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Endowing bilayer transition-metal dichalcogenides (TMDs) with tunable magnetism is significant to investigate the coupling of multiple electron degrees of freedom (DOFs). However, effectively inducing and tuning the magnetic interaction of bilayer TMDs are still challenges. Herein, we report a strategy to tune the interlayer exchange interaction of centimeter-scale MoS2 bilayer with substitutional doping of Co ion, by introducing sulfur vacancy (VS) to modulate the interlayer electronic coupling. This strategy could transform the interlayer exchange interaction from antiferromagnetism (AFM) to ferromagnetism (FM), as revealed by the magnetic measurements. Experimental characterizations and theoretical calculations indicate that the enhanced magnetization is mainly because the hybridization of Co 3d band and VS-induced impurity band alters the forms of interlayer orbital hybridizations between the partial Co atoms in upper and lower layers, and also enhances the intralayer FM. Our work paves the way for tuning the interlayer exchange interaction with defects and could be extended to other two-dimensional (2D) magnetic materials.


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Sulfur-vacancy-tunable interlayer magnetic coupling in centimeter- scale MoS2 bilayer

Show Author's information Hengli Duan1,§Guinan Li1,§Hao Tan1Chao Wang1( )Qian Li1Chuanchuan Liu2Yuewei Yin2Xiaoguang Li2Zeming Qi1( )Wensheng Yan1( )
National Synchrotron Radiation Laboratory University of Science and Technology of ChinaHefei 230029 China
Hefei National Laboratory for Physical Sciences at the Microscale Department of Physics, and CAS Key Laboratory of Strongly-coupled Quantum Matter Physics University of Science and Technology of ChinaHefei 230026 China

§ Hengli Duan and Guinan Li contributed equally to this work.

Abstract

Endowing bilayer transition-metal dichalcogenides (TMDs) with tunable magnetism is significant to investigate the coupling of multiple electron degrees of freedom (DOFs). However, effectively inducing and tuning the magnetic interaction of bilayer TMDs are still challenges. Herein, we report a strategy to tune the interlayer exchange interaction of centimeter-scale MoS2 bilayer with substitutional doping of Co ion, by introducing sulfur vacancy (VS) to modulate the interlayer electronic coupling. This strategy could transform the interlayer exchange interaction from antiferromagnetism (AFM) to ferromagnetism (FM), as revealed by the magnetic measurements. Experimental characterizations and theoretical calculations indicate that the enhanced magnetization is mainly because the hybridization of Co 3d band and VS-induced impurity band alters the forms of interlayer orbital hybridizations between the partial Co atoms in upper and lower layers, and also enhances the intralayer FM. Our work paves the way for tuning the interlayer exchange interaction with defects and could be extended to other two-dimensional (2D) magnetic materials.

Keywords: interlayer coupling, interlayer exchange interaction, 2D magnetic materials, S-vacancy, large-area growth

References(50)

1

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.

2

Bonilla, M.; Kolekar, S.; Ma, Y. J.; Diaz, H. C.; Kalappattil, V.; Das, R.; Eggers, T.; Gutierrez, H. R.; Phan, M. H.; Batzill, M. Strong room-temperature ferromagnetism in VSe2 monolayers on van der Waals substrates. Nat. Nanotechnol. 2018, 13, 289–293.

3

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

4

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

5

Yuan, H. T.; Bahramy, M. S.; Morimoto, K.; Wu, S. F.; Nomura, K.; Yang, B. J.; Shimotani, H.; Suzuki, R.; Toh, M.; Kloc, C. et al. Zeeman-type spin splitting controlled by an electric field. Nat. Phys. 2013, 9, 563–569.

6

Fei, Z. Y.; Zhao, W. J.; Palomaki, T. A.; Sun, B. S.; Miller, M. K.; Zhao, Z. Y.; Yan, J. Q.; Xu, X. D.; Cobden, D. H. Ferroelectric switching of a two-dimensional metal. Nature 2018, 560, 336–339.

7

Li, L.; Wu, M. H. Binary compound bilayer and multilayer with vertical polarizations: Two-dimensional ferroelectrics, multiferroics, and nanogenerators. ACS Nano 2017, 11, 6382–6388.

