Visualization of phase evolution in model organic photovoltaic structures via energy-filtered transmission electron microscopy.

The morphology of the active layer in an organic photovoltaic bulk-heterojunction device is controlled by the extent and nature of phase separation during processing. We have studied the effects of fullerene crystallinity during heat treatment in model structures consisting of a layer of poly(3-hexylthiophene) (P3HT) sandwiched between two layers of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Utilizing a combination of focused ion-beam milling and energy-filtered transmission electron microscopy, we monitored the local changes in phase distribution as a function of annealing time at 140 °C. In both cases, dissolution of PCBM within the surrounding P3HT was directly visualized and quantitatively described. In the absence of crystalline PCBM, the overall phase distribution remained stable after intermediate annealing times up to 60 s, whereas microscale PCBM aggregates were observed after annealing for 300 s. Aggregate growth proceeded vertically from the substrate interface via uptake of PCBM from the surrounding region, resulting in a large PCBM-depleted region in their vicinity. When precrystallized PCBM was present, amorphous PCBM was observed to segregate from the intermediate P3HT layer and ripen the crystalline PCBM underneath, owing to the far lower solubility of crystalline PCBM within P3HT. This process occurred rapidly, with segregation already evident after annealing for 10 s and with uptake of nearly all of the amorphous PCBM by the crystalline layer after 60 s. No microscale aggregates were observed in the precrystallized system, even after annealing for 300 s.