One of the most challenging issues facing the organic photovoltaic community is to realize a high fill factor (FF) even with thick active layers. This is because the thick active layer is beneficial for photon absorption but makes charge collection difficult, which is primarily restricted by nongeminate recombination in solar cells. In this work, we have studied nongeminate recombination in four kinds of polymer solar cells based on blends of donor-conjugated polymers with different crystallinities and acceptor-conjugated polymers with a naphthalene diimide unit by using transient photovoltage and photocurrent techniques. As a result, we find that nongeminate recombination is considerably suppressed with an increasing degree of crystallinity of donor polymers, leading to a high FF of more than 0.6 even with an active layer thickness of 300 nm. The origin of such a phenomenon is further discussed in terms of variations in the states of mixed phases with a cascaded energy structure between crystalline domains and amorphous domains evaluated by conductive atomic force microscopy.
Keywords: all-polymer solar cells; cascaded energy structure; fill factor; nongeminate recombination; thick active layer.