Thermodynamic Routes to Novel Metastable Nitrogen-Rich Nitrides

Wenhao Sun, Aaron Holder, Bernardo Orvañanos, Elisabetta Arca, Andriy Zakutayev, Stephan Lany, Gerbrand Ceder

Research output: Contribution to journalArticlepeer-review

120 Scopus Citations


Compared to oxides, the nitrides are relatively unexplored, making them a promising chemical space for novel materials discovery. Of particular interest are nitrogen-rich nitrides, which often possess useful semiconducting properties for electronic and optoelectronic applications. However, such nitrogen-rich compounds are generally metastable, and the lack of a guiding theory for their synthesis has limited their exploration. Here, we review the remarkable metastability of observed nitrides, and examine the thermodynamics of how reactive nitrogen precursors can stabilize metastable nitrogen-rich compositions during materials synthesis. We map these thermodynamic strategies onto a predictive computational search, training a data-mined ionic substitution algorithm specifically for nitride discovery, which we combine with grand-canonical DFT-SCAN phase stability calculations to compute stabilizing nitrogen chemical potentials. We identify several new nitrogen-rich binary nitrides for experimental investigation, notably the transition metal nitrides Mn3N4, Cr3N4, V3N4, and Nb3N5, the main group nitride SbN, and the pernitrides FeN2, CrN2, and Cu2N2. By formulating rational thermodynamic routes to metastable compounds, we expand the search space for functional technological materials beyond equilibrium phases and compositions.

Original languageAmerican English
Pages (from-to)6936-6946
Number of pages11
JournalChemistry of Materials
Issue number16
StatePublished - 22 Aug 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

NREL Publication Number

  • NREL/JA-5K00-70097


  • chemical stability
  • computation theory
  • metastable phases
  • nitrogen
  • thermodynamics
  • transition metals


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