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Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry

Nature Chemistry volume 8, pages 597–602 (2016)Cite this article

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Abstract

Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical and electronic properties. Exfoliated black phosphorus (BP)—a layered two-dimensional semiconductor—exhibits favourable charge-carrier mobility, tunable bandgap and highly anisotropic properties, but it is chemically reactive and degrades rapidly in ambient conditions. Here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated BP even after three weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus–carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent and alters the electronic properties of exfoliated BP, ultimately yielding a strong, tunable p-type doping that simultaneously improves the field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated BP, and thus improves its prospects for nanoelectronic applications.

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Figure 1: Aryl diazonium functionalization of BP.
Figure 2: Spectroscopic characterization of BP with increasing 10 mM aryl diazonium functionalization.
Figure 3: Chemical passivation of BP.
Figure 4: Effect of covalent functionalization on charge transport in exfoliated BP FETs.

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Acknowledgements

We acknowledge useful discussions with J. Kang and X. Liu. This research was supported by the Office of Naval Research (N00014-14-1-0669), the Materials Research Science and Engineering Center (MRSEC) of Northwestern University (NSF DMR-1121262), the National Institute of Standards and Technology (NIST CHiMaD 70NANB14H012) and the Department of Energy (DE-FG02-09ER16109). The work made use of the NUANCE Center, which has received support from the MRSEC (NSF DMR-1121262), State of Illinois and Northwestern University. Raman spectroscopy measurements were conducted at Argonne National Laboratory's Center for Nanoscale Materials, a US Department of Energy, Office of Science, Office of Basic Energy Sciences User Facility, under Contract No. DE-AC02-06CH11357.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Northwestern University, Evanston, 60208, Illinois, USA

    Christopher R. Ryder, Joshua D. Wood, Spencer A. Wells, Deep Jariwala, Tobin J. Marks & Mark C. Hersam

  2. Department of Chemistry, Northwestern University, Evanston, 60208, Illinois, USA

    Yang Yang, Tobin J. Marks, George C. Schatz & Mark C. Hersam

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  1. Christopher R. Ryder
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Contributions

C.R.R. conceived the experiments with the assistance of J.D.W. and S.A.W., executed the aryl diazonium chemistry, performed the AFM and Raman spectroscopy measurements and analysis, and prepared the manuscript. J.D.W. performed XPS measurements and analysis and contributed to the analysis of AFM and Raman spectroscopy data. S.A.W. fabricated BP FETs and analysed the device data. Y.Y. conducted DFT calculations and their analysis with the guidance of G.C.S. D.J. assisted with BP FET measurements and analysis. T.J.M. and M.C.H. oversaw the development and execution of the research. All the authors contributed to the revision of the manuscript.

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Correspondence to Mark C. Hersam.

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The authors declare no competing financial interests.

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Ryder, C., Wood, J., Wells, S. et al. Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry. Nature Chem 8, 597–602 (2016). https://doi.org/10.1038/nchem.2505

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