In Situ Thermal Decomposition of Exfoliated Two-Dimensional Black Phosphorus

Abstract

With a semiconducting band gap and high charge carrier mobility, two-dimensional (2D) black phosphorus (BP), often referred to as phosphorene, holds significant promise for next generation electronics and optoelectronics. However, as a 2D material, it possesses a higher surface area to volume ratio than bulk BP, suggesting that its chemical and thermal stability will be modified. Herein, an atomic-scale microscopic and spectroscopic study is performed to characterize the thermal degradation of mechanically exfoliated 2D BP. From in situ scanning/transmission electron microscopy, decomposition of 2D BP is observed to occur at ~400 °C in vacuum, in contrast to the 550 °C bulk BP sublimation temperature. This decomposition initiates via eye-shaped cracks along the [001] direction and then continues until only a thin, amorphous red phosphorous like skeleton remains. In situ electron energy loss spectroscopy, energy-dispersive X-ray spectroscopy, and energy-loss near-edge structure changes provide quantitative insight into this chemical transformation process.

arXiv commentIn press: 4 figures in main manuscript, 27 pages with supporting information

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• Electrical characterization of fully encapsulated ultra thin black phosphorus-based heterostructures with graphene contacts
• The Electronic Properties of Phosphorene/Graphene and Phosphorene/Hexagonal Boron Nitride Heterostructures
• Chemically Tailoring Semiconducting Two-Dimensional Transition Metal Dichalcogenides and Black Phosphorus
• Rotationally Commensurate Growth of MoS2 on Epitaxial Graphene
• Highly Itinerant Atomic Vacancies in Phosphorene
• High-Pressure Synthesis and Characterization of $\beta$-GeSe - A Semiconductor with Six-Rings in an Uncommon Boat Conformation
• Point Defects and Grain Boundaries in Rotationally Commensurate MoS2 on Epitaxial Graphene
• Exfoliation of Few-Layer Black Phosphorus in Low-Boiling-Point Solvents and Its Application in Li-Ion Batteries
• Tuning the ferro- to para-electric transition temperature and dipole orientation of group-IV monochalcogenide monolayers
• The Critical Role of Substrate in Stabilizing Phosphorene Nanoflake: A Theoretical Exploration
• Band renormalization of blue phosphorus on Au(111)
• Thermal Stability and Anisotropic Sublimation of Two-Dimensional Colloidal Bi2Te3 and Bi2Se3 Nanocrystals
• A Perspective on Recent Advances in Phosphorene Functionalization and its Application in Devices
• Atomic-scale imaging of few-layer black phosphorus and its reconstructed edge
• Phosphorene Edge Reconstruction by Self-Rolling
• Nano-imaging of the edge-dependent optical polarization anisotropy of black phosphorus
• Fabrication and Imaging of Monolayer Phosphorene with Preferred Edge Configurations via Graphene-Assisted Layer-by-Layer Thinning
• Novel polystyrene-based nanocomposites by phosphorene dispersion
• Thermal Sublimation: a Scalable and Controllable Thinning Method for the Fabrication of Few-Layer Black Phosphorus
• STM Study of Exfoliated Few Layer Black Phosphorus Annealed in Ultrahigh Vacuum
• Power dissipation and electrical breakdown in black phosphorus
• Evolution of Intrinsic Vacancies and Prolonged Lifetime of Vacancy Clusters in Black Phosphorene
• Oxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors
• Metastable Interlayer Frenkel Pair Defects by Dipole-like Strain Fields for Dimensional Distortion in Black Phosphorus
• Band gap reconstruction at the interface between black phosphorus and a gold electrode
• Mechanistic insights on the phosphorene degradation
• Thermodynamic stability and vibrational anharmonicity of black phosphorene-beyond quasi-harmonic analysis
• Study of Black Phosphorus Using Angle-Resolved Polarized Raman Spectroscopy with 442 nm Excitation
• Monolayer phosphorene under time-dependent magnetic field
• Design of Phosphorene for Hydrogen Evolution Performance Comparable to Platinum