Skip to main content
SpringerLink
Log in

Electronic structure of exfoliated millimeter-sized monolayer WSe2 on silicon wafer

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

The monolayer WSe2 is interesting and important for future application in nanoelectronics, spintronics and valleytronics devices, because it has the largest spin splitting and longest valley coherence time among all the known monolayer transition-metal dichalcogenides (TMDs). To obtain the large-area monolayer TMDs crystal is the first step to manufacture scalable and high-performance electronic devices. In this letter, we have successfully fabricated millimeter-sized monolayer WSe2 single crystals with very high quality, based on our improved mechanical exfoliation method. With such superior samples, using standard high resolution angle-resolved photoemission spectroscopy, we did comprehensive electronic band structure measurements on our monolayer WSe2. The overall band features point it to be a 1.2 eV direct band gap semiconductor. Its spin splitting of the valence band at K point is found as 460 meV, which is 30 meV less than the corresponding band splitting in its bulk counterpart. The effective hole masses of valence bands are determined as 2.344 me at Γ, and 0.529 me as well as 0.532 me at K for the upper and lower branch of splitting bands, respectively. And screening effect from substrate is shown to substantially impact on the electronic properties. Our results provide important insights into band structure engineering in monolayer TMDs. Our monolayer WSe2 crystals may constitute a valuable device platform.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Geim, A. K. Graphene: Status and prospects. Science2009, 324, 1530–1534.

    CAS  Google Scholar 

  2. Pacilé, D.; Meyer, J. C.; Girit, Ç. Ö.; Zett, A. The two-dimensional phase of boron nitride: Few-atomic-layer sheets and suspended membranes. Appl. Phys. Lett.2008, 92, 133107.

    Google Scholar 

  3. Liu, H.; Neal, A. T.; Zhu, Z; Luo, Z.; Xu, X. F.; Tománek, D.; Ye, P. D. Phosphorene: An unexplored 2D semiconductor with a high hole mobility. ACS Nano2014, 8, 4033-4011.

    CAS  Google Scholar 

  4. Wang, Q. H.; Kalantar-Zadeh, K.; Kis, A.; Coleman, J. N.; Strano, M. S. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat. Nanotechnol.2012, 7, 699–712.

    CAS  Google Scholar 

  5. Wilson, J. A.; Yoffe, A. D. The transition metal dichalcogenides discussion and interpretation of the observed optical, electrical and structural properties. Adv. Phys.1969, 18, 193–335.

    CAS  Google Scholar 

  6. Huang, B.; Clark, G.; Navarro-Moratalla, E.; Klein, D. R.; Cheng, R.; Seyler, K. L.; Zhong, D.; Schmidgall, E.; McGuire, M. A.; Cobden, D. H. et al. Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit. Nature2017, 546, 270–273.

    CAS  Google Scholar 

  7. Deng, Y. J.; Yu, Y. J.; Song, Y. C.; Zhang, J. Z.; Wang, N. Z.; Sun, Z. Y.; Yi, Y. F.; Wu, Y. Z.; Wu, S. W.; Zhu, J. Y. et al. Gate-tunable room-temperature ferromagnetism in two-dimensional Fe3GeTe2. Nature2018, 563, 94–99.

    CAS  Google Scholar 

  8. Ellis, J. K.; Lucero, M. J.; Scuseria, G. E. The indirect to direct band gap transition in multilayered MoS2 as predicted by screened hybrid density functional theory. Appl. Phys. Lett.2011, 99, 261908.

    Google Scholar 

  9. Mak, K. F.; Lee, C.; Hone, J.; Shan, J.; Heinz, T. F. Atomically thin MoS2: A new direct-gap semiconductor. Phys. Rev. Lett.2010, 105, 136805.

    Google Scholar 

  10. Zhu, Z. Y.; Cheng, Y. C.; Schwingenschlögl, U. Giant spin-orbit-induced spin splitting in two-dimensional transition-metal dichalcogenide semiconductors. Phys. Rev. B2011, 84, 153402.

