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Substrate-directed synthesis of MoS2 nanocrystals with tunable dimensionality and optical properties

Nature Nanotechnology volume 15, pages 29–34 (2020)Cite this article

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Abstract

Two-dimensional transition-metal dichalcogenide (TMD) crystals are a versatile platform for optoelectronic, catalytic and quantum device studies. However, the ability to tailor their physical properties through explicit synthetic control of their morphology and dimensionality is a major challenge. Here we demonstrate a gas-phase synthesis method that substantially transforms the structure and dimensionality of TMD crystals without lithography. Synthesis of MoS2 on Si(001) surfaces pre-treated with phosphine yields high-aspect-ratio nanoribbons of uniform width. We systematically control the width of these nanoribbons between 50 and 430 nm by varying the total phosphine dosage during the surface treatment step. Aberration-corrected electron microscopy reveals that the nanoribbons are predominantly 2H phase with zig-zag edges and an edge quality that is comparable to, or better than, that of graphene and TMD nanoribbons prepared through conventional top-down processing. Owing to their restricted dimensionality, the nominally one-dimensional MoS2 nanocrystals exhibit photoluminescence 50 meV higher in energy than that from two-dimensional MoS2 crystals. Moreover, this emission is precisely tunable through synthetic control of crystal width. Directed crystal growth on designer substrates has the potential to enable the preparation of low-dimensional materials with prescribed morphologies and tunable or emergent optoelectronic properties.

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Fig. 1: Substrate-directed synthesis of 1D MoS2 nanocrystals of tunable width.
Fig. 2: Aberration-corrected STEM and spectroscopy of 1D MoS2 nanocrystals.
Fig. 3: Optical spectroscopy of 1D and tapered MoS2 nanocrystals.
Fig. 4: Experimental and computational support for a proposed mechanism for 1D MoS2 nanocrystal growth.

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Data availability

The data that support the findings of this study are available from the corresponding author (T.J.K.) upon reasonable request.

Code availability

The cluster expansion code used in the current study is available from T.M. upon reasonable request.

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Acknowledgements

We thank B. Frank and H. Fairbrother at Johns Hopkins University (JHU) for assistance with XPS, and also thank the JHU Raman Scattering user centre. T.J.K. acknowledges start-up funding from JHU. J.K. acknowledges postdoctoral funding from the National Research Foundation of Korea (grant no. 2018R1A6A3A03010591). H.-G.P. acknowledges support from the National Research Foundation of Korea (grant no. 2018R1A3A3000666). T.M. acknowledges funding from the National Science Foundation (grant no. DMR-1352373). W.X. and D.H.G. acknowledge funding from the Air Force Office of Scientific Research MURI programme (no. FA9550-16-1-0031). T.H.B. acknowledges funding from the Office of Naval Research through the Naval Research Laboratory Base Program. D.J. and K.J. acknowledge support for this work by the US Army Research Office (contract no. W911NF1910109). T.J.K. and T.M. acknowledge supercomputer resources from the Maryland Advanced Research Computing Center. The near-field microscopy work was carried out at the Singh Center for Nanotechnology at University of Pennsylvania, which is supported by the NSF National Nanotechnology Coordinated Infrastructure Program under grant NNCI-1542153.

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Authors and Affiliations

  1. Department of Chemistry, Johns Hopkins University, Baltimore, MD, USA

    Tomojit Chowdhury, Jungkil Kim, Erick C. Sadler & Thomas J. Kempa

  2. Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, MD, USA

    Chenyang Li, Tim Mueller & Thomas J. Kempa

  3. Department of Physics, Korea University, Seoul, Republic of Korea

    Seong Won Lee & Hong-Gyu Park

  4. Department of Electrical and Systems Engineering, University of Pennsylvania, Philadelphia, PA, USA

    Kiyoung Jo & Deep Jariwala

  5. Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, MD, USA

    Weinan Xu & David H. Gracias

  6. Department of Physics and Astronomy, Johns Hopkins University, Baltimore, MD, USA

    Natalia V. Drichko

  7. Materials Science and Technology Division, United States Naval Research Laboratory, Washington, DC, USA

    Todd H. Brintlinger

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  1. Tomojit Chowdhury
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Contributions

T.J.K. and T.C. conceived the idea of using designer substrates to direct crystal growth, and designed experiments. All synthetic efforts were conducted by T.C., J.K. and E.C.S. with input and supervision from T.J.K. Sample preparations for STEM, Raman and PL studies were conducted by T.C., W.X. and S.W.L with input and supervision from H.-G.P., D.H.G., and T.J.K. Simulations were performed by C.L. with supervision and other mechanistic insights from T.M. and T.J.K. Raman and PL experiments were conducted by T.C., J.K. and S.W.L. with input and supervision from N.V.D., H.-G.P. and T.J.K. Near-field PL studies were conducted by K.J., T.C. and J.K. with input and supervision from D.J. and T.J.K. STEM experiments were conducted by T.H.B. with subsequent analyses by T.H.B. and T.J.K. The manuscript was written by T.J.K and T.C. with input from co-authors. All authors reviewed the manuscript before its submission.

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Correspondence to Thomas J. Kempa.

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Peer review information Nature Nanotechnology thanks Xidong Duan and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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Chowdhury, T., Kim, J., Sadler, E.C. et al. Substrate-directed synthesis of MoS2 nanocrystals with tunable dimensionality and optical properties. Nat. Nanotechnol. 15, 29–34 (2020). https://doi.org/10.1038/s41565-019-0571-2

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