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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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.
DiSalvo, F. J. & Clarke, S. J. Ternary nitrides: a rapidly growing class of new materials. Curr. Opin. Solid State Mater. Sci. 2, 241–249 (1996).
Höhn, P. & Niewa, R. Nitrides of non-main group elements. Handb. Solid State Chem. 1, 251–359 (2017).
Tareen, A. K., Priyanga, G. S., Behara, S., Thomas, T. & Yang, M. Mixed ternary transition metal nitrides: a comprehensive review of synthesis, electronic structure, and properties of engineering relevance. Prog. Solid State Chem. 53, 1–26 (2018).
Amano, H., Kito, M., Hiramatsu, K. & Akasaki, I. P-type conduction in Mg-doped GaN treated with low-energy electron beam irradiation (LEEBI). Jpn. J. Appl. Phys. 28, L2112–L2114 (1989).
Pust, P. et al. Narrow-band red-emitting Sr[LiAl3N4]:Eu2+ as a next-generation LED-phosphor material. Nat. Mater. 13, 891–896 (2014).
Vepřek, S. & Reiprich, S. A concept for the design of novel superhard coatings. Thin Solid Films 268, 64–71 (1995).
Jacobsen, C. J. H. Novel class of ammonia synthesis catalysts. Chem. Commun. 2000, 1057–1058 (2000).
Coey, J. & Sun, H. Improved magnetic properties by treatment of iron-based rare earth intermetallic compounds in ammonia. J. Magn. Magn. Mater. 87, L251–L254 (1990).
Balbarin, V., Dover, R. V. & Disalvo, F. The high temperature preparation and property measurements of CaTaN2: a ternary superconducting nitride. J. Phys. Chem. Solids 57, 1919–1927 (1996).
Lee, K., Kim, S. W., Toda, Y., Matsuishi, S. & Hosono, H. Dicalcium nitride as a two-dimensional electride with an anionic electron layer. Nature 494, 336–340 (2013).
Burton, L. A., Ricci, F., Chen, W., Rignanese, G.-M. & Hautier, G. High-throughput identification of electrides from all known inorganic materials. Chem. Mater. 30, 7521–7526 (2018).
Huang, H., Jin, K.-H. & Liu, F. Alloy engineering of topological semimetal phase transition in MgTa2−xNbxN3. Phys. Rev. Lett. 120, 136403 (2018).
Zakutayev, A. Design of nitride semiconductors for solar energy conversion. J. Mater. Chem. A 4, 6742–6754 (2016).
Mori-Sánchez, P. et al. Origin of the low compressibility in hard nitride spinels. Phys. Rev. B 68, 064115 (2003).
Elder, S. H., Disalvo, F. J., Topor, L. & Navrotsky, A. Thermodynamics of ternary nitride formation by ammonolysis: application to lithium molybdenum nitride (LiMoN2), sodium tungsten nitride (Na3WN3), and sodium tungsten oxide nitride (Na3WO3N). Chem. Mater. 5, 1545–1553 (1993).
Mchale, J. M., Navrotsky, A., Kowach, G. R., Balbarin, V. E. & Disalvo, F. J. Energetics of ternary nitrides: Li−Ca−Zn−N and Ca−Ta−N systems. Chem. Mater. 9, 1538–1546 (1997).
Curtarolo, S. et al. The high-throughput highway to computational materials design. Nat. Mater. 12, 191–201 (2013).
Jain, A, Shin, Y. & Persson, K. A. Computational predictions of energy materials using density functional theory. Nat. Rev. Mater. 1, 15004 (2016).
Collins, C. et al. Accelerated discovery of two crystal structure types in a complex inorganic phase field. Nature 546, 280–284 (2017).
Gautier, R. et al. Prediction and accelerated laboratory discovery of previously unknown 18-electron ABX compounds. Nat. Chem. 7, 308–316 (2015).
Hautier, G., Fischer, C. C., Jain, A., Mueller, T. & Ceder, G. Finding nature’s missing ternary oxide compounds using machine learning and density functional theory. Chem. Mater. 22, 3762–3767 (2010).
