On the crystal forms of NDI-C6: annealing and deposition procedures to access elusive polymorphs

NDI-C6 has been extensively studied for its semiconducting properties and its processability. It is known to have several polymorphs and a high thermal expansion. Here we report the full thermal characterization of NDI-C6 by combining differential scanning calorimetry, variable temperature X-ray powder diffraction, and hot stage microscopy, which revealed two different thermal behaviours depending on the annealing process. The ranking of stability was determined by the temperature and energy involved in the transitions: Form alpha is stable from RT up to 175 degrees C, Form beta is metastable at all temperatures, Form gamma is stable in the range 175-178 degrees C, and Form delta in the range 178-207 degrees C followed by the melt at 207 degrees C. We determined the crystal structure of Form gamma at 54 degrees C from powder. The analysis of the thermal expansion principal axis shows that Form alpha and Form gamma possess negative thermal expansion (X1) and massive positive thermal expansion (X3) which are correlated to the thermal behaviour observed. We were able to isolate pure Form alpha, Form beta, and Form gamma in thin films and we found a new metastable form, called Form epsilon, by spin coating deposition of a toluene solution of NDI-C6 on Si/SiO2 substrates.