Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Transition from direct to inverted charge transport Marcus regions in molecular junctions via molecular orbital gating

Nature Nanotechnology volume 13, pages 322–329 (2018)Cite this article

Subjects

Abstract

Solid-state molecular tunnel junctions are often assumed to operate in the Landauer regime, which describes essentially activationless coherent tunnelling processes. In solution, on the other hand, charge transfer is described by Marcus theory, which accounts for thermally activated processes. In practice, however, thermally activated transport phenomena are frequently observed also in solid-state molecular junctions but remain poorly understood. Here, we show experimentally the transition from the Marcus to the inverted Marcus region in a solid-state molecular tunnel junction by means of intra-molecular orbital gating that can be tuned via the chemical structure of the molecule and applied bias. In the inverted Marcus region, charge transport is incoherent, yet virtually independent of temperature. Our experimental results fit well to a theoretical model that combines Landauer and Marcus theories and may have implications for the interpretation of temperature-dependent charge transport measurements in molecular junctions.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Illustrations of the junctions and description of the combined Marcus–Landauer model.
Fig. 2: Temperature-dependent measurements of the SAM-based junctions.
Fig. 3: Temperature-dependent measurements of the single-molecule junctions.
Fig. 4: Fits to the combined Marcus–Landauer theory.

Similar content being viewed by others

References

  1. Yuan, L. et al. Controlling the direction of rectification in a molecular diode. Nat. Commun. 6, 6324 (2015).

    Article  Google Scholar 

  2. Du, W. et al. On-chip molecular electronic plasmon sources based on self-assembled monolayer tunnel junctions. Nat. Photon. 10, 274–280 (2016).

    Article  Google Scholar 

  3. Chikkaraddy, R. et al. Single-molecule strong coupling at room temperature in plasmonic nanocavities. Nature 535, 127–130 (2016).

    Article  Google Scholar 

  4. Vilan, A., Aswal, D. & Cahen, D. Large-area, ensemble molecular electronics: Motivation and challenges. Chem. Rev. 117, 4248–4286 (2017).

    Article  Google Scholar 

  5. Jeong, H., Kim, D., Xiang, D. & Lee, T. High-yield functional molecular electronic devices. ACS Nano 11, 6511–6548 (2017).

    Article  Google Scholar 

  6. Shpaisman, H. et al. Structure Matters: Correlating temperature dependent electrical transport through alkyl monolayers with vibrational and photoelectron spectroscopies. Chem. Sci. 3, 851–862 (2012).

    Article  Google Scholar 

  7. McCreery, R. L. & Bergren, A. J. Progress with molecular electronic junctions: Meeting experimental challenges in design and fabrication. Adv. Mater. 21, 4303–4322 (2009).

    Article  Google Scholar 

  8. Landauer, R. Spatial variation of currents and fields due to localized scatterers in metallic conduction. IBM J. Res. Dev. 1, 223–231 (1957).

    Article  Google Scholar 

  9. Joachim, C. & Ratner, M. A. Molecular electronics: Some views on transport junctions and beyond. Proc. Natl Acad. Sci. USA 102, 8801–8808 (2005).

    Article  Google Scholar 

  10. Moth-Poulsen, K. & Bjørnholm, T. Molecular electronics with single molecules in solid-state devices. Nat. Nanotech. 4, 551–556 (2009).

    Article  Google Scholar 

  11. Garrigues, A. R. et al. A single-level tunnel model to account for electrical transport through single molecule- and self-assembled monolayer-based junctions. Sci. Rep. 6, 26517 (2016).

    Article  Google Scholar 

  12. Migliore, A., Schiff, P. & Nitzan, A. On the relationship between molecular state and single electron pictures in simple electrochemical junctions. Phys. Chem. Chem. Phys. 14, 13746–13753 (2012).

    Article  Google Scholar 

  13. Hines, T. et al. Transition from tunneling to hopping in single molecular junctions by measuring length and temperature dependence. J. Am. Chem. Soc. 132, 11658–11664 (2010).

    Article  Google Scholar 

  14. Ho Choi, S., Kim, B. & Frisbie, C. D. Electrical resistance of long conjugated molecular wires. Science 320, 1482–1486 (2008).

    Article  Google Scholar 

  15. Sayed, S. Y., Fereiro, J. A., Yan, H., McCreery, R. L. & Bergren, A. J. Charge transport in molecular electronic junctions: Compression of the molecular tunnel barrier in the strong coupling regime. Proc. Natl Acad. Sci. USA 109, 11498–11503 (2012).

    Article  Google Scholar 

  16. Zhao, X. et al. Oligo(aryleneethynylene)s with terminal pyridyl groups: Synthesis and length dependence of the tunneling-to-hopping transition of single-molecule conductances. Chem. Mater. 25, 4340–4347 (2013).

    Article  Google Scholar 

  17. Koch, M., Ample, F., Joachim, C. & Grill, L. Voltage-dependent conductance of a single graphene nanoribbon. Nat. Nanotech. 7, 713–717 (2012).

