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Nano Research 2018, 11(12): 6227-6236 https://doi.org/10.1007/s12274-018-2142-5
Research Article | Issue | Published: 21 July 2018

Intrinsic excitonic emission and valley Zeeman splitting in epitaxial MS2 (M = Mo and W) monolayers on hexagonal boron nitride

Show Author's Information Chunxiao Cong1,§( ),  Chenji Zou2,§,  Bingchen Cao2,§,  Lishu Wu2,  Jingzhi Shang2( ),  Haomin Wang3,  Zhijun Qiu1( ),  Laigui Hu1,  Pengfei Tian1,  Ran Liu1,  Ting Yu2( )
State Key Laboratory of ASIC and SystemSchool of Information Science and TechnologyFudan UniversityShanghai200433China
Division of Physics and Applied PhysicsSchool of Physical and Mathematical SciencesNanyang Technological UniversitySingapore637371Singapore
State Key Laboratory of Functional Materials for InformaticsShanghai Institute of Microsystem and Information TechnologyChinese Academy of Sciences865 Changning RoadShanghai200050China

§ Chunxiao Cong, Chenji Zou, and Bingchen Cao contributed equally to this work.

Keywords:
chemical vapor deposition, transition metal dichalcogenides, intrinsic excitonic emission, valley Zeeman splitting, hexagonal boron nitride
Cite this article:
Cong C, Zou C, Cao B, et al. Intrinsic excitonic emission and valley Zeeman splitting in epitaxial MS2 (M = Mo and W) monolayers on hexagonal boron nitride. Nano Research, 2018, 11(12): 6227-6236. https://doi.org/10.1007/s12274-018-2142-5
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Abstract Full text Electronic supplementary material About this article

Two-dimensional (2D) semiconductors, represented by 2D transition metal dichalcogenides (TMDs), exhibit rich valley physics due to strong spin-orbit/spin-valley coupling. The most common way to probe such 2D systems is to utilize optical methods, which can monitor light emissions from various excitonic states and further help in understanding the physics behind such phenomena. Therefore, 2D TMDs with good optical quality are in great demand. Here, we report a method to directly grow epitaxial WS2 and MoS2 monolayers on hexagonal boron nitride (hBN) flakes with a high yield and high optical quality; these monolayers show better intrinsic light emission features than exfoliated monolayers from natural crystals. For the first time, the valley Zeeman splitting of WS2 and MoS2 monolayers on hBN has been visualized and systematically investigated. This study paves a new way to produce high optical quality WS2 and MoS2 monolayers and to exploit their intrinsic properties in a multitude of applications.


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About this article

Intrinsic excitonic emission and valley Zeeman splitting in epitaxial MS2 (M = Mo and W) monolayers on hexagonal boron nitride

Show Author's information Chunxiao Cong1,§( ), Chenji Zou2,§, Bingchen Cao2,§, Lishu Wu2, Jingzhi Shang2( ), Haomin Wang3, Zhijun Qiu1( ), Laigui Hu1, Pengfei Tian1, Ran Liu1, Ting Yu2( )
State Key Laboratory of ASIC and SystemSchool of Information Science and TechnologyFudan UniversityShanghai200433China
Division of Physics and Applied PhysicsSchool of Physical and Mathematical SciencesNanyang Technological UniversitySingapore637371Singapore
State Key Laboratory of Functional Materials for InformaticsShanghai Institute of Microsystem and Information TechnologyChinese Academy of Sciences865 Changning RoadShanghai200050China

§ Chunxiao Cong, Chenji Zou, and Bingchen Cao contributed equally to this work.

Abstract

Two-dimensional (2D) semiconductors, represented by 2D transition metal dichalcogenides (TMDs), exhibit rich valley physics due to strong spin-orbit/spin-valley coupling. The most common way to probe such 2D systems is to utilize optical methods, which can monitor light emissions from various excitonic states and further help in understanding the physics behind such phenomena. Therefore, 2D TMDs with good optical quality are in great demand. Here, we report a method to directly grow epitaxial WS2 and MoS2 monolayers on hexagonal boron nitride (hBN) flakes with a high yield and high optical quality; these monolayers show better intrinsic light emission features than exfoliated monolayers from natural crystals. For the first time, the valley Zeeman splitting of WS2 and MoS2 monolayers on hBN has been visualized and systematically investigated. This study paves a new way to produce high optical quality WS2 and MoS2 monolayers and to exploit their intrinsic properties in a multitude of applications.

