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High-mobility band-like charge transport in a semiconducting two-dimensional metal–organic framework

Nature Materials volume 17, pages 1027–1032 (2018)Cite this article

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Abstract

Metal–organic frameworks (MOFs) are hybrid materials based on crystalline coordination polymers that consist of metal ions connected by organic ligands. In addition to the traditional applications in gas storage and separation or catalysis, the long-range crystalline order in MOFs, as well as the tunable coupling between the organic and inorganic constituents, has led to the recent development of electrically conductive MOFs as a new generation of electronic materials. However, to date, the nature of charge transport in the MOFs has remained elusive. Here we demonstrate, using high-frequency terahertz photoconductivity and Hall effect measurements, Drude-type band-like transport in a semiconducting, π–d conjugated porous Fe3(THT)2(NH4)3 (THT, 2,3,6,7,10,11-triphenylenehexathiol) two-dimensional MOF, with a room-temperature mobility up to ~ 220 cm2 V–1 s–1. The temperature-dependent conductivity reveals that this mobility represents a lower limit for the material, as mobility is limited by impurity scattering. These results illustrate the potential for high-mobility semiconducting MOFs as active materials in thin-film optoelectronic devices.

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Fig. 1: Morphology, crystalline structure and band gap of Fe3(THT)2(NH4)3 2D MOFs.
Fig. 2: Room-temperature photoconductivity of Fe3(THT)2(NH4)3 2D MOFs measured by THz spectroscopy.
Fig. 3: Temperature dependence of photoconductivity of Fe3(THT)2(NH4)3 2D MOFs measured by THz spectroscopy and Hall effect d.c. conductivity.

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The experimental and computational data that support the findings of this study are available from the corresponding authors upon request.

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Acknowledgements

This work was financially supported by the ERC Grant on 2DMATER, HIPER-G and EU Graphene Flagship, European Science Foundation (ESF), Coordination Networks: Building Blocks for Functional Systems (SPP 1928, COORNET) and the German Science Council. Financial support by the Max Planck Society is also acknowledged. We acknowledge the CFAED (Center for Advancing Electronics Dresden). E.C. acknowledges financial support from the Max Planck Graduate Center and the Regional Government of Comunidad de Madrid under project 2017-T1/AMB-5207. R.D. gratefully appreciates funding from the Alexander von Humboldt-Foundation. H.A. and A.E. are grateful to the Initiative and Networking Fund of the Helmholtz Association of German Research Centers through the International Helmholtz Research School for Nanoelectronic Networks, IHRS NANONET (VH-KO-606). We appreciate LPKF Laser & Electronics for the fabrication of the Hall bar geometry by laser ablation. We acknowledge the Dresden Center for Nanoanalysis (DCN) at TUD and P. Formanek (Leibniz Institute for Polymer Research, IPF, Dresden) for the use of facilities, and we appreciate X. Zhang, T. Zhang, F. Ortmann and K. S. Schellhammer for the helpful discussion. P.P. and T.H. thank ZIH Dresden for providing high-performance computing facilities.

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Author notes

  1. These authors contributed equally: Renhao Dong and Peng Han.

Authors and Affiliations

  1. Center for Advancing Electronics Dresden & Department of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, Germany

    Renhao Dong, Zhe Zhang, Stefan C. B. Mannsfeld, Thomas Heine & Xinliang Feng

  2. Max Planck Institute for Polymer Research, Mainz, Germany

    Peng Han, Marco Ballabio, Melike Karakus, Mischa Bonn & Enrique Cánovas

  3. Helmholtz-Zentrum Dresden-Rossendorf and Center for Advancing Electronics Dresden, Dresden, Germany

    Himani Arora, Artur Erbe & Thomas Heine

  4. Max Planck Institute for Chemical Physics of Solids, Dresden, Germany

    Chandra Shekhar, Peter Adler & Claudia Felser

  5. Wilhelm-Ostwald-Institute of Physical and Theoretical Chemistry, Leipzig University , Leipzig, Germany

    Petko St. Petkov & Thomas Heine

  6. University of Sofia, Faculty of Chemistry and Pharmacy , Sofia, Bulgaria

    Petko St. Petkov

  7. Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA Nanociencia), Madrid, Spain

    Enrique Cánovas

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Contributions

X.F., R.D., M.Bonn and E.C. conceived and designed the project. R.D. synthesized the THT precursor, prepared the 2D MOFs and conducted the structural, compositional and property characterizations. P.H. and M.K. conducted the THz experiments, P.H., M.Ballabio, M.Bonn and E.C. contributed to the THz data analysis and interpretation. H.A., A.E., R.D. and C.S. fabricated the devices and performed the d.c. conductivity by a two-/four-probe method and Hall effect measurements. Z.Z., R.D. and S.C.B.M. evaluated the d.c. conductivity by the two-probe method at room temperature. P.A. and C.F. contributed the Mössbauer spectroscopy investigations. P.S.P. and T.H. performed the DFT calculations of the 2D MOFs. R.D., X.F., M.Bonn and E.C. co-wrote the paper. All the authors discussed the results and commented on the manuscript.

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Correspondence to Xinliang Feng or Enrique Cánovas.

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Supplementary Figures 1–24, Supplementary Tables 1–4, Supplementary References 1–31

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Dong, R., Han, P., Arora, H. et al. High-mobility band-like charge transport in a semiconducting two-dimensional metal–organic framework. Nature Mater 17, 1027–1032 (2018). https://doi.org/10.1038/s41563-018-0189-z

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