Abstract
Two-dimensional (2D) van der Waals (vdW) heterostructures have attracted considerable attention in recent years1,2,3,4,5. The most widely used method of fabrication is to stack mechanically exfoliated micrometre-sized flakes6,7,8,9,10,11,12,13,14,15,16,17,18, but this process is not scalable for practical applications. Despite thousands of 2D materials being created, using various stacking combinations1,2,3,19,20,21, hardly any large 2D superconductors can be stacked intact into vdW heterostructures, greatly restricting the applications for such devices. Here we report a high-to-low temperature strategy for controllably growing stacks of multiple-layered vdW superconductor heterostructure (vdWSH) films at a wafer scale. The number of layers of 2D superconductors in the vdWSHs can be precisely controlled, and we have successfully grown 27 double-block, 15 triple-block, 5 four-block and 3 five-block vdWSH films (where one block represents one 2D material). Morphological, spectroscopic and atomic-scale structural analyses reveal the presence of parallel, clean and atomically sharp vdW interfaces on a large scale, with very little contamination between neighbouring layers. The intact vdW interfaces allow us to achieve proximity-induced superconductivity and superconducting Josephson junctions on a centimetre scale. Our process for making multiple-layered vdWSHs can easily be generalized to other situations involving 2D materials, potentially accelerating the design of next-generation functional devices and applications22,23,24.
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 51 print issues and online access
$199.00 per year
only $3.90 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
The data that support the findings of this study are available from the corresponding authors on reasonable request.
References
Geim, A. K. & Grigorieva, I. V. Van der Waals heterostructures. Nature 499, 419–425 (2013).
Liu, Y. et al. Van der Waals heterostructures and devices. Nat. Rev. Mater. 1, 16042 (2016).
Novoselov, K. S., Mishchenko, A., Carvalho, A. & Neto, A. H. C. 2D materials and van der Waals heterostructures. Science 353, aac9439 (2016).
Liu, Y., Huang, Y. & Duan, X. Van der Waals integration before and beyond two-dimensional materials. Nature 567, 323–333 (2019).
Yang, H. et al. Two-dimensional materials prospects for non-volatile spintronic memories. Nature 606, 663–673 (2022).
Yankowitz, M. et al. Emergence of superlattice Dirac points in graphene on hexagonal boron nitride. Nat. Phys. 8, 382–386 (2012).
Dean, C. R. et al. Hofstadter’s butterfly and the fractal quantum Hall effect in moiré superlattices. Nature 497, 598–602 (2013).
Ponomarenko, L. A. et al. Cloning of Dirac fermions in graphene superlattices. Nature 497, 594–597 (2013).
Wang, L. et al. One-dimensional electrical contact to a two-dimensional material. Science 342, 614–617 (2013).
Lee, G.-H., Kim, S., Jhi, S.-H. & Lee, H.-J. Ultimately short ballistic vertical graphene Josephson junctions. Nat. Commun. 6, 6181 (2015).
Yabuki, N. et al. Supercurrent in van der Waals Josephson junction. Nat. Commun. 7, 10616 (2016).
Kang, K. et al. Layer-by-layer assembly of two-dimensional materials into wafer-scale heterostructures. Nature 550, 229–233 (2017).
Kim, M. et al. Strong proximity Josephson coupling in vertically stacked NbSe2–graphene–NbSe2 van der Waals junctions. Nano Lett. 17, 6125–6130 (2017).
Cao, Y. et al. Unconventional superconductivity in magic-angle graphene superlattices. Nature 556, 43–50 (2018).
Jin, C. et al. Observation of moiré excitons in WSe2/WS2 heterostructure superlattices. Nature 567, 76–80 (2019).
Idzuchi, H. et al. Unconventional supercurrent phase in Ising superconductor Josephson junction with atomically thin magnetic insulator. Nat. Commun. 12, 5332 (2021).
Wu, H. et al. The field-free Josephson diode in a van der Waals heterostructure. Nature 604, 653–656 (2022).
Ai, L. et al. Van der Waals ferromagnetic Josephson junctions. Nat. Commun. 12, 6580 (2021).
Chhowalla, M. et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 5, 263–275 (2013).
