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Photooxidation and quantum confinement effects in exfoliated black phosphorus

Nature Materials volume 14, pages 826–832 (2015)Cite this article

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Abstract

Thin layers of black phosphorus have recently raised interest owing to their two-dimensional (2D) semiconducting properties, such as tunable direct bandgap and high carrier mobilities. This lamellar crystal of phosphorus atoms can be exfoliated down to monolayer 2D-phosphane (also called phosphorene) using procedures similar to those used for graphene. Probing the properties has, however, been challenged by a fast degradation of the thinnest layers on exposure to ambient conditions. Herein, we investigate this chemistry using in situ Raman and transmission electron spectroscopies. The results highlight a thickness-dependent photoassisted oxidation reaction with oxygen dissolved in adsorbed water. The oxidation kinetics is consistent with a phenomenological model involving electron transfer and quantum confinement as key parameters. A procedure carried out in a glove box is used to prepare mono-, bi- and multilayer 2D-phosphane in their pristine states for further studies on the effect of layer thickness on the Raman modes. Controlled experiments in ambient conditions are shown to lower the Ag1/Ag2 intensity ratio for ultrathin layers, a signature of oxidation.

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Figure 1: Photooxidation of multilayer 2D-phosphane under constant illumination at room temperature.
Figure 2: Chemical analysis by hyperspectral TEM-EELS spectroscopy of a multilayer 2D-phosphane exfoliated under ambient light in air.
Figure 3: Evolution of the photooxidation reaction in ambient conditions of multilayer 2D-phosphane probed by TEM-EELS analysis.
Figure 4: High-angle annular dark-field (HAADF) contrast images and core-loss images of oxidized multilayer 2D-phosphane recorded at 80 kV.
Figure 5: Raman spectroscopy (λ = 532 nm) at 300 K of n-layer 2D-phosphane and bulk P(black) exfoliated using an improved exfoliation method in a glove box.
Figure 6: Raman characteristics (λ = 532 nm) at 300 K of n-layer 2D-phosphane as a function of AFM thickness and Raman signature of oxidation for n = 1, 2 and 3.

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Acknowledgements

The authors acknowledge the assistance of A. Dietrich for early sample preparation and experiments and T. Szkopek for insightful discussions. The authors also thank P. Moraille, from the Central Facilities at the Université de Montreal, for help on controlled atmosphere AFM measurements. This work was made possible by financial support from the Natural Sciences and Engineering Research Council of Canada (NSERC) and the Fonds de Recherche du Québec—Nature et Technologie (FRQNT). This research has also received partial funding from the European Union Seventh Framework Program under grant agreement no. 604391 Graphene Flagship.

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Author notes

  1. Alexandre Favron and Etienne Gaufrès: These authors contributed equally to this work.

Authors and Affiliations

  1. Regroupement Québécois sur les Matériaux de Pointe (RQMP) and Département de physique, Université de Montréal, Montréal, Québec H3C 3J7, Canada

    Alexandre Favron & Richard Leonelli

  2. RQMP and Département de chimie, Université de Montréal, Montréal, Québec H3C 3J7, Canada

    Etienne Gaufrès, Nathalie Y-W. Tang, Pierre L. Lévesque & Richard Martel

  3. Laboratoire d’Etude des Microstructures, UMR 104 CNRS-Onera, Châtillon, France

    Frédéric Fossard & Annick Loiseau

  4. RQMP and Département de génie physique, Polytechnique Montréal, Montréal, Québec H3C 3A7, Canada

    Anne-Laurence Phaneuf-L’Heureux & Sébastien Francoeur

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  1. Alexandre Favron
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Contributions

A.F., E.G., F.F. and A-L.P-L’H. performed the experiments and analysed the results. A.F., E.G., P.L.L., S.F. and R.M. designed the experiments and developed the model. N.Y-W.T. helped with sample preparation. A.L., R.L., S.F. and R.M. supervised the work and discussed the results. All authors contributed to the scientific discussions, manuscript preparation and final revision.

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Correspondence to Richard Martel.

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The authors declare no competing financial interests.

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Favron, A., Gaufrès, E., Fossard, F. et al. Photooxidation and quantum confinement effects in exfoliated black phosphorus. Nature Mater 14, 826–832 (2015). https://doi.org/10.1038/nmat4299

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