Electro- and opto-mutable properties of MgO nanoclusters adsorbed on mono- and double-layer graphene

Inspired by recent experiments, the trapping of molecules in 2D materials has gained increasing attention due to the unique ability of the molecules to modulate the electronic and optical properties of 2D materials, which calls for fundamental understanding and predictive design strategies. Herein, we focus on mono- and double-layer graphene encapsulating various MgO clusters and explore their diverse electronic and optical properties using a number of high-level first-principles calculations. By correlating the stability of adsorption, geometry, charge transfer, band structures, optical absorption spectrum, and the van der Waals pressure, our results decode various synergies in electro- and opto-mutable properties of MgO/graphene systems. We found that 2D-MgO flakes on graphene layers exhibit surface polarization effects - in contrast to their isolated neutral flakes - and show a significant charge transfer from graphene to n-doped flakes, breaking the symmetry of graphene layers. We obtained a van der Waals pressure of ∼0.7 (0.9) GPa on bilayer graphene encapsulating MgO nanoclusters, which matches extremely well with experiment. While there is one quantum emission in the visible light region for a single MgO flake, a wide range of visible light is accessible for MgO on mono- and double-layer graphene. Overall, these findings provide new physical insights and design strategies to modulate 2D materials with several applications in optoelectronics while significantly broadening the spectrum of strategies for fabricating new hybrid 2D heterostructures by encapsulating external molecules.