Skip to main content
Log in

Controllable defects implantation in MoS2 grown by chemical vapor deposition for photoluminescence enhancement

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

Abstract

Photoluminescence (PL) of transition metal dichalcogenides (TMDs) can be engineered by controlling the density of defects, which provide active sites for electron-hole recombination, either radiatively or non-radiatively. However, the implantation of defects by external stimulation, such as uniaxial tension and irradiation, tends to introduce local damages or structural non-homogeneity, which greatly degrades their luminescence properties and impede their applicability in constructing optoelectronic devices. In this paper, we present a strategy to introduce a controllable level of defects into the MoS2 monolayers by adding a hydrogen flow during the chemical vapor deposition, without sacrificing their luminescence characteristics. The density of the defect is controlled directly by the concentration of hydrogen. For an appropriate hydrogen flux, the monolayer MoS2 sheets have three times stronger PL emission at the excitonic transitions, compared with those samples with nearly perfect crystalline structure. The defect-bounded exciton transitions at lower energies arising in the defective samples and are maximized when the total PL is the strongest. However, the B exciton, exhibits a monotonic decline as the defect density increases. The Raman spectra of the defective MoS2 reveal a redshift (blueshift) of the in-plane (out-of-plane) vibration modes as the hydrogen flux increases. All the evidence indicates that the generated defects are in the form of sulfur vacancies. This study renders the high-throughput synthesis of defective MoS2 possible for catalysis or light emitting applications.

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

Access this article

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

Instant access to the full article PDF.

Similar content being viewed by others

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. 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.

    Article  Google Scholar 

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

    Article  Google Scholar 

  5. Wi, S.; Kim, H.; Chen, M. K.; Nam, H.; Guo, L. J.; Meyhofer, E.; Liang, X. G. Enhancement of photovoltaic response in multilayer MoS2 induced by plasma doping. ACS Nano 2014, 8, 5270–5281.

    Article  Google Scholar 

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

    Article  Google Scholar 

  7. Sundaram, R. S.; Engel, M.; Lombardo, A.; Krupke, R.; Ferrari, A. C.; Avouris, P.; Steiner, M. Electroluminescence in single layer MoS2. Nano Lett. 2013, 13, 1416–1421.

    Article  Google Scholar 

  8. Reed, J. C.; Zhu, A. Y.; Zhu, H.; Yi, F.; Cubukcu, E. Wavelength tunable microdisk cavity light source with a chemically enhanced MoS2 emitter. Nano Lett. 2015, 15, 1967–1971.

  9. Lukowski, M. A.; Daniel, A. S.; Meng, F.; Forticaux, A.; Li, L. S.; Jin, S. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets. J. Am. Chem. Soc. 2013, 135, 10274–10277.

    Article  Google Scholar 

  10. Zong, X.; Wu, G. P.; Yan, H. J.; Ma, G. J.; Shi, J. Y.; Wen, F. Y.; Wang, L.; Li, C. Photocatalytic H2 evolution on MoS2/CdS catalysts under visible light irradiation. J. Phys. Chem. C 2010, 114, 1963–1968.

    Article  Google Scholar 

  11. Chow, P. K.; Jacobs-Gedrim, R. B.; Gao, J.; Lu, T. M.; Yu, B.; Terrones, H.; Koratkar, N. Defect-induced photoluminescence in monolayer semiconducting transition metal dichalcogenides. ACS Nano 2015, 9, 1520–1527.

    Article  Google Scholar 

  12. Tongay, S.; Suh, J.; Ataca, C.; Fan, W.; Luce, A.; Kang, J. S.; Liu, J.; Ko, C.; Raghunathanan, R.; Zhou, J. et al. Defects activated photoluminescence in two-dimensional semiconductors: Interplay between bound, charged, and free excitons. Sci. Rep. 2013, 3, 2657.

    Article  Google Scholar 

  13. Pierucci, D.; Henck, H.; Ben Aziza, Z.; Naylor, C. H.; Balan, A.; Rault, J. E.; Silly, M. G.; Dappe, Y. J.; Bertran, F.; Le Fèvre, P. et al. Tunable doping in hydrogenated single layered molybdenum disulfide. ACS Nano 2017, 11, 1755–1761.

