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.

绿磷及其单层变体绿色磷光体（GreenP）是二维（2D）磷多晶型物的最新成员。新的多晶型物具有高稳定性，可调节的直接带隙，出色的电子传输和方向各向异性的特性。所有这些独特的功能可以使其成为各种电子，光学和传感设备中的新竞争者。在这里，我们介绍了原始和有缺陷的GreenP对主要环境气体（即NH ₃，NO，NO ₂，CO，CO ₂和H _2）的气敏特性O）结合使用密度泛函理论，统计热力学建模和非平衡格林函数方法（NEGF）。计算得出的吸附能，态密度（DOS），电荷转移和晶体轨道哈密顿量（COHP）表明，NOP，NO ₂，CO，CO ₂被吸附在GreenP上，比NH ₃和H ₂ O都强。通过范德华相互作用弱吸收。此外，通过硫取代掺杂可以选择性地朝着强化关键NO吸附₂因为之间的增强的电荷转移的气体p掺杂物和分析物的轨道。宏观可测量的吸附密度的统计估计表明，即使在十亿分之一（ppb）的超低浓度下，也可以在环境温度下实际吸附大量的NO ₂分子。此外，掺杂S的GreenP的电流-电压（IV）特性在暴露于NO _2时会发生变化，这表明传感设备具有出色的灵敏度。我们的工作揭示了新型GreenP作为有前途的化学气体传感器的有前途的应用。