    Google Scholar 

  11. Cheiwchanchamnangij, T.; Lambrecht, W. R. L. Quasiparticle band structure calculation of monolayer, bilayer, and bulk MoS2. Phys. Rev. B2012, 85, 205302.

    Google Scholar 

  12. Kumar, A.; Ahluwalia, P. K. Electronic structure of transition metal dichalcogenides monolayers 1H-MX2 (M = Mo, W; X = S, Se, Te) from ab-initio theory: New direct band gap semiconductors. Eur. Phys. J. B2012, 85, 186.

    Google Scholar 

  13. Zhang, Y.; Chang, T. R.; Zhou, B.; Cui, Y. T.; Yan, H.; Liu, Z. K.; Schmitt, F.; Lee, J.; Moore, R.; Chen, Y. L. et al. Direct observation of the transition from indirect to direct bandgap in atomically thin epitaxial MoSe2. Nat. Nanotechnol.2014, 9, 111–115.

    CAS  Google Scholar 

  14. Xiao, D.; Liu, G. B.; Feng, W. X.; Xu, X. D.; Yao, W. Coupled spin and valley physics in monolayers of MoS2 and other group-VI dichalcogenides. Phys. Rev. Lett.2012, 108, 196802.

    Google Scholar 

  15. Cao, T.; Wang, G.; Han, W. P.; Ye, H. Q.; Zhu, C. R.; Shi, J. R.; Niu, Q.; Tan, P. H.; Wang, E. G.; Liu, B. L. et al. Valley-selective circular dichroism of monolayer molybdenum disulphide. Nat. Commun.2012, 3, 887.

    Google Scholar 

  16. Zeng, H. L.; Dai, J. F.; Yao, W.; Xiao, D.; Cui, X. D. Valley polarization in MoS2 monolayers by optical pumping. Nat. Nanotechnol.2012, 7, 490–493.

    CAS  Google Scholar 

  17. Riley, J. M.; Mazzola, F.; Dendzik, M.; Michiardi, M.; Takayama, T.; Bawden, L.; Granerød, C.; Leandersson, M.; Balasubramanian, T.; Hoesch, M. et al. Direct observation of spin-polarized bulk bands in an inversionsymmetric semiconductor. Nat. Phys.2014, 10, 835–839.

    CAS  Google Scholar 

  18. Splendiani, A.; Sun, L.; Zhang, Y. B.; Li, T. S.; Kim, T.; Chim, C. Y.; Galli, G.; Wang, F. Emerging photoluminescence in monolayer MoS2. Nano Lett.2010, 10, 1271–1275.

    CAS  Google Scholar 

  19. Ramasubramaniam, A. Large excitonic effects in monolayers of molybdenum and tungsten dichalcogenides. Phys. Rev. B2012, 86, 115409.

    Google Scholar 

  20. Zhu, B. R.; Chen, X.; Cui, X. D. Exciton binding energy of monolayer WS2. Sci. Rep.2015, 5, 9218.

    Google Scholar 

  21. Ugeda, M. M.; Bradley, A. J.; Shi, S. F.; da Jornada, F. H.; Zhang, Y.; Qiu, D. Y.; Ruan, W.; Mo, S. K.; Hussain, Z.; Shen, Z. X. et al. Giant bandgap renormalization and excitonic effects in a monolayer transition metal dichalcogenide semiconductor. Nat. Mater.2014, 13, 1091–1095.

    CAS  Google Scholar 

  22. Radisavljevic, B.; Radenovic, A.; Brivio, J.; Giacometti, V.; Kis, A. Single-layer MoS2 transistors. Nat. Nanotechnol.2011, 6, 147–150.

