Control of Surface and Edge Oxidation on Phosphorene

Kaci L. Kuntz, Rebekah A. Wells, Jun Hu, Teng Yang, Baojuan Dong, Huaihong Guo, Adam H. Woomer, Daniel L. Druffel, Anginelle Alabanza, David Tománek, Scott C. Warren

Research output: Contribution to journalArticle

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Abstract

Phosphorene is emerging as an important two-dimensional semiconductor, but controlling the surface chemistry of phosphorene remains a significant challenge. Here, we show that controlled oxidation of phosphorene determines the composition and spatial distribution of the resulting oxide. We used X-ray photoemission spectroscopy to measure the binding energy shifts that accompany oxidation. We interpreted these spectra by calculating the binding energy shift for 24 likely bonding configurations, including phosphorus oxides and hydroxides located on the basal surface or edges of flakes. After brief exposure to high-purity oxygen or high-purity water vapor at room temperature, we observed phosphorus in the +1 and +2 oxidation states; longer exposures led to a large population of phosphorus in the +3 oxidation state. To provide insight into the spatial distribution of the oxide, transmission electron microscopy was performed at several stages during the oxidation. We found crucial differences between oxygen and water oxidants: while pure oxygen produced an oxide layer on the van der Waals surface, water oxidized the material at pre-existing defects such as edges or steps. We propose a mechanism based on the thermodynamics of electron transfer to interpret these observations. This work opens a route to functionalize the basal surface or edges of two-dimensional (2D) black phosphorus through site-selective chemical reactions and presents the opportunity to explore the synthesis of 2D phosphorene oxide by oxidation.

LanguageEnglish (US)
Pages9126-9135
Number of pages10
JournalACS Applied Materials and Interfaces
Volume9
Issue number10
DOIs
StatePublished - Mar 15 2017

Fingerprint

Oxides
Oxidation
Phosphorus
Oxygen
Binding energy
Spatial distribution
Hydroxides
Steam
Photoelectron spectroscopy
X ray spectroscopy
Surface chemistry
Surface waters
Oxidants
Water vapor
Chemical reactions
Thermodynamics
Semiconductor materials
Transmission electron microscopy
Defects
Electrons

Keywords

  • 2D materials
  • binding energy shift
  • black phosphorus
  • DFT
  • edge functionalization
  • oxidation
  • phosphorene
  • surface functionalization

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Kuntz, K. L., Wells, R. A., Hu, J., Yang, T., Dong, B., Guo, H., ... Warren, S. C. (2017). Control of Surface and Edge Oxidation on Phosphorene. ACS Applied Materials and Interfaces, 9(10), 9126-9135. DOI: 10.1021/acsami.6b16111

Control of Surface and Edge Oxidation on Phosphorene. / Kuntz, Kaci L.; Wells, Rebekah A.; Hu, Jun; Yang, Teng; Dong, Baojuan; Guo, Huaihong; Woomer, Adam H.; Druffel, Daniel L.; Alabanza, Anginelle; Tománek, David; Warren, Scott C.

In: ACS Applied Materials and Interfaces, Vol. 9, No. 10, 15.03.2017, p. 9126-9135.

Research output: Contribution to journalArticle

Kuntz, KL, Wells, RA, Hu, J, Yang, T, Dong, B, Guo, H, Woomer, AH, Druffel, DL, Alabanza, A, Tománek, D & Warren, SC 2017, 'Control of Surface and Edge Oxidation on Phosphorene' ACS Applied Materials and Interfaces, vol. 9, no. 10, pp. 9126-9135. DOI: 10.1021/acsami.6b16111
Kuntz KL, Wells RA, Hu J, Yang T, Dong B, Guo H et al. Control of Surface and Edge Oxidation on Phosphorene. ACS Applied Materials and Interfaces. 2017 Mar 15;9(10):9126-9135. Available from, DOI: 10.1021/acsami.6b16111
Kuntz, Kaci L. ; Wells, Rebekah A. ; Hu, Jun ; Yang, Teng ; Dong, Baojuan ; Guo, Huaihong ; Woomer, Adam H. ; Druffel, Daniel L. ; Alabanza, Anginelle ; Tománek, David ; Warren, Scott C./ Control of Surface and Edge Oxidation on Phosphorene. In: ACS Applied Materials and Interfaces. 2017 ; Vol. 9, No. 10. pp. 9126-9135
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