Morphological behavior of thin polyhedral oligomeric silsesquioxane films at the molecular scale

► XRR was used to study the structure of thin films of polyhedral oligomeric silsesquioxanes. ► The morphology of POSS films can be tuned by adjusting of different factors on the molecular scale. ► Different types of coatings (monolayer, bilayer or thicker film) are observed. ► The role of conformational and energetic factors is discussed.