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Visualizing grain boundaries in monolayer MoSe2 using mild H2O vapor etching

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Abstract

Beyond graphene, two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted significant attention owing to their potential in next-generation nanoelectronics and optoelectronics. Nevertheless, grain boundaries are ubiquitous in large-area as-grown TMD materials and would significantly affect their band structure, electrical transport, and optical properties. Therefore, the characterization of grain boundaries is essential for engineering the properties and optimizing the growth in TMD materials. Although the existence of boundaries can be measured using scanning tunneling microscopy, transmission electron microscopy, or nonlinear optical microscopy, a universal, convenient, and accurate method to detect boundaries with a twist angle over a large scale is still lacking. Herein, we report a high-throughput method using mild hot H2O etching to visualize grain boundaries of TMDs under an optical microscope, while ensuring that the method is nearly noninvasive to grain domains. This technique utilizes the reactivity difference between stable grain domains and defective grain boundaries and the mild etching capacity of hot water vapor. As grain boundaries of two domains with twist angles have defective lines, this method enables to visualize all types of grain boundaries unambiguously. Moreover, the characterization is based on an optical microscope and therefore naturally of a large scale. We further demonstrate the successful application of this method to other TMD materials such as MoS2 and WSe2. Our technique facilitates the large-area characterization of grain boundaries and will accelerate the controllable growth of large single-crystal TMDs.

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References

  1. 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.

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  4. Mak, K. F.; He, K. L.; Shan, J.; Heinz, T. F. Control of valley polarization in monolayer MoS2 by optical helicity. Nat. Nanotechnol. 2012, 7, 494–498.

    Article  Google Scholar 

  5. 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.

    Article  Google Scholar 

  6. Jones, A. M.; Yu, H. Y.; Ghimire, N. J.; Wu, S. F.; Aivazian, G.; Ross, J. S.; Zhao, B.; Yan, J. Q.; Mandrus, D. G.; Xiao, D. et al. Optical generation of excitonic valley coherence in monolayer WSe2. Nat. Nanotechnol. 2013, 8, 634–638.

    Article  Google Scholar 

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

    Article  Google Scholar 

  8. Kang, K.; Xie, S. E.; Huang, L. J.; Han, Y. M.; Huang, P. Y.; Mak, K. F.; Kim, C. J.; Muller, D.; Park, J. High-mobility three-atom-thick semiconducting films with wafer-scale homogeneity. Nature 2015, 520, 656–660.

    Article  Google Scholar 

  9. 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.

    Article  Google Scholar 

  10. Mak, K. F.; McGill, K. L.; Park, J.; McEuen, P. L. The valley hall effect in MoS2 transistors. Science 2014, 344, 1489–1492.

    Article  Google Scholar 

  11. Kim, J.; Hong, X. P.; Jin, C. H.; Shi, S. F.; Chang, C. Y. S.; Chiu, M. H.; Li, L. J.; Wang, F. Ultrafast generation of pseudo-magnetic field for valley excitons in WSe2 monolayers. Science 2014, 346, 1205–1208.

    Article  Google Scholar 

  12. 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. 2013, 111, 216805.

    Article  Google Scholar 

  13. Ye, Z. L.; Cao, T.; O’Brien, K.; Zhu, H. Y.; Yin, X. B.; Wang, Y.; Louie, S. G.; Zhang, X. Probing excitonic dark states in single-layer tungsten disulphide. Nature 2014, 513, 214–218.

    Article  Google Scholar 

  14. Wang, G.; Marie, X.; Gerber, I.; Amand, T.; Lagarde, D.; Bouet, L.; Vidal, M.; Balocchi, A.; Urbaszek, B. Giant enhancement of the optical second-harmonic emission of WSe2 monolayers by laser excitation at exciton resonances. Phys. Rev. Lett. 2015, 114, 097403.

    Article  Google Scholar 

  15. Koppens, F. H. L.; Mueller, T.; Avouris, P.; Ferrari, A. C.; Vitiello, M. S.; Polini, M. Photodetectors based on graphene, other two-dimensional materials and hybrid systems. Nat. Nanotechnol. 2014, 9, 780–793.

    Article  Google Scholar 

  16. Zhang, H. Ultrathin two-dimensional nanomaterials. ACS Nano 2015, 9, 9451–9469.

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  19. Yin, Z. Y.; Li, H.; Li, H.; Jiang, L.; Shi, Y. M.; Sun, Y. H.; Lu, G.; Zhang, Q.; Chen, X. D.; Zhang, H. Single-layer MoS2 phototransistors. ACS Nano 2012, 6, 74–80.

