Investigating molecular orbitals with submolecular precision on pristine sites and single atomic vacancies of monolayer h-BN


Understanding the influence of adsorption sites to the electronic properties of adsorbed molecules on two-dimensional (2D) ultrathin insulator is of essential importance for future organic-inorganic hybrid nanodevices. Here, the adsorption and electronic states of manganese phthalocyanine (MnPc) on a single layer of hexagonal boron nitride (h-BN) have been comprehensively studied by low-temperature scanning tunneling microscopy/spectroscopy and tight binding calculations. The frontier orbitals of the MnPc can change drastically by reversible manipulation of individual MnPc molecules onto and away from the single atomic vacancies at the h-BN surface. Particularly, the change of the molecular electronic configuration can be controlled depending on whether the atomic vacancy is below the metal center or the ligand of the MnPc. These findings give new insight into defect-engineering of the organic-inorganic hybrid nanodevices down to submolecular level.

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L. W. L., Y. L. W. and T. Z. thank the Beijing Natural Science Foundation (Nos. 4192054 and Z190006), the National Natural Science Foundation of China (Nos. 61971035, 61901038, and 61725107), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB30000000), and the Beijing Institute of Technology Research Fund Program for Young Scholars (No. 3050011181814). L. W. L. and O. G. would like to thank the EU-EMPA COFUND Project BONMAT and the Swiss National Science Foundation (Nos. CRSI20-122 703 and 200021_149627).

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Correspondence to Liwei Liu or Oliver Gröning.

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Liu, L., Dienel, T., Günzburger, G. et al. Investigating molecular orbitals with submolecular precision on pristine sites and single atomic vacancies of monolayer h-BN. Nano Res. (2020).

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  • hexagonal boron nitride
  • phthalocyanine
  • single atomic vacancy
  • molecular orbital
  • scanning tunneling microscopy