Abstract
The growth of wafer-scale single-crystal two-dimensional transition metal dichalcogenides (TMDs) on insulating substrates is critically important for a variety of high-end applications1,2,3,4. Although the epitaxial growth of wafer-scale graphene and hexagonal boron nitride on metal surfaces has been reported5,6,7,8, these techniques are not applicable for growing TMDs on insulating substrates because of substantial differences in growth kinetics. Thus, despite great efforts9,10,11,12,13,14,15,16,17,18,19,20, the direct growth of wafer-scale single-crystal TMDs on insulating substrates is yet to be realized. Here we report the successful epitaxial growth of two-inch single-crystal WS2 monolayer films on vicinal a-plane sapphire surfaces. In-depth characterizations and theoretical calculations reveal that the epitaxy is driven by a dual-coupling-guided mechanism, where the sapphire plane–WS2 interaction leads to two preferred antiparallel orientations of the WS2 crystal, and sapphire step edge–WS2 interaction breaks the symmetry of the antiparallel orientations. These two interactions result in the unidirectional alignment of nearly all the WS2 islands. The unidirectional alignment and seamless stitching of WS2 islands are illustrated via multiscale characterization techniques; the high quality of WS2 monolayers is further evidenced by a photoluminescent circular helicity of ~55%, comparable to that of exfoliated WS2 flakes. Our findings offer the opportunity to boost the production of wafer-scale single crystals of a broad range of two-dimensional materials on insulators, paving the way to applications in integrated devices.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
Source data are provided with this paper. The data that support the findings of this study are available within the paper and Supplementary Information. Additional data are available from the corresponding authors upon reasonable request.
References
Wang, Q. H. et al. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat. Nanotechnol. 7, 699–712 (2012).
Radisavljevic, B. et al. Single-layer MoS2 transistors. Nat. Nanotechnol. 6, 147–150 (2011).
Mak, K. F., McGill, K. L., Park, J. & McEuen, P. L. The valley Hall effect in MoS2 transistors. Science 344, 1489–1492 (2014).
Jin, C. H. et al. Imaging of pure spin-valley diffusion current in WS2-WSe2 heterostructures. Science 360, 893–896 (2018).
Xu, X. Z. et al. Ultrafast epitaxial growth of metre-sized single-crystal graphene on industrial Cu foil. Sci. Bull. 62, 1074–1080 (2017).
Wang, L. et al. Epitaxial growth of a 100-square-centimetre single-crystal hexagonal boron nitride monolayer on copper. Nature 570, 91–95 (2019).
Lee, J. S. et al. Wafer-scale single-crystal hexagonal boron nitride film via self-collimated grain formation. Science 362, 817–821 (2018).
Chen, T. A. et al. Wafer-scale single-crystal hexagonal boron nitride monolayers on Cu (111). Nature 579, 219–223 (2020).
Chen, L. et al. Step-edge-guided nucleation and growth of aligned WSe2 on sapphire via a layer-over-layer growth mode. ACS Nano 9, 8368–8375 (2015).
Chubarov, M. et al. Wafer-scale epitaxial growth of unidirectional WS2 monolayers on sapphire. ACS Nano 15, 2532–2541 (2021).
Lee, Y. H. et al. Synthesis of large-area MoS2 atomic layers with chemical vapor deposition. Adv. Mater. 24, 2320–2325 (2012).
Najmaei, S. et al. Vapour phase growth and grain boundary structure of molybdenum disulphide atomic layers. Nat. Mater. 12, 754–759 (2013).
van der Zande, A. M. et al. Grains and grain boundaries in highly crystalline monolayer molybdenum disulphide. Nat. Mater. 12, 554–561 (2013).
Zheng, J. et al. High yield exfoliation of two-dimensional chalcogenides using sodium naphthalenide. Nat. Commun. 5, 2995 (2014).
Dumcenco, D. et al. Large-area epitaxial monolayer MoS2. ACS Nano 9, 4611–4620 (2015).
Gao, Y. et al. Large-area synthesis of high-quality and uniform monolayer WS2 on reusable Au foils. Nat. Commun. 6, 8569 (2015).
Zhou, J. D. et al. A library of atomically thin metal chalcogenides. Nature 556, 355–359 (2018).
Yang, P. et al. Epitaxial growth of centimeter-scale single-crystal MoS2 monolayer on Au (111). ACS Nano 14, 5036–5045 (2020).
Li, J. et al. General synthesis of two-dimensional van der Waals heterostructure arrays. Nature 579, 368–374 (2020).
Wang, Q. Q. et al. Wafer-scale highly oriented monolayer MoS2 with large domain sizes. Nano Lett. 20, 7193–7199 (2020).
Sang, X. H. et al. In situ edge engineering in two-dimensional transition metal dichalcogenides. Nat. Commun. 9, 2051 (2018).
Kurita, T., Uchida, K. & Oshiyama, A. Atomic and electronic structures of α-Al2O3 surfaces. Phys. Rev. B 82, 155319 (2010).
Dong, J. C., Zhang, L. N., Dai, X. Y. & Ding, F. The epitaxy of 2D materials growth. Nat. Commun. 11, 5862 (2020).