Keywords: chemical vapor deposition, transition metal dichalcogenides, intrinsic excitonic emission, valley Zeeman splitting, hexagonal boron nitride

References(52)

1

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

Duan, X. D.; Wang, C.; Pan, A. L.; Yu, R. Q.; Duan, X. F. Two-dimensional transition metal dichalcogenides as atomically thin semiconductors: Opportunities and challenges. Chem. Soc. Rev. 2015, 44, 8859–8876.
DOI Google Scholar
3

Yu, H. Y.; Cui, X. D.; Xu, X. D.; Yao, W. Valley excitons in two-dimensional semiconductors. Natl. Sci. Rev. 2015, 2, 57–70.
DOI Google Scholar
4

Peng, B.; Ang, P. K.; Loh, K. P. Two-dimensional dichalcogenides for light-harvesting applications. Nano Today 2015, 10, 128–137.
DOI Google Scholar
5

Withers, F.; Del Pozo-Zamudio, O.; Mishchenko, A.; Rooney, A. P.; Gholinia, A.; Watanabe, K.; Taniguchi, T.; Haigh, S. J.; Geim, A. K.; Tartakovskii, A. I. et al. Light-emitting diodes by band-structure engineering in van der Waals heterostructures. Nat. Mater. 2015, 14, 301–306.
DOI Google Scholar
6

Wu, S. F.; Buckley, S.; Schaibley, J. R.; Feng, L. F.; Yan, J. Q.; Mandrus, D. G.; Hatami, F.; Yao, W.; Vučković, J.; Majumdar, A. et al. Monolayer semiconductor nanocavity lasers with ultralow thresholds. Nature 2015, 520, 69–72.
DOI Google Scholar
7

Ye, Y.; Wong, Z. J.; Lu, X. F.; Ni, X. J.; Zhu, H. Y.; Chen, X. H.; Wang, Y.; Zhang, X. Monolayer excitonic laser. Nat. Photonics 2015, 9, 733–737.
DOI Google Scholar
8

Zhang, Y. J.; Oka, T.; Suzuki, R.; Ye, J. T.; Iwasa, Y. Electrically switchable chiral light-emitting transistor. Science 2014, 344, 725–728.
DOI Google Scholar
9

Ross, J. S.; Klement, P.; Jones, A. M.; Ghimire, N. J.; Yan, J. Q.; Mandrus, D. G.; Taniguchi, T.; Watanabe, K.; Kitamura, K.; Yao, W. et al. Electrically tunable excitonic light-emitting diodes based on monolayer WSe2 p–n junctions. Nat. Nanotechnol. 2014, 9, 268–272.
DOI Google Scholar
10

Eda, G.; Maier, S. A. Two-dimensional crystals: Managing light for optoelectronics. ACS Nano 2013, 7, 5660–5665.
DOI Google Scholar
11

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.
DOI Google Scholar
12

Zeng, H. L.; Cui, X. D. An optical spectroscopic study on two-dimensional group-VI transition metal dichalcogenides. Chem. Soc. Rev. 2015, 44, 2629–2642.
DOI Google Scholar
13

Cong, C. X.; Shang, J. Z.; Wang, Y. L.; Yu, T. Optical properties of 2D semiconductor WS2. Adv. Opt. Mater. 2018, 6, 1700767.
DOI Google Scholar
14

Shang, J. Z.; Cong, C. X.; Wang, Z. L.; Peimyoo, N.; Wu, L. S.; Zou, C. J.; Chen, Y.; Chin, X. Y.; Wang, J. P.; Soci, C. et al. Room-temperature 2D semiconductor activated verticalcavity surface-emitting lasers. Nat. Commun. 2017, 8, 543.
DOI Google Scholar
15

Lee, Y. H.; Zhang, X. Q.; Zhang, W. J.; Chang, M. T.; Lin, C. T.; Chang, K. D.; Yu, Y. C.; Wang, J. T. W.; Chang, C. S.; Li, L. J. et al. Synthesis of large-area MoS2 atomic layers with chemical vapor deposition. Adv. Mater. 2012, 24, 2320–2325.
DOI Google Scholar
16

