A map of the inorganic ternary metal nitrides

Abstract

Exploratory synthesis in new chemical spaces is the essence of solid-state chemistry. However, uncharted chemical spaces can be difficult to navigate, especially when materials synthesis is challenging. Nitrides represent one such space, where stringent synthesis constraints have limited the exploration of this important class of functional materials. Here, we employ a suite of computational materials discovery and informatics tools to construct a large stability map of the inorganic ternary metal nitrides. Our map clusters the ternary nitrides into chemical families with distinct stability and metastability, and highlights hundreds of promising new ternary nitride spaces for experimental investigation—from which we experimentally realized seven new Zn- and Mg-based ternary nitrides. By extracting the mixed metallicity, ionicity and covalency of solid-state bonding from the density functional theory (DFT)-computed electron density, we reveal the complex interplay between chemistry, composition and electronic structure in governing large-scale stability trends in ternary nitride materials.

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Fig. 1: A map of the inorganic ternary metal nitrides, coloured to represent the thermodynamic stability of the ternary nitride with the lowest formation energy.
Fig. 2: Experimental realization of seven predicted Zn- and Mg-based ternary nitrides.
Fig. 3: Thermochemical origins of ternary nitride stability.
Fig. 4: Electronic structure origins of ternary nitride stability.

Data availability

We have made the structures and energies of the newly predicted nitrides freely available on the Materials Project (www.materialsproject.org) for readers interested in further investigation. All other data are available from the corresponding authors on request.

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Acknowledgements

Funding for this study was provided by the US Department of Energy, Office of Science, Basic Energy Sciences, under contract no. UGA-0-41029-16/ER392000 as a part of the Department of Energy Energy Frontier Research Center for Next Generation of Materials Design: Incorporating Metastability. This research used resources of the Center for Functional Nanomaterials, which is a US Department of Energy Office of Science Facility, at Brookhaven National Laboratory under contract no. DE-SC0012704. This work also used computational resources sponsored by the Department of Energy’s Office of Energy Efficiency and Renewable Energy, located at NREL. C.J.B. and A.M.H. acknowledge support in part from the Research Corporation for Science Advancement through the Scialog: Advanced Energy Storage award programme. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. W.S. thanks S. Y. Chan and N. U. Gulls for discussions and support.

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W.S., B.O., A.M.H., S.L. and G.C. performed ternary nitride structure prediction; W.S., C.J.B., A.M.H. and S.L. computed phase stability; W.S. constructed the map; E.A., S.R.B., B.M., J.T., W.T. and A.Z. synthesized ternary nitride thin films; synchrotron XRD characterization was performed by B.-R.C., M.F.T. and L.T.S.; W.S., C.J.B., A.M.H. and G.C. performed the metallicity, ionicity and covalency analysis. W.S., C.J.B., A.M.H. and G.C. wrote the manuscript, with contributions and revisions from all authors.

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Correspondence to Wenhao Sun or Aaron M. Holder.

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Supplementary Information

Supplementary Sections 1–9, Supplementary Figs. 1–14, Supplementary Table 1, Supplementary ref. 1.

Supplementary Interactive Map

Compressed interactive HTML file of the map shown in Figure 1. When decompressed, and a particular ternary nitride space selected, a ternary phase diagram is presented along with a table of calculated stable and metastable compounds, their formation enthalpies, energies with respect to the convex hull and, for metastable compounds, their decomposition products and the nitrogen chemical potentials or pressures at which they can be stabilized.

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Sun, W., Bartel, C.J., Arca, E. et al. A map of the inorganic ternary metal nitrides. Nat. Mater. 18, 732–739 (2019). https://doi.org/10.1038/s41563-019-0396-2

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