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Single-molecule photoelectron tunnelling spectroscopy

Nature Materials volume 22, pages 1007–1012 (2023)Cite this article

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Abstract

Experimental mapping of transmission is essential for understanding and controlling charge transport through molecular devices and materials. Here we developed a single-molecule photoelectron tunnelling spectroscopy approach for mapping transmission beyond the HOMO–LUMO gap of the single diketopyrrolopyrrole molecule junction using an ultrafast-laser combined scanning tunnelling microscope-based break junction set-up at room temperature. Two resonant transport channels of ultrafast photocurrent are found by our photoelectron tunnelling spectroscopy, ranging from 1.31 eV to 1.77 eV, consistent with the LUMO + 1 and LUMO + 2 in the transmission spectrum obtained by density functional theory calculations. Moreover, we observed the modulation of resonant peaks by varying bias voltages, which demonstrates the ability to quantitatively characterize the effect of the electric field on frontier molecular orbitals. Our single-molecule photoelectron tunnelling spectroscopy offers an avenue that allows us to explore the nature of energy-dependent charge transport through single-molecule junctions.

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Fig. 1: Single-molecule conductance and photocurrent measurements.
Fig. 2: Resonant transport of photoelectron in single-molecule junctions.
Fig. 3: Bias voltage dependence of photoelectron tunnelling spectroscopy.

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Data availability

The main data supporting the findings of this study are provided with this paper. Source data are provided with this paper.

Code availability

The data analysis of conductance measurements was performed using our open-source code XME analysis, which is available at https://github.com/Pilab-XMU/XMe_DataAnalysis. The computation details are available from the corresponding authors upon request.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (numbers 22250003 (W.H.), 21722305 (W.H.), 22173075 (J.L.) and 21933012 (J.L.)) and the Fundamental Research Funds for the Central Universities (numbers 20720220020 (J.L.), 20720220072 (J.L.), 20720200068 (J.L.), 20720190002 (W.H.)). We thank K.-Q. Lin and J. Yi at Xiamen University for helpful discussions and Z. Luo at Xiamen University for providing the continuous-wave laser. We also acknowledge the support from the ultra-precision laboratory at IKKEM for offering the experimental platforms.

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  1. These authors contributed equally: Haojie Liu, Lijue Chen, Hao Zhang.

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering & Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University, Xiamen, China

    Haojie Liu, Lijue Chen, Hao Zhang, Zhangqiang Yang, Jingyao Ye, Ping Zhou, Chao Fang, Wei Xu, Jia Shi, Junyang Liu, Ye Yang & Wenjing Hong

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Contributions

W.H. supervised the project. W.H., Y.Y. and L.C. originally conceived the concept and designed the experiments. L.C., H.L., Z.Y., J.L. and J.S. designed and constructed the set-up. H.L., L.C. and H.Z. performed the experiments. C.F. and P.Z. performed the thermopower measurements. H.L. and L.C. conceived and developed the data analysis method. W.X. synthesized the molecules. J.Y. carried out the DFT calculations. H.L. and L.C. prepared the manuscript with input from other authors.

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Correspondence to Wenjing Hong.

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Nature Materials thanks Jun Takeda and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Table of contents, Supplementary Discussion and Figs. 1–27.

Supplementary Data 1

The atomic coordinates of the optimized computational models.

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Liu, H., Chen, L., Zhang, H. et al. Single-molecule photoelectron tunnelling spectroscopy. Nat. Mater. 22, 1007–1012 (2023). https://doi.org/10.1038/s41563-023-01591-4

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