Flexible 2D Crystals of Polycyclic Aromatics Stabilized by Static Distortion Waves

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Matthias Meissner - , Friedrich Schiller University Jena (Author)
  • Falko Sojka - , Friedrich Schiller University Jena (Author)
  • Lars Matthes - , Friedrich Schiller University Jena (Author)
  • Friedhelm Bechstedt - , Friedrich Schiller University Jena (Author)
  • Xinliang Feng - , Chair of Molecular Functional Materials (cfaed), Max Planck Institute for Polymer Research (Author)
  • Klaus Müllen - , Max Planck Institute for Polymer Research (Author)
  • Stefan C.B. Mannsfeld - , Chair of Organic Devices (cfaed) (Author)
  • Roman Forker - , Friedrich Schiller University Jena (Author)
  • Torsten Fritz - , Friedrich Schiller University Jena, Osaka University (Author)

Abstract

The epitaxy of many organic films on inorganic substrates can be classified within the framework of rigid lattices which helps to understand the origin of energy gain driving the epitaxy of the films. Yet, there are adsorbate-substrate combinations with distinct mutual orientations for which this classification fails and epitaxy cannot be explained within a rigid lattice concept. It has been proposed that tiny shifts in atomic positions away from ideal lattice points, so-called static distortion waves (SDWs), are responsible for the observed orientational epitaxy in such cases. Using low-energy electron diffraction and scanning tunneling microscopy, we provide direct experimental evidence for SDWs in organic adsorbate films, namely hexa-peri-hexabenzocoronene on graphite. They manifest as wave-like sub-Ångström molecular displacements away from an ideal adsorbate lattice which is incommensurate with graphite. By means of a density-functional-theory based model, we show that, due to the flexibility in the adsorbate layer, molecule-substrate energy is gained by straining the intermolecular bonds and that the resulting total energy is minimal for the observed domain orientation, constituting the orientational epitaxy. While structural relaxation at an interface is a common assumption, the combination of the precise determination of the incommensurate epitaxial relation, the direct observation of SDWs in real space, and their identification as the sole source of epitaxial energy gain constitutes a comprehensive proof of this effect.

Details

Original languageEnglish
Pages (from-to)6474-6483
Number of pages10
JournalACS nano
Volume10
Issue number7
Publication statusPublished - 26 Jul 2016
Peer-reviewedYes

Keywords

Keywords

  • density functional theory (DFT), epitaxial graphene, low-energy electron diffraction (LEED), natural graphite, orientational epitaxy, polycyclic aromatic hydrocarbon (PAH), scanning tunneling microscopy (STM)