Controlling the pore size in conjugated polymer films via crystallization-driven phase separation

A wide range of possible applications in sensors and optoelectronic devices have focused considerable attention on porous membranes made of semi-conducting polymers. In this study, porous films of poly(3-hexylthiophene) (P3HT) were conveniently constructed through spin-coating of solutions of a blend of P3HT and polyethylene glycol (PEG). Pores were formed by phase separation driven simultaneously by incompatibility and crystallization. The influence of the polymer concentration (c), molecular weight (M-n) and spin-coating temperature (T-sp) on the pore size and structure was investigated. With increasing c from 0.5 to 5.0 wt%, the pore diameter (d) varied from approximate to 1.3 m to approximate to 38 m. Similarly, we observed a substantial increase of d with increasing M-n of PEG, while changing M-n of P3HT did not affect d. Micron- and nano-scale pores coexisted in porous P3HT films. While incompatibility of P3HT and PEG caused the formation of nano-pores, micron-scale pores resulted from crystallization in the PEG-rich domains by forcing PEG molecules to diffuse from the surrounding PEG-P3HT blend region to the crystal growth front.