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Molecular topology and the surface chemical bond: alternant versus nonalternant aromatic systems as functional structural elements

DOI: 10.1103/PhysRevX.9.011030 DOI Help

Authors: Benedikt P. Klein (Philipps-Universität Marburg) , Nadine J. Van Der Heijden (Utrecht University) , Stefan R. Kachel (Philipps-Universität Marburg) , Markus Franke (Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich) , Claudio K. Krug (Philipps-Universität Marburg) , Katharina K. Greulich (Philipps-Universität Marburg) , Lukas Ruppenthal (Philipps-Universität Marburg) , Philipp Müller (Philipps-Universität Marburg) , Phil Rosenow (Philipps-Universität Marburg) , Shayan Parhizkar (Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich) , Francois C. Bocquet (Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich) , Martin Schmid (Philipps-Universität Marburg) , Wolfgang Hieringer (Universität Erlangen-Nürnberg) , Reinhard J. Maurer (University of Warwick) , Ralf Tonner (Philipps-Universität Marburg) , Christian Kumpf (Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich) , Ingmar Swart (Utrecht University) , J. Michael Gottfried (Philipps-Universität Marburg)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Physical Review X , VOL 9 , PAGES 011030

State: Published (Approved)
Published: February 2019
Diamond Proposal Number(s): 16259

Open Access Open Access

Abstract: The interaction of carbon-based aromatic molecules and nanostructures with metals can strongly depend on the topology of their π-electron systems. This is shown with a model system using the isomers azulene, which has a nonalternant π system with a 5-7 ring structure, and naphthalene, which has an alternant π system with a 6-6 ring structure. We found that azulene can interact much more strongly with metal surfaces. On copper (111), its zero-coverage desorption energy is 1.86 eV, compared to 1.07 eV for naphthalene. The different bond strengths are reflected in the adsorption heights, which are 2.30 Å for azulene and 3.04 Å for naphthalene, as measured by the normal incidence x-ray standing wave technique. These differences in the surface chemical bond are related to the electronic structure of the molecular π systems. Azulene has a lowlying LUMO that is close to the Fermi energy of Cu and strongly hybridizes with electronic states of the surface, as is shown by photoemission, near-edge x-ray absorption fine-structure, and scanning tunneling microscopy data in combination with theoretical analysis. According to density functional theory calculations, electron donation from the surface into the molecular LUMO leads to negative charging and deformation of the adsorbed azulene. Noncontact atomic force microscopy confirms the deformation, while Kelvin probe force microscopy maps show that adsorbed azulene partially retains its in-plane dipole. In contrast, naphthalene experiences only minor adsorption-induced changes of its electronic and geometric structure. Our results indicate that the electronic properties of metal-organic interfaces, as they occur in organic (opto)electronic devices, can be tuned through modifications of the π topology of the molecular organic semiconductor, especially by introducing 5-7 ring pairs as functional structural elements.

Journal Keywords: Azulene; Napthalene; Graphene

Diamond Keywords: Semiconductors

Subject Areas: Materials, Chemistry, Physics

Instruments: I09-Surface and Interface Structural Analysis

Other Facilities: BESSY-II

Added On: 15/02/2019 12:40


Discipline Tags:

Surfaces Hard condensed matter - electronic properties Physics Chemistry Materials Science Organic Chemistry

Technical Tags:

Diffraction X-ray Standing Wave (XSW)