van der Waals-induced chromatic shifts in hydrogen-bonded two-dimensional porphyrin arrays on boron nitride

Vladimir V. Korolkov, Simon A. Svatek, Alex Summerfield, James Kerfoott, Lixu Yang, Takashi Taniguchi, Kenji Watanabe, Neil R. Champness, Nicholas A. Besley, Peter H. Beton

Research output: Contribution to journalArticlepeer-review

28 Citations (Scopus)
25 Downloads (Pure)

Abstract

The fluorescence of a two-dimensional supramolecular network of 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) adsorbed on hexagonal boron nitride (hBN) is red-shifted due to, primarily, adsorbate–substrate van der Waals interactions. TCPP is deposited from solution on hBN and forms faceted islands with typical dimensions of 100 nm and either square or hexagonal symmetry. The molecular arrangement is stabilized by in-plane hydrogen bonding as determined by a combination of molecular-resolution atomic force microscopy performed under ambient conditions and density functional theory; a similar structure is observed on MoS2 and graphite. The fluorescence spectra of submonolayers of TCPP on hBN are red-shifted by ∼30 nm due to the distortion of the molecule arising from van der Waals interactions, in agreement with time-dependent density functional theory calculations. Fluorescence intensity variations are observed due to coherent partial reflections at the hBN interface, implying that such hybrid structures have potential in photonic applications.
Original languageEnglish
Pages (from-to)10347-10355
Number of pages9
JournalACS Nano
Volume9
Issue number10
Early online date14 Sep 2015
DOIs
Publication statusPublished - 27 Oct 2015

Keywords

  • boron nitride
  • fluorescence
  • molybdenum disulfide
  • atomic force microscopy
  • porphyrin

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