In situ thermal decomposition of exfoliated two-dimensional black phosphorus

Xiaolong Liu, Joshua D. Wood, Kan Sheng Chen, Eunkyung Cho, Mark C. Hersam*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

152 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)773-778
Number of pages6
JournalJournal of Physical Chemistry Letters
Issue number5
StatePublished - Mar 5 2015


  • STEM
  • TEM
  • black phosphorus
  • phosphorene
  • sublimation
  • thermal

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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