    Article  Google Scholar 

  20. Xia, F. N.; Wang, H.; Xiao, D.; Dubey, M.; Ramasubramaniam, A. Two-dimensional material nanophotonics. Nat. Photonics 2014, 8, 899–907.

    Article  Google Scholar 

  21. Mak, K. F.; Shan, J. Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides. Nat. Photonics 2016, 10, 216–226.

    Article  Google Scholar 

  22. Zhang, W. J.; Wang, Q. X.; Chen, Y.; Wang, Z.; Wee, A. T. S. Van der waals stacked 2D layered materials for optoelectronics. 2D Mater 2016, 3, 022001.

    Article  Google Scholar 

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

    Article  Google Scholar 

  24. Schaibley, J. R.; Yu, H. Y.; Clark, G.; Rivera, P.; Ross, J. S.; Seyler, K. L.; Yao, W.; Xu, X. D. Valleytronics in 2D materials. Nat. Rev. Mater. 2016, 1, 16055.

    Article  Google Scholar 

  25. Jaramillo, T. F.; Jørgensen, K. P.; Bonde, J.; Nielsen, J. H.; Horch, S.; Chorkendorff, I. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 2007, 317, 100–102.

    Article  Google Scholar 

  26. Chhowalla, M.; Shin, H. S.; Eda, G.; Li, L. J.; Loh, K. P.; Zhang, H. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 2013, 5, 263–275.

    Article  Google Scholar 

  27. Lu, Q. P.; Yu, Y. F.; Ma, Q. L.; Chen, B.; Zhang, H. 2D transition-metal-dichalcogenide-nanosheet-based composites for photocatalytic and electrocatalytic hydrogen evolution reactions. Adv. Mater. 2016, 28, 1917–1933.

    Article  Google Scholar 

  28. Zhang, X.; Lai, Z. C.; Tan, C. L.; Zhang, H. Solution-processed two-dimensional MoS2 nanosheets: Preparation, hybridization, and applications. Angew. Chem., Int. Ed. 2016, 55, 8816–8838.

    Article  Google Scholar 

  29. Tan, C. L.; Cao, X. H.; Wu, X. J.; He, Q. Y.; Yang, J.; Zhang, X.; Chen, J. Z.; Zhao, W.; Han, S. K.; Nam, G. H. et al. Recent advances in ultrathin two-dimensional nanomaterials. Chem. Rev. 2017, 117, 6225–6331.

    Article  Google Scholar 

  30. Britnell, L.; Ribeiro, R. M.; Eckmann, A.; Jalil, R.; Belle, B. D.; Mishchenko, A.; Kim, Y. J.; Gorbachev, R. V.; Georgiou, T.; Morozov, S. V. et al. Strong light-matter interactions in heterostructures of atomically thin films. Science 2013, 340, 1311–1314.

    Article  Google Scholar 

  31. Geim, A. K.; Grigorieva, I. V. Van der waals heterostructures. Nature 2013, 499, 419–425.

    Article  Google Scholar 

  32. Novoselov, K. S.; Mishchenko, A.; Carvalho, A.; Neto, A. H. C. 2D materials and van der waals heterostructures. Science 2016, 353, aac9439.

    Article  Google Scholar 

  33. Huang, Y. L.; Chen, Y. F.; Zhang, W. J.; Quek, S. Y.; Chen, C. H.; Li, L. J.; Hsu, W. T.; Chang, W. H.; Zheng, Y. J.; Chen, W. et al. Bandgap tunability at single-layer molybdenum disulphide grain boundaries. Nat. Commun. 2015, 6, 6298.

    Article  Google Scholar 

  34. Xu, H.; Liu, S. L.; Ding, Z. J.; Tan, S. J. R.; Yam, K. M.; Bao, Y.; Nai, C. T.; Ng, M. F.; Lu, J.; Zhang, C. et al. Oscillating edge states in one-dimensional MoS2 nanowires. Nat. Commun. 2016, 7, 12904.

    Article  Google Scholar 

  35. Yin, X. B.; Ye, Z. L.; Chenet, D. A.; Ye, Y.; O’Brien, K.; Hone, J. C.; Zhang, X. Edge nonlinear optics on a MoS2 atomic monolayer. Science 2014, 344, 488–490.

    Article  Google Scholar 

  36. Cheng, J. X.; Jiang, T.; Ji, Q. Q.; Zhang, Y.; Li, Z. M.; Shan, Y. W.; Zhang, Y. F.; Gong, X. G.; Liu, W. T.; Wu, S. W. Kinetic nature of grain boundary formation in as-grown MoS2 monolayers. Adv. Mater. 2015, 27, 4069–4074.

