Epitaxial growth of diindenoperylene ultrathin films on Ag(111) investigated by LT-STM and LEED

The epitaxial growth of the 1st and 2nd monolayer (ML) diindenoperylene (DIP) on Ag(111) has been systematically investigated using low temperature scanning tunneling microscopy, low energy electron diffraction and first-principles calculations. At one ML regime, DIP molecules commensurately arrange in either herringbone or brick-wall superstructures, depending on the deposition rate. Tip-induced structural transformation from herringbone to brick-wall is observed. Calculations based on density functional theory reveal that the top site of Ag(111) is energetically favorable for both superstructures. The 2nd ML DIP aggregate in either herringbone or brick-wall superstructures depending on the arrangements of the 1st ML DIP, indicating that the structural properties of DIP thin films on Ag(111) are sensitive to growth conditions. The observed variation in DIP ultrathin film structure may result in different electronic properties and have implications for DIP-based organic electronic devices, such as organic field-effect transistors or organic photovoltaic cells.