Defects in ion-implanted hcp-titanium: A first-principles study of electronic structures

The electronic structures of hexagonal closed-packed (h.c.p) titanium containing a vacancy and krypton impurity atoms at various insertion sites are calculated by first-principles methods in the framework of the density-functional theory (DFT). The density of states (DOS) for titanium containing a vacancy defect shows resonance-like features. Also, the bulk electron density decreases from ∼0.15/Å3 to ∼0.05/Å3 at the vacancy centre. Electronic structure calculations have been performed to investigate what underlies the krypton site preference in titanium. The DOS of the nearest-neighbour (NN) titanium atoms to the octahedral krypton appears to be less distorted (relative to pure titanium) when compared to the NN titanium atoms to the tetrahedral krypton. The electronic density deformation maps show that polarization of the titanium atoms is stronger when the krypton atom is located at the tetrahedral site. Since krypton is a closed-shell atom, thus precluding any bonding with the titanium atoms, we may conclude that the polarization of the electrons in the vicinity of the inserted krypton atoms and the distortion of the DOS of the NN titanium atoms to the krypton serve to indicate which defect site is preferred when a krypton atom is inserted into titanium. Based on these considerations, we conclude that the substitutional site is the most favourable one, and the octahedral is the preferred interstitial site, in agreement with recent DFT calculations of the energetics of krypton impurity sites.

► We model a vacancy and krypton impurity atoms at various insertion sites in titanium, using first-principles methods. ► The density of states (DOS) for titanium containing a vacancy defect shows resonance-like features. ► The DOS of the nearest-neighbour (NN) titanium atoms to the octahedral interstitial site krypton is less distorted. ► Electronic polarization of the NN titanium atoms is strongest when the krypton atom is located at the tetrahedral site. ► Substitutional site is the most favourable site while the octahedral site is the more preferred interstitial site.