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

Kerfoot, James; Korolkov, Vladimir V.; Nizovtsev, Anton S.; Jones, Ryan; Taniguchi, Takashi; Watanabe, Kenji; Lesanovsky, Igor; Olmos, Beatriz; Besley, Nicholas A.; Besley, Elena; Beton, Peter H.

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


Authors

James Kerfoot

Vladimir V. Korolkov

Anton S. Nizovtsev

Ryan Jones

Takashi Taniguchi

Kenji Watanabe

Beatriz Olmos

Nicholas A. Besley

PETER BETON peter.beton@nottingham.ac.uk
Professor of Physics



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.

Citation

Kerfoot, J., Korolkov, V. V., Nizovtsev, A. S., Jones, R., Taniguchi, T., Watanabe, K., …Beton, P. H. (2018). Substrate-induced shifts and screening in the fluorescence spectra of supramolecular adsorbed organic monolayers. Journal of Chemical Physics, 149(5), Article 054701. https://doi.org/10.1063/1.5041418

Journal Article Type Article
Acceptance Date Jul 17, 2018
Online Publication Date Aug 1, 2018
Publication Date Aug 7, 2018
Deposit Date Jul 19, 2018
Publicly Available Date Mar 29, 2024
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 149
Issue 5
Article Number 054701
DOI https://doi.org/10.1063/1.5041418
Public URL https://nottingham-repository.worktribe.com/output/946824
Publisher URL https://aip.scitation.org/doi/10.1063/1.5041418

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