Crystallization and self-nucleation of conjugated polymers

It is well known that the specific conditions under which polymer crystallization occurs dictate the resulting semicrystalline morphology and, therefore, the final mechanical, optical, and diffusive properties of the solidified material. For conjugated polymers, even seemingly small differences in crystallinity, orientation, or tie chains can result in significant changes in charge transport properties; however, the interplay between chain structure, crystallization conditions, and structure development remains elusive because they are typically processed in solution (for example, by spin-coating) where ill-defined conditions are prevalent. Here, we explore the role of molecular attributes on the crystallization behavior of poly-3-hexylthiophene under well-defined conditions. The results indicate that molecular characteristics play an important role in the way crystallization proceeds, and that self-nucleation strategies can be used effectively to manipulate crystallization conditions.