Density functional calculations of Ti nanoclusters in the metastable Mg-Ti system

Mg-Ti-H thin films exhibit interesting optical and electrical properties, offering a wide range of possible applications from coatings on solar collectors and smart windows to optical hydrogen sensors and semiconductor devices. However, Ti is known to be immiscible in Mg, and the microstructure of Mg-Ti thin films is not fully understood. In this work density functional theory calculations were used to investigate the Mg_100-yTi_y system with 1.56≤y≤98.44 . The crystal structure, mixing enthalpy, and electronic structure were compared for two different distributions of Ti: quasirandom and segregated. It was found that although the crystal structures did not differ significantly, the formation enthalpy per Ti atom was lowered by up to ∼0.5eV when Ti was arranged in nanoclusters. This gives support to previous experimental findings of chemical short-range order in Mg-Ti thin films [R. Gremaud , Phys. Rev. B 77, 144204 (2008)10.1103/PhysRevB.77.144204]. As a consequence of the decrease in the mixing enthalpy upon clustering the occurrence of short-range chemical order in all reported metastable Mg-Ti alloys with extended solubility is proposed. Further inquires into the influence of the size of the clusters revealed that the mixing enthalpy reaches a minimum after which further growth makes little difference, indicating that the phenomenon of nanoscale clustering must be understood separately from the larger scale phase separation occurring in an equilibrium process. The relaxed crystal structures were compared to experimental values from several sources and lattice-parameter variations as well as deviations from Vegard’s law were discussed. Dependence of the size and shape of the nanoclusters on synthesis method is offered as an explanation for the large variation among the experimental lattice parameters. Local density of states calculations illustrated how segregated Ti forms a local environment resembling pure Ti while it was necessary to perform Bader analysis in order to obtain the correct picture of the charge transfer between Mg and Ti. Randomly distributed Ti atoms affect the charge distribution severely and the further the Ti atoms are apart the larger is the charge transfer from Mg. It was shown that a very limited amount of Ti nearest neighbors is sufficient for Ti to experience an imitation of elemental state, removing the driving force for further nucleation.