Structure formation in perfluoropentacene:diindenoperylene blends and its impact on transient effects in the optical properties studied in real-time during growth

We discuss the result of the competing effects of favourable intermolecular interactions and steric incompatibilities due to the size mismatch of perfluoropentacene (PFP) and diindenoperylene (DIP) on the structure formation and associated optical properties in mixed films. Using real-time grazing incidence X-ray diffraction we investigate the size of coherently scattering islands l_s as a function of film thickness and mixing ratio. We find that for PFP:DIP 1:2 blends l_s is by a factor of ∼4 smaller than in pure DIP films, while l_s of the PFP:DIP 2:1 blends is not significantly reduced compared with pure PFP. Yet, we observe an increase in l_s with film thickness for all of the samples, independent on the mixing ratio. In parallel with the structural characterization we investigate the evolution of the absorption spectra in the visible spectral range and its dependence on l_s in situ during film growth using differential reflectance spectroscopy. We observe a surprisingly strong effect of changes in the structural order on the shape of ε_{2, xy}(E), evident by a pronounced evolution of characteristic peaks in the thickness range from 1.6 nm to 9.6 nm. The combined results of the real-time experiments allow to identify the thickness dependent crystal grain size as the origin of the observed transient effects in the absorption spectra.