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Experimental analysis of charge redistribution due to chemical bonding by high-resolution transmission electron microscopy

Nature Materials volume 10, pages 209–215 (2011)Cite this article

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Abstract

The electronic charge density distribution or the electrostatic atomic potential of a solid or molecule contains information not only on the atomic structure, but also on the electronic properties, such as the nature of the chemical bonds or the degree of ionization of atoms. However, the redistribution of charge due to chemical bonding is small compared with the total charge density, and therefore difficult to measure. Here, we demonstrate an experimental analysis of charge redistribution due to chemical bonding by means of high-resolution transmission electron microscopy (HRTEM). We analyse charge transfer on the single-atom level for nitrogen-substitution point defects in graphene, and confirm the ionicity of single-layer hexagonal boron nitride. Our combination of HRTEM experiments and first-principles electronic structure calculations opens a new way to investigate electronic configurations of point defects, other non-periodic arrangements or nanoscale objects that cannot be studied by an electron or X-ray diffraction analysis.

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Figure 1: Charge distribution, projected potentials and TEM simulations for nitrogen-doped graphene.
Figure 3: Analysis of the nitrogen substitution defect.
Figure 2: Nitrogen dopants in graphene.
Figure 4: Simulated TEM images for hBN.
Figure 5: Experimental data for hBN.

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Acknowledgements

We gratefully acknowledge financial support by the German Research Foundation (DFG) and the Ministry of Science, Research and the Arts (MWK) of the state Baden-Württemberg within the Sub-Angstrom Low-Voltage Electron Microscopy project (SALVE) and by the DFG within research project SFB 569. T.I. acknowledges the JSPS Postdoctoral Fellowship for Research Abroad. G.A-S. acknowledges the support of CONACyT-DAAD scholarship.

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Author notes

  1. Jannik C. Meyer

    Present address: Present address: University of Vienna, Department of Physics, 1090 Vienna, Austria,

Authors and Affiliations

  1. Central Facility for Electron Microscopy, Group of Electron Microscopy of Materials Science, University of Ulm, 89081 Ulm, Germany

    Jannik C. Meyer, Simon Kurasch, Andrey Chuvilin, Gerardo Algara-Siller & Ute Kaiser

  2. Max Planck Institute for Solid State Research, Heisenbergstr. 1, 70569 Stuttgart, Germany

    Hye Jin Park, Viera Skakalova, Siegmar Roth, Takayuki Iwasaki, Ulrich Starke & Jurgen H. Smet

  3. Institute of Theoretical Chemistry, University of Ulm, 89069 Ulm, Germany

    Daniela Künzel & Axel Groß

  4. CIC nanoGUNE Consolider, Av. de Tolosa 76, 20018, San Sebastian, Spain and IKERBASQUE, Basque Foundation for Science, 48011, Bilbao, Spain

    Andrey Chuvilin

  5. Technical University Ilmenau, 98693 Ilmenau, Germany

    Gerardo Algara-Siller

  6. School of Electrical Engineering, WCU Flexible Nanosystems, Korea University, Seoul 136-713, Korea

    Siegmar Roth

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Contributions

J.C.M., A.C. and S.K. carried out TEM experiments. J.C.M., S.K. and A.C. analysed the data. S.K. carried out DFT calculations and TEM simulations based on WIEN2k. A.C. contributed to TEM simulations, discussions and analysis. H.J.P., V.S., S.R. and J.H.S. developed the synthesis of nitrogen-doped graphene. D.K. and A.G. carried out DFT calculations using the Vienna Ab initio Simulation Package. G.A-S. contributed to TEM simulations. T.I. and U.S. made Auger spectroscopy measurements. U.K. supervised part of the work. J.C.M. conceived and designed the study and wrote the paper. S.K. and U.K. co-wrote the paper.

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Correspondence to Jannik C. Meyer or Ute Kaiser.

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Meyer, J., Kurasch, S., Park, H. et al. Experimental analysis of charge redistribution due to chemical bonding by high-resolution transmission electron microscopy. Nature Mater 10, 209–215 (2011). https://doi.org/10.1038/nmat2941

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