Meredig, B. et al. Combinatorial screening for new materials in unconstrained composition space with machine learning. Phys. Rev. B 89, 094104 (2014).
Jain, A., Hautier, G., Ong, S. P. & Persson, K. New opportunities for materials informatics: resources and data mining techniques for uncovering hidden relationships. J. Mater. Res. 31, 977–994 (2016).
Isayev, O. et al. Materials cartography: representing and mining materials space using structural and electronic fingerprints. Chem. Mater. 27, 735–743 (2015).
Hoffmann, R. How chemistry and physics meet in the solid state. Angew. Chem. Int. Ed. 26, 846–878 (1987).
Hinuma, Y. et al. Discovery of earth-abundant nitride semiconductors by computational screening and high-pressure synthesis. Nat. Commun. 7, 11962 (2016).
Gharavi, M. A., Armiento, R., Alling, B. & Eklund, P. Theoretical study of phase stability, crystal and electronic structure of MeMgN2 (Me = Ti, Zr, Hf) compounds. J. Mater. Sci. 53, 4294–4305 (2018).
Ching, W. Y., Mo, S.-D., Tanaka, I. & Yoshiya, M. Prediction of spinel structure and properties of single and double nitrides. Phys. Rev. B 63, 064102 (2001).
Sarmiento-Pérez, R., Cerqueira, T. F. T., Körbel, S., Botti, S. & Marques, M. A. L. Prediction of stable nitride perovskites. Chem. Mater. 27, 5957–5963 (2015).
Hautier, G., Fischer, C., Ehrlacher, V., Jain, A. & Ceder, G. Data mined ionic substitutions for the discovery of new compounds. Inorg. Chem. 50, 656–663 (2011).
Sun, W. et al. Thermodynamic routes to novel metastable nitrogen-rich nitrides. Chem. Mater. 29, 6936–6946 (2017).
Ong, S. P. et al. Python materials genomics (pymatgen): a robust, open-source Python library for materials analysis. Comp. Mater. Sci. 68, 314–319 (2013).
Jain, A. et al. Commentary: The Materials Project: a materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013).
Kemp, C. & Tenenbaum, J. B. The discovery of structural form. Proc. Natl Acad. Sci. USA 105, 10687–10692 (2008).
Johnson, S. C. Hierarchical clustering schemes. Psychometrika 32, 241–254 (1967).
Gower, J. C. A general coefficient of similarity and some of its properties. Biometrics 27, 857 (1971).
Pettifor, D. G. The structures of binary compounds. I. Phenomenological structure maps. J. Phys. C: Solid State Phys. 19, 285–313 (1986).
Sun, W. et al. The thermodynamic scale of inorganic crystalline metastability. Sci. Adv. 2, e1600225 (2016).
Bartel, C. J. et al. Physical descriptor for the Gibbs energy of inorganic crystalline solids and temperature-dependent materials chemistry. Nat. Commun. 9, 4168 (2018).
Choi, J. & Gillan, E. G. Solvothermal metal azide decomposition routes to nanocrystalline metastable nickel, iron, and manganese nitrides. Inorg. Chem. 48, 4470–4477 (2009).
Caskey, C. M., Richards, R. M., Ginley, D. S. & Zakutayev, A. Thin film synthesis and properties of copper nitride, a metastable semiconductor. Mater. Horiz. 1, 424–430 (2014).
Bikowski, A. et al. Design of metastable tin titanium nitride semiconductor alloys. Chem. Mater. 29, 6511–6517 (2017).
Arca, E. et al. Redox-mediated stabilization in zinc molybdenum nitrides. J. Am. Chem. Soc. 140, 4293–4301 (2018).
Horvath-Bordon, E. et al. High-pressure chemistry of nitride-based materials. Chem. Soc. Rev. 35, 987–1014 (2006).
Amsler, M., Hegde, V. I., Jacobsen, S. D. & Wolverton, C. Exploring the high-pressure materials genome. Phys. Rev. X 8, 041021 (2018).
