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Hybrid metal–organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly

Nature Materials volume 16, pages 349–355 (2017)Cite this article

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Abstract

Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal–organic frameworks and coordination polymers. However, the lack of ‘solid’ inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal–organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal–organic framework linkers.

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Figure 1: Schematic of synthesis and structure of MOC crystals.
Figure 2: ‘Face-on’ growth mechanism of 1ADCu.
Figure 3: Relative stabilities of 1ADCu NWs with different diameters.
Figure 4: Prediction of growth mode and crystal structure of 4DICu.
Figure 5: Theoretical and experimental investigation of electronic properties.
Figure 6: SEM micrographs of MOC crystals beyond copper thiolates.

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Acknowledgements

The authors thank M. Soltis and I. Mathews at SLAC National Accelerator Laboratory and S. Teat at Lawrence Berkeley National Laboratory for assistance with SC-XRD, and Y. Liang at Lawrence Berkeley National Laboratory for help with DFT computations. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF). This work was supported by the Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering, under contract DE-AC02-76SF00515. The work done at the Justus-Liebig University was further supported by the Deutsche Forschungsgemeinschaft, Priority Program ‘Dispersion’ (SPP 1807, Schr 597/27-1). Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource (SSRL), a Directorate of SLAC National Accelerator Laboratory and an Office of Science User Facility operated for the US Department of Energy Office of Science by Stanford University. The SSRL Structural Molecular Biology Program is supported by the DOE Office of Biological and Environmental Research, and by the National Institutes of Health, National Institute of General Medical Sciences (including P41GM103393). The contents of this publication are solely the responsibility of the authors and do not necessarily represent the official views of NIGMS or NIH. This research used resources of the National Energy Research Scientific Computing Center (NERSC) and Advanced Light Source (ALS), both of which are DOE Office of Science User Facilities supported by the Office of Science of the US Department of Energy under Contract No. DE-AC02-05CH11231.

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Author notes

  1. Hao Yan, J. Nathan Hohman and Fei Hua Li: These authors contributed equally to this work.

Authors and Affiliations

  1. Stanford Institute for Materials and Energy Sciences, Stanford, California 94305, USA

    Hao Yan, Fei Hua Li, Chunjing Jia, Bin Wu, Jeremy E. P. Dahl, Robert M. K. Carlson, Taeho Roy Kim, Thomas P. Devereaux, Zhi-Xun Shen & Nicholas A. Melosh

  2. Department of Materials Science and Engineering, Stanford, California 94305, USA

    Hao Yan, Fei Hua Li, Bin Wu, Taeho Roy Kim & Nicholas A. Melosh

  3. Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    J. Nathan Hohman

  4. Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Coyoacán, CDMX 04510, México

    Diego Solis-Ibarra

  5. Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany

    Boryslav A. Tkachenko, Andrey A. Fokin & Peter R. Schreiner

  6. Geballe Laboratory for Advanced Materials, Stanford University, Stanford, California 94305, USA

    Arturas Vailionis

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Contributions

H.Y., J.N.H., Z.-X.S., P.R.S. and N.A.M. conceived the idea. H.Y., J.N.H., F.H.L., B.W. and T.R.K. performed the growth experiments and the physical measurements. H.Y., F.H.L., C.J. and T.P.D. performed the DFT computations. D.S.-I. and A.V. solved the crystal structures from SC-XRD data. J.E.P.D., R.M.K.C., B.A.T., A.A.F. and P.R.S. provided the diamondoids and synthesized their derivatives. H.Y., J.N.H. and N.A.M. wrote the paper. All authors contributed to the discussion and revision of the paper.

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Correspondence to Nicholas A. Melosh.

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Supplementary information

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Crystallographic data for 1ADCu (CIF 258 kb)

Supplementary Information

Crystallographic data for 4DICu (CIF 273 kb)

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Yan, H., Hohman, J., Li, F. et al. Hybrid metal–organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly. Nature Mater 16, 349–355 (2017). https://doi.org/10.1038/nmat4823

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