    CAS  Google Scholar 

  23. Chhowalla, M.; Jena, D.; Zhang, H. Two-dimensional semiconductors for transistors. Nat. Rev. Mater.2016, 1, 16052.

    CAS  Google Scholar 

  24. Lopez-Sanchez, O.; Lembke, D.; Kayci, M.; Radenovic, A.; Kis, A. Ultrasensitive photodetectors based on monolayer MoS2. Nat. Nanotechnol.2013, 8, 497–501.

    CAS  Google Scholar 

  25. Liu, Y.; Weiss, N. O.; Duan, X. D.; Cheng, H. C.; Huang, Y.; Duan, X. F. Van der Waals heterostructures and devices. Nat. Rev. Mater.2016, 1, 16042.

    CAS  Google Scholar 

  26. Xu, X. D.; Yao, W.; Xiao, D.; Heinz, T. F. Spin and pseudospins in layered transition metal dichalcogenides. Nat. Phys.2014, 10, 343–350.

    CAS  Google Scholar 

  27. Zhang, Y.; Ugeda, M. M.; Jin, C. C.; Shi, S. F.; Bradley, A. J.; Martín- Recio, A.; Ryu, H.; Kim, J.; Tang, S. J.; Kim, Y. et al. Electronic structure, surface doping, and optical response in epitaxial WSe2 thin films. Nano Lett.2016, 16, 2485–2491.

    CAS  Google Scholar 

  28. Hao, K.; Moody, G.; Wu, F. C.; Dass, C. K.; Xu, L. X.; Chen, C. H.; Sun, L. Y.; Li, M. Y.; Li, L. J.; MacDonald, A. H. et al. Direct measurement of exciton valley coherence in monolayer WSe2. Nat. Phys.2016, 12, 677–682.

    CAS  Google Scholar 

  29. Le, D.; Barinov, A.; Preciado, E.; Isarraraz, M.; Tanabe, I.; Komesu, T.; Troha, C.; Bartels, L.; Rahman, T. S.; Dowben, P. A. Spin-orbit coupling in the band structure of monolayer WSe2. J. Phys.: Condens. Matter2015, 27, 182201.

    Google Scholar 

  30. Wilson, N. R.; Nguyen, P. V.; Seyler, K.; Rivera, P.; Marsden, A. J.; Laker, Z. P. L.; Constantinescu, G. C.; Kandyba, V.; Barinov, V.; Hine, N. D. M. et al. Determination of band offsets, hybridization, and exciton binding in 2D semiconductor heterostructures. Sci. Adv.2017, 3, e1601832.

    Google Scholar 

  31. Huang, Y.; Sutter, E.; Shi, N. N.; Zheng, J. B.; Yang, T. Z.; Englund, T.; Gao, H. J.; Sutter, P. Reliable exfoliation of large-area high-quality flakes of graphene and other two-dimensional materials. ACS Nano2015, 9, 10612–10620.

    CAS  Google Scholar 

  32. Liu, G. D.; Wang, G. L.; Zhu, Y.; Zhang, H. B.; Zhang, G. C.; Wang, X. Y.; Zhou, Y.; Zhang, W. T; Liu, H. Y.; Zhao, L. et al. Development of a vacuum ultraviolet laser-based angle-resolved photoemission system with a superhigh energy resolution better than 1 meV. Rev. Sci. Instrum.2008, 79, 023105.

    Google Scholar 

  33. Coehoorn, R.; Haas, C.; Dijkstra, J.; Flipse, C. J. F.; de Groot, R. A.; Wold, A. Electronic structure of MoSe2, MoS2, and WSe2. I. Band-structure calculations and photoelectron spectroscopy. Phys. Rev. B1987, 35, 6195–6202.

    CAS  Google Scholar 

  34. Blake, P.; Hill, E. W.; Neto, A. H. C.; Novoselov, K. S.; Jiang, D.; Yang, R.; Booth, T. J.; Geim, A. K. Making graphene visible. Appl. Phys. Lett.2007, 91, 063124.

