Role of N Defects on Thermally Induced Atomic-Scale Structural Changes in Transition-Metal Nitrides

Transition-metal nitrides (TMN) have exceptional stability, which underlies their use in various applications. Here, we study the role of N point defects on the stability of prototype TMNs using first-principles calculations. We find that distinct regimes for TMN changes relate to specific atomic-scale mechanisms, namely, diffusion of N interstitials (I(N)), of I(N) pairs, and of N vacancies. The activation of these processes occurs sequentially as the temperature is raised in a range of several hundreds of degrees, accounting for observed TMN changes under widely different conditions.