Quantum confinement and edge effects on electronic properties of zigzag green phosphorene nanoribbons

First-principles density-functional theory calculations were performed to investigate quantum confinement and edge effects on electronic properties of zigzag green phosphorene nanoribbons (ZGPNRs) with edge chemical species including H, OH, F, Cl, O, and S for the ribbons width in the range of 0.5–3.7 nm. The ZGPNRs were obtained from relaxed two-dimensional green phosphorene monolayer with different cutting strategies and the most energetically favorable ribbon configuration was selected for further exploration of size and edge effects. It was found that the electronic properties of the ZGPNRs are strongly associated with the ribbon width and edge chemical species. They show either semiconducting or metallic features depending on the edge functionalization species. The ZGPNRs show semiconducting behavior with the edge species of H, OH, F, or Cl (Group I), while they exhibit metallic characteristics with pristine or O, S edges (Group II). The conduction band minimum and valence band maximum of the ZGPNRs with the Group I edge are primarily located at the inner P atoms and the edge P and functionalization atoms have little contribution. However, for the Group II edge, the electronic bands crossing the Fermi level are dominantly contributed by the edge atoms. It was also found that the band gap and work function of the ZGPNRs are sensitively tunable by varying ribbon width and edge functionalization species. (paper)