Gong, Y. J.; Ye, G. L.; Lei, S. D.; Shi, G.; He, Y. M.; Lin, J. H.; Zhang, X.; Vajtai, R.; Pantelides, S. T.; Zhou, W. et al. Synthesis of millimeter-scale transition metal dichalcogenides single crystals. Adv. Funct. Mater. 2016, 26, 2009–2015.
DOI Google Scholar
17

Cong, C. X.; Shang, J. Z.; Wu, X.; Cao, B. C.; Peimyoo, N.; Qiu, C. Y.; Sun, L. T.; Yu, T. Synthesis and optical properties of large-area single-crystalline 2D semiconductor WS2 monolayer from chemical vapor deposition. Adv. Opt. Mater. 2014, 2, 131–136.
DOI Google Scholar
18

van der Zande, A. M.; Huang, P. Y.; Chenet, D. A.; Berkelbach, T. C.; You, Y.; 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.
DOI Google Scholar
19

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.
DOI Google Scholar
20

Gao, Y.; Liu, Z. B.; Sun, D. M.; Huang, L.; Ma, L. P.; Yin, L. C.; Ma, T.; Zhang, Z. Y.; Ma, X. L.; Peng, L. M. et al. Large-area synthesis of high-quality and uniform monolayer WS2 on reusable Au foils. Nat. Commun. 2015, 6, 8569.
DOI Google Scholar
21

Yu, H.; Liao, M. Z.; Zhao, W. J.; Liu, G. D.; Zhou, X. J.; Wei, Z.; Xu, X. Z.; Liu, K. H.; Hu, Z. H.; Deng, K. et al. Wafer-scale growth and transfer of highly-oriented monolayer MoS2 continuous films. ACS Nano 2017, 11, 12001–12007.
DOI Google Scholar
22

Zhao, W. F.; Yu, H.; Liao, M. Z.; Zhang, L.; Zou, S. Z.; Yu, H. J.; He, C. J.; Zhang, J. Y.; Zhang, G. Y.; Lin, X. C. Large area growth of monolayer MoS2 film on quartz and its use as a saturable absorber in laser mode-locking. Semicond. Sci. Technol. 2017, 32, 025013.
DOI Google Scholar
23

Ji, Q. Q.; Zhang, Y. F.; Gao, T.; Zhang, Y.; Ma, D. L.; Liu, M. X.; Chen, Y. B.; Qiao, X. F.; Tan, P. H.; Kan, M. et al. Epitaxial monolayer MoS2 on mica with novel photoluminescence. Nano Lett. 2013, 13, 3870–3877.
DOI Google Scholar
24

Okada, M.; Sawazaki, T.; Watanabe, K.; Taniguch, T.; Hibino, H.; Shinohara, H.; Kitaura, R. Direct chemical vapor deposition growth of WS2 atomic layers on hexagonal boron nitride. ACS Nano 2014, 8, 8273–8277.
DOI Google Scholar
25

Kobayashi, Y.; Sasaki, S.; Mori, S.; Hibino, H.; Liu, Z.; Watanabe, K.; Taniguchi, T.; Suenaga, K.; Maniwa, Y.; Miyata, Y. Growth and optical properties of high-quality monolayer WS2 on graphite. ACS Nano 2015, 9, 4056–4063.
DOI Google Scholar
26

Cadiz, F.; Courtade, E.; Robert, C.; Wang, G.; Shen, Y.; Cai, H.; Taniguchi, T.; Watanabe, K.; Carrere, H.; Lagarde, D. et al. Excitonic linewidth approaching the homogeneous limit in MoS2-based van der Waals heterostructures. Phys. Rev. X 2017, 7, 021026.
DOI Google Scholar
27

Cui, X.; Lee, G. H.; Kim, Y. D.; Arefe, G.; Huang, P. Y.; Lee, C. H.; Chenet, D. A.; Zhang, X.; Wang, L.; Ye, F. et al. Multi-terminal transport measurements of MoS2 using a van der Waals heterostructure device platform. Nat. Nanotechnol. 2015, 10, 534–540.
DOI Google Scholar
28

Jin, C. H.; Kim, J.; Suh, J.; Shi, Z. W.; Chen, B.; Fan, X.; Kam, M.; Watanabe, K.; Taniguchi, T.; Tongay, S. et al. Interlayer electron-phonon coupling in WSe2/hBN heterostructures. Nat. Phys. 2017, 13, 127–131.
DOI Google Scholar
29

