Vapor growth of V-doped MoS₂ monolayers with enhanced B-exciton emission and broad spectral response

Abstract

Dynamically engineering the optical and electrical properties in two-dimensional (2D) materials is of great significance for designing the related functions and applications. The introduction of foreign-atoms has previously been proven to be a feasible way to tune the band structure and related properties of 3D materials; however, this approach still remains to be explored in 2D materials. Here, we systematically demonstrate the growth of vanadium-doped molybdenum disulfide (V-doped MoS₂) monolayers via an alkali metal-assisted chemical vapor deposition method. Scanning transmission electron microscopy demonstrated that V atoms substituted the Mo atoms and became uniformly distributed in the MoS₂ monolayers. This was also confirmed by Raman and X-ray photoelectron spectroscopy. Power-dependent photoluminescence spectra clearly revealed the enhanced B-exciton emission characteristics in the V-doped MoS₂ monolayers (with low doping concentration). Most importantly, through temperature-dependent study, we observed efficient valley scattering of the B-exciton, greatly enhancing its emission intensity. Carrier transport experiments indicated that typical p-type conduction gradually arisen and was enhanced with increasing V composition in the V-doped MoS₂, where a clear n-type behavior transited first to ambipolar and then to lightly p-type charge carrier transport. In addition, visible to infrared wide-band photodetectors based on V-doped MoS₂ monolayers (with low doping concentration) were demonstrated. The V-doped MoS₂ monolayers with distinct B-exciton emission, enhanced p-type conduction and broad spectral response can provide new platforms for probing new physics and offer novel materials for optoelectronic applications.

Key words： Atomic substitution; V-doped MoS₂; Distinct B-exciton; Broad spectral response

References

1 Li, W., Gong, X., Yu, Z., Ma, L., Sun, W., Gao, S., Koroglu, C., Wang, W., Liu, L., Li, T., Ning, H., Fan, D., Xu, Y., Tu, X., Xu, T., Sun, L., Wang, W., Lu, J., Ni, Z., Li, J., Duan, X., Wang, P., Nie, Y., Qiu, H., Shi, Y., Pop, E., Wang, J., Wang, X.: Approaching the quantum limit in two-dimensional semiconductor contacts. Nature 613(7943), 274–279 (2023)

2 Kang, K., Xie, S., Huang, L., Han, Y., 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 520(7549), 656–660 (2015)

3 Radisavljevic, B., Radenovic, A., Brivio, J., Giacometti, V., Kis, A.: Single-layer MoS₂ transistors. Nat. Nanotech. 6(3), 147–150 (2011)

4 Zi, Y., Zhu, J., Hu, L., Wang, M., Huang, W.: Nanoengineering of tin monosulfide (SnS)-based structures for emerging applications. Small Science 2(3), 2100098 (2022)

5 Li, T., Guo, W., Ma, L., Li, W., Yu, Z., Han, Z., Gao, S., Liu, L., Fan, D., Wang, Z., Yang, Y., Lin, W., Luo, Z., Chen, X., Dai, N., Tu, X., Pan, D., Yao, Y., Wang, P., Nie, Y., Wang, J., Shi, Y., Wang, X.: Epitaxial growth of wafer-scale molybdenum disulfide semiconductor single crystals on sapphire. Nat. Nanotech. 16(11), 1201–1207 (2021)

6 Lin, Z., Liu, Y., Halim, U., Ding, M., Liu, Y., Wang, Y., Jia, C., Chen, P., Duan, X., Wang, C., Song, F., Li, M., Wan, C., Huang, Y., Duan, X.: Solution-processable 2D semiconductors for high-performance large-area electronics. Nature 562(7726), 254–258 (2018)

7 Huang, W., Zhu, J., Wang, M., Hu, L., Tang, Y., Shu, Y., Xie, Z., Zhang, H.: Emerging mono-elemental bismuth nanostructures: controlled synthesis and their versatile applications. Adv. Funct. Mater.Funct. Mater. 31(10), 2007584 (2021)

8 Lopez-Sanchez, O., Lembke, D., Kayci, M., Radenovic, A., Kis, A.: Ultrasensitive photodetectors based on monolayer MoS₂. Nat. Nanotech. 8(7), 497–501 (2013)

9 Zhu, J., Wei, S., Tang, J., Hu, Y., Dai, X., Zi, Y., Wang, M., Xiang, Y., Huang, W.: MXene V₂CTx nanosheet/bismuth quantum dot-based heterostructures for enhanced flexible photodetection and nonlinear photonics. ACS Appl. Nano Mater. 6(14), 13629–13636 (2023)