Mounet, N. et al. Two-dimensional materials from high-throughput computational exfoliation of experimentally known compounds. Nat. Nanotechnol. 13, 246–252 (2018).
Zhou, J. et al. A library of atomically thin metal chalcogenides. Nature 556, 355–359 (2018).
Baumgartner, C. et al. Supercurrent rectification and magnetochiral effects in symmetric Josephson junctions. Nat. Nanotechnol. 17, 39–44 (2022).
Pal, B. et al. Josephson diode effect from Cooper pair momentum in a topological semimetal. Nat. Phys. 18, 1228–1233 (2022).
Lee, G.-H. et al. Graphene-based Josephson junction microwave bolometer. Nature 586, 42–46 (2020).
Lee, C.-H. et al. Atomically thin p–n junctions with van der Waals heterointerfaces. Nat. Nanotechnol. 9, 676–681 (2014).
Iannaccone, G., Bonaccorso, F., Colombo, L. & Fiori, G. Quantum engineering of transistors based on 2D materials heterostructures. Nat. Nanotechnol. 13, 183–191 (2018).
Lüpke, F. et al. Proximity-induced superconducting gap in the quantum spin Hall edge state of monolayer WTe2. Nat. Phys. 16, 526–530 (2020).
Jin, G. et al. Heteroepitaxial van der Waals semiconductor superlattices. Nat. Nanotechnol. 16, 1092–1098 (2021).
Zhao, B. et al. High-order superlattices by rolling up van der Waals heterostructures. Nature 591, 385–390 (2021).
Rogée, L. et al. Ferroelectricity in untwisted heterobilayers of transition metal dichalcogenides. Science 376, 973–978 (2022).
Kezilebieke, S. et al. Topological superconductivity in a van der Waals heterostructure. Nature 588, 424–428 (2020).
Kretinin, A. V. et al. Electronic properties of graphene encapsulated with different two-dimensional atomic crystals. Nano Lett. 14, 3270–3276 (2014).
Gong, Y. et al. Vertical and in-plane heterostructures from WS2/MoS2 monolayers. Nat. Mater. 13, 1135–1142 (2014).
Yang, T. et al. Van der Waals epitaxial growth and optoelectronics of large-scale WSe2/SnS2 vertical bilayer p–n junctions. Nat. Commun. 8, 1906 (2017).
Li, J. et al. General synthesis of two-dimensional van der Waals heterostructure arrays. Nature 579, 368–374 (2020).
Yang, W. et al. Epitaxial growth of single-domain graphene on hexagonal boron nitride. Nat. Mater. 12, 792–797 (2013).
Bonilla, M. et al. Strong room-temperature ferromagnetism in VSe2 monolayers on van der Waals substrates. Nat. Nanotechnol. 13, 289–293 (2018).
Wang, H. et al. High-quality monolayer superconductor NbSe2 grown by chemical vapour deposition. Nat. Commun. 8, 394 (2017).
Lin, H. et al. Growth of environmentally stable transition metal selenide films. Nat. Mater. 18, 602–607 (2019).
Saito, Y., Nojima, T. & Iwasa, Y. Highly crystalline 2D superconductors. Nat. Rev. Mater. 2, 16094 (2017).
Yan, M. et al. Lorentz-violating type-II Dirac fermions in transition metal dichalcogenide PtTe2. Nat. Commun. 8, 257 (2017).
Ma, H. et al. Thickness-tunable synthesis of ultrathin type-II Dirac semimetal PtTe2 single crystals and their thickness-dependent electronic properties. Nano Lett. 18, 3523–3529 (2018).
Dumcenco, D. O., Kobayashi, H., Liu, Z., Huang, Y.-S. & Suenaga, K. Visualization and quantification of transition metal atomic mixing in Mo1−xWxS2 single layers. Nat. Commun. 4, 1351 (2013).
Koma, A., Sunouchi, K. & Miyajima, T. Fabrication of ultrathin heterostructures with van der Waals epitaxy. J. Vac. Sci. Technol. B 3, 724 (1985).
Yi, H. et al. Crossover from Ising- to Rashba-type superconductivity in epitaxial Bi2Se3/monolayer NbSe2 heterostructures. Nat. Mater. 21, 1366–1372 (2022).