8

Wu, S. F.; Ross, J. S.; Liu, G. B.; Aivazian, G.; Jones, A.; Fei, Z. Y.; Zhu, W. G.; Xiao, D.; Yao, W.; Cobden, D. et al. Electrical tuning of valley magnetic moment through symmetry control in bilayer MoS2. Nat. Phys. 2013, 9, 149–153.

9

Lee, J.; Mak, K. F.; Shan, J. Electrical control of the valley Hall effect in bilayer MoS2 transistors. Nat. Nanotechnol. 2016, 11, 421–425.

10

Liu, X. E.; Pyatakov, A. P.; Ren, W. Magnetoelectric coupling in multiferroic bilayer VS2. Phys. Rev. Lett. 2020, 125, 247601.

11

Jones, A. M.; Yu, H. Y.; Ross, J. S.; Klement, P.; Ghimire, N. J.; Yan, J. Q.; Mandrus, D. G.; Yao, W.; Xu, X. D. Spin-layer locking effects in optical orientation of exciton spin in bilayer WSe2. Nat. Phys. 2014, 10, 130–134.

12

Cheng, Y. C.; Zhu, Z. Y.; Mi, W. B.; Guo, Z. B.; Schwingenschlögl, U. Prediction of two-dimensional diluted magnetic semiconductors: Doped monolayer MoS2 systems. Phys. Rev. B 2013, 87, 100401.

13

Fu, S. C.; Kang, K.; Shayan, K.; Yoshimura, A.; Dadras, S.; Wang, X. T.; Zhang, L. H.; Chen, S. W.; Liu, N.; Jindal, A. et al. Enabling room temperature ferromagnetism in monolayer MoS2 via in situ iron-doping. Nat. Commun. 2020, 11, 2034.

14

Ramasubramaniam, A.; Naveh, D. Mn-doped monolayer MoS2: An atomically thin dilute magnetic semiconductor. Phys. Rev. B 2013, 87, 195201.

15

Chen, W. J.; Sun, Z. Y.; Wang, Z. J.; Gu, L. H.; Xu, X. D.; Wu, S. W.; Gao, C. L. Direct observation of van der Waals stacking- dependent interlayer magnetism. Science 2019, 366, 983–987.

16

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. Nature 2017, 546, 270–273.

17

Sharpe, A. L.; Fox, E. J.; Barnard, A. W.; Finney, J.; Watanabe, K.; Taniguchi, T.; Kastner, M. A.; Goldhaber-Gordon, D. Emergent ferromagnetism near three-quarters filling in twisted bilayer graphene. Science 2019, 365, 605–608.

18

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. Nature 2018, 563, 94–99.

19

Gong, C.; Li, L.; Li, Z. L.; Ji, H. W.; Stern, A.; Xia, Y.; Cao, T.; Bao, W.; Wang, C. Z.; Wang, Y. et al. Discovery of intrinsic ferromagnetism in two-dimensional van der Waals crystals. Nature 2017, 546, 265–269.

20

Sivadas, N.; Okamoto, S.; Xu, X. D.; Fennie, C. J.; Xiao, D. Stacking-dependent magnetism in bilayer CrI3. Nano Lett. 2018, 18, 7658–7664.

21

Jiang, P. H.; Wang, C.; Chen, D. C.; Zhong, Z. C.; Yuan, Z.; Lu, Z. Y.; Ji, W. Stacking tunable interlayer magnetism in bilayer CrI3. Phys. Rev. B 2019, 99, 144401.

22

Jiang, S. W.; Li, L. Z.; Wang, Z. F.; Mak, K. F.; Shan, J. Controlling magnetism in 2D CrI3 by electrostatic doping. Nat. Nanotechnol. 2018, 13, 549–553.

23

Li, T. X.; Jiang, S. W.; Sivadas, N.; Wang, Z. F.; Xu, Y.; Weber, D.; Goldberger, J. E.; Watanabe, K.; Taniguchi, T.; Fennie, C. J. et al. Pressure-controlled interlayer magnetism in atomically thin CrI3. Nat. Mater. 2019, 18, 1303–1308.

