Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Charge density wave order in 1D mirror twin boundaries of single-layer MoSe2

Nature Physics volume 12, pages 751–756 (2016)Cite this article

Subjects

Abstract

We provide direct evidence for the existence of isolated, one-dimensional charge density waves at mirror twin boundaries (MTBs) of single-layer semiconducting MoSe2. Such MTBs have been previously observed by transmission electron microscopy and have been predicted to be metallic in MoSe2 and MoS21,2,3,4,5,6,7. Our low-temperature scanning tunnelling microscopy/spectroscopy measurements revealed a substantial bandgap of 100 meV opening at the Fermi energy in the otherwise metallic one-dimensional structures. We found a periodic modulation in the density of states along the MTB, with a wavelength of approximately three lattice constants. In addition to mapping the energy-dependent density of states, we determined the atomic structure and bonding of the MTB through simultaneous high-resolution non-contact atomic force microscopy. Density functional theory calculations based on the observed structure reproduced both the gap opening and the spatially resolved density of states.

Access through your institution
Buy or subscribe

This is a preview of subscription content, access via your institution

Access options

Access through your institution

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Morphology and electronic structure of mirror twin boundaries in monolayer MoSe2.
Figure 2: Local density of states of mirror twin boundaries with an energy gap around the Fermi level.
Figure 3: Atomic resolution nc-AFM image of a mirror twin boundary reveals the precise atomic structure.
Figure 4: Effect of a Peierls distortion on the electronic band structure of mirror twin boundaries in monolayer MoSe2 from DFT calculations.

Similar content being viewed by others

References

  1. van der Zande, A. M. et al. Grains and grain boundaries in highly crystalline monolayer molybdenum disulphide. Nature Mater. 12, 554–561 (2013).

    ADS  Google Scholar 

  2. Lehtinen, O. et al. Atomic scale microstructure and properties of Se-deficient two-dimensional MoSe2 . ACS Nano 9, 3274–3283 (2015).

    Google Scholar 

  3. Zou, X., Liu, Y. & Yakobson, B. I. Predicting dislocations and grain boundaries in two-dimensional metal-disulfides from the first principles. Nano Lett. 13, 253–258 (2013).

    ADS  Google Scholar 

  4. Zhou, W. et al. Intrinsic structural defects in monolayer molybdenum disulfide. Nano Lett. 13, 2615–2622 (2013).

    ADS  Google Scholar 

  5. Liu, H. et al. Dense network of one-dimensional midgap metallic modes in monolayer MoSe2 and their spatial undulations. Phys. Rev. Lett. 113, 066105 (2014).

    ADS  Google Scholar 

  6. Gibertini, M. & Marzari, N. Emergence of one-dimensional wires of free carriers in transition-metal-dichalcogenide nanostructures. Nano Lett. 15, 6229–6238 (2015).

    ADS  Google Scholar 

  7. Le, D. & Rahman, T. S. Joined edges in MoS2: metallic and half-metallic wires. J. Phys. Condens. Matter 25, 312201 (2013).

    ADS  Google Scholar 

  8. Lahiri, J. et al. An extended defect in graphene as a metallic wire. Nature Nanotech. 5, 326–329 (2010).

    ADS  Google Scholar 

  9. Yazyev, O. V. & Louie, S. G. Electronic transport in polycrystalline graphene. Nature Mater. 9, 806–809 (2010).

    ADS  Google Scholar 

  10. Ugeda, M. M., Brihuega, I., Guinea, F. & Gómez-Rodríguez, J. M. Missing atom as a source of carbon magnetism. Phys. Rev. Lett. 104, 096804 (2010).

    ADS  Google Scholar 

  11. Tsen, A. W. et al. Tailoring electrical transport across grain boundaries in polycrystalline graphene. Science 336, 1143–1146 (2012).

    ADS  Google Scholar 

  12. López-Polín, G. et al. Increasing the elastic modulus of graphene by controlled defect creation. Nature Phys. 11, 26–31 (2015).