    Google Scholar 

  35. Huang, Y.; Sutter, E.; Sadowski, J. T.; Cotlet, M.; Monti, O. L. A.; Racke, D. A.; Neupane, M. R.; Wickramaratne, D.; Lake, R. K. et al. Tin disulfide-an emerging layered metal dichalcogenide semiconductor: Materials properties and device characteristics. ACS Nano2014, 8, 10743–10755.

    CAS  Google Scholar 

  36. Fang, H.; Chuang, S.; Chang, T. C.; Takei, K.; Takahashi, T.; Javey, A. High-performance single layered WSe2 p-FETs with chemically doped contacts. Nano Lett.2012, 12, 3788–3792.

    CAS  Google Scholar 

  37. Liu, W.; Kang, J. H.; Sarkar, D.; Khatami, Y.; Jena, D.; Banerjee, K. Role of metal contacts in designing high-performance monolayer n-type WSe2 field effect transistors. Nano Lett.2013, 13, 1983–1990.

    CAS  Google Scholar 

  38. Huang, Y.; Wang, X.; Zhang, X.; Chen, X. J.; Li, B. W.; Wang, B.; Huang, M.; Zhu, C. Y.; Zhang, X. W.; Bacsa, W. S. et al. Raman spectral band oscillations in large graphene bubbles. Phy. Rev. Lett.2018, 120, 186104.

    CAS  Google Scholar 

  39. Zhang, X.; Qiao, X. F.; Shi, W.; Wu, J. B.; Jiang, D. S.; Tan, P. H. Phonon and Raman scattering of two-dimensional transition metal dichalcogenides from monolayer, multilayer to bulk material. Chem. Soc. Rev.2015, 44, 2757–2785.

    CAS  Google Scholar 

  40. Zibouche, N.; Kuc, A.; Musfeldt, J.; Heine, T. Transition-metal dichalcogenides for spintronic applications. Ann. Phys.2014, 526, 395–401.

    CAS  Google Scholar 

  41. Dendzik, M.; Michiardi, M.; Sanders, C.; Bianchi, C.; Miwa, J. A.; Grønborg, S. S.; Lauritsen, J. V.; Bruix, A.; Hammer, B.; Hofmann, P. Growth and electronic structure of epitaxial single-layer WS2 on Au(111). Phy. Rev. B2015, 92, 245442.

    Google Scholar 

  42. Miwa, J. A.; Ulstrup, S.; Sørensen, S. G.; Dendzik, M.; Čabo, A. G.; Bianchi, M.; Lauritsen, J. V.; Hofmann, P. Electronic structure of epitaxial single-layer MoS2. Phy. Rev. Lett.2015, 114, 046802.

    Google Scholar 

  43. Shanavas, S. K.; Satpathy, S. Effective tight-binding model for MX2 under electric and magnetic fields. Phys. Rev. B2015, 91, 235145.

    Google Scholar 

  44. Liu, G. B.; Shan, W. Y.; Yao, Y. G.; Yao, W.; Xiao, D. Three-band tight-binding model for monolayers of group-VIB transition metal dichalcogenides. Phys. Rev. B2013, 88, 085433.

    Google Scholar 

  45. Ci, P. H.; Chen, P. B.; Kang, J.; Suzuki, R.; Choe, H. S.; Suh, J.; Ko, C.; Park, T.; Shen, K.; Iwasa, Y. et al. Quantifying van der Waals interactions in layered transition metal dichalcogenides from pressure-enhanced valence band splitting. Nano Lett.2017, 17, 4982–4988.

    CAS  Google Scholar 

  46. Dou, X. M.; Ding, K.; Jiang, D. S.; Fan, X. F.; Sun, B. Q. Probing spin- orbit coupling and interlayer coupling in atomically thin molybdenum disulfide using hydrostatic pressure. ACS Nano2016, 10, 1619–1624.

    CAS  Google Scholar 

  47. Zhang, Y. W.; Li, H.; Wang, H. M.; Liu, R.; Zhang, R. L.; Qiu, Z. J. On valence-band splitting in layered MoS2. ACS Nano, 2015, 9, 8514–8519.