    Article  Google Scholar 

  18. Amdursky, N., Ferber, D., Pecht, I., Sheves, M. & Cahen, D. Redox activity distinguishes solid-state electron transport from solution-based electron transfer in a natural and artificial protein: cytochrome C and hemin-doped human serum albumin. Phys. Chem. Chem. Phys. 15, 17142–17149 (2013).

    Article  Google Scholar 

  19. Kumar, K. S., Pasula, R. R., Lim, S. & Nijhuis, C. A. Long-range tunneling processes across ferritin-based junctions. Adv. Mater. 28, 1824–1830 (2016).

    Article  Google Scholar 

  20. Nerngchamnong, N. et al. The role of van der Waals forces in the performance of molecular diodes. Nat. Nanotech. 8, 113–118 (2013).

    Article  Google Scholar 

  21. Garrigues, A. R., Wang, L., del Barco, E. & Nijhuis, C. A. Electrostatic control over temperature-dependent tunnelling across a single-molecule junction. Nat. Commun. 7, 11595 (2016).

    Article  Google Scholar 

  22. Li, Y., Zhao, J., Yin, X., Liu, H. & Yin, G. Conformational analysis of diphenylacetylene under the influence of an external electric field. Phys. Chem. Chem. Phys. 9, 1186–1193 (2007).

    Article  Google Scholar 

  23. Nijhuis, C. A., Reus, W. F., Barber, J. R., Dickey, M. D. & Whitesides, G. M. Charge transport and rectification in arrays of SAM-based tunneling junctions. Nano Lett. 10, 3611–3619 (2010).

    Article  Google Scholar 

  24. Thompson, D. & Nijhuis, C. A. Even the odd numbers help: Failure modes of SAM-based tunnel junctions probed via odd-even effects revealed in synchrotrons and supercomputers. Acc. Chem. Res. 49, 2061–2069 (2016).

    Article  Google Scholar 

  25. Migliore, A. & Nitzan, A. Nonlinear charge transport in redox molecular junctions: A Marcus perspective. ACS Nano 5, 6669–6685 (2011).

    Article  Google Scholar 

  26. Migliore, A. & Nitzan, A. Irreversibility and hysteresis in redox molecular conduction junctions. J. Am. Chem. Soc. 135, 9420–9432 (2013).

    Article  Google Scholar 

  27. Jeong, H. et al. Redox-induced asymmetric electrical characteristics of ferrocene-alkanethiolate molecular devices on rigid and flexible substrates. Adv. Funct. Mater. 24, 2472–2480 (2014).

    Article  Google Scholar 

  28. Müller-Meskamp, L. et al. Field-emission resonances at tip/α,ω-mercaptoalkyl ferrocene/Au interfaces studied by STM. Small 5, 496–502 (2009).

    Article  Google Scholar 

  29. Mentovich, E. D. et al. Gated-controlled rectification of a self-assembled monolayer-based transistor. J. Phys. Chem. C. 117, 8468–8474 (2013).

    Article  Google Scholar 

  30. Metzger, R. M. Unimolecular electronics. Chem. Rev. 115, 5056–5115 (2015).

    Article  Google Scholar 

  31. Capozzi, B. et al. Single-molecule diodes with high rectification ratios through environmental control. Nat. Nanotech. 10, 522–527 (2015).

    Article  Google Scholar 

  32. Poot, M. et al. Temperature dependence of three-terminal molecular junctions with sulfur end-functionalized tercyclohexylidenes. Nano Lett. 6, 1031–1035 (2006).

    Article  Google Scholar 

  33. Baldea, I. Protocol for disentangling the thermally activated contribution to the tunneling-assisted charge transport. Analytical results and experimental relevance. Phys. Chem. Chem. Phys. 19, 11759–11770 (2017).

    Article  Google Scholar 

  34. van der Wiel, W. G. et al. Electron transport through double quantum dots. Rev. Mod. Phys. 75, 1–22 (2002).

    Article  Google Scholar 

  35. Schröer, D. M. et al. Kondo effect in a one-electron double quantum dot: Oscillations of the Kondo current in a weak magnetic field. Phys. Rev. B 74, 233301 (2006).

    Article  Google Scholar 

  36. Mason, N., Biercuk, M. J. & Marcus, C. M. Local gate control of a carbon nanotube double quantum dot. Science 303, 655–658 (2004).

    Article  Google Scholar 

  37. Garrigues, A. R. et al. Temperature dependent charge transport across tunnel junctions of single-molecules and self-assembled monolayers: a comparative study. Dalton Trans. 45, 17153–17159 (2016).

    Article  Google Scholar 

  38. Nijhuis, C. A., Reus, W. F. & Whitesides, G. M. Molecular rectification in metal–SAM–metal oxide–metal junctions. J. Am. Chem. Soc. 131, 17814–17827 (2009).

    Article  Google Scholar 

  39. Chiechi, R. C., Weiss, E. A., Dickey, M. D. & Whitesides, G. M. Eutectic gallium-indium (EGaIn): A moldable liquid metal for electrical characterization of self-assembled monolayers. Angew. Chem. Int. Ed. 47, 142–144 (2008).

