The Role of H2O and O2 Molecules and Phosphorus Vacancies in the Structure Instability of Phosphorene

Abstract

The poor structural stability of phosphorene in air was commonly ascribed to humidity and oxygen molecules. Recent exfoliation of phosphorene in deoxygenated water promotes the need to re-examine the role of H2O and O2 molecules. Considering the presence of high population of vacancies in phosphorene, we investigate the interaction of H2O and O2 molecules with vacancy-contained phosphorene using first-principles calculations. In contrast to the common notion that physisorbed molecules tend to have a stronger adsorption at vacancy sites, we show that H2O has nearly the same adsorption energy at the vacancy site as that at the perfect one. Charge transfer analysis shows that O2 is a strong electron scavenger, which transfers the lone-pair electrons of the phosphorus atoms to the 2π* antibonding orbital of O2. As a result, the barrier for the O-O bond splitting to form O-P bonds is reduced from 0.81 eV at the perfect site to 0.59 eV at the defect site, leading to an about 5000 faster oxidizing rate at the defect site than at the perfect site at room temperature. Hence, our work reveals that the vacancy in phosphorene shows a stronger oxygen affinity than the perfect phosphorene lattice site. Structural degradation of phosphorene due to oxidization may occur rapidly at edges and grain boundaries where vacancies tend to agglomerate.

References in corpus (12)

• Magnetism in Graphene Induced by Single-Atom Defects
• Effective Passivation of Exfoliated Black Phosphorus Transistors against Ambient Degradation
• Strain-Engineering Anisotropic Electrical Conductance of Phosphorene and Few-Layer Black Phosphorus
• Layer-dependent Band Alignment and Work Function of Few-Layer Phosphorene
• Photovoltaic effect in few-layer black phosphorus PN junctions defined by local electrostatic gating
• Solvent Exfoliation of Electronic-Grade, Two-Dimensional Black Phosphorus
• Oxygen defects in phosphorene
• Mechanical and Electronic Properties of MoS${}_2$ Nanoribbons and Their Defects
• The potential applications of phosphorene as anode materials in Li-ion batteries
• Device Perspective for Black Phosphorus Field-Effect Transistors: Contact Resistance, Ambipolar and Scaling
• Large Electronic Anisotropy and Enhanced Chemical Activity of Highly Rippled Phosphorene
• Novel polystyrene-based nanocomposites by phosphorene dispersion

Cited by in corpus (15)

• Solution-processed two-dimensional materials for next-generation photovoltaics
• Exploring the Charge Localization and Band Gap Opening of Borophene: A First-Principles Study
• Atomic-scale mechanisms of defect- and light-induced oxidation and degradation of InSe
• Environmental Stability of Bismuthene: Oxidation Mechanism and Structural Stability of 2D Pnictogens
• A First-Principles Study on the Adsorption of Small Molecules on Arsenene: Comparison of Oxidation Kinetics in Arsenene, Antimonene, Phosphorene and InSe
• First-Principles Prediction of Two-Dimensional B3C2P3 and B2C4P2: Structural Stability, Fundamental Properties, and Renewable Energy Applications
• Anisotropic buckling of few-layer black phosphorus
• Family of Two Dimensional Transition Metal Dichlorides Fundamental Properties, Structural Defects, and Environmental Stability
• Point Defects in Two-Dimensional γ-Phosphorus Carbide
• Oxygen Deficient α-MoO3 with Promoted Adsorption and State-Quenching of H2O for Gas Sensor: A DFT Study
• Versatile van der Waals Heterostructures of Gamma-GeSe with h-BN/Graphene/MoS2
• Long-Term Environmental Stability of Nitrogen-Healed Black Phosphorus
• Evolution of Intrinsic Vacancies and Prolonged Lifetime of Vacancy Clusters in Black Phosphorene
• Theoretical insight into the interaction of O2 and H2O molecules with the perfect and the defective InSe monolayers
• 2D Black Phosphorus Carbide: Rippling and Formation of Nanotubes