    Article  Google Scholar 

  14. Nan, H. Y.; Wang, Z. L.; Wang, W. H.; Liang, Z.; Lu, Y.; Chen, Q.; He, D. W.; Tan, P. H.; Miao, F.; Wang, X. R. et al. Strong photoluminescence enhancement of MoS2 through defect engineering and oxygen bonding. ACS Nano 2014, 8, 5738–5745.

    Article  Google Scholar 

  15. Han, H. V.; Lu, A. Y.; Lu, L. S.; Huang, J. K.; Li, H.; Hsu, C. L.; Lin, Y. C.; Chiu, M. H.; Suenaga, K.; Chu, C. W. et al. Photoluminescence enhancement and structure repairing of monolayer MoSe2 by hydrohalic acid treatment. ACS Nano 2016, 10, 1454–1461.

    Article  Google Scholar 

  16. Tongay, S.; Zhou, J.; Ataca, C.; Liu, J.; Kang, J. S.; Matthews, T. S.; You, L.; Li, J. B.; Grossman, J. C.; Wu, J. Q. Broad-range modulation of light emission in two-dimensional semiconductors by molecular physisorption gating. Nano Lett. 2013, 13, 2831–2836.

    Article  Google Scholar 

  17. Amani, M.; Lien, D. H.; Kiriya, D.; Xiao, J.; Azcatl, A.; Noh, J.; Madhvapathy, S. R.; Addou, R.; Santosh, K. C.; Dubey, M. et al. Near-unity photoluminescence quantum yield in MoS2. Science 2015, 350, 1065–1068.

    Article  Google Scholar 

  18. Ross, J. S.; Wu, S. F.; Yu, H. Y.; Ghimire, N. J.; Jones, A. M.; Aivazian, G.; Yan, J. Q.; Mandrus, D. G.; Xiao, D.; Yao, W. et al. Electrical control of neutral and charged excitons in a monolayer semiconductor. Nat. Commun. 2013, 4, 1474.

    Article  Google Scholar 

  19. Hui, Y. Y.; Liu, X. F.; Jie, W. J.; Chan, N. Y.; Hao, J. H.; Hsu, Y. T.; Li, L. J.; Guo, W. L.; Lau, S. P. Exceptional tunability of band energy in a compressively strained trilayer MoS2 sheet. ACS Nano 2013, 7, 7126–7131.

    Article  Google Scholar 

  20. Sigle, D. O.; Mertens, J.; Herrmann, L. O.; Bowman, R. W.; Ithurria, S.; Dubertret, B.; Shi, Y.; Yang, H. Y.; Tserkezis, C.; Aizpurua, J. et al. Monitoring morphological changes in 2D monolayer semiconductors using atom-thick plasmonic nanocavities. ACS Nano 2015, 9, 825–830.

    Article  Google Scholar 

  21. Komsa, H. P.; Kotakoski, J.; Kurasch, S.; Lehtinen, O.; Kaiser, U.; Krasheninnikov, A. V. Two-dimensional transition metal dichalcogenides under electron irradiation: Defect production and doping. Phys. Rev. Lett. 2012, 109, 035503.

    Article  Google Scholar 

  22. Mishra, P.; Tangi, M.; Ng, T. K.; Hedhili, M. N.; Anjum, D. H.; Alias, M. S.; Tseng, C. C.; Li, L. J.; Ooi, B. S. Impact of N-plasma and Ga-irradiation on MoS2 layer in molecular beam epitaxy. Appl. Phys. Lett. 2017, 110, 012101.

    Article  Google Scholar 

  23. Azcatl, A.; Qin, X. Y.; Prakash, A.; Zhang, C. X.; Cheng, L. X.; Wang, Q. X.; Lu, N.; Kim, M. J.; Kim, J.; Cho, K. et al. Covalent nitrogen doping and compressive strain in MoS2 by remote N2 plasma exposure. Nano Lett. 2016, 16, 5437–5443.

    Article  Google Scholar 

  24. Shen, C.; Zhang, J.; Shi, D. X.; Zhang, G. Y. Photoluminescence enhancement in monolayer molybdenum disulfide by annealing in air. Acta Chim. Sinica 2015, 73, 954–958.

    Article  Google Scholar 

  25. Ye, G. L.; Gong, Y. J.; Lin, J. H.; Li, B.; He, Y. M.; Pantelides, S. T.; Zhou, W.; Vajtai, R.; Ajayan, P. M. Defects engineered monolayer MoS2 for improved hydrogen evolution reaction. Nano Lett. 2016, 16, 1097–1103.

