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.
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The data that support the findings of this study are available from the corresponding authors on reasonable request.
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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).
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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.
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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.
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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
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DOI: https://doi.org/10.1038/s41586-023-06404-x
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