Influence of nanomorphology on the photovoltaic action of polymer–fullerene composites

Composites of conjugated poly(3-hexylthiophene) (P3HT) and the fullerene derivative [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) demonstrate an efficient photogeneration of mobile charge carriers. Thermal annealing of P3HT:PCBM based devices gives rise to a significant increase of the photovoltaic efficiency, as follows from measurements of the external quantum efficiency and the current-voltage characteristics. Upon annealing, the absorption spectrum of the P3HT:PCBM composite undergoes a strong modification, whereas in the pure components it remains unchanged. The absorption of the annealed blends becomes stronger and red shifted in the wavelength region ascribed to P3HT, while the absorption due to the PCBM contribution does not change. Atomic force microscope measurements on P3HT:PCBM disclose some variation in morphology due to the crystallization of PCBM. The concentration of the PCBM clusters and their size (up to 500 nm) were found to be correlated with the amount of PCBM in the blend. We have studied the performance of photovoltaic devices with different weight ratios of P3HT:PCBM, namely, 1:3, 1:2, 1:1.5, 1:1, 1:0.9, 1:0.8, and 1:0.7. The photocurrent and the power conversion efficiency showed a maximum between 1:1 and 1:0.9. We conclude the variation in the absorption spectrum and the red shift to result from molecular diffusion of PCBM out of the polymer matrix upon annealing. The growth of the PCBM clusters leads to formation of percolation paths and, therefore, improves the photocurrent. Above a certain concentration, the PCBM crystals provide mechanical stress on the metal electrode, therefore possibly damaging the interface. Optimization of the composite weight ratio reveals the important role played by morphology for the transport properties of bulk heterojunction P3HT:PCBM based solar cells.