    Article  Google Scholar 

  26. 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 

  27. Zafar, A.; Nan, H. Y.; Zafar, Z.; Wu, Z. T.; Jiang, J.; You, Y. M.; Ni, Z. H. Probing the intrinsic optical quality of CVD grown MoS2. Nano Res. 2017, 10, 1608–1617.

    Article  Google Scholar 

  28. Gurarslan, A.; Yu, Y. F.; Su, L. Q.; Yu, Y. L.; Suarez, F.; Yao, S. S.; Zhu, Y.; Ozturk, M.; Zhang, Y.; Cao, L. Y. Surface-energy-assisted perfect transfer of centimeter-scale monolayer and few-layer MoS2 films onto arbitrary substrates. ACS Nano 2014, 8, 11522–11528.

    Article  Google Scholar 

  29. Goodman, A. J.; Willard, A. P.; Tisdale, W. A. Exciton trapping is responsible for the long apparent lifetime in acid-treated MoS2. Phys. Rev. B 2017, 96, 121404.

    Article  Google Scholar 

  30. Zhu, Z. Y.; Cheng, Y. C.; Schwingenschlögl, U. Giant spin-orbit-induced spin splitting in two-dimensional transition-metal dichalcogenide semiconductors. Phys. Rev. B 2011, 84, 153402.

    Article  Google Scholar 

  31. Saigal, N.; Ghosh, S. Evidence for two distinct defect related luminescence features in monolayer MoS2. Appl. Phys. Lett. 2016, 109, 122105.

    Article  Google Scholar 

  32. Saigal, N.; Ghosh, S. Phonon induced luminescence decay in monolayer MoS2 on SiO2/Si substrates. Appl. Phys. Lett. 2015, 107, 242103.

    Article  Google Scholar 

  33. Tosun, M.; Chan, L.; Amani, M.; Roy, T.; Ahn, G. H.; Taheri, P.; Carraro, C.; Ager, J. W.; Maboudian, R.; Javey, A. Air-stable n-doping of WSe2 by anion vacancy formation with mild plasma treatment. ACS Nano 2016, 10, 6853–6860.

    Article  Google Scholar 

  34. Parkin, W. M.; Balan, A.; Liang, L. B.; Das, P. M.; Lamparski, M.; Naylor, C. H.; Rodríguez-Manzo, J. A.; Johnson, A. T. C.; Meunier, V.; Drndić, M. Raman shifts in electron-irradiated monolayer MoS2. ACS Nano 2016, 10, 4134–4142.

    Article  Google Scholar 

  35. Bae, S.; Sugiyama, N.; Matsuo, T.; Raebiger, H.; Shudo, K.; Ohno, K. Defect-induced vibration modes of Ar+-irradiated MoS2. Phys. Rev. Appl. 2017, 7, 024001.

    Article  Google Scholar 

  36. Mignuzzi, S.; Pollard, A. J.; Bonini, N.; Brennan, B.; Gilmore, I. S.; Pimenta, M. A.; Richards, D.; Roy, D. Effect of disorder on Raman scattering of single-layer MoS2. Phys. Rev. B 2015, 91, 195411.

    Article  Google Scholar 

  37. Huang, J. K.; Pu, J.; Hsu, C. L.; Chiu, M. H.; Juang, Z. Y.; Chang, Y. H.; Chang, W. H.; Iwasa, Y.; Takenobu, T.; Li, L. J. Large-area synthesis of highly crystalline WSe2 monolayers and device applications. ACS Nano 2014, 8, 923–930.

    Article  Google Scholar 

  38. Yoo, Y.; Degregorio, Z. P.; Johns, J. E. Seed crystal homogeneity controls lateral and vertical heteroepitaxy of monolayer MoS2 and WS2. J. Am. Chem. Soc. 2015, 137, 14281–14287.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Lihua Qian or Shunping Zhang.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wu, K., Li, Z., Tang, J. et al. Controllable defects implantation in MoS2 grown by chemical vapor deposition for photoluminescence enhancement. Nano Res. 11, 4123–4132 (2018). https://doi.org/10.1007/s12274-018-1999-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-018-1999-7

Keywords

Navigation