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Distinguishing adjacent molecules on a surface using plasmon-enhanced Raman scattering

Abstract

Unambiguous chemical identification of individual molecules closely packed on a surface can offer the possibility to address single chemical species and monitor their behaviour at the individual level1,2,3. Such a degree of spatial resolution can in principle be achieved by detecting their vibrational fingerprints using tip-enhanced Raman scattering (TERS)4,5,6,7,8,9,10. The chemical specificity of TERS can be combined with the high spatial resolution of scanning probe microscopy techniques11,12,13, an approach that has stimulated extensive research in the field14,15,16,17,18,19,20,21,22,23,24,25,26,27,28. Recently, the development of nonlinear TERS in a scanning tunnelling microscope has pushed the spatial resolution down to 0.5 nm, allowing the identification of the vibrational fingerprints of isolated molecules on Raman-silent metal surfaces13. Although the nonlinear TERS component is likely to help sharpen the optical contrast of the acquired image, the TERS signal still contains a considerable contribution from the linear term, which is spatially less confined. Therefore, in the presence of different adjacent molecules, a mixing of Raman signals may result. Here, we show that using a nonlinear scanning tunnelling microscope-controlled TERS set-up, two different adjacent molecules that are within van der Waals contact and of very similar chemical structure (a metal-centred porphyrin and a free-base porphyrin) on a silver surface can be distinguished in real space. In addition, with the help of density functional theory simulations, we are also able to determine their adsorption configurations and orientations on step edges and terraces.

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Figure 1: Comparison of TERS spectra for ZnTPP and H2TBPP on Ag(111).
Figure 2: Distinguishing between ZnTPP and H2TBPP domains.
Figure 3: Distinguishing adjacent different molecules at step edges.

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Acknowledgements

This work is supported by the National Basic Research Program of China, the Strategic Priority Research Program of the Chinese Academy of Sciences and the National Natural Science Foundation of China. The density functional theory simulations were performed in the Supercomputing Center of the University of Science and Technology of China.

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Contributions

Z.C.D. and J.G.H. conceived and designed the experiments. S.J., R.Z., C.R.H., M.H.L. and Z.C.D. performed experiments and analysed data. S.J., Y.Z., Y.L., J.L.Y. and Z.C.D. contributed to data interpretation and theoretical simulations. Z.C.D., S.J., Y.L. and J.G.H. co-wrote the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Zhenchao Dong or J. G. Hou.

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The authors declare no competing financial interests.

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Jiang, S., Zhang, Y., Zhang, R. et al. Distinguishing adjacent molecules on a surface using plasmon-enhanced Raman scattering. Nature Nanotech 10, 865–869 (2015). https://doi.org/10.1038/nnano.2015.170

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