The discrete nature of inhomogeneity: the initial stages and local configurations of TiOPc during bilayer growth on Ag(111)†
The operation of organic optoelectronic devices relies notably on the bulk properties of compound molecular species, but even more so on the influence of interfaces thereof since it is at the interface where elemental electronic processes take place. Their identification and characterization thereby requires that these critical sections of a device are well defined and can be prepared with low defect density. In this context titanyl phthalocyanine (TiOPc) arises as an excellent candidate that reveals the formation of a stable bilayer structure with a characteristic “up-down” molecular arrangement that optimizes the dipole–dipole interaction within the bilayer. In our experimental study, long-range ordered TiOPc bilayers have been grown on Ag(111) surfaces and analyzed using infrared absorption spectroscopy and scanning tunneling microscopy. By monitoring the prominent TiO stretching mode in IRAS and identifying local configurations in STM, a microscopic model for the growth of TiOPc bilayers on Ag(111) is suggested. We demonstrate that defect structures within these bilayers lead to characteristic vibrational signatures which react sensitively to the local environment of the molecules. Thermal desorption spectroscopy reveals a high thermal stability of the TiOPc bilayer up to 500 K, which is attributed to hydrogen bonds between oxygen of the titanyl unit and the hydrogen rim of phthalocyanines in the second layer, in addition to contributions arising from the oppositely oriented axial dipole moments and the ubiquitous van der Waals interactions.