Substrate-induced shifts and screening in the fluorescence spectra of supramolecular adsorbed organic monolayers

Kerfoot, James and Korolkov, Vladimir V. and Nizovtsev, Anton S. and Jones, Ryan and Taniguchi, Takashi and Watanabe, Kenji and Lesanovsky, Igor and Olmos, Beatriz and Besley, Nicholas A. and Besley, Elena and Beton, Peter H. (2018) Substrate-induced shifts and screening in the fluorescence spectra of supramolecular adsorbed organic monolayers. Journal of Chemical Physics . ISSN 1089-7690 (In Press)

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Abstract

We have investigated the influence of the substrate on the fluorescence of adsorbed organic molecules. Monolayer films of perylene-3,4,9,10-tetracarboxylic-3,4,9,10-diimide (PTCDI), a supramolecular network formed from PTCDI and melamine, and perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) have been deposited on hexagonal boron nitride (hBN). The principal peaks in the fluorescence spectra of these films were red-shifted by up to 0.37 eV relative to published measurements for molecules in helium droplets. Smaller shifts (~0.03 eV) arising from interactions between neighbouring molecules are investigated by comparing the fluorescence of distinct arrangements of PTCDI, which are templated by supramolecular self-assembly and determined with molecular resolution using atomic force microscopy under ambient conditions. We compare our experimental results with red-shifts calculated using a combination of a perturbative model and density functional theory which account for, respectively, resonant and non-resonant effects of a dielectric hBN substrate. We show that the substrate gives rise to a red-shift in the fluorescence of an adsorbed molecule and also screens the interactions between neighbouring transition dipole moments; both these effects depend on the refractive index of the substrate.

Item Type: Article
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
University of Nottingham, UK > Faculty of Science > School of Physics and Astronomy
Depositing User: Eprints, Support
Date Deposited: 19 Jul 2018 08:55
Last Modified: 19 Jul 2018 09:00
URI: http://eprints.nottingham.ac.uk/id/eprint/53030

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