Degradation of Black Phosphorus (BP): The Role of Oxygen and Water

Abstract

Black phosphorus (BP) has attracted significant interest as a monolayer or few-layer material with extraordinary electrical and optoelectronic properties. However, degradation in air and other environments is an unresolved issue that may limit future applications. In particular the role of different ambient species has remained controversial. Here, we report systematic experiments combined with ab-initio calculations that address the effects of oxygen and water in the degradation of BP. Our results show that BP rapidly degrades whenever oxygen is present, but is unaffected by deaerated (i.e., O2 depleted) water. This behavior is rationalized by oxidation involving a facile dissociative chemisorption of O2, whereas H2O molecules are weakly physisorbed and do not dissociate on the BP surface. Oxidation (by O2) turns the hydrophobic pristine BP surface progressively hydrophilic. Our results have implications on the development of encapsulation strategies for BP, and open new avenues for exploration of phenomena in aqueous solutions including solution-gating, electrochemistry, and solution-phase approaches for exfoliation, dispersion, and delivery of BP.

References in corpus (24)

• Two Dimensional Atomic Crystals
• Black phosphorus field-effect transistors
• Ultrahigh electron mobility in suspended graphene
• Phosphorene: A New 2D Material with High Carrier Mobility
• Van der Waals Density Functional for General Geometries
• Anomalous Lattice Vibrations of Single and Few-Layer MoS2
• Van der Waals density functionals applied to solids
• High-mobility transport anisotropy and linear dichroism in few-layer black phosphorus
• Rediscovering Black Phosphorus: A Unique Anisotropic 2D Material for Optoelectronics and Electronics
• A Higher-Accuracy van der Waals Density Functional
• Tunable Band Gap and Anisotropic Optical Response in Few-layer Black Phosphorus
• Isolation and characterization of few-layer black phosphorus
• Effective Passivation of Exfoliated Black Phosphorus Transistors against Ambient Degradation
• Liquid exfoliation of solvent-stabilised black phosphorus: applications beyond electronics
• Environmental instability of few-layer black phosphorus
• Covalent Functionalization and Passivation of Exfoliated Black Phosphorus via Aryl Diazonium Chemistry
• 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
• Accessing the transport properties of pristine few-layer black phosphorus by van der Waals passivation in inert atmosphere
• Thickness-Dependent Interfacial Coulomb Scattering in Atomically Thin Field-Effect Transistors
• Degradation of Phosphorene in Air: Understanding at Atomic Level
• Stable Aqueous Dispersions of Optically and Electronically Active Phosphorene
• The role of water in the preparation and stabilization of high quality phosphorene flakes

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• Evolution of Intrinsic Vacancies and Prolonged Lifetime of Vacancy Clusters in Black Phosphorene
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