Three-Phase Morphology of Semicrystalline Polymer Semiconductors: A Quantitative Analysis.

Quantitative morphological analysis is essential to the fundamental understanding of semiconducting polymers. Temperature modulated differential scanning calorimetry is used to determine the amount of crystalline and noncrystalline phases within regioregular poly(3-hexylthiophene) (rrP3HT). Careful optimization of the experimental conditions shows that the glass transition of rrP3HT consists of three parts corresponding to the devitrification of the side chains, mobile amorphous fraction (MAF), and rigid amorphous fraction (RAF), consecutively. Measurements taken from this, as well as from the melting transition, allows the first calculation of the degree of crystallinity, MAF and RAF, to be achieved in a single experiment for rrP3HT. This technique thus enables the morphological phases to be determined and potentially related to the performance of electronic devices made from semiconducting polymers.