Molecular Reorientation during the Initial Growth of Perfluoropentacene on Ag(110)

[Image: see text] Perfluoropentacene (PFP) is an organic material that has been widely studied over the last years and has already found applications in organic electronics. However, fundamental physical questions, such as the structural formation and the preferential orientation of the molecules during deposition on metal surfaces, are still not fully understood. In this work, we report on a unique in-plane molecular reorientation during the completion of the first monolayer of PFP on the Ag(110) surface. To characterize the molecular alignment, we have monitored the deposition process in real time using polarization-dependent differential reflectance spectroscopy and reflectance anisotropy spectroscopy. Abrupt changes in the optical signals reveal an intricate sequence of reorientation transitions of the PFP molecules upon monolayer completion and during the formation of the second monolayer, eventually leading to a full alignment of the long molecular axis along the [001] direction of the substrate and an enhanced structural ordering. Scanning tunneling microscopy and low-energy electron diffraction confirm the observed molecular reorientation upon monolayer compression and provide further details on the structural and orientational ordering of the PFP monolayer before and after compression.