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Step engineering for nucleation and domain orientation control in WSe2 epitaxy on c-plane sapphire

Nature Nanotechnology volume 18, pages 1295–1302 (2023)Cite this article

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Abstract

Epitaxial growth of two-dimensional transition metal dichalcogenides on sapphire has emerged as a promising route to wafer-scale single-crystal films. Steps on the sapphire act as sites for transition metal dichalcogenide nucleation and can impart a preferred domain orientation, resulting in a substantial reduction in mirror twins. Here we demonstrate control of both the nucleation site and unidirectional growth direction of WSe2 on c-plane sapphire by metal–organic chemical vapour deposition. The unidirectional orientation is found to be intimately tied to growth conditions via changes in the sapphire surface chemistry that control the step edge location of WSe2 nucleation, imparting either a 0° or 60° orientation relative to the underlying sapphire lattice. The results provide insight into the role of surface chemistry on transition metal dichalcogenide nucleation and domain alignment and demonstrate the ability to engineer domain orientation over wafer-scale substrates.

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Fig. 1: Preferred orientation of WSe2 domains.
Fig. 2: Domain nucleation at step edges.
Fig. 3: Competition between the step edge and underlying sapphire symmetry.
Fig. 4: Domain orientation and step edge termination.
Fig. 5: Coalescence of unidirectional WSe2 domains.
Fig. 6: Properties of coalesced WSe2 monolayers.

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Data availability

Additional data relevant to the conclusions of this study are available in the Supplementary Information. Growth and characterization data associated with the samples produced in this study are available via ScholarSphere52. This includes substrate preparation and recipe data for samples grown by MOCVD in the 2DCC-MIP facility and standard characterization data including AFM images, room-temperature Raman/photoluminescence spectra and field-emission scanning electron microscopy images of the samples. Videos associated with the DFT results are included as Supplementary Videos 1–8 and are available via figshare at https://doi.org/10.6084/m9.figshare.23274647 (ref. 53). Additional datasets related to DFT, SHG, TEM, FET and low-temperature photoluminescence are available from the corresponding author upon request.

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Acknowledgements

The work was financially supported by the National Science Foundation (NSF) through the Pennsylvania State University 2D Crystal Consortium–Materials Innovation Platform (2DCC-MIP) under NSF cooperative agreement numbers DMR-1539916 and DMR-2039351. S.B. and N.A. acknowledge support provided by NSF Career grant number DMR-1654107. T.V.M. and J.M.R. acknowledge support from the Defense Technical Information Center under award number FA9550-21-1-0460. N.T. acknowledges support from the NSF Graduate Research Fellowship Program under grant number DGE1255832. K.Z. and S.H. acknowledge support from NSF under grant numbers ECCS-1943895 and ECCS-2246564 and Air Force Office of Scientific Research under grant number FA9550-22-1-0408. SHG measurements were supported by the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy Office of Science User Facility at Oak Ridge National Laboratory.

Author information

Author notes

  1. These authors contributed equally: Haoyue Zhu, Nadire Nayir, Tanushree H. Choudhury.

Authors and Affiliations

  1. 2D Crystal Consortium Materials Innovation Platform, Materials Research Institute, The Pennsylvania State University, University Park, PA, USA

    Haoyue Zhu, Nadire Nayir, Tanushree H. Choudhury, Benjamin Huet, Saptarshi Das, Nasim Alem, Vincent H. Crespi, Adri C. T. van Duin & Joan M. Redwing

  2. Department of Physics, Karamanoglu Mehmetbey University, Karaman, Turkey

    Nadire Nayir

  3. Department of Mechanical Engineering, The Pennsylvania State University, University Park, PA, USA

    Nadire Nayir & Adri C. T. van Duin

  4. Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai, India

    Tanushree H. Choudhury

  5. Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA, USA

    Anushka Bansal, Saiphaneendra Bachu, Thomas V. Mc Knight, Nicholas Trainor, Nasim Alem & Joan M. Redwing

  6. Department of Electrical Engineering, The Pennsylvania State University, University Park, PA, USA

    Kunyan Zhang & Shengxi Huang

  7. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Alexander A. Puretzky

  8. Department of Electrical Engineering, Western Michigan University, Kalamazoo, MI, USA

    Krystal York, Robert A. Makin & Steven M. Durbin

  9. Department of Engineering Science and Mechanics, The Pennsylvania State University, University Park, PA, USA

    Aaryan Oberoi & Saptarshi Das

  10. Materials Research Institute, The Pennsylvania State University, University Park, PA, USA

    Ke Wang

  11. Department of Electrical and Computer Engineering, Rice University, Houston, TX, USA

    Shengxi Huang

  12. Department of Physics, The Pennsylvania State University, University Park, PA, USA

    Vincent H. Crespi

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Contributions

H.Z. and T.H.C. carried out MOCVD growth, AFM, field-emission scanning electron microscopy and in-plane XRD characterization and data analysis with assistance from K.Y., T.V.M.K., N.T., R.A.M. and S.M.D. N.N., V.H.C. and A.C.T.v.D. carried out DFT calculations. A.B. and B.H. performed in-plane XRD, layer transfer and Raman/photoluminescence characterizations. K.Z. and S.H. performed low-temperature and polarization-resolved photoluminescence measurements. A.A.P. performed SHG characterization. S.B., N.A. and K.W. performed transmission electron microscopy characterizations. A.O. and S.D. fabricated and tested backgated FETs. H.Z., N.N., T.H.C. and J.M.R. co-wrote the manuscript with input from all authors. All authors contributed to the discussions.

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Correspondence to Joan M. Redwing.

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Nature Nanotechnology thanks Wouter Mortelmans and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–26 and Discussion.

Supplementary Video 1

Nucleation of a TRIANGULAR WSe2 on the BOTTOM terrace of a MIXED Se/O step.

Supplementary Video 2

Nucleation of a TRIANGULAR WSe2 on the TOP terrace of a MIXED Se/O step.

Supplementary Video 3

Nucleation of a TRIANGULAR WSe2 on the BOTTOM terrace of a SINGLE Se step.

Supplementary Video 4

Nucleation of a TRIANGULAR WSe2 on the TOP terrace of a SINGLE Se step.

Supplementary Video 5

Nucleation of a RIBBON WSe2 on the BOTTOM terrace of a MIXED Se/O step.

Supplementary Video 6

Nucleation of a RIBBON WSe2 on the TOP terrace of a MIXED Se/O step.

Supplementary Video 7

Nucleation of a RIBBON WSe2 on the BOTTOM terrace of a SINGLE Se step.

Supplementary Video 8

Nucleation of a RIBBON WSe2 on the TOP terrace of a SINGLE Se step.

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Zhu, H., Nayir, N., Choudhury, T.H. et al. Step engineering for nucleation and domain orientation control in WSe2 epitaxy on c-plane sapphire. Nat. Nanotechnol. 18, 1295–1302 (2023). https://doi.org/10.1038/s41565-023-01456-6

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