10 Huang, W., Wang, M., Hu, L., Wang, C., Xie, Z., Zhang, H.: Recent advances in semiconducting monoelemental selenium nanostructures for device applications. Adv. Funct. Mater. Funct. Mater. 30(42), 2003301 (2020)

11 Wang, C., Xu, J., Wang, Y., Song, Y., Guo, J., Huang, W., Ge, Y., Hu, L., Liu, J., Zhang, H.: MXene (Ti₂NTx): synthesis, characteristics and application as a thermo-optical switcher for all-optical wavelength tuning laser. Sci. China Mater. 64(1), 259–265 (2021)

12 Rong, K., Duan, X., Wang, B., Reichenberg, D., Cohen, A., Liu, C.-L., Mohapatra, P.K., Patsha, A., Gorovoy, V., Mukherjee, S., Kleiner, V., Ismach, A., Koren, E., Hasman, E.: Spin-valley Rashba monolayer laser. Nat. Mater. 22(9), 1085–1093 (2023)

13 Zi, Y., Hu, Y., Pu, J., Wang, M., Huang, W.: Recent progress in interface engineering of nanostructures for photoelectrochemical energy harvesting applications. Small 19(19), 2208274 (2023)

14 Mak, K.F., He, K., Shan, J., Heinz, T.F.: Control of valley polarization in monolayer MoS₂ by optical helicity. Nat. Nanotech. 7(8), 494 (2012)

15 Huang, W., Ma, C., Li, C., Zhang, Y., Hu, L., Chen, T., Tang, Y., Ju, J., Zhang, H.: Highly stable MXene (V₂CTx)-based harmonic pulse generation. Nanophotonics 9(8), 2577–2585 (2020)

16 Mak, K.F., Lee, C., Hone, J., Shan, J., Heinz, T.F.: Atomically thin MoS₂: a new direct-gap semiconductor. Phys. Rev. Lett. 105(13), 136805 (2010)

17 Steinhoff, A., Kim, J.H., Jahnke, F., Rosner, M., Kim, D.S., Lee, C., Han, G.H., Jeong, M.S., Wehling, T.O., Gies, C.: Efficient excitonic photoluminescence in direct and indirect band gap monolayer MoS₂. Nano Lett. 15(10), 6841–6847 (2015)

18 Wu, F., Qu, F., MacDonald, A.H.: Exciton band structure of monolayer MoS₂. Phys. Rev. B 91(7), 075310 (2015)

19 Cheiwchanchamnangij, T., Lambrecht, W.R.L.: Quasiparticle band structure calculation of monolayer, bilayer, and bulk MoS₂. Phys. Rev. B 85(20), 205302 (2012)

20 Splendiani, A., Sun, L., Zhang, Y., Li, T., Kim, J., Chim, C.-Y., Galli, G., Wang, F.: Emerging photoluminescence in monolayer MoS₂. Nano Lett. 10(4), 1271–1275 (2010)

21 Berghäuser, G., Malic, E.: Analytical approach to excitonic properties of MoS₂. Phys. Rev. B 89(12), 125309 (2014)

22 Zhou, W., Zou, X., Najmaei, S., Liu, Z., Shi, Y., Kong, J., Lou, J., Ajayan, P.M., Yakobson, B.I., Idrobo, J.-C.: Intrinsic structural defects in monolayer molybdenum disulfide. Nano Lett. 13(6), 2615–2622 (2013)

23 Addou, R., Colombo, L., Wallace, R.M.: Surface defects on natural MoS₂. ACS Appl. Mater. Interfaces 7(22), 11921–11929 (2015)

24 Duong, D.L., Yun, S.J., Kim, Y., Kim, S.-G., Lee, Y.H.: Long-range ferromagnetic ordering in vanadium-doped WSe₂ semiconductor. Appl. Phys. Lett. 115(24), 242406 (2019)

25 Fan, S., Yun, S.J., Yu, W.J., Lee, Y.H.: Tailoring quantum tunneling in a vanadium-doped WSe₂/SnSe₂ heterostructure. Adv. Sci. 7(3), 1902751 (2020)

