Bulk materials made of silicon cage clusters doped with Ti, Zr, or Hf

We investigate the feasibility of assembling the exceptionally stable isovalent X@Si(16) (X = Ti, Zr and Hf) nanoparticles to form new bulk materials. We use first-principles density functional theory. Our results predict the formation of stable, wide band-gap materials crystallizing in HCP structures in which the cages bind weakly, similar to fullerite. This study suggests new pathways through which endohedral cage clusters may constitute a viable means toward the production of synthetic materials with pre-defined physical and chemical properties.