24

Liu, K. H.; Zhang, L. M.; Cao, T.; Jin, C. H.; Qiu, D. A.; Zhou, Q.; Zettl, A.; Yang, P. D.; Louie, S. G.; Wang, F. Evolution of interlayer coupling in twisted molybdenum disulfide bilayers. Nat. Commun. 2014, 5, 4966.

25

Huang, S. X.; Ling, X.; Liang, L. B.; Kong, J.; Terrones, H.; Meunier, V.; Dresselhaus, M. S. Probing the interlayer coupling of twisted bilayer MoS2 using photoluminescence spectroscopy. Nano Lett. 2014, 14, 5500–5508.

26

van der Zande, A. M.; Kunstmann, J.; Chernikov, A.; Chenet, D. A.; You, Y. M.; Zhang, X. X.; Huang, P. Y.; Berkelbach, T. C.; Wang, L.; Zhang, F. et al. Tailoring the electronic structure in bilayer molybdenum disulfide via interlayer twist. Nano Lett. 2014, 14, 3869–3875.

27

Tian, X. Z.; Kim, D. S.; Yang, S. Z.; Ciccarino, C. J.; Gong, Y. J.; Yang, Y.; Yang, Y.; Duschatko, B.; Yuan, Y. K.; Ajayan, P. M. et al. Correlating the three-dimensional atomic defects and electronic properties of two-dimensional transition metal dichalcogenides. Nat. Mater. 2020, 19, 867–873.

28

Yin, Y.; Han, J. C.; Zhang, Y. M.; Zhang, X. H.; Xu, P.; Yuan, Q.; Samad, L.; Wang, X. J.; Wang, Y.; Zhang, Z. H. et al. Contributions of phase, sulfur vacancies, and edges to the hydrogen evolution reaction catalytic activity of porous molybdenum disulfide nanosheets. J. Am. Chem. Soc. 2016, 138, 7965–7972.

29

Park, S.; Park, J.; Abroshan, H.; Zhang, L.; Kim, J. K.; Zhang, J. M.; Guo, J. H.; Siahrostami, S.; Zheng, X. L. Enhancing catalytic activity of MoS2 basal plane S-vacancy by Co cluster addition. ACS Energy Lett. 2018, 3, 2685–2693.

30

Hu, J. T.; Yu, L.; Deng, J.; Wang, Y.; Cheng, K.; Ma, C.; Zhang, Q. H.; Wen, W.; Yu, S. S.; Pan, Y. et al. Sulfur vacancy-rich MoS2 as a catalyst for the hydrogenation of CO2 to methanol. Nat. Catal. 2021, 4, 242–250.

31

Cai, L.; He, J. F.; Liu, Q. H.; Yao, T.; Chen, L.; Yan, W. S.; Hu, F. C.; Jiang, Y.; Zhao, Y. D.; Hu, T. D. et al. Vacancy-induced ferromagnetism of MoS2 nanosheets. J. Am. Chem. Soc. 2015, 137, 2622–2627.

32

Wang, S. S.; Pacios, M.; Bhaskaran, H.; Warner, J. H. Substrate control for large area continuous films of monolayer MoS2 by atmospheric pressure chemical vapor deposition. Nanotechnology 2016, 27, 085604.

33

Shepherd, W. H. Doping of epitaxial silicon films. J. Electrochem. Soc. 1968, 115, 541–545.

34

Wu, T. Y. Some morphological studies for optimum growth conditions of vapor epitaxial GaAs1-xPx. J. Cryst. Growth 1974, 21, 85–92.

35

Lee, J.; Pak, S.; Giraud, P.; Lee, Y. W.; Cho, Y.; Hong, J.; Jang, A. R.; Chung, H. S.; Hong, W. K.; Jeong, H. Y. et al. Thermodynamically stable synthesis of large-scale and highly crystalline transition metal dichalcogenide monolayers and their unipolar n–n heterojunction devices. Adv. Mater. 2017, 29, 1702206.

36

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.

37

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.

38

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.