26 Duan, H., Guo, P., Wang, C., Tan, H., Hu, W., Yan, W., Ma, C., Cai, L., Song, L., Zhang, W., Sun, Z., Wang, L., Zhao, W., Yin, Y., Li, X., Wei, S.: Beating the exclusion rule against the coexistence of robust luminescence and ferromagnetism in chalcogenide monolayers. Nat. Commun.Commun. 10(1), 1584 (2019)

27 Zhou, J., Lin, J., Sims, H., Jiang, C., Cong, C., Brehm, J.A., Zhang, Z., Niu, L., Chen, Y., Zhou, Y., Wang, Y., Liu, F., Zhu, C., Yu, T., Suenaga, K., Mishra, R., Pantelides, S.T., Zhu, Z.-G., Gao, W., Liu, Z., Zhou, W.: Synthesis of co-doped MoS₂ monolayers with enhanced valley splitting. Adv. Mater. 32(29), 2003123 (2020)

28 Zou, J., Cai, Z., Lai, Y., Tan, J., Zhang, R., Feng, S., Wang, G., Lin, J., Liu, B., Cheng, H.-M.: Doping concentration modulation in vanadium-doped monolayer molybdenum disulfide for synaptic transistors. ACS Nano 15(4), 7340–7347 (2021)

29 Zhang, L., Wang, Z., Zhang, J., Chen, B., Liang, Z., Quan, X., Dai, Y., Huang, J., Wang, Y., Liang, S.-J., Long, M., Si, M., Miao, F., Peng, Y.: Quasi-continuous tuning of carrier polarity in monolayered molybdenum dichalcogenides through substitutional vanadium doping. Adv. Funct. Mater.Funct. Mater. 32(46), 2204760 (2022)

30 Zhang, J., Zhu, Y., Tebyetekerwa, M., Li, D., Liu, D., Lei, W., Wang, L., Zhang, Y., Lu, Y.: Vanadium-doped monolayer MoS₂ with tunable optical properties for field-effect transistors. ACS Appl. Nano Mater. 4(1), 769–777 (2020)

31 Zhou, J., Lin, J., Huang, X., Zhou, Y., Chen, Y., Xia, J., Wang, H., Xie, Y., Yu, H., Lei, J., Wu, D., Liu, F., Fu, Q., Zeng, Q., Hsu, C.H., Yang, C., Lu, L., Yu, T., Shen, Z., Lin, H., Yakobson, B.I., Liu, Q., Suenaga, K., Liu, G., Liu, Z.: A library of atomically thin metal chalcogenides. Nature 556(7701), 355–359 (2018)

32 Li, S., Wang, S., Tang, D.-M., Zhao, W., Xu, H., Chu, L., Bando, Y., Golberg, D., Eda, G.: Halide-assisted atmospheric pressure growth of large WSe2 and WS₂ monolayer crystals. Appl. Mater. Today 1(1), 60–66 (2015)

33 Ganta, D., Sinha, S., Haasch, R.T.: 2-D material molybdenum disulfide analyzed by XPS. Surf. Sci. Spectra 21(1), 19–27 (2014)

34 Qin, J.-K., Shao, W.-Z., Xu, C.-Y., Li, Y., Ren, D.-D., Song, X.-G., Zhen, L.: Chemical vapor deposition growth of degenerate p-Type Mo-doped ReS₂ films and their homojunction. ACS Appl. Mater. Interfaces 9(18), 15583–15591 (2017)

35 Gao, J., Kim, Y.D., Liang, L., Idrobo, J.C., Chow, P., Tan, J., Li, B., Li, L., Sumpter, B.G., Lu, T.-M., Meunier, V., Hone, J., Koratkar, N.: Transition-metal substitution doping in synthetic atomically thin semiconductors. Adv. Mater. 28(44), 9735–9743 (2016)

36 Gao, D., Xue, Q., Mao, X., Wang, W., Xu, Q., Xue, D.: Ferromagnetism in ultrathin VS₂ nanosheets. J. Mater. Chem. C 1(37), 5909–5916 (2013)

37 Li, Y., Zhang, J., Zheng, G., Sun, Y., Hong, S.S., Xiong, F., Wang, S., Lee, H.R., Cui, Y.: Lateral and vertical two-dimensional layered topological insulator heterostructures. ACS Nano 9(11), 10916–10921 (2015)

38 Fang, W., Zhao, H., Xie, Y., Fang, J., Xu, J., Chen, Z.: Facile hydrothermal synthesis of VS₂/graphene nanocomposites with superior high-rate capability as lithium-ion battery cathodes. ACS Appl. Mater. Interfaces 7(23), 13044–13052 (2015)