Wang, Z. F.; Shan, J.; Mak, K. F. Valley- and spin-polarized Landau levels in monolayer WSe2. Nat. Nanotechnol. 2016, 12, 144–149.
DOI Google Scholar
30

Ajayi, O. A.; Ardelean, J. V.; Shepard, G. D.; Wang, J.; Antony, A.; Taniguchi, T.; Watanabe, K.; Heinz, T. F.; Strauf, S.; Zhu, X. Y. et al. Approaching the intrinsic photoluminescence linewidth in transition metal dichalcogenide monolayers. 2D Mater. 2017, 4, 031011.
DOI Google Scholar
31

Manca, M.; Glazov, M. M.; Robert, C.; Cadiz, F.; Taniguchi, T.; Watanabe, K.; Courtade, E.; Amand, T.; Renucci, P.; Marie, X. et al. Enabling valley selective exciton scattering in monolayer WSe2 through upconversion. Nat. Commun. 2017, 8, 14927.
DOI Google Scholar
32

Chow, C. M.; Yu, H. Y.; Jones, A. M.; Yan, J. Q.; Mandrus, D. G.; Taniguchi, T.; Watanabe, K.; Yao, W.; Xu, X. D. Unusual exciton-phonon interactions at van der Waals engineered interfaces. Nano Lett. 2017, 17, 1194–1199.
DOI Google Scholar
33

Yu, H.; Yang, Z. Z.; Du, L. J.; Zhang, J.; Shi, J.; Chen, W.; Chen, P.; Liao, M. Z.; Zhao, J.; Meng, J. L. et al. Precisely aligned monolayer MoS2 epitaxially grown on h-BN basal plane. Small 2017, 13, 1603005.
DOI Google Scholar
34

Yan, A. M.; Velasco, J.; Kahn, S.; Watanabe, K.; Taniguchi, T.; Wang, F.; Crommie, M. F.; Zettl, A. Direct growth of single- and few-layer MoS2 on h-BN with preferred relative rotation angles. Nano Lett. 2015, 15, 6324–6331.
DOI Google Scholar
35

Okada, M.; Miyauchi, Y.; Matsuda, K.; Taniguchi, T.; Watanabe, K.; Shinohara, H.; Kitaura, R. Observation of biexcitonic emission at extremely low power density in tungsten disulfide atomic layers grown on hexagonal boron nitride. Sci. Rep. 2017, 7, 322.
DOI Google Scholar
36

MacNeill, D.; Heikes, C.; Mak, K. F.; Anderson, Z.; Kormányos, A.; Zólyomi, V.; Park, J.; Ralph, D. C. Breaking of valley degeneracy by magnetic field in monolayer MoSe2. Phys. Rev. Lett. 2015, 114, 037401.
DOI Google Scholar
37

Aivazian, G.; Gong, Z. R.; Jones, A. M.; Chu, R. L.; Yan, J.; Mandrus, D. G.; Zhang, C. W.; Cobden, D.; Yao, W.; Xu, X. Magnetic control of valley pseudospin in monolayer WSe2. Nat. Phys. 2015, 11, 148–152.
DOI Google Scholar
38

Li, Y. L.; Ludwig, J.; Low, T.; Chernikov, A.; Cui, X.; Arefe, G.; Kim, Y. D.; van der Zande, A. M.; Rigosi, A.; Hill, H. M. et al. Valley splitting and polarization by the Zeeman effect in monolayer MoSe2. Phys. Rev. Lett. 2014, 113, 266804.
DOI Google Scholar
39

Srivastava, A.; Sidler, M.; Allain, A. V.; Lembke, D. S.; Kis, A.; Imamoğlu, A. Valley Zeeman effect in elementary optical excitations of monolayer WSe2. Nat. Phys. 2015, 11, 141–147.
DOI Google Scholar
40

Wang, G.; Bouet, L.; Lagarde, D.; Vidal, M.; Balocchi, A.; Amand, T.; Marie, X.; Urbaszek, B. Valley dynamics probed through charged and neutral exciton emission in monolayer WSe2. Phys. Rev. B 2014, 90, 075413.
DOI Google Scholar
41

Zhu, C. R.; Zhang, K.; Glazov, M.; Urbaszek, B.; Amand, T.; Ji, Z. W.; Liu, B. L.; Marie, X. Exciton valley dynamics probed by Kerr rotation in WSe2 monolayers. Phys. Rev. B 2014, 90, 161302.
DOI Google Scholar
42