    CAS  Google Scholar 

  48. Fan, X. F.; Singh, D. J.; Zheng, W. T. Valence band splitting on multilayer MoS2: Mixing of spin−orbit coupling and interlayer coupling. J. Phys. Chem. Lett.2016, 7, 2175–2781.

    CAS  Google Scholar 

  49. Alidoust, N.; Bian, G.; Xu, S. Y.; Sankar, R.; Neupane, M.; Liu, C.; Belopolski, I.; Qu, D. X.; Denlinger, J. D.; Chou, F. C. et al. Observation of monolayer valence band spin-orbit effect and induced quantum well states in MoX2. Nat. Commun.2014, 5, 4673.

    CAS  Google Scholar 

  50. Smith, N. V.; Fisher, G. B. Photoemission studies of the alkali metals. II. Rubidium and cesium. Phys. Rev. B1971, 3, 3662.

    Google Scholar 

  51. Adelung, R.; Brandt, J.; Kipp, L.; Skibowski, M. Reconfiguration of charge density waves by surface nanostructures on TaS2. Phys. Rev. B2000, 63, 165327.

    Google Scholar 

  52. Chiang, T. C. Photoemission studies of quantum well states in thin films. Surf. Sci. Rep.2000, 39, 181–235.

    CAS  Google Scholar 

  53. Absor, M. A. U.; Kotaka, H.; Ishii, F.; Saito, M. Strain-controlled spin splitting in the conduction band of monolayer WS2. Phys. Rev. B2016, 94, 115131.

    Google Scholar 

  54. Kormányos, A.; Burkard, G.; Gmitra, M.; Fabian, J.; Zólyomi, V.; Drummond, N. D.; Fal’ko, V. k·p theory for two-dimensional transition metal dichalcogenide semiconductors. 2D Mater.2015, 2, 022001.

    Google Scholar 

Download references

Acknowledgements

This work is supported by the National Science Foundation of China (Nos. 11574367 and 11874405), the National Key Research and Development Program of China (Nos. 2016YFA0300600, 2018YFA0704200, and 2019YFA0308000), and the Youth Innovation Promotion Association of CAS (Nos. 2017013 and 2019007).

Author information

Authors and Affiliations

  1. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, China

    Wenjuan Zhao, Yuan Huang, Cheng Shen, Cong Li, Yongqing Cai, Yu Xu, Hongtao Rong, Qiang Gao, Yang Wang, Lin Zhao, Lihong Bao, Qingyan Wang, Guangyu Zhang, Hongjun Gao, Xingjiang Zhou & Guodong Liu

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Wenjuan Zhao, Yuan Huang, Cheng Shen, Cong Li, Yongqing Cai, Yu Xu, Hongtao Rong, Qiang Gao, Yang Wang, Hongjun Gao & Xingjiang Zhou

  3. Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Zuyan Xu

  4. Songshan Lake Materials Laboratory, Dongguan, 523808, China

    Xingjiang Zhou & Guodong Liu

  5. Beijing Academy of Quantum Information Sciences, Beijing, 100193, China

    Xingjiang Zhou

Authors
  1. Wenjuan Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yuan Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Cheng Shen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Cong Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yongqing Cai
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yu Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Hongtao Rong
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Qiang Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Yang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Lin Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Lihong Bao
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Qingyan Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Guangyu Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Hongjun Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Zuyan Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Xingjiang Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Guodong Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Yuan Huang, Xingjiang Zhou or Guodong Liu.

Additional information

Notes

The authors declare no competing financial interest.

Electronic Supplementary Material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhao, W., Huang, Y., Shen, C. et al. Electronic structure of exfoliated millimeter-sized monolayer WSe2 on silicon wafer. Nano Res. 12, 3095–3100 (2019). https://doi.org/10.1007/s12274-019-2557-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-019-2557-7

Keywords

Search

Navigation