Ab initio calculations within the density-functional theory formalism are performed to investigate the chemical functionalization of a graphene-like monolayer of silicon -silicene -with B, N, Al or P atoms. The structural, electronic, magnetic and vibrational properties are reported. The most preferable adsorption sites are found to be valley, bridge, valley and hill site for B, N, Al and P adatoms, respectively. All the relaxed systems with adsorbed/substituted atoms exhibit metallic behaviour with strongly bonded B, N, Al, and P atoms accompanied by an appreciable electron transfer from silicene to the B, N and P adatom/substituent. The Al atoms exhibit opposite charge transfer, with n-type doping of silicene and weaker bonding. The adatoms/substituents induce characteristic branches in the phonon spectrum of silicene, which can be probed by Raman measurements. Using molecular dynamics we found that the systems under study are stable up to at least T = 500 K. Our results demonstrate that silicene has a very reactive and functionalizable surface.

During the synthesis of ultra-thin materials with hexagonal lattice structure Stone-Wales (SW) type of defects are quite likely to be formed and the existence of such topological defects in the graphene-like structures results in dramatical changes of their electronic and mechanical properties. Here we investigate the formation and reactivity of such SW defects in silicene. We report the energy barrier for the formation of SW defects in freestanding (∼2.4 eV) and Ag(111)-supported (∼2.8 eV) silicene and found it to be significantly lower than in graphene (∼9.2 eV). Moreover, the buckled nature of silicene provides a large energy barrier for the healing of the SW defect and therefore defective silicene is stable even at high temperatures. Silicene with SW defects is semiconducting with a direct bandgap of 0.02 eV and this value depends on the concentration of defects. Furthermore, nitrogen substitution in SW defected silicene shows that the defect lattice sites are the least preferable substitution locations for the N atoms. Our findings show the easy formation of SW defects in silicene and also provide a guideline for bandgap engineering in silicenebased materials through such defects.

Ab initio calculations within the density functional theory formalism are performed to investigate the stability and electronic properties of fluorinated bilayer graphene (bilayer fluorographene). A comparison is made to previously investigated graphane, bilayer graphane, and fluorographene. Bilayer fluorographene is found to be a much more stable material than bilayer graphane. Its electronic band structure is similar to that of monolayer fluorographene, but its electronic band gap is significantly larger (about 1 eV). We also calculate the effective masses around the Γ-point for fluorographene and bilayer fluorographene and find that they are isotropic, in contrast to earlier reports. Furthermore, it is found that bilayer fluorographene is almost as strong as graphene, as its 2D Young's modulus is approximately 300 N m −1 .

Stable monolayer materials based on existing, well known and stable two-dimensional crystal fluorographene and molybdenum disulfide are predicted to exhibit a huge magnetocrystalline anisotropy when functionalized with adsorbed transition metal atoms at vacant sides. Ab initio calculations within the density-functional theory formalism were performed to investigate the adsorption of the transitional metals in a single S (or F) vacancy of monolayer molybdenum disulfide (or fluorographene). We found strong bonding of the transitional metal atoms to the vacant sites with binding energies ranging from 2.5 to 5.2 eV. Our calculations revealed that these systems with adsorbed metal atoms exhibit a magnetic anisotropy, specifically the structures including Os and Ir show a giant magnetocrystalline anisotropy energy of 31-101 meV. Our results demonstrate the possibility of obtaining stable monolayer materials with huge magnetocrystalline anisotropy based on preexisting, well known and stable two-dimensional crystals: fluorographene and molybdenum disulfide. We believe that the results obtained here are useful not only for deeper understanding of the origin of magnetocrystalline anisotropy but also for the design of monolayer optoelectronic devices with novel functionalities.

Ab initio calculations within the density-functional theory formalism are performed to investigate the ground state, electric charge doping, and electronic properties of titanium and titanium dioxide monolayers adsorbed on a graphene surface. A new ground state structrure of Ti monolayer adsorbed on graphene is reported which is shown to be stable up to T = 500 K. Effects due to lower and higher Ti adatoms coverage are studied. We find that the adsorbed Ti provides a strong n-type doping which supports recent experimental observations. On the other hand, TiO2 can induce both p-and n-type doping in the carbon monolayer depending on whether oxygen or titanium atoms are closest to the substrate. We identify the structures which are responsible for the experimentally observed autocompensation mechanism that leads to the reversion of adsorbate effects after oxidation of the adsorbed Ti.