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Intrinsically patterned two-dimensional materials for selective adsorption of molecules and nanoclusters

Abstract

Two-dimensional (2D) materials have been studied extensively as monolayers1,2,3,4,5, vertical or lateral heterostructures6,7,8. To achieve functionalization, monolayers are often patterned using soft lithography and selectively decorated with molecules9,10. Here we demonstrate the growth of a family of 2D materials that are intrinsically patterned. We demonstrate that a monolayer of PtSe2 can be grown on a Pt substrate in the form of a triangular pattern of alternating 1T and 1H phases. Moreover, we show that, in a monolayer of CuSe grown on a Cu substrate, strain relaxation leads to periodic patterns of triangular nanopores with uniform size. Adsorption of different species at preferred pattern sites is also achieved, demonstrating that these materials can serve as templates for selective self-assembly of molecules or nanoclusters, as well as for the functionalization of the same substrate with two different species.

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Figure 1: 1H/1T tiling pattern in monolayer PtSe2.
Figure 2: Reversible transition and selective adsorption of 1H/1T tiling pattern.
Figure 3: Patterned CuSe monolayer with periodic nanopores.
Figure 4: Selective adsorption on patterned CuSe with periodic nanopores.

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References

  1. Novoselov, K. S. et al. A roadmap for graphene. Nature 490, 192–200 (2012).

    Article  CAS  Google Scholar 

  2. Oughaddou, H. et al. Silicene, a promising new 2D material. Prog. Surf. Sci. 90, 46–83 (2015).

    Article  CAS  Google Scholar 

  3. Desai, S. B. et al. MoS2 transistors with 1-nanometer gate lengths. Science 354, 99–102 (2016).

    Article  CAS  Google Scholar 

  4. Chhowalla, M. et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 5, 263–275 (2013).

    Article  Google Scholar 

  5. Yin, K. Unsupported single-atom-thick copper oxide monolayers. 2D Mater. 4, 011001 (2017).

    Article  Google Scholar 

  6. Geim, A. K. & Grigorieva, I. V. Van der Waals heterostructures. Nature 499, 419–425 (2013).

    Article  CAS  Google Scholar 

  7. Eda, G. et al. Coherent atomic and electronic heterostructures of single-layer MoS2 . ACS Nano 6, 7311–7317 (2012).

    Article  CAS  Google Scholar 

  8. Withers, F. Light-emitting diodes by band-structure engineering in van der Waals heterostructures. Nat. Mater. 14, 301–306 (2015).

    Article  CAS  Google Scholar 

  9. Jung, M. W. et al. Novel fabrication of flexible graphene-based chemical sensors with heaters using soft lithographic patterning method. ACS Appl. Mater. Interfaces 6, 13319–13323 (2014).

    Article  CAS  Google Scholar 

  10. Joshi, S. et al. Control of molecular organization and energy level alignment by an electronically nanopatterned boron nitride template. ACS Nano 8, 430–442 (2014).

    Article  CAS  Google Scholar 

  11. Cho, S. et al. Phase patterning for ohmic homojunction contact in MoTe2 . Science 349, 625–628 (2015).

    Article  CAS  Google Scholar 

  12. Voiry, D. et al. The role of electronic coupling between substrate and 2D MoS2 nanosheets in electrocatalytic production of hydrogen. Nat. Mater. 15, 1003–1009 (2016).

    Article  CAS  Google Scholar 

  13. Pan, L. D., Zhang, L. Z., Song, B. Q., Du, S. X. & Gao, H.-J. Graphyne- and graphdiyne-based nanoribbons: density functional theory calculations of electronic structures. Appl. Phys. Lett. 98, 173102 (2011).

    Article  Google Scholar 

  14. Gao, G., Jiao, Y., Waclawik, E. R. & Du, A. Single atom (Pd/Pt) supported on graphitic carbon nitride as an efficient photocatalyst for visible-light reduction of carbon dioxide. J. Am. Chem. Soc. 138, 6292–6297 (2016).

    Article  CAS  Google Scholar 

  15. Zhang, H., Li, Y., Hou, J., Tu, K. & Chen, Z. FeB6 monolayers: the graphene-like material with hypercoordinate transition metal. J. Am. Chem. Soc. 138, 5644–5651 (2016).

    Article  CAS  Google Scholar 

  16. Pan, Y. et al. Highly ordered, millimeter-scale, continuous, single-crystalline graphene monolayers formed on Ru(0001). Adv. Mater. 21, 2777–2780 (2009).