Yang, M. et al. Strong optical absorption in CuTaN2 nitride delafossite. Energy Environ. Sci. 6, 2994 (2013).
Aykol, M., Dwaraknath, S. S., Sun, W. & Persson, K. A. Thermodynamic limit for synthesis of metastable inorganic materials. Sci. Adv. 4, eaaq0148 (2018).
Kuech, T. F., Babcock, S. E. & Mawst, L. Growth far from equilibrium: examples from III-V semiconductors. Appl. Phys. Rev. 3, 040801 (2016).
Lambrecht, W. R. L. & Punya, A. in III-Nitride Semiconductors and their Modern Devices (ed. Gil, B.) 519–585 (Oxford Univ. Press, 2013).
Veal, T. D. et al. Band gap dependence on cation disorder in ZnSnN2 solar absorber. Adv. Energy Mater. 5, 1501462 (2015).
Anderson, W. P., Burdett, J. K. & Czech, P. T. What is the metallic bond? J. Am. Chem. Soc. 116, 8808–8809 (1994).
Walsh, A., Sokol, A. A., Buckeridge, J., Scanlon, D. O. & Catlow, C. R. A. Oxidation states and ionicity. Nat. Mater. 17, 958–964 (2018).
van Arkel, A. E. Molecules and crystals in inorganic chemistry. J. Chem. Educ. 34, 417 (1957).
Etourneau, J., Portier, J. & Ménil, F. The role of the inductive effect in solid state chemistry: how the chemist can use it to modify both the structural and the physical properties of the materials. J. Alloys Compd. 188, 1–7 (1992).
Gregory, D. H. Structural families in nitride chemistry. J. Chem. Soc. Dalton Trans. 1999, 259–270 (1999).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 6, 15–50 (1996).
Jain, A. et al. A high-throughput infrastructure for density functional theory calculations. Comp. Mater. Sci. 50, 2295–2310 (2011).
Ong, S. P. et al. The materials application programming interface (API): a simple, flexible and efficient API for materials data based on REpresentational State transfer (REST) principles. Comp. Mater. Sci. 97, 209–215 (2015).
Dice, L. R. Measures of the amount of ecologic association between species. Ecology 26, 297–302 (1945).
Scerri, E. R. in The Periodic Table: Into the 21st Century (eds Rouvray, D. and King, B.) 142–160 (Science Research, 2004).
Bar-Joseph, Z., Gifford, D. K. & Jaakkola, T. S. Fast optimal leaf ordering for hierarchical clustering. Bioinformatics 17, S22–S29 (2001).
Bhadram, V. S., Kim, D. Y. & Strobel, T. A. High-pressure synthesis and characterization of incompressible titanium pernitride. Chem. Mater. 28, 1616–1620 (2016).
Niwa, K. et al. Highly coordinated iron and cobalt nitrides synthesized at high pressures and high temperatures. Inorg. Chem. 56, 6410–6418 (2017).
Yu, S. et al. Emergence of novel polynitrogen molecule-like species, covalent chains, and layers in magnesium–nitrogen MgxNy phases under high pressure. J. Phys. Chem. C 121, 11037–11046 (2017).
Bykov, M. et al. Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains. Nat. Commun. 9, 2756 (2018).
Manz, T. A. & Limas, N. G. Introducing DDEC6 atomic population analysis: part 1. Charge partitioning theory and methodology. RSC Adv. 6, 47771–47801 (2016).
Manz, T. A. Introducing DDEC6 atomic population analysis: part 3. Comprehensive method to compute bond orders. RSC Adv. 7, 45552–45581 (2017).
Maintz, S., Deringer, V. L., Tchougréeff, A. L. & Dronskowski, R. LOBSTER: a tool to extract chemical bonding from plane-wave based DFT. J. Comput. Chem. 37, 1030–1035 (2016).
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.
The authors declare no competing interests.
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Supplementary Sections 1–9, Supplementary Figs. 1–14, Supplementary Table 1, Supplementary ref. 1.
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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