Point defect formation at finite temperatures with machine learning force fields†

Abstract

Point defects dictate the properties of many functional materials. The standard approach to modelling the thermodynamics of defects relies on a static description, where the change in Gibbs free energy is approximated by the internal energy. This approach has a low computational cost, but ignores contributions from atomic vibrations and structural configurations that can be accessed at finite temperatures. We train a machine learning force field (MLFF) to explore dynamic defect behaviour using Te⁺¹_i and V⁺²_Te in CdTe as exemplars. We consider the different entropic contributions (e.g., electronic, spin, vibrational, orientational, and configurational) and compare methods to compute the defect free energies, ranging from a harmonic treatment to a fully anharmonic approach based on thermodynamic integration. We find that metastable configurations are populated at room temperature and thermal effects increase the predicted concentration of Te⁺¹_i by two orders of magnitude — and can thus significantly affect the predicted properties. Overall, our study underscores the importance of finite-temperature effects and the potential of MLFFs to model defect dynamics at both synthesis and device operating temperatures.