Creating new layered structures at high pressures: SiS(2)

Old and novel layered structures are attracting increasing attention for their physical, electronic, and frictional properties. SiS(2), isoelectronic to SiO(2), CO(2) and CS(2), is a material whose phases known experimentally up to 6 GPa exhibit 1D chain-like, 2D layered and 3D tetrahedral structures. We present highly predictive ab initio calculations combined with evolutionary structure search and molecular dynamics simulations of the structural and electronic evolution of SiS(2) up to 100 GPa. A highly stable CdI2-type layered structure, which is octahedrally coordinated with space group [Image: see text] surprisingly appears between 4 and up to at least 100 GPa. The tetrahedral-octahedral switch is naturally expected upon compression, unlike the layered character realized here by edge-sharing SiS(6) octahedral units connecting within but not among sheets. The predicted phase is semiconducting with an indirect band gap of about 2 eV at 10 GPa, decreasing under pressure until metallization around 40 GPa. The robustness of the layered phase suggests possible recovery at ambient pressure, where calculated phonon spectra indicate dynamical stability. Even a single monolayer is found to be dynamically stable in isolation, suggesting that it could possibly be sheared or exfoliated from bulk [Image: see text]-SiS(2).