    ADS  Google Scholar 

  13. Mak, K. F., Lee, C., Hone, J., Shan, J. & Heinz, T. F. Atomically thin MoS2: a new direct-gap semiconductor. Phys. Rev. Lett. 105, 136805 (2010).

    ADS  Google Scholar 

  14. Splendiani, A. et al. Emerging photoluminescence in monolayer MoS2 . Nano Lett. 10, 1271–1275 (2010).

    ADS  Google Scholar 

  15. Zhang, Y. et al. Direct observation of the transition from indirect to direct bandgap in atomically thin epitaxial MoSe2 . Nature Nanotech. 9, 111–115 (2014).

    ADS  Google Scholar 

  16. Baugher, B. W. H., Churchill, H. O. H., Yang, Y. & Jarillo-Herrero, P. Intrinsic electronic transport properties of high-quality monolayer and bilayer MoS2 . Nano Lett. 13, 4212–4216 (2013).

    ADS  Google Scholar 

  17. Kang, K. et al. High-mobility three-atom-thick semiconducting films with wafer-scale homogeneity. Nature 520, 656–660 (2015).

    ADS  Google Scholar 

  18. Qiu, D. Y., da Jornada, F. H. & Louie, S. G. Optical spectrum of MoS2: many-body effects and diversity of exciton states. Phys. Rev. Lett. 111, 216805 (2013).

    ADS  Google Scholar 

  19. Bernardi, M., Palummo, M. & Grossman, J. C. Extraordinary sunlight absorption and one nanometer thick photovoltaics using two-dimensional monolayer materials. Nano Lett. 13, 3664–3670 (2013).

    ADS  Google Scholar 

  20. Britnell, L. et al. Strong light–matter interactions in heterostructures of atomically thin films. Science 340, 1311–1314 (2013).

    ADS  Google Scholar 

  21. Ugeda, M. M. et al. Giant bandgap renormalization and excitonic effects in a monolayer transition metal dichalcogenide semiconductor. Nature Mater. 13, 1091–1095 (2014).

    ADS  Google Scholar 

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

    Google Scholar 

  23. Lee, C.-H. et al. Atomically thin p–n junctions with van der Waals heterointerfaces. Nature Nanotech. 9, 676–681 (2014).

    ADS  Google Scholar 

  24. Qiu, H. et al. Hopping transport through defect-induced localized states in molybdenum disulphide. Nature Commun. 4, 2642 (2013).

    ADS  Google Scholar 

  25. Cai, L. et al. Vacancy-induced ferromagnetism of MoS2 nanosheets. J. Am. Chem. Soc. 137, 2622–2627 (2015).

    Google Scholar 

  26. Bao, W. et al. Visualizing nanoscale excitonic relaxation properties of disordered edges and grain boundaries in monolayer molybdenum disulfide. Nature Commun. 6, 7993 (2015).

    ADS  Google Scholar 

  27. Zhang, Z., Zou, X., Crespi, V. H. & Yakobson, B. I. Intrinsic magnetism of grain boundaries in two-dimensional metal dichalcogenides. ACS Nano 7, 10475–10481 (2013).

    Google Scholar 

  28. Lauritsen, J. V. et al. Hydrodesulfurization reaction pathways on MoS2 nanoclusters revealed by scanning tunneling microscopy. J. Catal. 224, 94–106 (2004).

    Google Scholar 

  29. Jaramillo, T. F. et al. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317, 100–102 (2007).

    ADS  Google Scholar 

  30. Grüner, G. Density Waves in Solids (Perseus, 2000).

    Google Scholar 

  31. Peierls, R. E. Quantum Theory of Solids (Oxford Univ. Press, 1955).

    MATH  Google Scholar 

  32. Peng, J.-P. et al. Molecular beam epitaxy growth and scanning tunneling microscopy study of TiSe2 ultrathin films. Phys. Rev. B 91, 121113 (2015).

