We compare the performances of organic photovoltaic cells (OPVCs) based on binary and ternary planar heterojunctions. The organic active layers are pentathiophene (5T), subphthalocyanine (SubPc) and fullerene (C60). SubPc being an ambipolar material we used it either as electron acceptor in binary OPVCs or as central layer in ternary cells in order to increase the efficiency of OPVCs using 5T as electron donor. So, the different OPVC configurations were 5T/C60, 5T/SubPc and 5T/SubPc/C60. The effect of the different organic layer thicknesses on the device performances was studied. In order to understand the behavior of the different OPVC configurations, we proceeded with a morphological study. The influence of the high roughness of the 5T layer on the OPVCs performances is discussed. The best OPVCs performances are obtained with the binary structure 5T/SubPc. Its maximum efficiency corresponds to an increase of 50% compared to the OPVC based on the couple 5T/C60. External Quantum Efficiency measurements show that both layers participate to the current generation. The efficiency increase is mainly due to the increase of the open circuit voltage ([Formula: see text]). In the case of ternary OPVCs, [Formula: see text] is limited by the band structure of 5T and C60, moreover, the efficiency is also limited by the poor charge collection efficiency of the ternary structure and the series resistance of the three stacked organic layers.
