Elucidating the Ambient Stability and Gas Sensing Mechanism of Nickel-Decorated Phosphorene for NO(2) Detection: A First-Principles Study

[Image: see text] In the field of layered two-dimensional functional materials, black phosphorus has attracted considerable attention in many applications due to its outstanding electrical properties. It has experimentally shown superior chemical sensing performance for the room temperature detection of NO(2), highlighting high sensitivity at a ppb level. Unfortunately, pristine black phosphorus demonstrated an unstable functionality due to the fast degradation of the material when exposed to the ambient atmosphere. In the present work, a deepened investigation by density functional theory was carried out to study how nickel decoration of phosphorene can improve the stability of the material. Further, an insight into the sensing mechanism of nickel-loaded phosphorene toward NO(2) was given and compared to pristine phosphorene. This first-principles study proved that, by introducing nickel adatoms, the band gap of the material decreases and the positions of the conduction band minimum and the valence band maximum move toward each other, resulting in a drop in the conduction band minimum under the redox potential of O(2)/O(2)(–), which may result in a more stable material. Studying the adsorption of O(2) molecules on pristine phosphorene, we also proved that all oxygen molecules coming from the surrounding atmosphere react with phosphorus atoms in the layer, resulting in the oxidation of the material forming oxidized phosphorus species (PO(x)). Instead, by introducing nickel adatoms, part of the oxygen from the surrounding atmosphere reacts with nickel atoms, resulting in a decrease of the oxidation rate of the material and in subsequent long-term stability of the device. Finally, possible reaction paths for the detection of NO(2) are given by charge transfer analyses, occurring at the surface during the adsorption of oxygen molecules and the interaction with the target gas.