Li, M.-Y. et al. Epitaxial growth of a monolayer WSe2-MoS2 lateral p-n junction with an atomically sharp interface. Science 349, 524–528 (2015).
Acknowledgements
This work was supported by the National Key R&D Program of China (grant 2018YFA0305800), the Natural Science Foundation of China (51972163, 11904163, 11974156 and 12104218), the Fundamental Research Funds for the Central Universities (020414380201 and 020414380176), the Natural Science Foundation of Jiangsu Province (BK20190010), the Fok Ying-Tong Education Foundation of China (171038), the China National Postdoctoral Program for Innovative Talents (BX2021120), the Guangdong Innovative and Entrepreneurial Research Team Program (2019ZT08C044), the Shenzhen Science and Technology Program (KQTD20190929173815000 and 20200925161102001), the Science, Technology and Innovation Commission of Shenzhen Municipality (ZDSYS20190902092905285), the Presidential Fund and the Development and Reform Commission of Shenzhen Municipality. Technical assistance was provided by the SUSTech Core Research Facilities and Pico-Centre. Part of this work was performed at the Quantum Science Center of Guangdong–Hong Kong–Macao Greater Bay Area (Guangdong).
Author information
Authors and Affiliations
Contributions
L.G. conceived and supervised the project. L.G., J.L., J.X. and Z.Z. designed the experiments. Z.Z. performed the sample growth, the AFM, the Raman and PL characterizations and the electrical transport measurements. X.H., W.L. and X.X. helped with the device fabrication and electrical transport measurements. Z.F. helped with the growth experiments. J.X. helped with the AFM and the Raman and PL measurements. F.H., G.W. and J.L. fabricated the cross-sectional TEM samples and performed STEM. Z.Z., F.H. and L.G. analysed the data and wrote the manuscript, and G.Y., J.X. and J.L. revised it. All the authors discussed the results and commented on the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature thanks Zheng Liu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Additional information
Extended data
is available for this paper at https://doi.org/10.1038/s41586-023-06404-x.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Extended data figures and tables
Extended Data Fig. 1 Growth temperature and Raman spectra of various TMDCs and vdW heterostructures.
a, Two-step vapour deposition grown six transition metal disulphides (W, Mo, Nb, Ti, V, Ta), eight diselenides (W, Mo, Nb, Ti, V, Ta, Fe, Pt) and five ditellurides (W, Mo, Nb, Ti, Pt). b-d, Multi-cycled growth of twenty-six double-block vdW heterostructures, fifteen triple-block vdW heterostructures and five fourfold-block vdW heterostructures followed by the High-to-Low strategy. More wafer-scale vdW heterostructure films will be controllably grown following the same strategy. e, Variable temperature resistances of the superconducting bilayer TaS2 (2 nm thick) under different out-of-plane magnetic fields, the 2 nm thick Ta film is compared.
Extended Data Fig. 2 Feasibility of stack-grown vdWSHs by the High-to-Low strategy.
a, Typical AFM image across the vdWSH of 1L MoS2\3L NbSe2, the bottom plot is the corresponding height profile labelled by a blue dash line. The morphologies for the bottom and top blocks both show homogeneity. b, Typical optical image and corresponding Raman intensity mappings of double-block vdWSH film consisting of bottom NbSe2 and top PtTe2, they both present homogenous. c, Raman spectra of individual NbSe2, PtTe2, stack-grown vdWSH film of NbSe2\PtTe2 following the High-to-Low strategy, transferred vdWSH film of PtTe2 on NbSe2. Raman characteristic peaks of NbS2 and PtTe2 appear in the stack-grown and transferred (Tr) MoS2\NbSe2 films. d, Optical image of the stack grown double-block vdW heterostructures on sapphire, consisting of bottom 1L WS2 and top 1L MoS2. e, Typical PL spectra of individual WS2, MoS2, their double-block vdW heterostructure films via stack growth and standard wet transfer (Tr). The PL spectra of individual WS2 and MoS2 are collected at the transition regions, indicating they are intact during the multi-cycled growth procedures. f, Typical AFM image across the vdW heterostructure of WS2\MoS2, the bottom plot is the corresponding height profile labelled by a red dash line. The morphologies for the bottom and top blocks both show homogeneity. g, Schematic of growing vdW heterostructure films against two-step vapour deposition and hence forming alloy disulphates, where W and Mo films are continuously deposited on the growth substrate and WxMo1-xS2 is formed after sulfurization. h, Raman spectra of individual WS2, MoS2, stack grown vdW heterostructure film of WS2\MoS2, transferred (Tr) WS2\MoS2 and grown WxMo1-xS2, the Raman characteristic peaks (A1g and E2g) of WS2 and MoS2 appear in the stack grown and transferred WS2\MoS2 films, but there are no corresponding peaks in the WxMo1-xS2 film, confirming the feasibility of each two-step vapour deposition procedure.
