A Cu3BHT-Graphene van der Waals Heterostructure with Strong Interlayer Coupling for Highly Efficient Photoinduced Charge Separation

Zhiyong Wang; Shuai Fu; Wenjie Zhang; Baokun Liang; Tsai Jung Liu; Mike Hambsch; Jonas F. Pöhls; Yufeng Wu; Jianjun Zhang; Tianshu Lan; Xiaodong Li; Haoyuan Qi; Miroslav Polozij; Stefan C.B. Mannsfeld; Ute Kaiser; Mischa Bonn; R. Thomas Weitz; Thomas Heine; Stuart S.P. Parkin; Hai I. Wang; Renhao Dong; Xinliang Feng

doi:10.1002/adma.202311454

A Cu₃BHT-Graphene van der Waals Heterostructure with Strong Interlayer Coupling for Highly Efficient Photoinduced Charge Separation

Zhiyong Wang, Shuai Fu, Wenjie Zhang, Baokun Liang, Tsai Jung Liu, Mike Hambsch, Jonas F. Pöhls, Yufeng Wu, Jianjun Zhang, Tianshu Lan, Xiaodong Li, Haoyuan Qi, Miroslav Polozij, Stefan C.B. Mannsfeld, Ute Kaiser, Mischa Bonn, R. Thomas Weitz, Thomas Heine, Stuart S.P. Parkin^*, Hai I. Wang^*Renhao Dong^*, Xinliang Feng^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Two-dimensional van der Waals heterostructures (2D vdWhs) are of significant interest due to their intriguing physical properties critically defined by the constituent monolayers and their interlayer coupling. Synthetic access to 2D vdWhs based on chemically tunable monolayer organic 2D materials remains challenging. Herein, the fabrication of a novel organic–inorganic bilayer vdWh by combining π-conjugated 2D coordination polymer (2DCP, i.e., Cu₃BHT, BHT = benzenehexathiol) with graphene is reported. Monolayer Cu₃BHT with detectable µm²-scale uniformity and atomic flatness is synthesized using on-water surface chemistry. A combination of diffraction and imaging techniques enables the determination of the crystal structure of monolayer Cu₃BHT with atomic precision. Leveraging the strong interlayer coupling, Cu₃BHT-graphene vdWh exhibits highly efficient photoinduced interlayer charge separation with a net electron transfer efficiency of up to 34% from Cu₃BHT to graphene, superior to those of reported bilayer 2D vdWhs and molecular-graphene vdWhs. This study unveils the potential for developing novel 2DCP-based vdWhs with intriguing physical properties.

Original language	English
Article number	2311454
Journal	Advanced Materials
Volume	36
Issue number	21
Early online date	21 Feb 2024
DOIs	https://doi.org/10.1002/adma.202311454
Publication status	Published - 23 May 2024

Bibliographical note

Publisher Copyright:
© 2024 The Authors. Advanced Materials published by Wiley-VCH GmbH.

Funding

Z.W., S.F., and W.Z. contributed equally to this work. This work was financially supported by the National Natural Science Foundation of China (22272092), ERC starting grant (FC2DMOF, No. 852909), ERC Consolidator Grant (T2DCP), DFG project (2D polyanilines, No. 426572620), H2020-FETOPEN (PROGENY, 899205), CRC 1415 (Chemistry of Synthetic Two-Dimensional Materials, No. 417590517), SPP 2244 (2DMP), GRK2861 (No. 491865171), EMPIR-20FUN03-COMET, as well as the German Science Council and Center of Advancing Electronics Dresden (cfaed). R.D. thanks Taishan Scholars Program of Shandong Province (tsqn201909047) and the Natural Science Foundation of Shandong Province (ZR2023JQ005). The authors acknowledge cfaed and Dresden Center for Nanoanalysis (DCN) at TUD and Dr. Petr Formanek, Prof. Andreas Fery, Anna Maria Dominic, and Prof. Inez M. Weidinger for the use of the TEM facility at IPF, as well as the Raman measurement. The authors acknowledge SOLEIL for the provision of synchrotron radiation facilities and the authors would like to thank Dr. Arnaud Hemmerle for assistance in using beamline SIRIUS. T.L., M.P., and T.H. thank ZIH Dresden for the use of computational resources.

