Abstract
Controlling the electrical conductance and in particular the occurrence of quantum interference in single-molecule junctions through gating effects has potential for the realization of high-performance functional molecular devices. In this work we used an electrochemically gated, mechanically controllable break junction technique to tune the electronic behaviour of thiophene-based molecular junctions that show destructive quantum interference features. By varying the voltage applied to the electrochemical gate at room temperature, we reached a conductance minimum that provides direct evidence of charge transport controlled by an anti-resonance arising from destructive quantum interference. Our molecular system enables conductance tuning close to two orders of magnitude within the non-faradaic potential region, which is significantly higher than that achieved with molecules not showing destructive quantum interference. Our experimental results, interpreted using quantum transport theory, demonstrate that electrochemical gating is a promising strategy for obtaining improved in situ control over the electrical performance of interference-based molecular devices.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
The data that support the findings of this study are available from the corresponding author upon reasonable request.
References
Guedon, C. M. et al. Observation of quantum interference in molecular charge transport. Nat. Nanotech. 7, 305–309 (2012).
Lambert, C. J. Basic concepts of quantum interference and electron transport in single-molecule electronics. Chem. Soc. Rev. 44, 875–888 (2015).
Garner, M. H. et al. Comprehensive suppression of single-molecule conductance using destructive σ-interference. Nature 558, 415–419 (2018).
Frisenda, R., Janssen, V. A. E. C., Grozema, F. C., van der Zant, H. S. J. & Renaud, N. Mechanically controlled quantum interference in individual π-stacked dimers. Nat. Chem. 8, 1099 (2016).
Baer, R. & Neuhauser, D. Phase coherent electronics: a molecular switch based on quantum interference. J. Am. Chem. Soc. 124, 4200–4201 (2002).
Hsu, L. Y. & Rabitz, H. Single-molecule phenyl-acetylene-macrocycle-based optoelectronic switch functioning as a quantum-interference-effect transistor. Phys. Rev. Lett. 109, 186801 (2012).
Bergfield, J. P., Solomon, G. C., Stafford, C. A. & Ratner, M. A. Novel quantum interference effects in transport through molecular radicals. Nano Lett. 11, 2759–2764 (2011).
Manrique, D. Z. et al. A quantum circuit rule for interference effects in single-molecule electrical junctions. Nat. Commun. 6, 6389 (2015).
Sangtarash, S. et al. Searching the hearts of graphene-like molecules for simplicity, sensitivity, and logic. J. Am. Chem. Soc. 137, 11425–11431 (2015).
Liu, X. S. et al. Gating of quantum interference in molecular junctions by heteroatom substitution. Angew. Chem. Int. Ed. 56, 173–176 (2017).
Huang, C. et al. Single-molecule detection of dihydroazulene photo-thermal reaction using break junction technique. Nat. Commun. 8, 15436 (2017).
Song, H. et al. Observation of molecular orbital gating. Nature 462, 1039–1043 (2009).
Perrin, M. L. et al. Large tunable image-charge effects in single-molecule junctions. Nat. Nanotech. 8, 282 (2013).
Huang, C., Rudnev, A. V., Hong, W. & Wandlowski, T. Break junction under electrochemical gating: testbed for single-molecule electronics. Chem. Soc. Rev. 44, 889–901 (2015).
Nichols, R. J. & Higgins, S. J. Single molecule nanoelectrochemistry in electrical junctions. Acc. Chem. Res. 49, 2640–2648 (2016).
Capozzi, B. et al. Tunable charge transport in single-molecule junctions via electrolytic gating. Nano Lett. 14, 1400–1404 (2014).
Xiang, L. et al. Gate-controlled conductance switching in DNA. Nat. Commun. 8, 14471 (2017).
Baghernejad, M. et al. Highly-effective gating of single-molecule junctions: an electrochemical approach. Chem. Commun. 50, 15975–15978 (2014).
Brooke, R. J. et al. Single-molecule electrochemical transistor utilizing a nickel-pyridyl spinterface. Nano Lett. 15, 275–280 (2015).
Kay, N. J. et al. Single-molecule electrochemical gating in ionic liquids. J. Am. Chem. Soc. 134, 16817–16826 (2012).
Ruiz, M. P. et al. Bioengineering a single-protein junction. J. Am. Chem. Soc. 139, 15337–15346 (2017).
Ting, T.-C. et al. Energy-level alignment for single-molecule conductance of extended metal-atom chains. Angew. Chem. Int. Ed. 54, 15734–15738 (2015).
Capozzi, B. et al. Mapping the transmission functions of single-molecule junctions. Nano Lett. 16, 3949–3954 (2016).