Extended Data Fig. 3 Characterizations of triple-block vdW heterostructure films.
a, Typical AFM image of the thickness transition region of a vdW heterostructure film consisting of bottom WS2, middle MoS2 and top MoSe2 monolayers. The lower panel is the corresponding height profile labelled by the purple dash line, each block presents homogenous with the thickness of ~0.9 nm, ~0.6 nm and ~0.7 nm, respectively. b, Typical Raman spectra of individual WS2, MoS2, MoSe2, double-block WS2\MoS2, and triple-block WS2\MoS2\MoSe2 films, all the Raman spectra of individual TMDCs and double-block vdW heterostructure are collected at the transition regions of the triple-block vdW heterostructure film, indicating they are intact during the multi-cycled growth procedures. c. XPS survey spectra for individual WS2, MoS2, MoSe2 films, and the stack grown triple-block WS2\MoS2\MoSe2 film. d, Corresponding XPS fine spectra of W 4f, Se 3d, S 2p and Mo 3d core levels for the triple-block vdW heterostructure film, all the elements present the effective bond states.
Extended Data Fig. 4 Characterizations of fourfold-block vdWSH films.
a, Typical millimetre-scale optical image of the fourfold-block vdWSH film consisting of bottom WS2, second MoS2, third MoSe2 monolayers and fourth 2L NbSe2. b, AFM image of the fourfold-block vdWSH film. The lower panel is the corresponding height profile labelled by a blue dash line, showing that the total thickness of vdWSH film is homogenous ~4.0 nm with 1L WS2, 1L MoS2, 1L MoSe2 and 2L NbSe2 (total 5 layers). c, Joint AFM images over the region of 150 μm × 60 μm, showing homogeneity over the large scale. d, Typical Raman spectra of individual WS2, MoS2, MoSe2, NbSe2, and fourfold-block WS2\MoS2\MoSe2\NbSe2 film, all the Raman spectra of individual TMDCs are collected at the transition regions of fourfold-block vdWSH film, indicating they are intact during the multi-cycled growth procedures. e, Variable temperature resistances of the fourfold-block vdWSHs with 2L NbSe2 as a top block, the superconducting behaviours of NbSe2 still present good even on the bottom triple-block vdWSH substrates.
Extended Data Fig. 5 Characterizations of fivefold-block vdWSH films.
a, Typical optical image and Raman intensity mapping of the fivefold-block vdWSH film consisting of bottom WS2, second MoS2, third MoSe2 monolayers, fourth 2L NbSe2 and top 2L PtTe2. All the Raman intensities are collected from their corresponding A1g peaks, respectively. b, Typical Raman spectra of individual WS2, MoS2, MoSe2, NbSe2, PtTe2, and fivefold-block WS2\MoS2\MoSe2\NbSe2\PtTe2 film, all the Raman spectra of individual TMDCs are collected at the transition regions of fivefold-block vdWSH film, indicating they are intact during the multi-cycled growth procedures. c, XPS fine spectra of W 4f, Se 3d, Pt 4f, S 2p, Nb 3d, Mo 3d and Te 3d core levels for the fivefold-block vdWSH film, all the elements present the effective bond states.
Extended Data Fig. 6 Stack growth of homogenous multi-block vdWSH films on 4-inch SiO2/Si wafers.
a, Photos of double-block, triple-block, fourfold-block and fivefold-block vdWSHs films consisting of 1L WS2, 1L WS2, 1L MoSe2, 2L NbSe2 and 2L PtTe2, they look homogenous at each growth cycle. b, The corresponding Raman spectra collected at different points of the stack grown vdWH films, indicating the vdWSH films are highly homogenous.
