Novel green phosphorene as a superior chemical gas sensing material

Green phosphorus and its monolayer variant, green phosphorene (GreenP), are the recent members of two-dimensional (2D) phosphorus polymorphs. The new polymorph possesses the high stability, tunable direct bandgap, exceptional electronic transport, and directionally anisotropic properties. All these unique features could reinforce it the new contender in a variety of electronic, optical, and sensing devices. Herein, we present gas-sensing characteristics of pristine and defected GreenP towards major environmental gases (i. e., NH₃, NO, NO₂, CO, CO₂, and H₂O) using combination of the density functional theory, statistical thermodynamic modeling, and the non-equilibrium Green's function approach (NEGF). The calculated adsorption energies, density of states (DOS), charge transfer, and Crystal Orbital Hamiltonian Population (COHP) reveal that NO, NO₂, CO, CO₂ are adsorbed on GreenP, stronger than both NH₃ and H₂O, which are weakly physisorbed via van der Waals interactions. Furthermore, substitutional doping by sulfur can selectively intensify the adsorption towards crucial NO₂ gas because of the enhanced charge transfer between p orbitals of the dopant and the analyte. The statistical estimation of macroscopic measurable adsorption densities manifests that the significant amount of NO₂ molecules can be practically adsorbed at ambient temperature even at the ultra-low concentration of part per billion (ppb). In addition, the current-voltage (I-V) characteristics of S-doped GreenP exhibit a variation upon NO₂ exposure, indicating the superior sensitivity in sensing devices. Our work sheds light on the promising application of the novel GreenP as promising chemical gas sensors.