Shang, J. Z.; Shen, X. N.; Cong, C. X.; Peimyoo, N.; Cao, B. C.; Eginligil, M.; Yu, T. Observation of excitonic fine structure in a 2D transition-metal dichalcogenide semiconductor. ACS Nano 2015, 9, 647–655.
DOI Google Scholar
43

Shang, J. Z.; Cong, C. X.; Shen, X. N.; Yang, W. H.; Zou, C. J.; Peimyoo, N.; Cao, B. C.; Eginligil, M.; Lin, W.; Huang, W. et al. Revealing electronic nature of broad bound exciton bands in two-dimensional semiconducting WS2 and MoS2. Phys. Rev. Mater. 2017, 1, 074001.
DOI Google Scholar
44

Christopher, J. W.; Goldberg, B. B.; Swan, A. K. Long tailed trions in monolayer MoS2: Temperature dependent asymmetry and resulting red-shift of trion photoluminescence spectra. Sci. Rep. 2017, 7, 14062.
DOI Google Scholar
45

Berkdemir, A.; Gutiérrez, H. R.; Botello-Méndez, A. R.; Perea-López, N.; Elías, A. L.; Chia, C. I.; Wang, B.; Crespi, V. H.; López-Urías, F.; Charlier, J. C. et al. Identification of individual and few layers of WS2 using Raman spectroscopy. Sci. Rep. 2013, 3, 1755.
DOI Google Scholar
46

Desai, S. B.; Seol, G.; Kang, J. S.; Fang, H.; Battaglia, C.; Kapadia, R.; Ager, J. W.; Guo, J.; Javey, A. Strain-induced indirect to direct bandgap transition in multilayer WSe2. Nano Lett. 2014, 14, 4592–4597.
DOI Google Scholar
47

Lin, Y. X.; Ling, X.; Yu, L. L.; Huang, S. X.; Hsu, A. L.; Lee, Y. H.; Kong, J.; Dresselhaus, M. S.; Palacios, T. Dielectric screening of excitons and trions in single-layer MoS2. Nano Lett. 2014, 14, 5569–5576.
DOI Google Scholar
48

Chernikov, A.; Berkelbach, T. C.; Hill, H. M.; Rigosi, A.; Li, Y. L.; Aslan, O. B.; Reichman, D. R.; Hybertsen, M. S.; Heinz, T. F. Exciton binding energy and nonhydrogenic Rydberg series in monolayer WS2. Phys. Rev. Lett. 2014, 113, 076802.
DOI Google Scholar
49

Zhu, B. R.; Chen, X.; Cui, X. D. Exciton binding energy of monolayer WS2. Sci. Rep. 2015, 5, 9218.
DOI Google Scholar
50

Mitioglu, A. A.; Plochocka, P.; Jadczak, J. N.; Escoffier, W.; Rikken, G. L. J. A.; Kulyuk, L.; Maude, D. K. Optical manipulation of the exciton charge state in single-layer tungsten disulfide. Phys. Rev. B 2013, 88, 245403.
DOI Google Scholar
51

Szyniszewski, M.; Mostaani, E.; Drummond, N. D.; Fal'ko, V. I. Binding energies of trions and biexcitons in twodimensional semiconductors from diffusion quantum Monte Carlo calculations. Phys. Rev. B 2017, 95, 081301.
DOI Google Scholar
52

Zhang, D. K.; Kidd, D. W.; Varga, K. Excited biexcitons in transition metal dichalcogenides. Nano Lett. 2015, 15, 7002–7005.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 20 May 2018
Revised: 23 June 2018
Accepted: 02 July 2018
Published: 21 July 2018
Issue date: June 2021

Copyright

© Tsinghua University Press and Springer‐Verlag GmbH Germany, part of Springer Nature 2018

Acknowledgements

Acknowledgements

This work is supported by the National Natural Science Foundation of China (Nos. 61774040, 11774170, and 61774042), the Opening project of State Key Laboratory of Functional Materials for Informatics (Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences), the National Young 1000 Talent Plan of China, the Shanghai Municipal Natural Science Foundation (Nos. 16ZR1402500, 17ZR1446500, and 17ZR1446600), NTU Start-up grant M4080513, Singapore Ministry of Education (MOE) Tier 1 RG199/17, and Shanghai Pujiang Program (No. 16PJ1401000). C. C. thanks Dr. Ute Schmidt from WITec Company for AFM measurement.

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