Caskey, Christopher M.; Richards, Ryan M.; Ginley, David S. Mater. Horiz., Vol. 1, Issue 4 https://doi.org/10.1039/C4MH00049H	journal	January 2014
Design of nitride semiconductors for solar energy conversion Zakutayev, Andriy Journal of Materials Chemistry A, Vol. 4, Issue 18 https://doi.org/10.1039/C5TA09446A	journal	January 2016
Combinatorial insights into doping control and transport properties of zinc tin nitride Fioretti, Angela N.; Zakutayev, Andriy; Moutinho, Helio Journal of Materials Chemistry C, Vol. 3, Issue 42 https://doi.org/10.1039/C5TC02663F	journal	January 2015
Synthesis, structure, and optoelectronic properties of II–IV–V ₂ materials Martinez, Aaron D.; Fioretti, Angela N.; Toberer, Eric S. Journal of Materials Chemistry A, Vol. 5, Issue 23 https://doi.org/10.1039/C7TA00406K	journal	January 2017
Chemistry of interstitial molybdenum ternary nitrides MnMo3N (M=Fe, Co, n=3; M=Ni, n=2) Alconchel, Silvia; Sapiña, Fernando; Beltrán, Daniel Journal of Materials Chemistry, Vol. 8, Issue 8 https://doi.org/10.1039/a801643g	journal	January 1998
Synthesis and structure of new mixed alkaline-earth nitridomolybdates and nitridotungstates, (Ba,Ca)3[MN4] (M = Mo, W)Dedicated to Dr Marten G. Barker in memoriam. Baker, Charles F.; Barker, Marten G.; Blake, Alexander J. Dalton Transactions, Issue 6 https://doi.org/10.1039/b211138a	journal	February 2003
High-pressure chemistry of nitride-based materials Horvath-Bordon, Elisabeta; Riedel, Ralf; Zerr, Andreas Chemical Society Reviews, Vol. 35, Issue 10 https://doi.org/10.1039/b517778m	journal	January 2006
Formation of transition-metal nitrides from the reactions of lithium amides and anhydrous transition-metal chlorides Parkin, Ivan P.; Rowley, Adrian T. Journal of Materials Chemistry, Vol. 5, Issue 6 https://doi.org/10.1039/jm9950500909	journal	January 1995
Bandgap engineering of ZnSnP ₂ for high-efficiency solar cells Scanlon, David O.; Walsh, Aron Applied Physics Letters, Vol. 100, Issue 25 https://doi.org/10.1063/1.4730375	journal	June 2012
Development and application of an instrument for spatially resolved Seebeck coefficient measurements Zakutayev, Andriy; Luciano, Frank J.; Bollinger, Vincent P. Review of Scientific Instruments, Vol. 84, Issue 5 https://doi.org/10.1063/1.4804634	journal	May 2013
Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures Caskey, Christopher M.; Holder, Aaron; Shulda, Sarah The Journal of Chemical Physics, Vol. 144, Issue 14 https://doi.org/10.1063/1.4945561	journal	April 2016
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Implementation and performance of the frequency-dependent G W method within the PAW framework Shishkin, M.; Kresse, G. Physical Review B, Vol. 74, Issue 3 https://doi.org/10.1103/PhysRevB.74.035101	journal	July 2006
Van der Waals density functionals applied to solids Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos Physical Review B, Vol. 83, Issue 19 https://doi.org/10.1103/PhysRevB.83.195131	journal	May 2011
Correcting density functional theory for accurate predictions of compound enthalpies of formation: Fitted elemental-phase reference energies Stevanović, Vladan; Lany, Stephan; Zhang, Xiuwen Physical Review B, Vol. 85, Issue 11 https://doi.org/10.1103/PhysRevB.85.115104	journal	March 2012
Band-structure calculations for the 3 d transition metal oxides in G W Lany, Stephan Physical Review B, Vol. 87, Issue 8 https://doi.org/10.1103/PhysRevB.87.085112	journal	February 2013
Modeling amorphous thin films: Kinetically limited minimization Zawadzki, Paweł P.; Perkins, John; Lany, Stephan Physical Review B, Vol. 90, Issue 9 https://doi.org/10.1103/PhysRevB.90.094203	journal	September 2014
Charge-neutral disorder and polytypes in heterovalent wurtzite-based ternary semiconductors: The importance of the octet rule Quayle, Paul C.; Blanton, Eric W.; Punya, Atchara Physical Review B, Vol. 91, Issue 20 https://doi.org/10.1103/PhysRevB.91.205207	journal	May 2015
Monte Carlo simulations of disorder in ZnSn N 2 and the effects on the electronic structure Lany, Stephan; Fioretti, Angela N.; Zawadzki, Paweł P. Physical Review Materials, Vol. 1, Issue 3 https://doi.org/10.1103/PhysRevMaterials.1.035401	journal	August 2017
FINDSYM : program for identifying the space-group symmetry of a crystal Stokes, Harold T.; Hatch, Dorian M. Journal of Applied Crystallography, Vol. 38, Issue 1 https://doi.org/10.1107/S0021889804031528	journal	January 2005
The thermodynamic scale of inorganic crystalline metastability Sun, Wenhao; Dacek, Stephen T.; Ong, Shyue Ping Science Advances, Vol. 2, Issue 11 https://doi.org/10.1126/sciadv.1600225	journal	November 2016
Novel phase diagram behavior and materials design in heterostructural semiconductor alloys Holder, Aaron M.; Siol, Sebastian; Ndione, Paul F. Science Advances, Vol. 3, Issue 6 https://doi.org/10.1126/sciadv.1700270	journal	June 2017
Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid Brown, K. A.; Harris, D. F.; Wilker, M. B. Science, Vol. 352, Issue 6284 https://doi.org/10.1126/science.aaf2091	journal	April 2016
Crystal structure of tristrontium [tetranitridomolybdate(VI)], Sr3[MoN4] Höhn, P.; Kniep, R. Zeitschrift für Kristallographie - New Crystal Structures, Vol. 215, Issue 3 https://doi.org/10.1515/ncrs-2000-0309	journal	March 2000
A Review of Epitaxial Metal-Nitride Films by Polymer-Assisted Deposition Luo, Hongmei; Wang, Haiyan; Zou, Guifu Transactions on Electrical and Electronic Materials, Vol. 11, Issue 2 https://doi.org/10.4313/TEEM.2010.11.2.054	journal	April 2010

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A map of the inorganic ternary metal nitrides Sun, Wenhao; Bartel, Christopher J.; Arca, Elisabetta Nature Materials, Vol. 18, Issue 7 https://doi.org/10.1038/s41563-019-0396-2	journal	June 2019
Zn ₂ SbN ₃ : growth and characterization of a metastable photoactive semiconductor Arca, Elisabetta; Perkins, John D.; Lany, Stephan Materials Horizons, Vol. 6, Issue 8 https://doi.org/10.1039/c9mh00369j	journal	January 2019
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Title: Redox-Mediated Stabilization in Zinc Molybdenum Nitrides

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