Electron screening and strength of long-range Coulomb interactions in phosphorene: From bulk to nanoribbon

Abstract: Experimental observations of anisotropic tightly bound excitons in black phosphorene, and correlated phenomena such as room temperature magnetically active edges in phosphorene nanoribbons (PNRs), sparked discussions on the controversial screening of the Coulomb interaction in phosphorene-based materials. In this way, we investigate the first-principles electronic screening of the long-range Coulomb interaction in phosphorene from bulk to nanoribbon by employing ab initio calculations in conjunction with the constrained random-phase approximation. The bands near Fermi energy (E_F) are predominantly pz orbital characters, and due to the puckering, they are not well separated from the other bands with s, px, and specially py characters. This proximity in energy levels increases the contribution of px/py $\rightarrow$ pz transitions to the polarization function and significantly alters the Coulomb parameters. In semiconducting systems, the on-site Coulomb interaction values (Hubbard U) range from 4.1 to 6.5 eV and depend on the correlated subspace, electronic structure, nanoribbon's width, and edge passivation. Our long-range interaction has revealed a non-conventional screening in semiconducting nanoribbons. We have discovered that screening actually enhances the electron-hole interaction for separations larger than a critical distance r_c, which is contrary to what was previously seen in conventional semiconductors. In unpassivated zigzag nanoribbons, due to a metallic screening channel stemming from quasi-flat edge bands at E_F, we find U/W_b > 1 (the bandwidth W_b) and large gradient of inter-site Coulomb interactions, making them correlated materials. We have investigated the instability of the paramagnetic state of bare ZPNRs toward ferromagnetism using a Stoner model based on the calculated Hubbard U parameters.