    ADS  Google Scholar 

  33. Ugeda, M. M. et al. Characterization of collective ground states in single-layer NbSe2 . Nature Phys. 12, 92–97 (2016).

    ADS  Google Scholar 

  34. Heeger, A. J., Kivelson, S., Schrieffer, J. R. & Su, W.-P. Solitons in conducting polymers. Rev. Mod. Phys. 60, 781–850 (1988).

    ADS  Google Scholar 

  35. Yeom, H. W. et al. Instability and charge density wave of metallic quantum chains on a silicon surface. Phys. Rev. Lett. 82, 4898–4901 (1999).

    ADS  Google Scholar 

  36. Jérome, D. Organic conductors: from charge density wave TTF-TCNQ to superconducting (TMTSF)2PF6 . Chem. Rev. 104, 5565–5591 (2004).

    Google Scholar 

  37. Shin, J. S., Ryang, K.-D. & Yeom, H. W. Finite-length charge-density waves on terminated atomic wires. Phys. Rev. B 85, 073401 (2012).

    ADS  Google Scholar 

  38. Cheon, S., Kim, T.-H., Lee, S.-H. & Yeom, H. W. Chiral solitons in a coupled double Peierls chain. Science 350, 182–185 (2015).

    ADS  Google Scholar 

  39. Murata, H. & Koma, A. Modulated STM images of ultrathin MoSe2 films grown on MoS2(0001) studied by STM/STS. Phys. Rev. B 59, 10327–10334 (1999).

    ADS  Google Scholar 

  40. Gross, L., Mohn, F., Moll, N., Liljeroth, P. & Meyer, G. The chemical structure of a molecule resolved by atomic force microscopy. Science 325, 1110–1114 (2009).

    ADS  Google Scholar 

  41. Hapala, P. et al. Mechanism of high-resolution STM/AFM imaging with functionalized tips. Phys. Rev. B 90, 085421 (2014).

    ADS  Google Scholar 

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

    ADS  Google Scholar 

  43. Grüner, G. The dynamics of charge-density waves. Rev. Mod. Phys. 60, 1129–1181 (1988).

    ADS  Google Scholar 

  44. Horcas, I. et al. WSXM: a software for scanning probe microscopy and a tool for nanotechnology. Rev. Sci. Instrum. 78, 013705 (2007).

    ADS  Google Scholar 

  45. 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).

    ADS  Google Scholar 

Download references

Acknowledgements

We acknowledge P. Hapala for assistance with the nc-AFM image simulations. We thank our colleagues at the Molecular Foundry for stimulating discussion and assistance. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231 (user proposal #3282) (STM imaging, STM spectroscopy, theoretical simulations, and analysis). A.W.-B. and S.W. were supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Scientific User Facilities Division (NSRCs) Early Career Award. S.B. acknowledges fellowship support by the European Union under FP7-PEOPLE-2012-IOF-327581. ALS and SIMES were supported by Office of Basic Energy Science, US DOE, under contract numbers DE-AC02-05CH11231 and DE-AC02-76SF00515, respectively. H.R. acknowledges support from the Max Planck Korea/POSTECH Research Initiative of the NRF under Project No. NRF-2011-0031558. M.B.S. was supported by the Division of Materials Science and Engineering through the Chemical and Mechanical Properties of Surfaces and Interfaces Program. Portions of the computational work were done with NERSC resources. M.F.C. acknowledges support from National Science Foundation grant EFMA-1542741 (sample surface preparation development).

