Modeling of silicon- and aluminum-doped phosphorene nanoflakes

The electronic structure of phosphorene nanoflakes (PNFs) doped with Al and Si has been explored using hybrid functional BHandHlyp/def2-SVP and complete active space (CASSCF) methods. Doping increases the bond length alternation and changes the overall PNF shape. Doping also decreases singlet-triplet splitting in the PNFs. This effect is most notable for Si doping where singlet and triplet states become virtually degenerated. Doping also reduces band gaps and changes the nature of the ground states for Si-doped systems. The ground state of Si-doped PNFs becomes polyradicalic. In general, dopants with even number of valence electrons promote polyradicalic ground state. Doped systems show increased electron affinities (EAs), while the ionization potentials are much less affected. Larger EAs are related with the delocalization of an extra electron over the empty or partially empty 3p orbitals of the dopants. Doping increases the reorganization energies in all cases. Al-doped PNFs are the hole transport materials while Si-doped nanoflakes tend to be electron transport systems. Graphical abstract.