    Article  CAS  Google Scholar 

  17. Lee, M. et al. Ballistic miniband conduction in a graphene superlattice. Science 353, 1526–1529 (2016).

    Article  CAS  Google Scholar 

  18. Huang, S. et al. Ultrathin FeSe2 nanosheets: controlled synthesis and application as a heterogeneous catalyst in dye-sensitized solar cells. Chem. Eur. J. 21, 4085–4091 (2015).

    Article  CAS  Google Scholar 

  19. Wang, Y. et al. Monolayer PtSe2, a new semiconducting transition-metal-dichalcogenide, epitaxially grown by direct selenization of Pt. Nano Lett. 15, 4013–4018 (2015).

    Article  CAS  Google Scholar 

  20. Lin, J., Pantelides, S. T. & Zhou, W. Vacancy-induced formation and growth of inversion domains in transition-metal dichalcogenide monolayer. ACS Nano 9, 5189–5197 (2015).

    Article  CAS  Google Scholar 

  21. Lin, Y. C., Dumcenco, D. O., Huang, Y. S. & Suenaga, K. Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2 . Nat. Nanotech. 9, 391–396 (2014).

    Article  CAS  Google Scholar 

  22. Yamasaki, A. Electron correlation in the FeSe superconductor studied by bulk-sensitive photoemission spectroscopy. Phys. Rev. B 82, 184511 (2010).

    Article  Google Scholar 

  23. Cheng, Z. H. et al. High resolution scanning-tunneling-microscopy imaging of individual molecular orbitals by eliminating the effect of surface charge. Surf. Sci. 605, 415–418 (2011).

    Article  CAS  Google Scholar 

  24. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    Article  CAS  Google Scholar 

  25. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  CAS  Google Scholar 

  26. Ceperley, D. M. & Alder, B. J. Ground state of the electron gas by a stochastic method. Phys. Rev. Lett. 45, 566–569 (1980).

    Article  CAS  Google Scholar 

  27. Perdew, J. P. & Zunger, A. Self-interaction correction to density-functional approximations for many-electron systems. Phys. Rev. B 23, 5048–5079 (1981).

    Article  CAS  Google Scholar 

  28. Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA + U study. Phys. Rev. B 57, 1505–1509 (1998).

    Article  CAS  Google Scholar 

  29. Cococcioni, M. & de Gironcoli, S. Linear response approach to the calculation of the effective interaction parameters in the LDA + U method. Phys. Rev. B 71, 035105 (2005).

    Article  Google Scholar 

  30. Tersoff, J. & Hamann, D. R. Theory of the scanning tunneling microscope. Phys. Rev. B 31, 805–813 (1985).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We acknowledge the financial support from National Key Research and Development Projects of China (2016YFA0202300), the National Basic Research Program of China (2013CBA01600), the National Natural Science Foundation of China (Nos 61390501, 51572290, 61306015 and 61471337, 51325204) and the Chinese Academy of Sciences (Nos 1731300500015, XDB07030100, and the CAS Pioneer Hundred Talents Program). A portion of the research was performed in CAS Key Laboratory of Vacuum Physics. Work at Vanderbilt (S.T.P. and Y.Y.Z.) was supported by the US Department of Energy under grant DE-FG02-09ER46554 and by the McMinn Endowment. Computations by Y.Y.Z. were carried out at the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under Contract No. DE-AC02-05CH11231. The electron microscopy work was supported in part by the US Department of Energy, Office of Science, Basic Energy Science, Materials Sciences and Engineering Division, and through a user project at ORNL’s Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

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Contributions

H.-J.G. and S.T.P. conceived and coordinated the research project. X.L. designed the CuSe experiments. J.C.L. and K.Q. prepared CuSe samples and performed the STM experiments. Y.L.W. designed the PtSe2 experiments. Y.S., X.W., S.Y.Z., L.F.L., Y.Q.W., Z.L.L. and H.M.G. prepared PtSe2 samples and performed the STM experiments. T.L., C.L., J.O.W. and K.I. provided support for XPS experiments. D.N.L. and W.Z. performed the STEM experiments. Y.Y.Z., J.B.P., L.G., Y.F.Z., D.L.B. and J.T.S. performed the DFT calculations under the guidance of S.X.D. All authors participated in discussing the data and editing the manuscript.

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Correspondence to Y. L. Wang, S. X. Du or H.-J. Gao.

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The authors declare no competing financial interests.

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Lin, X., Lu, J., Shao, Y. et al. Intrinsically patterned two-dimensional materials for selective adsorption of molecules and nanoclusters. Nature Mater 16, 717–721 (2017). https://doi.org/10.1038/nmat4915

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