Controlling the electronic properties of 2D/3D pillared graphene and glass-like carbon via metal atom doping.

We present the results of investigation of the nanopore filling of planar layered and bulk pillared graphene (PGR) as well as films and 3D samples of glass-like porous carbon (GLC) with potassium atoms. The patterns of charge transfer, electronic structure, and shift of the Fermi level during the filling of nanopores with potassium atoms are established. It is found that the greatest charge transfer from potassium atoms to the carbon framework is observed in PGR with a density of 1.1-1.4 g cm-3 (that is, with a nanopore volume of 1300-1800 nm3) regardless of the framework topology. The maximum charge transfer occurs already when the mass fraction of potassium is 12 wt%. At the same potassium concentration, a maximum shift of the Fermi level to zero by ∼3 eV occurs in a bilayer PGR film with a density of 1.4 g cm-3. Thus, our work shows for the first time that the electronic properties of nanoporous materials doped with alkaline earth metals (in particular, potassium) can be controlled by varying the volume of doped nanopores, i.e. by controlling the density of the nanoporous material. We first demonstrated that the potassium doping of PGR would be more effective than potassium doping of GLC. It is established that 2D samples of PGR and GLC completely reproduce the electronic properties of the bulk samples and even surpass them in some parameters. To carry out research, we developed a new method for nanopore filling with dopant atoms based on both the randomness of the nanopore filling and the energy advantage of this process. This method allows us to reliably determine the maximum possible mass fraction (wt%) of dopant atoms of any porous material.