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Single-layer ionic conduction on carboxyl-terminated silane monolayers patterned by constructive lithography

Nature Materials volume 14, pages 613–621 (2015)Cite this article

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Abstract

Ionic transport plays a central role in key technologies relevant to energy, and information processing and storage, as well as in the implementation of biological functions in living organisms. Here, we introduce a supramolecular strategy based on the non-destructive chemical patterning of a highly ordered self-assembled monolayer that allows the reproducible fabrication of ion-conducting surface patterns (ion-conducting channels) with top –COOH functional groups precisely definable over the full range of length scales from nanometre to centimetre. The transport of a single layer of selected metal ions and the electrochemical processes related to their motion may thus be confined to predefined surface paths. As a generic solid ionic conductor that can accommodate different mobile ions in the absence of any added electrolyte, these ion-conducting channels exhibit bias-induced competitive transport of different ionic species. This approach offers unprecedented opportunities for the realization of designed ion-conducting systems with nanoscale control, beyond the inherent limitations posed by available ionic materials.

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Figure 1: Schematic representation (not to scale) of proposed bias-driven ionic transport in the different ion-conducting pattern configurations investigated in this study.
Figure 2: Experimental results obtained with ion-conducting macro-channels with silver electrodes (set-up as in Fig. 1b).
Figure 3: Experimental results obtained with ion-conducting macro-channels with titanium electrodes and with a titanium and a silver electrode.
Figure 4: Temperature dependence of the sheet conductance σs (in Ω−1) of ion-conducting macro-channels with silver or titanium electrodes.
Figure 5: Experimental results obtained with the ion-conducting macro–micro–nano-channel (set-up as in Fig. 1c).
Figure 6: Experimental results obtained with nano-channels directly contacted by silver electrodes (set-up as in Fig. 1d).

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Acknowledgements

This research was supported by the Israel Science Foundation (grant No. 931/12) and G. M. J. Schmidt Minerva Center of Supramolecular Architectures. We are grateful to I. Lubomirsky (Weizmann Inst.), E. Gileadi (Tel Aviv Univ.), I. Riess (Technion) and A. Yochelis (Ben-Gurion University of the Negev) for illuminating discussions, H. Cohen for the XPS measurements, G. Gotesman for assistance in the SEM imaging, B. Pasmantirer for assistance in the design of the probe station and equipment for the preparation of electrodes and macro-channels, and O. Westmark for assistance with the graphical presentation.

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Author notes

  1. Jonathan Berson and Doron Burshtain: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot 76100, Israel

    Jonathan Berson, Doron Burshtain, Assaf Zeira, Rivka Maoz & Jacob Sagiv

  2. Department of Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel

    Alexander Yoffe

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  1. Jonathan Berson
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Contributions

J.B.: AFM monolayer nanopatterning (CNL) and imaging, AFM electrical imaging, SEM imaging, analysis and summary of AFM and SEM data. D.B.: AFM monolayer nanopatterning (CNL) and imaging, design of the probe station and of electrochemical measurement set-ups, electrical measurements, analysis and summary of AFM, electrochemical and electrical data. A.Z.: AFM monolayer nanopatterning (CNL), monolayer macropatterning (CEP). A.Y.: development of non-destructive electron-beam deposition procedures for the fabrication of the electrodes and macro-channels. R.M.: supervision of the research, initiation and design of experimental set-ups, monolayer assembly and characterization, monolayer macropatterning (CEP), FTIR measurements, electrical measurements, analysis and summary of FTIR and electrical data. J.S.: initiation and supervision of the research, overall analysis and summary of the experimental results, writing of the manuscript. All authors discussed the results and commented on their interpretation.

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Correspondence to Rivka Maoz or Jacob Sagiv.

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The authors declare no competing financial interests.

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Berson, J., Burshtain, D., Zeira, A. et al. Single-layer ionic conduction on carboxyl-terminated silane monolayers patterned by constructive lithography. Nature Mater 14, 613–621 (2015). https://doi.org/10.1038/nmat4254

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