Phase Diagrams of Ternary π-Conjugated Polymer Solutions for Organic Photovoltaics.

Phase diagrams of ternary conjugated polymer solutions were constructed based on Flory-Huggins lattice theory with a constant interaction parameter. For this purpose, the poly(3-hexylthiophene-2,5-diyl) (P3HT) solution as a model system was investigated as a function of temperature, molecular weight (or chain length), solvent species, processing additives, and electron-accepting small molecules. Then, other high-performance conjugated polymers such as PTB7 and PffBT4T-2OD were also studied in the same vein of demixing processes. Herein, the liquid-liquid phase transition is processed through the nucleation and growth of the metastable phase or the spontaneous spinodal decomposition of the unstable phase. Resultantly, the versatile binodal, spinodal, tie line, and critical point were calculated depending on the Flory-Huggins interaction parameter as well as the relative molar volume of each component. These findings may pave the way to rationally understand the phase behavior of solvent-polymer-fullerene (or nonfullerene) systems at the interface of organic photovoltaics and molecular thermodynamics.