Thermodynamic Routes to Novel Stable and Metastable Nitride Semiconductors

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, nitrogen-rich nitrides are typically metastable, meaning they are rare in nature and difficult to synthesize. Here, we design rational thermodynamic routes to novel stable and metastable nitrogen-rich nitrides, and map these strategies onto a predictive computational search to identify stabilizable nitride materials across broad chemical spaces. Our search revealed dozens of new metastable nitrogen-rich binary nitrides which can be synthesized using reactive nitrogen precursors, and 87 previously unreported M₁-M₂-N ternary nitride systems with stable ternary nitrides. Using machine-learning algorithms, we cluster and map the ternary metal nitride space, elucidating the chemical families in this space to guide further materials exploration.