Funders	Funder number
Center of Advancing Electronics Dresden
Wissenschaftsrat
European Research Council	T2DCP, 852909, FC2DMOF
European Research Council
Deutsche Forschungsgemeinschaft	GRK2861, 899205, 417590517, 491865171, 426572620, SPP 2244
Deutsche Forschungsgemeinschaft
National Natural Science Foundation of China	22272092
National Natural Science Foundation of China
Natural Science Foundation of Shandong Province	ZR2023JQ005
Natural Science Foundation of Shandong Province
Taishan Scholar Project of Shandong Province	tsqn201909047
Taishan Scholar Project of Shandong Province

Keywords

2D van der Waals heterostructures
charge separation
conductive 2D coordination polymers
interlayer coupling

Access to Document

10.1002/adma.202311454Licence: CC BY

Advanced Materials - 2024 - Wang - A Cu3BHT‐Graphene van der Waals Heterostructure with Strong Interlayer Coupling forFinal published version, 6.44 MBLicence: CC BY

Cite this

Wang, Z., Fu, S., Zhang, W., Liang, B., Liu, T. J., Hambsch, M., Pöhls, J. F., Wu, Y., Zhang, J., Lan, T., Li, X., Qi, H., Polozij, M., Mannsfeld, S. C. B., Kaiser, U., Bonn, M., Weitz, R. T., Heine, T., Parkin, S. S. P., ... Feng, X. (2024). A Cu₃BHT-Graphene van der Waals Heterostructure with Strong Interlayer Coupling for Highly Efficient Photoinduced Charge Separation. Advanced Materials, 36(21), Article 2311454. https://doi.org/10.1002/adma.202311454

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title = "A Cu3BHT-Graphene van der Waals Heterostructure with Strong Interlayer Coupling for Highly Efficient Photoinduced Charge Separation",

abstract = "Two-dimensional van der Waals heterostructures (2D vdWhs) are of significant interest due to their intriguing physical properties critically defined by the constituent monolayers and their interlayer coupling. Synthetic access to 2D vdWhs based on chemically tunable monolayer organic 2D materials remains challenging. Herein, the fabrication of a novel organic–inorganic bilayer vdWh by combining π-conjugated 2D coordination polymer (2DCP, i.e., Cu3BHT, BHT = benzenehexathiol) with graphene is reported. Monolayer Cu3BHT with detectable µm2-scale uniformity and atomic flatness is synthesized using on-water surface chemistry. A combination of diffraction and imaging techniques enables the determination of the crystal structure of monolayer Cu3BHT with atomic precision. Leveraging the strong interlayer coupling, Cu3BHT-graphene vdWh exhibits highly efficient photoinduced interlayer charge separation with a net electron transfer efficiency of up to 34% from Cu3BHT to graphene, superior to those of reported bilayer 2D vdWhs and molecular-graphene vdWhs. This study unveils the potential for developing novel 2DCP-based vdWhs with intriguing physical properties.",

keywords = "2D van der Waals heterostructures, charge separation, conductive 2D coordination polymers, interlayer coupling",

author = "Zhiyong Wang and Shuai Fu and Wenjie Zhang and Baokun Liang and Liu, {Tsai Jung} and Mike Hambsch and P{\"o}hls, {Jonas F.} and Yufeng Wu and Jianjun Zhang and Tianshu Lan and Xiaodong Li and Haoyuan Qi and Miroslav Polozij and Mannsfeld, {Stefan C.B.} and Ute Kaiser and Mischa Bonn and Weitz, {R. Thomas} and Thomas Heine and Parkin, {Stuart S.P.} and Wang, {Hai I.} and Renhao Dong and Xinliang Feng",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Advanced Materials published by Wiley-VCH GmbH.",

