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J Phys Chem Lett. 2015 Mar 5;6(5):773-8. doi: 10.1021/acs.jpclett.5b00043. Epub 2015 Feb 12.

In Situ Thermal Decomposition of Exfoliated Two-Dimensional Black Phosphorus.

Author information

1
†Graduate Program in Applied Physics, Northwestern University, Evanston, Illinois 60208, United States.
2
‡Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States.
3
§Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
4
∥Department of Medicine, Northwestern University, Evanston, Illinois 60208, United States.

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 phosphorus 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.

KEYWORDS:

STEM; TEM; black phosphorus; phosphorene; sublimation; thermal

PMID:
26262651
DOI:
10.1021/acs.jpclett.5b00043
[Indexed for MEDLINE]

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