Creating new layered structures at high pressures: SiS₂

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 CdI$_2$-type layered structure, which is octahedrally coordinated with space group $P\bar{3}m1$ 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 $P\bar{3}m1$-SiS$_2$.