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Monolayer atomic crystal molecular superlattices

Wang, Chen and He, Qiyuan and Halim, Udayabagya and Liu, Yuanyue and Enbo, Zhu and Lin, Zhaoyang and Xiao, Hai and Duan, Xiangfeng and Feng, Ziying and Cheng, Rui and Weiss, Nathan O. and Ye, Guojun and Huang, Yun-Chiao and Wu, Hao and Cheng, Hung-Chieh and Shakir, Imran and Liao, Lei and Chen, Xianhui and Goddard, William A., III and Huang, Yu and Duan, Xiangfeng (2018) Monolayer atomic crystal molecular superlattices. Nature, 555 (7695). pp. 231-236. ISSN 0028-0836.

[img] Image (JPEG) (Extended Data Figure 1 : Stepwise reaction mechanism and its partition map) - Supplemental Material
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[img] Image (JPEG) (Extended Data Figure 2 : TEM EDX spectra of BP and MPMS) - Supplemental Material
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[img] Image (JPEG) (Extended Data Figure 3 : Raman spectra characterization of BP and MPMS) - Supplemental Material
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[img] Image (JPEG) (Extended Data Figure 4 : The calculated electronic band structure evolution from BP to MPMS) - Supplemental Material
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[img] Image (JPEG) (Extended Data Figure 5 : The on/off ratio and mobility of the MPMS devices and the recently reported few-layer and thin BP devices) - Supplemental Material
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[img] Image (JPEG) (Extended Data Figure 6 : Lateral BP–MPMS heterojunction) - Supplemental Material
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[img] Image (JPEG) (Extended Data Figure 7 : XRD patterns of MACMS obtained from six additional 2DACs) - Supplemental Material
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[img] Image (JPEG) (Extended Data Table 1: Key characteristics of MPMS and recently reported few-layer BP) - Supplemental Material
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Artificial superlattices, based on van der Waals heterostructures of two-dimensional atomic crystals such as graphene or molybdenum disulfide, offer technological opportunities beyond the reach of existing materials. Typical strategies for creating such artificial superlattices rely on arduous layer-by-layer exfoliation and restacking, with limited yield and reproducibility. The bottom-up approach of using chemical-vapour deposition produces high-quality heterostructures but becomes increasingly difficult for high-order superlattices. The intercalation of selected two-dimensional atomic crystals with alkali metal ions offers an alternative way to superlattice structures, but these usually have poor stability and seriously altered electronic properties. Here we report an electrochemical molecular intercalation approach to a new class of stable superlattices in which monolayer atomic crystals alternate with molecular layers. Using black phosphorus as a model system, we show that intercalation with cetyl-trimethylammonium bromide produces monolayer phosphorene molecular superlattices in which the interlayer distance is more than double that in black phosphorus, effectively isolating the phosphorene monolayers. Electrical transport studies of transistors fabricated from the monolayer phosphorene molecular superlattice show an on/off current ratio exceeding 10^7, along with excellent mobility and superior stability. We further show that several different two-dimensional atomic crystals, such as molybdenum disulfide and tungsten diselenide, can be intercalated with quaternary ammonium molecules of varying sizes and symmetries to produce a broad class of superlattices with tailored molecular structures, interlayer distances, phase compositions, electronic and optical properties. These studies define a versatile material platform for fundamental studies and potential technological applications.

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Liu, Yuanyue0000-0002-5880-8649
Xiao, Hai0000-0001-9399-1584
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2018 Macmillan Publishers Limited. received 20 January 2017; accepted 17 January 2018. The authors acknowledge the Electron Imaging Center for NanoMachines (EICN) at California NanoSystem Institute (CNSI) and Nanoelectronic Research Facility (NRF) at UCLA for technical support. Xiangfeng D. acknowledges support by National Science Foundation DMR1508144 (materials synthesis) and Office of Naval Research through grant number N00014-15-1-2368 (device fabrications). Y.H. acknowledges support by National Science Foundation EFRI-1433541. Y.L. was supported by a Resnick Prize Postdoctoral Fellowship at Caltech. L.L. acknowledges support through the 973 grant of MOST (No. 2013CBA01604). X.H.C. acknowledges support from the National Natural Science Foundation of China (Grant No. 11534010). W.A.G. and Y.L. were also supported by DOE DE-SC0014607. W.A.G acknowledges the Extreme Science and Engineering Discovery Environment (XSEDE) supported by National Science Foundation grant ACI-1053575. Y.L. acknowledges the computational resources sponsored by the DOE’s Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory, and the Texas Advanced Computing Center (TACC). I.S. thanks the Deanship of Scientific Research at King Saud University for its funding of this research through grant PEJP-17-01. Author Contributions: Xiangfeng D., Y.H. and C.W. co-designed the research. C.W. conducted device fabrication, electrical properties measurements and data analysis. C.W., Q.H. and U.H. conducted the intercalation experiments. C.W., U.H., Z.L. and Z.F. conducted structural and optical characterizations. Y.L., H.X. and W.A.G. contributed to the superlattice atomic and electronic structure calculations. E.Z. conducted the TEM studies. Q.H., Xidong D., Y.-C.H., H.W., H.-C.C., I.S. and L.L. contributed to the initial measurement system set-up, preparation of 2D materials and data analysis. R.C. contributed to the initial BP property characterization. N.O.W. contributed to the schematic drawing. G.J.Y. and X.H.C. prepared the initial BP material. Y.H. and Xiangfeng D. supervised the research. Xiangfeng D. and C.W. co-wrote the manuscript. All authors discussed the results and commented on the manuscript. Data availability: The data that support the findings of this study are available from the corresponding author on reasonable request. The authors declare no competing financial interests. Nature thanks N. Guisinger, K. Loh and Q. Xiong for their contribution to the peer review of this work.
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
Office of Naval Research (ONR)N00014-15-1-2368
Resnick Sustainability InstituteUNSPECIFIED
Ministry of Science and Technology (China)2013CBA01604
National Natural Science Foundation of China11534010
Department of Energy (DOE)DE-SC0014607
King Saud UniversityPEJP-17-01
Record Number:CaltechAUTHORS:20180111-131636552
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:84261
Deposited By: George Porter
Deposited On:08 Mar 2018 01:27
Last Modified:22 Mar 2019 23:12

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