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Substitutional Tin Acceptor States in Black Phosphorus

  • Mark Wentink
    Mark Wentink
    Department of Electronic and Electrical Engineering, University College London, WC1E 7JE London, U.K.
    London Centre for Nanotechnology, University College London, WC1H 0AH London, U.K.
    More by Mark Wentink
  • Julian Gaberle
    Julian Gaberle
    Department of Physics and Astronomy, University College London, WC1E 6BT London, U.K.
  • Martik Aghajanian
    Martik Aghajanian
    Departments of Materials and Physics and the Thomas Young Centre for Theory and Simulation of Materials, Imperial College London, SW7 2AZ London, U.K.
  • Arash A. Mostofi
    Arash A. Mostofi
    Departments of Materials and Physics and the Thomas Young Centre for Theory and Simulation of Materials, Imperial College London, SW7 2AZ London, U.K.
  • Neil J. Curson
    Neil J. Curson
    Department of Electronic and Electrical Engineering, University College London, WC1E 7JE London, U.K.
    London Centre for Nanotechnology, University College London, WC1H 0AH London, U.K.
  • Johannes Lischner
    Johannes Lischner
    Departments of Materials and Physics and the Thomas Young Centre for Theory and Simulation of Materials, Imperial College London, SW7 2AZ London, U.K.
  • Steven R. Schofield
    Steven R. Schofield
    Department of Physics and Astronomy, University College London, WC1E 6BT London, U.K.
    London Centre for Nanotechnology, University College London, WC1H 0AH London, U.K.
  • Alexander L. Shluger
    Alexander L. Shluger
    Department of Physics and Astronomy, University College London, WC1E 6BT London, U.K.
  • , and 
  • Anthony J. Kenyon*
    Anthony J. Kenyon
    Department of Electronic and Electrical Engineering, University College London, WC1E 7JE London, U.K.
    *Email: [email protected] (A.K.).
Cite this: J. Phys. Chem. C 2021, 125, 41, 22883–22889
Publication Date (Web):October 10, 2021
https://doi.org/10.1021/acs.jpcc.1c07115
Copyright © 2021 American Chemical Society

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    Abstract

    Abstract Image

    Nominally pure black phosphorus (BP) is commonly found to be a p-type semiconductor, suggesting the ubiquitious presence of impurity species or intrinsic, charged defects. Moreover, scanning tunneling microscopy (STM) images of black phosphorus reveal the presence of long-range double-lobed defect features superimposed onto the surface atomic lattice. We show that both the p-type doping of BP and the defect features observed in STM images can be attributed to substitutional tin impurities. We show that black phosphorus samples produced through two common synthesis pathways contain tin impurities, and we demonstrate that the ground state of substitutional tin impurities is negatively charged for a wide range of Fermi level positions within the BP band gap. The localized negative charge of the tin impurities induces hydrogenic states in the band gap, and it is the 2p level that sits at the valence band edge that gives rise to the double-lobed features observed in STM images.

    Cited By

    This article is cited by 4 publications.

    1. Rishav Harsh, Sourav Mondal, Devina Sharma, Mehdi Bouatou, Cyril Chacon, Maxim Ilyn, Celia Rogero, Vincent Repain, Amandine Bellec, Yann Girard, Sylvie Rousset, Raman Sankar, Woei Wu Pai, Shobhana Narasimhan, Jérôme Lagoute. Identification and Manipulation of Defects in Black Phosphorus. The Journal of Physical Chemistry Letters 2022, 13 (27) , 6276-6282. https://doi.org/10.1021/acs.jpclett.2c01370
    2. Yongjie Wang, Qiang Yu, Jie Li, Junyong Wang, Kai Zhang. Insight into the growth mechanism of black phosphorus. Frontiers of Physics 2023, 18 (4) https://doi.org/10.1007/s11467-023-1265-7
    3. Quanjie Zhong. Intrinsic and engineered properties of black phosphorus. Materials Today Physics 2022, 28 , 100895. https://doi.org/10.1016/j.mtphys.2022.100895
    4. Martik Aghajanian, Arash A. Mostofi, Johannes Lischner. Electronic structure of monolayer and bilayer black phosphorus with charged defects. Physical Review Materials 2022, 6 (4) https://doi.org/10.1103/PhysRevMaterials.6.044002

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