    Article  Google Scholar 

  40. Wan, A. et al. Arrays of high quality SAM-based junctions and their application in molecular diode based logic. Nanoscale 7, 19547–19556 (2015).

    Article  Google Scholar 

  41. Bard, A. J. & Faulkner, L. R. Electrochemical Methods: Fundamentals and Applications. (Wiley, New York, 1980).

    Google Scholar 

  42. Ishida, T. et al. High-resolution X-ray photoelectron spectra of organosulfur monolayers on Au(111): S(2p) spectral dependence on molecular species. Langmuir 15, 6799–6806 (1999).

    Article  Google Scholar 

  43. Watcharinyanon, S. et al. Molecular orientation of thiol-derivatized tetraphenylporphyrin on gold studied by XPS and NEXAFS. Surf. Sci. 603, 1026–1033 (2009).

    Article  Google Scholar 

  44. Shaporenko, A., Rössler, K., Lang, H. & Zharnikov, M. Self-assembled monolayers of ferrocene-substituted biphenyl ethynyl thiols on gold. J. Phys. Chem. B 110, 24621–24628 (2006).

    Article  Google Scholar 

  45. Kanuru, V. K. et al. Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111). J. Am. Chem. Soc. 132, 8081–8086 (2010).

    Article  Google Scholar 

  46. Yuan, L., Breuer, R., Jiang, L., Schmittel, M. & Nijhuis, C. A. A molecular diode with a statistically robust rectification ratio of three orders of magnitude. Nano Lett. 15, 5506–5512 (2015).

    Article  Google Scholar 

  47. Wan, A., Jiang, L., Sangeeth, C. S. S. & Nijhuis, C. A. Reversible soft top-contacts to yield molecular junctions with precise and reproducible electrical characteristics. Adv. Funct. Mater. 24, 4442–4456 (2014).

    Article  Google Scholar 

  48. Henderson, J. J., Ramsey, C. M., Barco, E. d., Mishra, A. & Christou, G. Fabrication of nanogapped single-electron transistors for transport studies of individual single-molecule magnets. J. Appl. Phys. 101, 09E102 (2007).

    Article  Google Scholar 

  49. José, M. S. et al. The SIESTA method for ab initio order-N materials simulation. J. Phys. Condens. Matter 14, 2745–2779 (2002).

    Article  Google Scholar 

  50. Frisch, M. J. et al. Gaussian 09, revision D.01. (Gaussian, Inc., Wallingford CT, 2013).

    Google Scholar 

Download references

Acknowledgements

L.Y., L.J.W., L.J., H.V.A. and C.A.N. acknowledge the Ministry of Education (MOE) for supporting this research under award no. MOE2015-T2-1-050, and the National Research Foundation, Prime Minister’s Office, Singapore, under its Medium-sized Centre Program. A.R.G., M.A.A. and E.B. acknowledge support from the National Science Foundation (grants NSF-ECCS #1402990 and #1518863). Yu Xiaojiang is kindly acknowledged for assisting at the SINS beam line at SSLS under NUS core support C-380-003-003-001.

Author information

Author notes

  1. Lejia Wang

    Present address: School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo, China

  2. These authors contributed equally: Li Yuan, Lejia Wang and Alvar R. Garrigues.

Authors and Affiliations

  1. Department of Chemistry, National University of Singapore, Singapore, Singapore

    Li Yuan, Lejia Wang, Li Jiang, Harshini Venkata Annadata & Christian A. Nijhuis

  2. Department of Physics, University of Central Florida, Orlando, Florida, USA

    Alvar R. Garrigues, Marta Anguera Antonana & Enrique Barco

  3. Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, Singapore, Singapore

    Christian A. Nijhuis

  4. NUSNNI-Nanocore, National University of Singapore, Singapore, Singapore

    Christian A. Nijhuis

Authors
  1. Li Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lejia Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Alvar R. Garrigues
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Li Jiang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Harshini Venkata Annadata
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Marta Anguera Antonana
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Enrique Barco
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Christian A. Nijhuis
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

L.J.W. synthesized and characterized the ferrocene-based molecules. L.Y. conducted the temperature-dependent measurements and characterized the ferrocene-based SAMs. L.J. performed the charge transport measurements at room temperature. H.V.A. performed the DFT calculations. A.R.G. conducted the single-molecule transport measurements and fitted the data to a double quantum dot model. M.A.A. assisted with the single-molecule measurements. E.B. supervised the single-molecule experiments and fitted the SAMs data. C.A.N. conceived and supervised the project. All the authors contributed to the writing of the article and interpretation of the results.

Corresponding authors

Correspondence to Enrique Barco or Christian A. Nijhuis.

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 Figures 1–43, Supplementary Tables 1–4, Supplementary Methods, Supplementary discussions.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yuan, L., Wang, L., Garrigues, A.R. et al. Transition from direct to inverted charge transport Marcus regions in molecular junctions via molecular orbital gating. Nature Nanotech 13, 322–329 (2018). https://doi.org/10.1038/s41565-018-0068-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41565-018-0068-4

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing