Lattice Matching as the Determining Factor for Molecular Tilt and Multilayer Growth Mode of the Nanographene Hexa-peri-hexabenzocoronene

The microstructure, morphology, and growth dynamics of hexa-peri-hexabenzocoronene (HBC, C42H18) thin films deposited on inert substrates of similar surface energies are studied with particular emphasis on the influence of substrate symmetry and substrate-molecule lattice matching on the resulting films of this material. By combining atomic force microscopy (AFM) with X-ray diffraction (XRD), X-ray absorption spectroscopy (NEXAFS), and in situ X-ray reflectivity (XRR) measurements, it is shown that HBC forms polycrystalline films on SiO2, where molecules are oriented in an upright fashion and adopt the known bulk structure. Remarkably, HBC films deposited on highly oriented pyrolytic graphite (HOPG) exhibit a new, substrate-induced polymorph, where all molecules adopt a recumbent orientation with planar pi-stacking. Formation of this new phase, however, depends critically on the coherence of the underlying graphite lattice since HBC grown on defective HOPG reveals the same orientation and phase as on SiO2. These results therefore demonstrate that the resulting film structure and morphology are not solely governed by the adsorption energy but also by the presence or absence of symmetry- and lattice-matching between the substrate and admolecules. Moreover, it highlights that weakly interacting substrates of high quality and coherence can be useful to induce new polymorphs with distinctly different molecular arrangements than the bulk structure.