Ismach, A., Segev, L., Wachtel, E. & Joselevich, E. Atomic-step-templated formation of single wall carbon nanotube patterns. Angew. Chem. Int. Ed. 43, 6140–6143 (2004).
Cheng, J. X. et al. Chiral selection rules for multi-photon processes in two-dimensional honeycomb materials. Opt. Lett. 44, 2141–2144 (2019).
Hong, J. H. et al. Exploring atomic defects in molybdenum disulphide monolayers. Nat. Commun. 6, 6293 (2015).
Qiu, H. et al. Hopping transport through defect-induced localized states in molybdenum disulphide. Nat. Commun. 4, 2642 (2013).
Wang, G. et al. In-plane propagation of light in transition metal dichalcogenide monolayers: optical selection rules. Phys. Rev. Lett. 119, 047401 (2017).
Zeng, H. L. et al. Valley polarization in MoS2 monolayers by optical pumping. Nat. Nanotechnol. 7, 490–493 (2012).
Zhu, B. R. et al. Anomalously robust valley polarization and valley coherence in bilayer WS2. Proc. Natl Acad. Sci. USA 111, 11606–11611 (2014).
Scrace, T. et al. Magnetoluminescence and valley polarized state of a two-dimensional electron gas in WS2 monolayers. Nat. Nanotechnol. 10, 603–607 (2015).
Plechinger, G. et al. Trion fine structure and coupled spin-valley dynamics in monolayer tungsten disulfide. Nat. Commun. 7, 12715 (2016).
Lu, J. M. et al. Evidence for two-dimensional Ising superconductivity in gated MoS2. Science 350, 1353–1357 (2015).
Kresse, G. & Furthmuller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 6, 15–50 (1996).
Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).
Henkelman, G., Uberuaga, B. P. & Jonsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).
Acknowledgements
This work was supported by the National Natural Science Foundation of China (52025023 (K.L.), 51991342 (K.L.), 52021006 (K.L.), 11888101 (E.W.) and 52102043 (X.X.)); the Key R&D Program of Guangdong Province (2020B010189001 (X.X.), 2019B010931001 (K.L.) and 2018B030327001 (D.Y.)); Science and Technology Program of Guangzhou (2019050001 (X.X.)); the Pearl River Talent Recruitment Program of Guangdong Province (2019ZT08C321 (X.X.)); Beijing Natural Science Foundation (JQ19004 (K.L.)); Guangdong Provincial Science Fund for Distinguished Young Scholars (2020B1515020043 (X.X.)); National Key R&D Program of China (2016YFA0300903 (K.L.), 2016YFA0300804 (P.G.) and 2019YFA0307800 (L.L.)); Guangdong Innovative and Entrepreneurial Research Team Program (2016ZT06D348 (D.Y.)); the Science, Technology and Innovation Commission of Shenzhen Municipality (KYTDPT20181011104202253 (D.Y.)); the Strategic Priority Research Program of Chinese Academy of Sciences (XDB33000000 (K.L.)); National Postdoctoral Program for Innovative Talents (BX20190016 (C.L.)); China Postdoctoral Science Foundation (2019M660280 (C.L.), 2019M660281 (R.Q.) and 2020T130022 (R.Q.)); and the Institute for Basic Science (IBS-R019-D1 (F.D.)), South Korea. The authors also acknowledge the use of the IBS-CMCM high-performance computing system simulator.
Author information
Authors and Affiliations
Contributions
K.L. conceived and supervised the project. J.W., X.X., Z.L., P.Z., G.C., C.C., C.L., Y. Zuo, G.X., M.W. and E.W. performed the sample growth. T.C. and F.D. performed the theoretical calculations. L.G., H.H., C.H., J. Liang, Z.T. and S.W. conducted the optical measurements. R.Q., Y.G., D.Y. and P.G. conducted the TEM measurements. D.D., J.T., Z.Y., L.L., R.Y., G.Z. and J. Lu conducted the electrical measurements. Zhibin Zhang, Zhihong Zhang, S.Z., J.Q., Y. Zhao, Q.J. and Q.L. conducted the AFM measurements. X.X. and X.F. conducted the LEED measurements. All the authors discussed the results and wrote the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Peer review information Nature Nanotechnology thanks Xiangfeng Duan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
Supplementary Figs. 1–25.
Source data
Source Data Fig. 2
Statistical source data.
Source Data Fig. 4
Statistical source data.
Rights and permissions
About this article
Cite this article
Wang, J., Xu, X., Cheng, T. et al. Dual-coupling-guided epitaxial growth of wafer-scale single-crystal WS2 monolayer on vicinal a-plane sapphire. Nat. Nanotechnol. 17, 33–38 (2022). https://doi.org/10.1038/s41565-021-01004-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41565-021-01004-0
This article is cited by
-
Remote epitaxy of single-crystal rhombohedral WS2 bilayers
Nature Communications (2024)
-
Biaxial strain tuned upconversion photoluminescence of monolayer WS2
Scientific Reports (2024)
-
Van der Waals epitaxy of tunable moirés enabled by alloying
Nature Materials (2024)
-
2D materials for logic device scaling
Nature Materials (2024)
-
Transistor engineering based on 2D materials in the post-silicon era
Nature Reviews Electrical Engineering (2024)
