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Chiral atomically thin films

Nature Nanotechnology volume 11, pages 520–524 (2016)Cite this article

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Abstract

Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics1,2, stereochemistry3,4 and spintronics5,6. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films1,2,7,8, or arrays of fabricated building blocks9,10,11, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg μm–1) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.

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Figure 1: Chiral atomically thin films produced by chiral stacking.
Figure 2: Programming CD spectra in twisted bilayer graphene with θ dependent interlayer optical transitions.
Figure 3: In-plane magnetic moment as the origin of the CD in twisted bilayer graphene.
Figure 4: Programming CD spectra in multilayer graphene films.

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References

  1. Tang, Y. & Cohen, A. E. Optical chirality and its interaction with matter. Phys. Rev. Lett. 104, 163901 (2010).

    Article  Google Scholar 

  2. Barron, L. D. Molecular Light Scattering and Optical Activity (Cambridge Univ. Press, 2009).

    Google Scholar 

  3. Smith, M. B. & March, J. March's Advanced Organic Chemistry: Reactions, Mechanisms and Structure (Wiley, 2007).

    Google Scholar 

  4. Inoue, Y. & Ramamurthy, V. Chiral Photochemistry (Marcel Dekker, 2004).

    Book  Google Scholar 

  5. Göhler, B. et al. Spin selectivity in electron transmission through self-assembled monolayers of double-stranded DNA. Science 331, 894–897 (2011).

    Article  Google Scholar 

  6. Koehl, W. F. et al. Current-induced spin polarization in gallium nitride. Appl. Phys. Lett. 95, 072110 (2009).

    Article  Google Scholar 

  7. Matsuo, K. & Gekko, K. Vacuum-ultraviolet circular dichroism study of saccharides by synchrotron radiation spectrophotometry. Carbohydr. Res. 339, 591–597 (2004).

    Article  CAS  Google Scholar 

  8. Verbiest, T. et al. Strong enhancement of nonlinear optical properties through supramolecular chirality. Science 282, 913–915 (1998).

    Article  CAS  Google Scholar 

  9. Kuwata-Gonokami, M. et al. Giant optical activity in quasi-two-dimensional planar nanostructures. Phys. Rev. Lett. 95, 227401 (2005).

    Article  Google Scholar 

  10. Gibbs, J. G., Mark, A. G., Eslami, S. & Fischer, P. Plasmonic nanohelix metamaterials with tailorable giant circular dichroism. Appl. Phys. Lett. 103, 213101 (2013).

    Article  Google Scholar 

  11. Shopsowitz, K. E., Qi, H., Hamad, W. Y. & Maclachlan, M. J. Free-standing mesoporous silica films with tunable chiral nematic structures. Nature 468, 422–425 (2010).

    Article  CAS  Google Scholar 

  12. Brown, L. et al. Polycrystalline graphene with single crystalline electronic structure. Nano Lett. 14, 5706–5711 (2014).

    Article  CAS  Google Scholar 

  13. Havener, R. W. et al. Hyperspectral imaging of structure and composition in atomically thin heterostructures. Nano Lett. 13, 3942–3946 (2013).

    Article  CAS  Google Scholar 

  14. Havener, R. W., Liang, Y., Brown, L., Yang, L. & Park, J. Van Hove singularities and excitonic effects in the optical conductivity of twisted bilayer graphene. Nano Lett. 14, 3353–3357 (2014).

    Article  CAS  Google Scholar 

  15. Lopes dos Santos, J. M. B., Peres, N. M. R. & Castro Neto, A. H. Graphene bilayer with a twist: electronic structure. Phys. Rev. Lett. 99, 256802 (2007).

    Article  CAS  Google Scholar 

  16. Li, G. et al. Observation of Van Hove singularities in twisted graphene layers. Nature Phys. 6, 109–113 (2010).

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  18. Stein, G., Stein, J. & Kleinsmith, L. J. (eds) Methods in Cell Biology Vol. 18 (Academic, 1978).

    Google Scholar 

  19. Moon, P. & Koshino, M. Optical absorption in twisted bilayer graphene. Phys. Rev. B 87, 205404 (2013).

    Article  Google Scholar 

  20. Lehtinen, P. O. et al. Magnetic properties and diffusion of adatoms on a graphene sheet. Phys. Rev. Lett. 91, 017202 (2003).

