Spatial periodicity in molecular switching

Abstract

The ultimate miniaturization of future devices will require the use of functional molecules at the nanoscale and their integration into larger architectures1,2. Switches represent a prototype of such functional molecules because they exhibit characteristic states of different physical/chemical properties, which can be addressed reversibly3. Recently, various switching entities have been studied and switching of single molecules on surfaces has been demonstrated4,5,6,7,8,9,10,11,12,13. However, for functional molecules to be used in a future device, it will be necessary to selectively address individual molecules, preferentially in an ordered pattern. Here, we show that azobenzene derivatives in the trans form, adsorbed in a homogeneous two-dimensional layer, can be collectively switched with spatial selectivity, thus forming a periodic pattern of cis isomers. We find that the probability of a molecule switching is not equally distributed, but is strongly dependent on both the surrounding molecules and the supporting surface, which precisely determine the switching capability of each individual molecule. Consequently, exactly the same lattices of cis isomers are created in repeated erasing and re-switching cycles. Our results demonstrate a conceptually new approach to spatially addressing single functional molecules.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Figure 1: Different surface structures caused by the molecular asymmetry of M-TBA.
Figure 2: Selective molecular switching for different structures.
Figure 3: Molecular switching in periodic arrays.
Figure 4: Erasing and re-switching.

References

  1. 1

    Joachim, C., Gimzewski, J. K. & Aviram, A. Electronics using hybrid-molecular and mono-molecular devices. Nature 408, 541–548 (2000).

    CAS  Article  Google Scholar 

  2. 2

    Heath, J. R. & Ratner, M. A. Molecular electronics. Physics Today 56, 43–49 (2003).

    CAS  Article  Google Scholar 

  3. 3

    Feringa, B. L. Molecular Switches (Wiley-VCH, Weinheim, 2001).

    Google Scholar 

  4. 4

    Choi, B.-Y. et al. Conformational molecular switch of the azobenzene molecule: A scanning tunnelling microscopy study. Phys. Rev. Lett. 96, 156106 (2006).

    Article  Google Scholar 

  5. 5

    Henzl, J., Mehlhorn, M., Gawronski, H., Rieder, K.-H. & Morgenstern, K. Reversible cis-trans isomerization of a single azobenzene molecule. Angew. Chem. Int. Ed. 45, 603–606 (2006).

    CAS  Article  Google Scholar 

  6. 6

    Alemani, M. et al. Electric field-induced isomerization of azobenzene by STM. J. Am. Chem. Soc. 128, 14446–14447 (2006).

    CAS  Article  Google Scholar 

  7. 7

    Hagen, S., Leyssner, F., Nandi, D., Wolf, M. & Tegeder, P. Reversible switching of tetra-tert-butyl-azobenzene on a Au(111) surface induced by light and thermal activation. Chem. Phys. Lett. 444, 85–90 (2007).

    CAS  Article  Google Scholar 

  8. 8

    Comstock, M. J. et al. Reversible photomechanical switching of individual engineered molecules at a metallic surface. Phys. Rev. Lett. 99, 038301 (2007).

  9. 9

    Pace, G. et al. Cooperative light-induced molecular movements of highly ordered azobenzene self-assembled monolayers. Proc. Natl Acad. Sci. 104, 9937–9942 (2007).

    CAS  Article  Google Scholar 

  10. 10

    Tsai, C.-S., Wang, J.-K., Skodje, R. T. & Lin, J.-C. A single molecule view of bistilbene photoisomerization on a surface using scanning tunnelling microscopy. J. Am. Chem. Soc. 127, 10788–10789 (2005).

    CAS  Article  Google Scholar 

  11. 11

    Katsonis, N. et al. Reversible conductance switching of single diarylethenes on a gold surface. Adv. Mater. 18, 1397–1400 (2006).

    CAS  Article  Google Scholar 

  12. 12

    Liljeroth, P., Repp, J. & Meyer, G. Current-induced hydrogen tautomerization and conductance switching of naphthalocyanine molecules. Science 317, 1203–1206 (2007).

    CAS  Article  Google Scholar 

  13. 13

    Alemani, M. et al. Adsorption and switching properties of azobenzene derivatives on different noble metal surfaces; Au(111), Cu(111) and Au(100). J. Phys. Chem. C 112, 10509–10514 (2008).

    CAS  Article  Google Scholar 

  14. 14

    Hammett, L. P. The effect of structure upon the reactions of organic compounds. Benzene derivatives. J. Am. Chem. Soc. 59, 96–103 (1937).

    CAS  Article  Google Scholar 

  15. 15

    Barth, J. V., Brune, H., Ertl, G. & Behm, R. J. Scanning tunnelling microscopy observations on the reconstructed Au(111) surface: Atomic structure, long-range superstructure, rotational domains and surface defects. Phys. Rev. B 42, 9307–9318 (1990).

    CAS  Article  Google Scholar 

  16. 16

    Vladimirova, M. et al. Supramolecular self-assembly and selective step decoration on the Au(111) surface. Europhys. Lett. 56, 254–260 (2001).

    CAS  Article  Google Scholar 

  17. 17

    Chen, W., Madhavan, V., Jamneala, T. & Crommie, M. F. Scanning tunnelling microscopy observation of an electronic superlattice at the surface of clean gold. Phys. Rev. Lett. 80, 1469–1472 (1998).

    CAS  Article  Google Scholar 

  18. 18

    Madueno, R., Räisänen, M. T., Silien, C. & Buck, M. Functionalizing hydrogen-bonded surface networks with self-assembled monolayers. Nature 454, 618–621 (2008).

    CAS  Article  Google Scholar 

  19. 19

    Meyer, G. A simple low-temperature ultrahigh-vacuum STM capable of atomic manipulation. Rev. Sci. Instrum. 67, 2960–2965 (1996).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

The authors thank K.-H. Rieder, J.I. Pascual and M. Wolf for careful reading of the manuscript. Financial support was provided by the German Research Foundation (DFG) through the SFB 658 (projects A1 and B8) and through contract no. GR 2697/1-2. C.D. thanks the Fondazione CRTrieste for financial support. This research was funded by the Progetto D4 (European Social Fund, Regione Friuli Venezia Giulia and Italian Ministry of Welfare).

Author information

Affiliations

Authors

Contributions

S.H. and L.G. conceived the experiments. C.D. and L.G. performed the experiments and analysed the data. M.V.P., J.S. and S.H. synthesized the molecules. L.G. wrote the paper. C.D., S.H. and L.G. discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Stefan Hecht or Leonhard Grill.

Supplementary information

Supplementary Information

Fig.1 to Fig.15 (PDF 8114 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Dri, C., Peters, M., Schwarz, J. et al. Spatial periodicity in molecular switching. Nature Nanotech 3, 649–653 (2008). https://doi.org/10.1038/nnano.2008.269

Download citation

Further reading