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Structural Determination and Nonlinear Optical Properties of New 1T‴-Type MoS2 Compound

  • Yuqiang Fang
    Yuqiang Fang
    State Key Laboratory of High Performance Ceramics and Super fine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    University of Chinese Academy of Sciences, Beijing 100049, China
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    • , 
  • Xiaozong Hu
    Xiaozong Hu
    State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Technology, Huazhong University of Science and Technology (HUST), Wuhan 430074, China
    More by Xiaozong Hu
    • , 
  • Wei Zhao
    Wei Zhao
    State Key Laboratory of High Performance Ceramics and Super fine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    More by Wei Zhao
    • , 
  • Jie Pan
    Jie Pan
    State Key Laboratory of High Performance Ceramics and Super fine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    More by Jie Pan
    • , 
  • Dong Wang
    Dong Wang
    State Key Laboratory of High Performance Ceramics and Super fine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    More by Dong Wang
    • , 
  • Kejun Bu
    Kejun Bu
    State Key Laboratory of High Performance Ceramics and Super fine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    University of Chinese Academy of Sciences, Beijing 100049, China
    More by Kejun Bu
    • , 
  • Yuanlv Mao
    Yuanlv Mao
    State Key Laboratory of High Performance Ceramics and Super fine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    University of Chinese Academy of Sciences, Beijing 100049, China
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    • , 
  • Shufen Chu
    Shufen Chu
    State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200030, China
    More by Shufen Chu
    • , 
  • Pan Liu*
    Pan Liu
    State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200030, China
    *[email protected] (P.L.)
    More by Pan Liu
    Orcidhttp://orcid.org/0000-0002-4063-9605
    • , 
  • Tianyou Zhai*
    Tianyou Zhai
    State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Technology, Huazhong University of Science and Technology (HUST), Wuhan 430074, China
    *[email protected] (T.Z.)
    More by Tianyou Zhai
    Orcidhttp://orcid.org/0000-0003-0985-4806
    • , and 
  • Fuqiang Huang*
    Fuqiang Huang
    State Key Laboratory of High Performance Ceramics and Super fine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
    *[email protected] (F.H.)
    More by Fuqiang Huang
    Orcidhttp://orcid.org/0000-0001-7727-0488
Cite this: J. Am. Chem. Soc. 2019, 141, 2, 790–793
Publication Date (Web):January 2, 2019
https://doi.org/10.1021/jacs.8b12133
Copyright © 2019 American Chemical Society
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Abstract

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Noncentrosymmetric MoS2 semiconductors (1H, 3R) possess not only novel electronic structures of spin–orbit coupling (SOC) and valley polarization but also remarkable nonlinear optical effects. A more interesting noncentrosymmetric structure, the so-called 1T‴-MoS2 layers, was predicted to be built up from [MoS6] octahedral motifs by theoreticians, but the bulk 1T‴ MoS2 or its single crystal structure has not been reported yet. Here, we have successfully harvested 1T‴ MoS2 single crystals by a topochemical method. The new layered structure is determined from single-crystal X-ray diffraction. The crystal crystallizes in space group P31m with a cell of a = b = 5.580(2) Å and c = 5.957(2) Å, which is a √3a × √3a superstructure of 1T MoS2 with corner-sharing Mo3 triangular trimers observed by the STEM. 1T‴ MoS2 is verified to be semiconducting and possesses a band gap of 0.65 eV, different from metallic nature of 1T or 1T′ MoS2. More surprisingly, the 1T‴ MoS2 does show strong optical second-harmonic generation signals. This work provides the first layered noncentrosymmetric semiconductor of edge-sharing MoS6 octahedra for the research of nonlinear optics.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.8b12133.

  • Preparation of 1T‴ MoS2 crystals and single crystal determination; electronic structure calculation by first principles; detailed crystal data including structural refinement statistics, anisotropic displacement parameters, selected bond distances, and bond angles of 1T‴ MoS2; SEM image and EDS spectrum of the sample (DOCX)

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Cited By

This article is cited by 17 publications.

  1. Haoqiang Ai, Youchao Kong, Di Liu, Feifei Li, Jiazhong Geng, Shuangpeng Wang, Kin Ho Lo, Hui Pan. 1T‴ Transition-Metal Dichalcogenides: Strong Bulk Photovoltaic Effect for Enhanced Solar-Power Harvesting. The Journal of Physical Chemistry C 2020, 124 (20) , 11221-11228. https://doi.org/10.1021/acs.jpcc.0c02498
  2. Tanweer Ahmed, Pavithra Bellare, Rahul Debnath, Ahin Roy, Narayanan Ravishankar, Arindam Ghosh. Thermal History-Dependent Current Relaxation in hBN/MoS2 van der Waals Dimers. ACS Nano 2020, Article ASAP.
  3. Calvin D. Quilty, Lisa M. Housel, David C. Bock, Mikaela R. Dunkin, Lei Wang, Diana M. Lutz, Alyson Abraham, Andrea M. Bruck, Esther S. Takeuchi, Kenneth J. Takeuchi, Amy C. Marschilok. Ex Situ and Operando XRD and XAS Analysis of MoS2: A Lithiation Study of Bulk and Nanosheet Materials. ACS Applied Energy Materials 2019, 2 (10) , 7635-7646. https://doi.org/10.1021/acsaem.9b01538
  4. Kenan Zhang, Changchun Ding, Yihong She, Zhen Wu, Changhui Zhao, Baojun Pan, Lijie Zhang, Wei Zhou, Qunchao Fan. CuFe2O4/MoS2 Mixed-Dimensional Heterostructures with Improved Gas Sensing Response. Nanoscale Research Letters 2020, 15 (1) https://doi.org/10.1186/s11671-020-3268-4
  5. Yao Zhou, Jing Zhang, Erhong Song, Junhao Lin, Jiadong Zhou, Kazu Suenaga, Wu Zhou, Zheng Liu, Jianjun Liu, Jun Lou, Hong Jin Fan. Enhanced performance of in-plane transition metal dichalcogenides monolayers by configuring local atomic structures. Nature Communications 2020, 11 (1) https://doi.org/10.1038/s41467-020-16111-0
  6. Ziyue Qian, Liying Jiao, Liming Xie. Phase Engineering of Two‐Dimensional Transition Metal Dichalcogenides. Chinese Journal of Chemistry 2020, 5 https://doi.org/10.1002/cjoc.202000064
  7. Tao Yang, Yaobin Li, Shiguo Han, Zhiyun Xu, Yi Liu, Xinyuan Zhang, Xitao Liu, Bing Teng, Junhua Luo, Zhihua Sun. Highly‐Anisotropic Dion–Jacobson Hybrid Perovskite by Tailoring Diamine into CsPbBr 3 for Polarization‐Sensitive Photodetection. Small 2020, 16 (14) , 1907020. https://doi.org/10.1002/smll.201907020
  8. Carsten Habenicht, Axel Lubk, Roman Schuster, Martin Knupfer, Bernd Büchner. Investigation of potassium-intercalated bulk MoS2 using transmission electron energy-loss spectroscopy. Physical Review B 2020, 101 (15) https://doi.org/10.1103/PhysRevB.101.155429
  9. Maofan Li, Shiguo Han, Bing Teng, Yaobin Li, Yi Liu, Xitao Liu, Junhua Luo, Maochun Hong, Zhihua Sun. Minute‐Scale Rapid Crystallization of a Highly Dichroic 2D Hybrid Perovskite Crystal toward Efficient Polarization‐Sensitive Photodetector. Advanced Optical Materials 2020, , 2000149. https://doi.org/10.1002/adom.202000149
  10. Yanfeng Ge, Wenhui Wan, Yulu Ren, Yong Liu. Large thermoelectric power factor of high-mobility transition-metal dichalcogenides with 1T″ phase. Physical Review Research 2020, 2 (1) https://doi.org/10.1103/PhysRevResearch.2.013134
  11. Ji-Hae Choi, Seung-Hoon Jhi. Origin of robust out-of-plane ferroelectricity in d 1 T -MoS 2 monolayer. Journal of Physics: Condensed Matter 2020, 32 (4) , 045702. https://doi.org/10.1088/1361-648X/ab4c67
  12. Fan Gan, Ningning Dong, Zhiwei Liu, Huimei Jia, Jun Wang, Yu Chen. Organic Small Molecule Covalently Functionalized Molybdenum Disulfide Hybrid Material for Optical Limiting. Bulletin of the Chemical Society of Japan 2020, 93 (1) , 26-31. https://doi.org/10.1246/bcsj.20190235
  13. Yi Liu, Zhenyue Wu, Xitao Liu, Shiguo Han, Yaobin Li, Tao Yang, Yu Ma, Maochun Hong, Junhua Luo, Zhihua Sun. Intrinsic Strong Linear Dichroism of Multilayered 2D Hybrid Perovskite Crystals toward Highly Polarized‐Sensitive Photodetection. Advanced Optical Materials 2019, 7 (23) , 1901049. https://doi.org/10.1002/adom.201901049
  14. Yao Chen, Xiaoming Deng, Jieya Wen, Jian Zhu, Zhenfeng Bian. Piezo-promoted the generation of reactive oxygen species and the photodegradation of organic pollutants. Applied Catalysis B: Environmental 2019, 258 , 118024. https://doi.org/10.1016/j.apcatb.2019.118024
  15. Yuanlv Mao, Yuqiang Fang, Jie Pan, Dong Wang, Kejun Bu, Xiangli Che, Wei Zhao, Fuqiang Huang. Synthesis, crystal structures and physical properties of A(H2O) MoS2 (A = K, Rb, Cs). Journal of Solid State Chemistry 2019, 279 , 120937. https://doi.org/10.1016/j.jssc.2019.120937
  16. Yinglu Jia, Min Zhao, Gaoyang Gou, Xiao Cheng Zeng, Ju Li. Niobium oxide dihalides NbOX 2 : a new family of two-dimensional van der Waals layered materials with intrinsic ferroelectricity and antiferroelectricity. Nanoscale Horizons 2019, 4 (5) , 1113-1123. https://doi.org/10.1039/C9NH00208A
  17. Yuanlv Mao, Yuqiang Fang, Dong Wang, Kejun Bu, Sishun Wang, Wei Zhao, Fuqiang Huang. Crystal structure and electrical resistance property of Rb 0.21 (H 2 O) y WS 2. Acta Crystallographica Section E Crystallographic Communications 2019, 75 (7) , 976-979. https://doi.org/10.1107/S2056989019007941

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