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Organic semiconductors are widely investigated for their application in photovoltaics and photodetectors. We show that the efficiency of these devices is strongly influenced by the position of the space charge region, due to unintentional doping, and wavelength-dependent absorption properties in bulk heterojunctions. Spray-coated P3HT:PCBM bulk heterojunction photodiodes with thicknesses up to 4.2 μm and semitransparent top contact enable the characterization of exciton generation and separation in both irradiation directions. A large difference in external quantum efficiency (EQE) is observed for top and bottom illuminated configurations and is explained by a bias dependent arrangement of the space charge region at the two contact electrodes. Numerical drift–diffusion simulations allow to get insight into first order mechanisms behind the spectral features of EQE data in highly-doped organic photodiodes. [ABSTRACT FROM AUTHOR]

Abstract: We have studied organic bulk heterojunction photovoltaic devices based on a bridged-bithiophene donor–acceptor type low-band gap polymer blended with PCBM and bis-PCBM. The impact of the molecular arrangement is discussed in terms of the correlation between the solar-cell performance and the degree of crystallization. Differential scanning calorimetry (DSC) and grazing-incidence X-ray diffraction (GIXRD) prove that films with bis-PCBM typically result in more amorphous blends than comparable films with PCBM. Electron tomography (ET) is used to visualize the three dimensional morphology of photoactive layers, confirming the presence of nanofibers, formed in different scales through the thickness in the blended films with mono and bis-fullerenes. [Copyright &y& Elsevier]