39 Sasaki, S., Kobayashi, Y., Liu, Z., Suenaga, K., Maniwa, Y., Miyauchi, Y., Miyata, Y.: Growth and optical properties of Nbdoped WS₂ monolayers. Appl. Phys. Express 9(7), 071201 (2016)

40 Ly, T.H., Yun, S.J., Thi, Q.H., Zhao, J.: Edge delamination of monolayer transition metal dichalcogenides. ACS Nano 11(7), 7534–7541 (2017)

41 Kaplan, D., Mills, K., Lee, J., Torrel, S., Swaminathan, V.: Excitation intensity dependent photoluminescence of annealed two-dimensional MoS₂ grown by chemical vapor deposition. J. Appl. Phys. 119(21), 214301 (2016)

42 Yan, T., Qiao, X., Liu, X., Tan, P., Zhang, X.: Photoluminescence properties and exciton dynamics in monolayer WSe₂. Appl. Phys. Lett. 105(10), 101901 (2014)

43 Tiong, K.K., Shou, T.S., Ho, C.H.: Temperature dependence piezoreflectance study of the effect of doping MoS₂ with rhenium. J. Phys. Condens. MatterCondens. Matter 12(14), 3441 (2000)

44 Perea-López, N., Lin, Z., Pradhan, N.R., Iñiguez-Rábago, A., Laura Elías, A., McCreary, A., Lou, J., Ajayan, P.M., Terrones, H., Balicas, L., Terrones, M.: CVD-grown monolayered MoS₂ as an effective photosensor operating at low-voltage. 2D Mater. 1(1), 011004 (2014)

45 Nie, C., Yu, L., Wei, X., Shen, J., Lu, W., Chen, W., Feng, S., Shi, H.: Ultrafast growth of large-area monolayer MoS₂ film via gold foil assistant CVD for a highly sensitive photodetector. Nanotechnology 28(27), (2017)

46 Zhou, Y.H., An, H.N., Gao, C., Zheng, Z.Q., Wang, B.: UV–Vis-NIR photodetector based on monolayer MoS₂. Mater. Lett. 237, 298–302 (2019)

47 Zhang, W., Chiu, M.-H., Chen, C.-H., Chen, W., Li, L.-J., Wee, A.T.S.: Role of metal contacts in high-performance phototransistors based on WSe2 monolayers. ACS Nano 8(8), 8653–8661 (2014)

48 Sun, M., Fang, Q., Xie, D., Sun, Y., Qian, L., Xu, J., Xiao, P., Teng, C., Li, W., Ren, T., Zhang, Y.: Heterostructured graphene quantum dot/WSe₂/Si photodetector with suppressed dark current and improved detectivity. Nano Res. 11(6), 3233–3243 (2018)

49 Vabbina, P., Choudhary, N., Chowdhury, A.-A., Sinha, R., Karabiyik, M., Das, S., Choi, W., Pala, N.: Highly sensitive wide band-width photodetector based on internal photoemission in CVD grown p-type MoS₂/graphene Schottky Junction. ACS Appl. Mater. Interfaces 7(28), 15206–15213 (2015)

50 Yang, T., Zheng, B., Wang, Z., Xu, T., Pan, C., Zou, J., Zhang, X., Qi, Z., Liu, H., Feng, Y., Hu, W., Miao, F., Sun, L., Duan, X., Pan, A.: Van der Waals epitaxial growth and optoelectronics of large-scale WSe₂/SnS₂ vertical bilayer p-n junctions. Nat. Commun. Commun. 8(1), 1906 (2017)

51 Zou, Z., Li, D., Liang, J., Zhang, X., Liu, H., Zhu, C., Yang, X., Li, L., Zheng, B., Sun, X., Zeng, Z., Yi, J., Zhuang, X., Wang, X., Pan, A.: Epitaxial synthesis of ultrathin beta-In₂Se₃/MoS₂ heterostructures with high visible/near-infrared photoresponse. Nanoscale 12(11), 6480–6488 (2020)

52 Sun, X., Liu, Y., Shi, J., Si, C., Du, J., Liu, X., Jiang, C., Yang, S.: Controllable synthesis of 2H–1T’ Mo_xRe_(1–x)S₂ lateral hetero-structures and their tunable optoelectronic properties. Adv. Mater. 35(38), 2304171 (2023)