As dipyranylidenes are excellent hole carriers, applications in organic solar cells or organic light emitting diode are envisaged. In the present study, we investigate the morphology of 2, 2′, 6, 6′-tetraphenyl-4, 4′-dipyranylidene (DIPO-Ph₄) deposited under vacuum on a silicon nitride (Si₃N₄) substrate, a paradigmatic system for the study of molecular crystal/inorganic substrate interfaces. Samples with various coating ratios and different thermal treatments were prepared. The films were characterized by atomic force microscopy and scanning transmission X-ray microscopy to gain insight into material growth. The results show a change in orientation at a molecular level depending upon the evaporation conditions. We are now able to tailor an organic layer with a specific molecular orientation and a specific electronic behavior.