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Nano Research 2023, 16(5): 7991-8002 https://doi.org/10.1007/s12274-022-5350-8
Research Article | Open Access | Issue | Published: 04 February 2023

Aromatic self-assembled monolayers with pentafluoro-λ6-sulfanyl (−SF5) termination: Molecular organization and charge transport properties

Show Author's Information Yangbiao Liu1,§,  Marc Zeplichal2,§,  Sonja Katzbach2,  Adrian Wiesner2,  Saunak Das1,  Andreas Terfort2( ),  Michael Zharnikov1( )
Angewandte Physikalische Chemie, Universität Heidelberg, Im Neuenheimer Feld 253, D-69120 Heidelberg, Germany
Institut für Anorganische und Analytische Chemie, Johann Wolfgang Goethe Universität Frankfurt, Max-von-Laue-Straße 7, D-60438 Frankfurt am Main, Germany

§ Yangbiao Liu and Marc Zeplichal contributed equally to this work.

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MonolayersSynthesis (chemical)Thin films
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Liu Y, Zeplichal M, Katzbach S, et al. Aromatic self-assembled monolayers with pentafluoro-λ6-sulfanyl (−SF5) termination: Molecular organization and charge transport properties. Nano Research, 2023, 16(5): 7991-8002. https://doi.org/10.1007/s12274-022-5350-8
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Abstract Full text Electronic supplementary material About this article

A series of molecules with oligophenylene backbone, thiolate anchoring group, and pentafluoro-λ6-sulfanyl (−SF5) tail group was synthesized and used as precursors to form self-assembled monolayers (SAMs) on Au(111) substrates. The resulting SAMs feature dense molecular packing, upright molecular orientation, and chemically homogeneous SAM-ambient interface, comprised entirely of the −SF5 moieties. These SAMs exhibit exceptional wetting and electrostatic properties, showing advancing water contact angles up to 103° and work function values up to 5.96 eV—probably the highest values reported for any aromatic monolayers on gold. They also feature a comparably low value of the tunnelling decay coefficient (0.38 ± 0.07 Å−1), typical of oligophenylene backbone, which is not affected by the introduction of the −SF5 group. The latter also hardly affects the current densities at a specific bias compared to analogous monolayers with other electronegative tail groups. The superior electrostatic and good charge transport properties of the designed, SF5-terminated SAMs make them potentially useful for interface engineering in organic electronics and photovoltaics.


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Electronic supplementary material
About this article

Aromatic self-assembled monolayers with pentafluoro-λ6-sulfanyl (−SF5) termination: Molecular organization and charge transport properties

Show Author's information Yangbiao Liu1,§, Marc Zeplichal2,§, Sonja Katzbach2, Adrian Wiesner2, Saunak Das1, Andreas Terfort2( ), Michael Zharnikov1( )
Angewandte Physikalische Chemie, Universität Heidelberg, Im Neuenheimer Feld 253, D-69120 Heidelberg, Germany
Institut für Anorganische und Analytische Chemie, Johann Wolfgang Goethe Universität Frankfurt, Max-von-Laue-Straße 7, D-60438 Frankfurt am Main, Germany

§ Yangbiao Liu and Marc Zeplichal contributed equally to this work.

Abstract

A series of molecules with oligophenylene backbone, thiolate anchoring group, and pentafluoro-λ6-sulfanyl (−SF5) tail group was synthesized and used as precursors to form self-assembled monolayers (SAMs) on Au(111) substrates. The resulting SAMs feature dense molecular packing, upright molecular orientation, and chemically homogeneous SAM-ambient interface, comprised entirely of the −SF5 moieties. These SAMs exhibit exceptional wetting and electrostatic properties, showing advancing water contact angles up to 103° and work function values up to 5.96 eV—probably the highest values reported for any aromatic monolayers on gold. They also feature a comparably low value of the tunnelling decay coefficient (0.38 ± 0.07 Å−1), typical of oligophenylene backbone, which is not affected by the introduction of the −SF5 group. The latter also hardly affects the current densities at a specific bias compared to analogous monolayers with other electronegative tail groups. The superior electrostatic and good charge transport properties of the designed, SF5-terminated SAMs make them potentially useful for interface engineering in organic electronics and photovoltaics.

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Received: 16 September 2022
Revised: 18 November 2022
Accepted: 20 November 2022
Published: 04 February 2023
Issue date: May 2023

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© The author(s) 2022

Acknowledgements

Acknowledgements

We thank the Helmholtz Zentrum Berlin (HZM) for the allocation of synchrotron radiation beamtime at BESSY II and financial support. We thank Dr. A. Asyuda for assistance at the initial stages of this project and Dr. M. Brzhezinskaya (HZM) for the assistance during the measurements at BESSY II. Y. L. thanks the China Scholarship Council (CSC) for the financial support. S. D. and M. Z. acknowledge the financial support by the German Research Foundation (Deutsche Forschungsgemeinschaft (DFG)) via grant ZH 63/39-1.

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Copyright: © 2022 by the author(s). This article is an open access article distributed under Creative Commons Attribution License (CC BY 4.0), visit https://creativecommons.org/licenses/by/4.0/.

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