Extended Data Fig. 7 Crystalline structure of a fivefold-block vdWSH film.
a, Cross-sectional STEM image of a vdWSH film consisting of 1L WS2, 1L MoS2, 1L MoSe2, 2L NbSe2 and 2L PtTe2 (total 7 layers), the left black line is the corresponding intensity profile, showing the average interlayer distance of 0.67 nm. The right coloured lines are the EDS spectra for W, Mo, Nb, Pt, S, Se and Te. b, Zoom-in cross-sectional STEM image of the fivefold-block vdWSH film, showing their intact crystalline structures. c, Corresponded EDS elemental mapping for W, Mo, Nb, Pt, S, Se and Te in b, showing the 2D materials are not alloyed during the multi-cycled growth procedures.
Extended Data Fig. 8 Additional information for Moiré superlattices in stack grown double-layers.
a, Typical STEM images of 1L WS2\1L NbSe2 film with the twist angle of 8° and 26°, the left panels are the corresponding atomic models for the Moiré superlattices, and the insets are the FFT patterns for the stack regions. b, Typical in-plane STEM image obtained at the thickness transition region of a partly detached WS2\MoSe2 film, inset is the corresponding FFT pattern for the double-block region and their twist angle is ~21°. The periodicity of the double-layered Moiré superlattice is ~0.85 nm, corresponding to a twist angle of 21.7°. Typical STEM images of 1L WS2\1L MoSe2 film with the twist angles of 0°, 8°, 15°, 21° and 27°. c, d, Typical STEM images of 1L WS2\1L MoS2 film with the twist angles of 0°, 4°, 14°, 21° and 24° (c) and 1L MoS2\1L MoSe2 film with the twist angle of 0°, 7° and 14° (d), all the twist angles are measured from their FFT patterns.
Extended Data Fig. 9 Additional information for proximity induced superconductivity in NbSe2\PtTe2 film.
a, Typical AFM images of 4L NbSe2\nL PtTe2 films and the corresponding height profiles, showing that the layer numbers of PtTe2 in the vdWSH films are precisely controllable. b, Various Raman spectra of NbSe2\PtTe2 film with varying PtTe2 thickness. As the thickness of the top PtTe2 increases, the intensity of the Raman characteristic peak of the bottom block NbSe2 gradually decreases. c, d, Variable temperature resistances of the 3.2 nm-thick NbSe2 in the double-block vdWSH film consisting of 1.6 nm-thick PtTe2 as top block under in-plane (c) and out-of-plane (d) magnetic fields, inset is the illustration of the four-probe electrical measurement.
Extended Data Fig. 10 Additional information for triple-block vdWSH films as superconducting Josephson junction.
a, Four-probe current-voltage (I-V) characteristics of a stack-grown NbSe2\MoSe2\NbSe2 vdWSH film using a large measurement scale. Two transition regions of hysteretic behaviours correspond to the critical current of the Josephson junction (Ic1) and the multi-layered NbSe2 electrode (Ic2). Inset is the schematic of the four-probe electrical measurement for the 4L NbSe2\2L MoSe2\4L NbSe2 vdWSH film. b, Temperature dependence of I-V characteristics of the stack grown NbSe2\MoSe2\NbSe2 film, the hysteretic behaviours become reduced gradually as increasing the temperature. c, Variable temperature resistances of the top and bottom 4L NbSe2 in the 1-year-aged NbSe2\MoSe2\NbSe2 film, and the junction resistance between bottom and top NbSe2. d, Current-voltage (I-V) characteristics of as-grown and 1-year-aged 4L NbSe2\2L MoSe2\4L NbSe2 vdWSH film, measured at 1.5 K. e, Four-probe I-V characteristics of a stack grown 4L NbSe2\4L NbSe2 film at 1.5 K. The critical current (Ic1) is denoted by black arrows, and there is no obvious hysteretic behaviour while the vdW gap is used as the superconducting barrier.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Zhou, Z., Hou, F., Huang, X. et al. Stack growth of wafer-scale van der Waals superconductor heterostructures. Nature 621, 499–505 (2023). https://doi.org/10.1038/s41586-023-06404-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41586-023-06404-x
This article is cited by
-
Superconducting tunnel junctions with layered superconductors
Quantum Frontiers (2024)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