    Article  CAS  Google Scholar 

  21. Levy, N. et al. Strain-induced pseudo-magnetic fields greater than 300 Tesla in graphene nanobubbles. Science 329, 544–547 (2010).

    Article  CAS  Google Scholar 

  22. Yang, N. & Cohen, A. E. Local geometry of electromagnetic fields and its role in molecular multipole transitions. J. Phys. Chem. B 115, 5304–5311 (2011).

    Article  CAS  Google Scholar 

  23. Sánchez-Castillo, A. & Noguez, C. Understanding optical activity in single-walled carbon nanotubes from first-principles studies. J. Phys. Chem. C 114, 9640–9644 (2010).

    Article  Google Scholar 

  24. Hidalgo, F., Sánchez-Castillo, A. & Noguez, C. Efficient first-principles method for calculating the circular dichroism of nanostructures. Phys. Rev. B 79, 075438 (2009).

    Article  Google Scholar 

  25. Noguez, C. & Hidalgo, F. Ab initio electronic circular dichroism of fullerenes, single-walled carbon nanotubes, and ligand-protected metal nanoparticles. Chirality 26, 553–562 (2014).

    Article  CAS  Google Scholar 

  26. Soler, J. M. et al. The SIESTA method for ab initio order-N materials simulation. J. Phys. Condens. Matter 14, 2745–2779 (2002).

    Article  CAS  Google Scholar 

  27. Troullier, N. & Martins, J. L. Efficient pseudopotentials for plane-wave calculations. Phys. Rev. B 43, 1993–2006 (1991).

    Article  CAS  Google Scholar 

  28. 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 

  29. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  CAS  Google Scholar 

  30. Xu, X., Yao, W., Xiao, D. & Heinz, T. F. Spin and pseudospins in layered transition metal dichalcogenides. Nature Phys. 10, 343–350 (2014).

    Article  CAS  Google Scholar 

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Acknowledgements

We thank P.L. McEuen, F. Wang, K.F. Mak and M.W. Graham for useful discussions and M.P. Levendorf for experimental help. This work was supported by the National Science Foundation (NSF) through the Cornell Center for Materials Research (NSF DMR-1120296), the AFOSR (FA2386-13-1-4118), and the Nano Material Technology Development Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT, and Future Planning (2012M3A7B4049887). Y. Ogawa was partially supported by Grant-in-Aid for JAPS Fellows. A. Sánchez-Castillo and C. Noguez were supported by DGAPA-UNAM (PAPIIT IN107615) and CONACyT (179454). Sample fabrication was performed at the Cornell Nanoscale Science & Technology Facility, a member of the National Nanotechnology Infrastructure Network, which is supported by the National Science Foundation (ECS-0335765).

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, 14853, New York, USA

    Cheol-Joo Kim, Zack Ziegler, Yui Ogawa & Jiwoong Park

  2. Escuela Superior de Apan, Universidad Autónoma del Estado de Hidalgo, Chimalpa Tlalayote, Municipio de Apan, Hidalgo, 43920, México

    A. Sánchez-Castillo

  3. Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga, Fukuoka, 816-8580, Japan

    Yui Ogawa

  4. Instituto de Física, Universidad Nacional Autónoma de México, Apartado Postal 20-364, México, D.F. 01000, México

    Cecilia Noguez

  5. Kavli Institute at Cornell for Nanoscale Science, Cornell University, Ithaca, 14853, New York, USA

    Jiwoong Park

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  1. Cheol-Joo Kim
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  2. A. Sánchez-Castillo
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  4. Yui Ogawa
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Contributions

C.-J.K. and J.P. designed the experiments. C.-J.K. and Y.O. grew graphene samples. C.-J.K. and Z.Z. conducted the sample fabrication and optical characterization. A.S.-C. and C.N. performed the first-principles calculation of CD effects. C.-J.K. and J.P. carried out data analysis and wrote the manuscript with input from all authors.

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Correspondence to Jiwoong Park.

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Kim, CJ., Sánchez-Castillo, A., Ziegler, Z. et al. Chiral atomically thin films. Nature Nanotech 11, 520–524 (2016). https://doi.org/10.1038/nnano.2016.3

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