    Article  Google Scholar 

  37. Yu, Z. H.; Pan, Y. M.; Shen, Y. T.; Wang, Z. L.; Ong, Z. Y.; Xu, T.; Xin, R.; Pan, L. J.; Wang, B. G.; Sun, L. T. et al. Towards intrinsic charge transport in monolayer molybdenum disulfide by defect and interface engineering. Nat. Commun. 2014, 5, 5290.

    Article  Google Scholar 

  38. Zhang, Y.; Zhang, Y. F.; Ji, Q. Q.; Ju, J.; Yuan, H. T.; Shi, J. P.; Gao, T.; Ma, D. L.; Liu, M. X.; Chen, Y. B. et al. Controlled growth of high-quality monolayer WS2 layers on sapphire and imaging its grain boundary. ACS Nano 2013, 7, 8963–8971.

    Article  Google Scholar 

  39. Najmaei, S.; Liu, Z.; Zhou, W.; Zou, X. L.; Shi, G.; Lei, S. D.; Yakobson, B. I.; Idrobo, J. C.; Ajayan, P. M.; Lou, J. Vapour phase growth and grain boundary structure of molybdenum disulphide atomic layers. Nat. Mater. 2013, 12, 754–759.

    Article  Google Scholar 

  40. van der Zande, A. M.; Huang, P. Y.; Chenet, D. A.; Berkelbach, T. C.; You, Y. M.; Lee, G. H.; Heinz, T. F.; Reichman, D. R.; Muller, D. A.; Hone, J. C. Grains and grain boundaries in highly crystalline monolayer molybdenum disulphide. Nat. Mater. 2013, 12, 554–561.

    Article  Google Scholar 

  41. Ly, T. H.; Chiu, M. H.; Li, M. Y.; Zhao, J.; Perello, D. J.; Cichocka, M. O.; Oh, H. M.; Chae, S. H.; Jeong, H. Y.; Yao, F. et al. Observing grain boundaries in CVD-grown monolayer transition metal dichalcogenides. ACS Nano 2014, 8, 11401–11408.

    Article  Google Scholar 

  42. Rong, Y. M.; He, K.; Pacios, M.; Robertson, A. W.; Bhaskaran, H.; Warner, J. H. Controlled preferential oxidation of grain boundaries in monolayer tungsten disulfide for direct optical imaging. ACS Nano 2015, 9, 3695–3703.

    Article  Google Scholar 

  43. Azizi, A.; Zou, X. L.; Ercius, P.; Zhang, Z. H.; Elias, A. L.; Perea-López, N.; Stone, G.; Terrones, M.; Yakobson, B. I.; Alem, N. Dislocation motion and grain boundary migration in two-dimensional tungsten disulphide. Nat. Commun. 2014, 5, 4867.

    Article  Google Scholar 

  44. Park, S.; Kim, M. S.; Kim, H.; Lee, J.; Han, G. H.; Jung, J.; Kim, J. Spectroscopic visualization of grain boundaries of monolayer molybdenum disulfide by stacking bilayers. ACS Nano 2015, 9, 11042–11048.

    Article  Google Scholar 

  45. Karvonen, L.; Säynätjoki, A.; Huttunen, M. J.; Autere, A.; Amirsolaimani, B.; Li, S. S.; Norwood, R. A.; Peyghambarian, N.; Lipsanen, H.; Eda, G. et al. Rapid visualization of grain boundaries in monolayer MoS2 by multiphoton microscopy. Nat. Commun. 2017, 8, 15714.

    Article  Google Scholar 

  46. Shehzad, M. A.; Hussain, S.; Lee, J.; Jung, J.; Lee, N.; Kim, G.; Seo, Y. Study of grains and boundaries of molybdenum diselenide and tungsten diselenide using liquid crystal. Nano Lett. 2017, 17, 1474–1481.

    Article  Google Scholar 

  47. Ly, T. H.; Zhao, J.; Cichocka, M. O.; Li, L. J.; Lee, Y. H. Dynamical observations on the crack tip zone and stress corrosion of two-dimensional MoS2. Nat. Commun. 2017, 8, 14116.

    Article  Google Scholar 

  48. Duong, D. L.; Han, G. H.; Lee, S. M.; Gunes, F.; Kim, E. S.; Kim, S. T.; Kim, H.; Ta, Q. H.; So, K. P.; Yoon, S. J. et al. Probing graphene grain boundaries with optical microscopy. Nature 2012, 490, 235–239.

    Article  Google Scholar 

  49. Kim, D. W.; Kim, Y. H.; Jeong, H. S.; Jung, H. T. Direct visualization of large-area graphene domains and boundaries by optical birefringency. Nat. Nanotechnol. 2012, 7, 29–34.