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month = may,

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Wang, Z, Fu, S, Zhang, W, Liang, B, Liu, TJ, Hambsch, M, Pöhls, JF, Wu, Y, Zhang, J, Lan, T, Li, X, Qi, H, Polozij, M, Mannsfeld, SCB, Kaiser, U, Bonn, M, Weitz, RT, Heine, T, Parkin, SSP, Wang, HI, Dong, R & Feng, X 2024, 'A Cu₃BHT-Graphene van der Waals Heterostructure with Strong Interlayer Coupling for Highly Efficient Photoinduced Charge Separation', Advanced Materials, vol. 36, no. 21, 2311454. https://doi.org/10.1002/adma.202311454

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T1 - A Cu3BHT-Graphene van der Waals Heterostructure with Strong Interlayer Coupling for Highly Efficient Photoinduced Charge Separation

AU - Wang, Zhiyong

AU - Fu, Shuai

AU - Zhang, Wenjie

AU - Liang, Baokun

AU - Liu, Tsai Jung

AU - Hambsch, Mike

AU - Pöhls, Jonas F.

AU - Wu, Yufeng

AU - Zhang, Jianjun

AU - Lan, Tianshu

AU - Li, Xiaodong

AU - Qi, Haoyuan

AU - Polozij, Miroslav

AU - Mannsfeld, Stefan C.B.

AU - Kaiser, Ute

AU - Bonn, Mischa

AU - Weitz, R. Thomas

AU - Heine, Thomas

AU - Parkin, Stuart S.P.

AU - Wang, Hai I.

AU - Dong, Renhao

AU - Feng, Xinliang

PY - 2024/5/23

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N2 - Two-dimensional van der Waals heterostructures (2D vdWhs) are of significant interest due to their intriguing physical properties critically defined by the constituent monolayers and their interlayer coupling. Synthetic access to 2D vdWhs based on chemically tunable monolayer organic 2D materials remains challenging. Herein, the fabrication of a novel organic–inorganic bilayer vdWh by combining π-conjugated 2D coordination polymer (2DCP, i.e., Cu3BHT, BHT = benzenehexathiol) with graphene is reported. Monolayer Cu3BHT with detectable µm2-scale uniformity and atomic flatness is synthesized using on-water surface chemistry. A combination of diffraction and imaging techniques enables the determination of the crystal structure of monolayer Cu3BHT with atomic precision. Leveraging the strong interlayer coupling, Cu3BHT-graphene vdWh exhibits highly efficient photoinduced interlayer charge separation with a net electron transfer efficiency of up to 34% from Cu3BHT to graphene, superior to those of reported bilayer 2D vdWhs and molecular-graphene vdWhs. This study unveils the potential for developing novel 2DCP-based vdWhs with intriguing physical properties.

AB - Two-dimensional van der Waals heterostructures (2D vdWhs) are of significant interest due to their intriguing physical properties critically defined by the constituent monolayers and their interlayer coupling. Synthetic access to 2D vdWhs based on chemically tunable monolayer organic 2D materials remains challenging. Herein, the fabrication of a novel organic–inorganic bilayer vdWh by combining π-conjugated 2D coordination polymer (2DCP, i.e., Cu3BHT, BHT = benzenehexathiol) with graphene is reported. Monolayer Cu3BHT with detectable µm2-scale uniformity and atomic flatness is synthesized using on-water surface chemistry. A combination of diffraction and imaging techniques enables the determination of the crystal structure of monolayer Cu3BHT with atomic precision. Leveraging the strong interlayer coupling, Cu3BHT-graphene vdWh exhibits highly efficient photoinduced interlayer charge separation with a net electron transfer efficiency of up to 34% from Cu3BHT to graphene, superior to those of reported bilayer 2D vdWhs and molecular-graphene vdWhs. This study unveils the potential for developing novel 2DCP-based vdWhs with intriguing physical properties.

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