Hong, W. et al. Single molecular conductance of tolanes: experimental and theoretical study on the junction evolution dependent on the anchoring group. J. Am. Chem. Soc. 134, 2292–2304 (2012).
Li, J., Shen, Y., Zhang, Y. & Liu, Y. Room-temperature ionic liquids as media to enhance the electrochemical stability of self-assembled monolayers of alkanethiols on gold electrodes. Chem. Commun. 2005, 360–362 (2005).
Guo, S., Hihath, J., Díez-Pérez, I. & Tao, N. Measurement and statistical analysis of single-molecule current–voltage characteristics, transition voltage spectroscopy, and tunneling barrier height. J. Am. Chem. Soc. 133, 19189–19197 (2011).
Leary, E. et al. Detecting mechanochemical atropisomerization within an STM break junction. J. Am. Chem. Soc. 140, 710–718 (2018).
Sadeghi, H. Theory of electron, phonon and spin transport in nanoscale quantum devices. Nanotechnology 29, 373001 (2018).
Ferrer, J. et al. Gollum: a next-generation simulation tool for electron, thermal and spin transport. New J. Phys. 16, 093029 (2014).
Shitanda, I., Kiryu, H. & Itagaki, M. Improvement in the long-term stability of screen-printed planar type solid-state Ag/AgCl reference electrode by introducing poly(dimethylsiloxane) liquid junction. Electrochim. Acta 58, 528–531 (2011).
Meszaros, G., Li, C., Pobelov, I. & Wandlowski, T. Current measurements in a wide dynamic range—applications in electrochemical nanotechnology. Nanotechnology 18, 424004 (2007).
Hong, W. et al. An MCBJ case study: the influence of π-conjugation on the single-molecule conductance at a solid/liquid interface. Beilstein J. Nanotechnol. 2, 699–713 (2011).
José, M. S. et al. The SIESTA method for ab initio order-N materials simulation. J. Phys. Condens. Matter 14, 2745–2779 (2002).
Acknowledgements
This research was supported by the National Key R&D Program of China (2017YFA0204902), the National Natural Science Foundation of China (21722305, 21673195, 21503179 and 21703188), the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning, the Natural Science Foundation of Shanghai (17ZR1447100), the Science and Technology Commission of Shanghai Municipality (14DZ2261000) and the China Postdoctoral Science Foundation (2017M622060) for funding work in Xiamen. It was also supported by EU Horizon 2020 project QuIET under grant agreement no. 767187 and UK EPSRC grants EP/N017188/1 and EP/M014452/1 and Leverhulme Trust (Leverhulme Early Career Fellowships no. ECF-2017-186 and ECF-2018-375) for funding instrumentation used in Lancaster. It was also supported by Hungarian and Czech Academies of Sciences (P2015-107) andHungarian Research Foundation (OTKA 112034) for funding instrumentation used in Hungary. The authors thank Z.-Q. Tian and B.-W. Mao, Xiamen University, for useful discussions.
Author information
Authors and Affiliations
Contributions
W.H. and J.B. conceived the idea and designed the experiments. W.H., C.L. and W.C. co-supervised the project. J.B., W.H., A.D. and S.S. wrote the manuscript with input from all authors. J.B., X.L. and X.H. carried out the break junction experiments and analysed the data. Q.Z. and W.C. synthesized and provided the structural characterization of the molecules. J.B. and S.L. performed the cyclic voltammetry measurements. Y.T., G.M., J.S. and W.H. built the electrical measurement instrument and wrote the software to control the break junction set-up. A.D., S.S., C.L. and H.S. performed the theoretical modelling. Z.T., J.L. and Y.Y. revised the manuscript. All authors discussed the experiments.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
Supplementary Sections 1–5, Supplementary Figures 1–10, Supplementary References 1–21
Rights and permissions
About this article
Cite this article
Bai, J., Daaoub, A., Sangtarash, S. et al. Anti-resonance features of destructive quantum interference in single-molecule thiophene junctions achieved by electrochemical gating. Nat. Mater. 18, 364–369 (2019). https://doi.org/10.1038/s41563-018-0265-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41563-018-0265-4
This article is cited by
-
Quantum interference enhances the performance of single-molecule transistors
Nature Nanotechnology (2024)
-
Graphene edge interference improves single-molecule transistors
Nature Nanotechnology (2024)
-
Molecule-based vertical transistor via intermolecular charge transport through π-π stacking
Nano Research (2024)
-
Local cation-tuned reversible single-molecule switch in electric double layer
Nature Communications (2023)
-
Real-time monitoring of reaction stereochemistry through single-molecule observations of chirality-induced spin selectivity
Nature Chemistry (2023)