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Direct observation of the layer-dependent electronic structure in phosphorene

Nature Nanotechnology volume 12, pages 21–25 (2017)Cite this article

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Abstract

Phosphorene, a single atomic layer of black phosphorus, has recently emerged as a new two-dimensional (2D) material that holds promise for electronic and photonic technologies1,2,3,4,5. Here we experimentally demonstrate that the electronic structure of few-layer phosphorene varies significantly with the number of layers, in good agreement with theoretical predictions. The interband optical transitions cover a wide, technologically important spectral range from the visible to the mid-infrared. In addition, we observe strong photoluminescence in few-layer phosphorene at energies that closely match the absorption edge, indicating that they are direct bandgap semiconductors. The strongly layer-dependent electronic structure of phosphorene, in combination with its high electrical mobility, gives it distinct advantages over other 2D materials in electronic and opto-electronic applications.

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Figure 1: Few-layer phosphorene samples.
Figure 2: Layer-dependent reflection spectra.
Figure 3: Layer-dependent PL spectra.
Figure 4: Evolution of optical resonance energy and band structure.

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Acknowledgements

L.L., Z.Z., F.Y. and Y.Z. acknowledge support from the NSF of China (grant nos 11425415 and 11421404) and the National Basic Research Program of China (973 Program; grant no. 2013CB921902). J.K., C.J. and F.W. acknowledge support from National Science Foundation EFRI program (EFMA-1542741). L.L. and Y.Z. also acknowledge support from Samsung Global Research Outreach (GRO) Program. Part of the sample fabrication was conducted at Fudan Nano-fabrication Lab. G.Y and X.C. acknowledge support from the NSF of China (grant no. 11534010), the ‘Strategic Priority Research Program’ of the Chinese Academy of Sciences (grant no. XDB04040100) and the National Basic Research Program of China (973 Program; grant no. 2012CB922002). K.W. and T.T. acknowledge support from the Elemental Strategy Initiative conducted by the MEXT, Japan. T.T. also acknowledges support by a Grant-in-Aid for Scientific Research on Innovative Areas, ‘Nano Informatics’ (grant nos 262480621 and 25106006) from JSPS. D.Y.Q., F.H.d.J. and S.G.L. thank T. Cao and Z. Li for discussions. The theoretical studies were supported by the Theory of Materials Program at the Lawrence Berkeley National Laboratory through the Office of Basic Energy Sciences, US Department of Energy under Contract no. DE-AC02-05CH11231, which provided for the ab initio GW-BSE calculations, and by the National Science Foundation under Grant no. DMR-1508412, which provided for the DFT calculations and theoretical analyses of the interlayer interactions and substrate screening. D.Y.Q. acknowledges support from the NSF Graduate Research Fellowship Grant no. DGE 1106400. This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the US Department of Energy, and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant no. ACI-1053575.

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Author notes

  1. Likai Li, Jonghwan Kim and Chenhao Jin: These authors contributed equally to this work

Authors and Affiliations

  1. State Key Laboratory of Surface Physics and Department of Physics, Fudan University, Shanghai, 200433, China

    Likai Li, Zuocheng Zhang, Fangyuan Yang & Yuanbo Zhang

  2. Collaborative Innovation Center of Advanced Microstructures, Nanjing, 210093, China

    Likai Li, Guo Jun Ye, Zuocheng Zhang, Fangyuan Yang, Xian Hui Chen & Yuanbo Zhang

  3. Department of Physics, University of California at Berkeley, Berkeley, 94720, California, USA

    Jonghwan Kim, Chenhao Jin, Diana Y. Qiu, Felipe H. da Jornada, Zhiwen Shi, Steven G. Louie & Feng Wang

  4. Hefei National Laboratory for Physical Science at Microscale and Department of Physics, University of Science and Technology of China, Hefei, Anhui, 230026, China

    Guo Jun Ye & Xian Hui Chen

  5. Key Laboratory of Strongly Coupled Quantum Matter Physics, University of Science and Technology of China, Hefei, Anhui, 230026, China

    Guo Jun Ye & Xian Hui Chen

  6. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, 94720, California, USA

    Diana Y. Qiu, Felipe H. da Jornada, Steven G. Louie & Feng Wang

  7. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China

    Long Chen & Wencai Ren

  8. Advanced Materials Laboratory, National Institute for Materials Science, 1-1 Namiki, Tsukuba, 305-0044, Japan

    Kenji Watanabe & Takashi Taniguchi

  9. Berkeley and the Lawrence Berkeley National Laboratory, Kavli Energy NanoSciences Institute at the University of California, Berkeley, 94720, California, USA

    Feng Wang

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  1. Likai Li
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Contributions

F.W., Y.Z. and X.H.C. conceived the project. G.J.Y., X.H.C., L.C. and W.R. grew the bulk crystal black phosphorus. L.L. fabricated and characterized the encapsulated samples. J.K. and C.J. designed and built the absorption and PL set-up. L.L., J.K. and C.J. obtained and analysed the absorption and PL spectra. C.J. performed the tight-binding phenomenological model. D.Y.Q., F.H.d.J. and S.G.L performed the ab initio DFT and GW-BSE calculations. Z.S. helped with FTIR measurements and Z.Z. and F.Y. helped with sample fabrication. K.W. and T.T. grew the hBN crystal. All authors discussed and wrote the manuscript.

Corresponding authors

Correspondence to Steven G. Louie, Xian Hui Chen, Yuanbo Zhang or Feng Wang.

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The authors declare no competing financial interests.

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Li, L., Kim, J., Jin, C. et al. Direct observation of the layer-dependent electronic structure in phosphorene. Nature Nanotech 12, 21–25 (2017). https://doi.org/10.1038/nnano.2016.171

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