Author information

Author notes

  1. Sara Barja and Sebastian Wickenburg: These authors contributed equally to this work.

Authors and Affiliations

  1. Molecular Foundry, Lawrence Berkeley National Laboratory, California 94720, USA

    Sara Barja, Sebastian Wickenburg, Zhen-Fei Liu, Ed Wong, D. Frank Ogletree, Jeffrey B. Neaton & Alexander Weber-Bargioni

  2. Materials Sciences Division, Lawrence Berkeley National Laboratory, California 94720, USA

    Sara Barja, Sebastian Wickenburg, Zhen-Fei Liu, Ed Wong, Miquel B. Salmeron, Feng Wang, Michael F. Crommie, D. Frank Ogletree, Jeffrey B. Neaton & Alexander Weber-Bargioni

  3. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    Yi Zhang, Hyejin Ryu, Zahid Hussain & Sung-Kwan Mo

  4. National Laboratory of Solid State Microstructures, School of Physics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China

    Yi Zhang

  5. Department of Physics, University of California at Berkeley, Berkeley, California 94720, USA

    Miguel M. Ugeda, Miquel B. Salmeron, Feng Wang, Michael F. Crommie & Jeffrey B. Neaton

  6. CIC nanoGUNE, Donostia-San Sebastián 20018, Spain

    Miguel M. Ugeda

  7. Ikerbasque, Basque Foundation for Science, Bilbao 48013, Spain

    Miguel M. Ugeda

  8. Stanford Institute of Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA

    Zhi-Xun Shen

  9. Department of Materials Science and Engineering, University of California Berkeley, California 94720, USA

    Miquel B. Salmeron

  10. Kavli Energy NanoSciences Institute at the University of California Berkeley and the Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    Feng Wang, Michael F. Crommie & Jeffrey B. Neaton

Authors
  1. Sara Barja
    View author publications

    Search author on:PubMed Google Scholar

  2. Sebastian Wickenburg
    View author publications

    Search author on:PubMed Google Scholar

  3. Zhen-Fei Liu
    View author publications

    Search author on:PubMed Google Scholar

  4. Yi Zhang
    View author publications

    Search author on:PubMed Google Scholar

  5. Hyejin Ryu
    View author publications

    Search author on:PubMed Google Scholar

  6. Miguel M. Ugeda
    View author publications

    Search author on:PubMed Google Scholar

  7. Zahid Hussain
    View author publications

    Search author on:PubMed Google Scholar

  8. Zhi-Xun Shen
    View author publications

    Search author on:PubMed Google Scholar

  9. Sung-Kwan Mo
    View author publications

    Search author on:PubMed Google Scholar

  10. Ed Wong
    View author publications

    Search author on:PubMed Google Scholar

  11. Miquel B. Salmeron
    View author publications

    Search author on:PubMed Google Scholar

  12. Feng Wang
    View author publications

    Search author on:PubMed Google Scholar

  13. Michael F. Crommie
    View author publications

    Search author on:PubMed Google Scholar

  14. D. Frank Ogletree
    View author publications

    Search author on:PubMed Google Scholar

  15. Jeffrey B. Neaton
    View author publications

    Search author on:PubMed Google Scholar

  16. Alexander Weber-Bargioni
    View author publications

    Search author on:PubMed Google Scholar

Contributions

S.B., S.W. and A.W.-B. conceived the work and designed the research strategy. S.B. and S.W. measured and analysed the STM/STS and nc-AFM data. Z.-F.L. performed the theoretical calculations. Y.Z. and H.R. performed the MBE growth and characterization of the samples. S.-K.M., Z.H. and Z.-X.S. supervised the MBE growth and sample characterization. J.B.N. supervised the theoretical calculations. M.M.U., E.W., M.B.S., F.W., M.F.C. and D.F.O. participated in the acquisition and interpretation of the experimental data. A.W.-B. supervised the STM/STS and nc-AFM measurements. S.B. wrote the manuscript with help from S.W., Z.-F.L., D.F.O., J.B.N. and A.W.-B. All authors contributed to the scientific discussion and manuscript revisions.

Corresponding authors

Correspondence to Sara Barja, D. Frank Ogletree or Alexander Weber-Bargioni.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 2474 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Barja, S., Wickenburg, S., Liu, ZF. et al. Charge density wave order in 1D mirror twin boundaries of single-layer MoSe2. Nature Phys 12, 751–756 (2016). https://doi.org/10.1038/nphys3730

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue date:

  • DOI: https://doi.org/10.1038/nphys3730

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing