Behavior of intrinsic defects in BaF2 under uniaxial compressions : An ab initio investigation

We revisit the defects and related optical properties of one of the prototypical scintillator materials, BaF2, by means of density functional theory calculations. The interstitial F atom is found to be the most favorable defect to be formed, while it is rather difficult to create a F vacancy, Ba vacancy and Ba interstitial intrinsically, unless external forces are applied to the lattice, such as shock compression. The migration barriers for the above defects are remarkably path dependent. For a Ba vacancy, the migration barrier in the (001) (loading) direction is significantly reduced compared to those in the perpendicular (100) and (010) directions, while the migration along the (101) direction has the least value, which is surprisingly smaller than that at ambient pressure. An interstitial Ba atom prefers to move along the (100) and (010) directions in a manner similar to collective diffusion. The F vacancy has the lowest energy barrier along the (001) direction, while uniaxial strain greatly hinders the diffusion of F interstitials. We also study the role of defects on the optical absorption and find that a F vacancy, and interstitial F and Ba atoms are able to introduce pronounced changes to the spectra, whereas the Ba vacancy only shows marginal effects. The favorable migration paths for the different types of defects under strain or pressure can contribute to the design of specific ionic conductor properties under extreme conditions.