ABSTRACT
In this chapter, we provide a survey on the thermal phase behavior of polymeric semiconductors and how to use such knowledge to manipulate their phase transformations and, in turn, their solid-state order towards technological and practical applications. We review here the most important critical features that dictate polymer semiconductors’ melting temperatures, glass-transition temperatures and solid-to-solid transformations, such as liquid-crystalline transitions and transformations between polymorphs. We summarize classical polymer science tools to manipulate these phase transitions and discuss some key concepts such as nucleation and growth, spinodal decomposition, and confinement. We will show, first on single component systems then moving to multicomponent systems, that a detailed understanding of how to manipulate phase transitions and knowledge of temperature/composition diagrams (deduced for specific processing conditions) allows establishment of protocols to precisely direct the solidification process of relevant components, enables manipulation of the molecular order over various length scales, and permits tailoring of the overall phase ‘morphologies’ and solid-state microstructure. This opens a library of means to influence in a controlled fashion the electronic characteristics of semiconducting polymers; it also has many potential consequences, e.g., for the fabrication of optoelectronic devices. [195 words]
