Defects in Silicene: Vacancy Clusters, Extended Line Defects, and Di-adatoms

Defects are almost inevitable during the fabrication process, and their existence strongly affects thermodynamic and (opto)electronic properties of two-dimensional materials. Very recent experiments have provided clear evidence for the presence of larger multi-vacancies in silicene, but their structure, stability, and formation mechanism remain largely unexplored. Here, we present a detailed theoretical study of silicene monolayer containing three types of defects: vacancy clusters, extended line defects (ELDs), and di-adatoms. First-principles calculations, along with ab initio molecular dynamics simulations, revealed the coalescence tendency of small defects and formation of highly stable vacancy clusters. The 5|8|5 ELD – the most favorable extended defect in both graphene and silicene sheets – is found to be easier to form in the latter case due to the mixed sp(2)/sp(3) hybridization of silicon. In addition, hybrid functional calculations that contain part of the Hatree-Fock exchange energy demonstrated that the introduction of single and double silicon adatoms significantly enhances the stability of the system, and provides an effective approach on tuning the magnetic moment and band gap of silicene.