First-principles study of siloxene and germoxene: stable conformations, electronic properties, and defects

Interest in two-dimensional (2D) forms of Si and Ge has surged recently, with a focus on silicene and germanene, the Si- and Ge-based analogues of graphene, as well as their derivatives. Siloxene and germoxene are 2D materials made of honeycomb Si and Ge backbone sheets that are decorated with H atoms and OH groups. Here we use first-principles calculations to probe the properties of their various conformations. We show that the most stable siloxene (and germoxene) polymorph is the so-called washboard structure, and not the chair geometry assumed in previous studies. The stability of the washboard configuration relates to the formation of a network of hydrogen bonds between its hydroxyl groups. We also find with hybrid functional calculations that siloxene and germoxene are wide band-gap semiconductors with gap values of 3.20 eV and 2.64 eV, respectively. Finally, we show that H and OH vacancies introduce spin polarization in these 2D materials and have a tendency to pair up in stable di-vacancies.