Improving the Reproducibility of P3HT:PCBM Solar Cells by Controlling the PCBM/Cathode Interface

Plastic photovoltaic devices offer a real potential for making solar energy economically viable. Unfortunately, bulk heterojunction (BHJ) solar cells fabricated from blends of the commonly used materials poly(3hexylthiophene), P3HT, and phenyl-C61-butyric acid methyl ester, PCBM, sometimes exhibit low efficiencies even when the procedures followed often produce solar cells with efficiencies exceeding 5%. In this Letter, we show that this irreproducibility is caused by subtleties in the film processing conditions that ultimately lead to poor electron extraction from the devices. For low-performing devices, photogeneration and charge extraction with a linearly increasing voltage ramp (photo-CELIV) measurements show an order-of-magnitude difference in the effective mobilities of the electrons and holes. Atomic force microscopy (AFM) experiments reveal that the top surface of these low-performing devices is nearly pure P3HT. We argue that small variations in the solvent evaporation kinetics during spin-coating of the BHJ active layer, which are difficult to control, cause PCBM to segregate toward the bottom of the P3HT film to different extents, explaining why electron extraction from the PCBM component of the BHJ is so difficult in poorly performing devices. Finally, we show that electron extraction can be greatly improved by spin-coating a thin PCBM layer on top of the BHJ before deposition of the cathode, allowing the reproducible fabrication of high-efficiency polymer solar cells.