Orientation, electronic decoupling and band dispersion of heptacene on modified and nanopatterned copper surfaces.

The adsorption of heptacene (7 A) on Cu(110) and Cu(110)-(2 × 1)-O was studied with scanning tunneling microscopy, photoemission orbital tomography and density functional calculations to reveal the influence of surface passivation on the molecular geometry and electronic states. We found that the charge transfer into the 7 A molecules on Cu(110) is completely suppressed for the oxygen-modified Cu surface. The molecules are aligned along the Cu-O rows and uncharged.

Charge and adsorption height dependence of the self-metalation of porphyrins on ultrathin MgO(001) films.

We have experimentally determined the adsorption structure, charge state, and metalation state of porphin, the fundamental building block of porphyrins, on ultrathin Ag(001)-supported MgO(001) films by scanning tunneling microscopy and photoemission spectroscopy, supported by calculations based on density functional theory. By tuning the substrate work function to values below and above the critical work function for charging, we succeeded in the preparation of 2H-P monolayers which contain negatively charged and uncharged molecules. It is shown that the porphin molecules self-metalate at room temperature, forming the corresponding Mg-porphin, irrespective of their charge state.

Large Distortion of Fused Aromatics on Dielectric Interlayers Quantified by Photoemission Orbital Tomography.

Polycyclic aromatic compounds with fused benzene rings offer an extraordinary versatility as next-generation organic semiconducting materials for nanoelectronics and optoelectronics due to their tunable characteristics, including charge-carrier mobility and optical absorption. Nonplanarity can be an additional parameter to customize their electronic and optical properties without changing the aromatic core. In this work, we report a combined experimental and theoretical study in which we directly observe large, geometry-induced modifications in the frontier orbitals of a prototypical dye molecule when adsorbed on an atomically thin dielectric interlayer on a metallic substrate.

Demonstrating the Impact of the Adsorbate Orientation on the Charge Transfer at Organic-Metal Interfaces.

Charge-transfer processes at molecule-metal interfaces play a key role in tuning the charge injection properties in organic-based devices and thus, ultimately, the device performance. Here, the metal's work function and the adsorbate's electron affinity are the key factors that govern the electron transfer at the organic/metal interface. In our combined experimental and theoretical work, we demonstrate that the adsorbate's orientation may also be decisive for the charge transfer.