Abstract
Evaluating the built-in functionality of nanomaterials under practical conditions is central for their proposed integration as active components in next-generation electronics. Low-dimensional materials from single atoms to molecules have been consistently resolved and manipulated under ultrahigh vacuum at low temperatures. At room temperature, atomic-scale imaging has also been performed by probing materials at the solid/liquid interface. We exploit this electrical interface to develop a robust electronic decoupling platform that provides precise information on molecular energy levels recorded using in situ scanning tunnelling microscopy/spectroscopy with high spatial and energy resolution in a high-density liquid environment. Our experimental findings, supported by ab initio electronic structure calculations and atomic-scale molecular dynamics simulations, reveal direct mapping of single-molecule structure and resonance states at the solid/liquid interface. We further extend this approach to resolve the electronic structure of graphene monolayers at atomic length scales under standard room-temperature operating conditions.
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Acknowledgements
The authors thank R. Stutz and H. Schmid for metal-deposition experiments, M. Tschudy for liquid-cell fabrication and E. Lörtscher for designing the noise-free laboratories. P.N. thanks H. Wolf, F. Schwarz and J. Boland for useful discussions. This work was supported by the Marie Curie Actions-Intra-European Fellowship (IEF-PHY) under grant agreement No 275074 ‘To Come’ within the 7th European Community Framework Programme. D.T. thanks Science Foundation Ireland (SFI) for financial support under Grant Number 11/SIRG/B2111 and the SFI/Higher Education Authority Irish Center for High-End Computing (ICHEC). This work was supported by the EC FP7ITN ‘FUNMOLS’ Project Number: PITN-GA-2008-212942.
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P.N. designed and performed the in situ STM/STS experiments. M.S. carried out the ellipsometry measurements and data analysis. A.M-O. and N.M. synthesized the functionalized C60 molecules and performed the electrochemical characterization. D.T. designed and performed the molecular dynamics simulations and DFT calculations. All authors contributed and commented on the manuscript and analysis of the data.
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Nirmalraj, P., Thompson, D., Molina-Ontoria, A. et al. Nanoelectrical analysis of single molecules and atomic-scale materials at the solid/liquid interface. Nature Mater 13, 947–953 (2014). https://doi.org/10.1038/nmat4060
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DOI: https://doi.org/10.1038/nmat4060
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