    Article  Google Scholar 

  50. Lee, J. H.; Lee, E. K.; Joo, W. J.; Jang, Y.; Kim, B. S.; Lim, J. Y.; Choi, S. H.; Ahn, S. J.; Ahn, J. R.; Park, M. H. et al. Wafer-scale growth of single-crystal monolayer graphene on reusable hydrogen-terminated germanium. Science 2014, 344, 286–289.

    Article  Google Scholar 

  51. Nguyen, V. L.; Shin, B. G.; Duong, D. L.; Kim, S. T.; Perello, D.; Lim, Y. J.; Yuan, Q. H.; Ding, F.; Jeong, H. Y.; Shin, H. S. et al. Seamless stitching of graphene domains on polished copper (111) foil. Adv. Mater. 2015, 27, 1376–1382.

    Article  Google Scholar 

  52. Xu, X. Z.; Zhang, Z. H.; Dong, J. C.; Yi, D.; Niu, J. J.; Wu, M. H.; Lin, L.; Yin, R. K.; Li, M. Q.; Zhou, J. Y. et al. Ultrafast epitaxial growth of metre-sized single-crystal graphene on industrial Cu foil. Sci. Bull. 2017, 62, 1074–1080.

    Article  Google Scholar 

  53. Hata, K.; Futaba, D. N.; Mizuno, K.; Namai, T.; Yumura, M.; Iijima, S. Water-assisted highly efficient synthesis of impurity-free single-walled carbon nanotubes. Science 2004, 306, 1362–1364.

    Article  Google Scholar 

  54. Zhang, R. F.; Zhang, Y. Y.; Zhang, Q.; Xie, H. H.; Qian, W. Z.; Wei, F. Growth of half-meter long carbon nanotubes based on Schulz–Flory distribution. ACS Nano 2013, 7, 6156–6161.

    Article  Google Scholar 

  55. Barja, S.; Wickenburg, S.; Liu, Z. F.; Zhang, Y.; Ryu, H. J.; Ugeda, M. M.; Hussain, Z.; Shen, Z. X.; Mo, S. K.; Wong, E. et al. Charge density wave order in 1D mirror twin boundaries of single-layer MoSe2. Nat. Phys. 2016, 12, 751–756.

    Article  Google Scholar 

  56. Chang, Y. H.; Zhang, W. J.; Zhu, Y. H.; Han, Y.; Pu, J.; Chang, J. K.; Hsu, W. T.; Huang, J. K.; Hsu, C. L.; Chiu, M. H. et al. Monolayer MoSe2 grown by chemical vapor deposition for fast photodetection. ACS Nano 2014, 8, 8582–8590.

    Article  Google Scholar 

  57. Ni, Z. H.; Wang, H. M.; Luo, Z. Q.; Wang, Y. Y.; Yu, T.; Wu, Y. H.; Shen, Z. X. The effect of vacuum annealing on graphene. J. Raman Spectrosc. 2010, 41, 479–483.

    Article  Google Scholar 

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Acknowledgements

This work was supported by the National Key R&D Program of China (Nos. 2016YFA0300903 and 2016YFA0300804), the National Natural Science Foundation of China (Nos. 21376029, 51522201, 11474006 and 51502007), the National Postdoctoral Program for Innovative Talents (No. BX201700014) and the National Program for Thousand Young Talents of China.

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  1. Jinhuan Wang, Xiaozhi Xu and Ruixi Qiao contributed equally to this work

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, China

    Jinhuan Wang, Qingze Jiao & Yun Zhao

  2. State Key Laboratory for Mesoscopic Physics, School of Physics, Peking University, Beijing, 100871, China

    Xiaozhi Xu, Ruixi Qiao, Jing Liang, Can Liu, Bohao Zheng & Kaihui Liu

  3. Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing, 100871, China

    Lei Liu

  4. International Centre for Quantum Materials, and Electron Microscopy Laboratory, School of Physics, Peking University, Beijing, 100871, China

    Peng Gao

  5. Department of Physics, South University of Science and Technology of China, Shenzhen, 518055, China

    Dapeng Yu

  6. Collaborative Innovation Centre of Quantum Matter, Beijing, 100871, China

    Kaihui Liu

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  1. Jinhuan Wang
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  2. Xiaozhi Xu
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Correspondence to Yun Zhao or Kaihui Liu.

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Wang, J., Xu, X., Qiao, R. et al. Visualizing grain boundaries in monolayer MoSe2 using mild H2O vapor etching. Nano Res. 11, 4082–4089 (2018). https://doi.org/10.1007/s12274-018-1991-2

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