Real-time X-ray diffraction measurements of structural dynamics and polymorphism in diindenoperylene growth

We investigate the temperature-dependent polymorphs in diindenoperylene (DIP) thin films on sapphire and silicon oxide substrates using in situ X-ray scattering. On both substrates the DIP unit cell is very similar to the high-temperature phase of bulk crystals, with the substrate stabilising this structure well below the temperature where a phase transition to a low-temperature phase is observed in the bulk. Lowering the substrate temperature for DIP growth leads to a change in molecular orientation and an additional polymorph appears, with both these effects being more pronounced on sapphire as compared to silicon oxide. Using real-time reciprocal-space mapping we observe an expansion of the in-plane unit cell during DIP growth, which may be due to changes in molecular orientation as well as strain in the first monolayers.