39

Zhang, L. L.; Wang, G.; Zhang, Y. B.; Cao, Z. P.; Wang, Y.; Cao, T. J.; Wang, C.; Cheng, B.; Zhang, W. Q.; Wan, X. G. et al. Tuning electrical conductance in bilayer MoS2 through defect-mediated interlayer chemical bonding. ACS Nano 2020, 14, 10265–10275.

40

Gerber, I. C.; Courtade, E.; Shree, S.; Robert, C.; Taniguchi, T.; Watanabe, K.; Balocchi, A.; Renucci, P.; Lagarde, D.; Marie, X. et al. Interlayer excitons in bilayer MoS2 with strong oscillator strength up to room temperature. Phys. Rev. B 2019, 99, 035443.

41

Dhall, R.; Neupane, M. R.; Wickramaratne, D.; Mecklenburg, M.; Li, Z.; Moore, C.; Lake, R. K.; Cronin, S. Direct bandgap transition in many-layer MoS2 by plasma-induced layer decoupling. Adv. Mater. 2015, 27, 1573–1578.

42

Xia, M.; Li, B.; Yin, K. B.; Capellini, G.; Niu, G.; Gong, Y. J.; Zhou, W.; Ajayan, P. M.; Xie, Y. H. Spectroscopic signatures of AA' and AB stacking of chemical vapor deposited bilayer MoS2. ACS Nano 2015, 9, 12246–12254.

43

Ankudinov, A. L.; Ravel, B.; Rehr, J. J.; Conradson, S. D. Real-space multiple-scattering calculation and interpretation of X-ray-absorption near-edge structure. Phys. Rev. B 1998, 58, 7565–7576.

44

Zhao, Y. Y.; Luo, X.; Li, H.; Zhang, J.; Araujo, P. T.; Gan, C. K.; Wu, J.; Zhang, H.; Quek, S. Y.; Dresselhaus, M. S. et al. Interlayer breathing and shear modes in few-trilayer MoS2 and WSe2. Nano Lett. 2013, 13, 1007–1015.

45

Plechinger, G.; Mooshammer, F.; Castellanos-Gomez, A.; Steele, G.; Schüller, C.; Korn, T. Optical spectroscopy of interlayer coupling in artificially stacked MoS2 layers. 2D Mater. 2015, 2, 034016.

46

Matte, H. S. S. R.; Subrahmanyam, K. S.; Rao, C. N. R. Novel magnetic properties of graphene: Presence of both ferromagnetic and antiferromagnetic features and other aspects. J. Phys. Chem. C 2009, 113, 9982–9985.

47

Radhakrishnan, S.; Das, D.; Samanta, A.; de los Reyes, C. A.; Deng, L. Z.; Alemany, L. B.; Weldeghiorghis, T. K.; Khabashesku, V. N.; Kochat, V.; Jin, Z. H. et al. Fluorinated h-BN as a magnetic semiconductor. Sci. Adv. 2017, 3, e1700842.

48

Coey, J. M. D.; Venkatesan, M.; Fitzgerald, C. B. Donor impurity band exchange in dilute ferromagnetic oxides. Nat. Mater. 2005, 4, 173–179.

49

Kanamori, J. Superexchange interaction and symmetry properties of electron orbitals. J. Phys. Chem. Solids 1959, 10, 87–98.

50

Ehrenberg, H.; Wiesmann, M.; Garcia-Jaca, J.; Weitzel, H.; Fuess, H. Magnetic structures of the high-pressure modifications of CoMoO4 and CuMoO4. J. Magn. Magn. Mater. 1998, 182, 152–160.

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Acknowledgements

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Received: 05 March 2021
Revised: 29 April 2021
Accepted: 03 May 2021
Published: 10 September 2021
Issue date: February 2022

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© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 11975234, 11775225, 12075243, 12005227, 51790491, U2032150 and U1732148), the Users with Excellence Program of Hefei Science Center CAS (Nos. 2019HSC-UE002, 2020HSC-UE002, 2020HSC- CIP013 and 2021HSC-UE002), the Postdoctoral Science Foundation of China (Nos. 2020M682041, 2020TQ0316 and 2019M662202), the National Key Research and Development Program of China (No. 2019YFA0307900), and partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication. The authors would like to thank SSRF, BSRF and NSRL for the synchrotron beamtime.

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