Cascade heterojunction (CHJ) organic solar cells have recently emerged as an alternative to conventional bulk heterojunctions and series-connected tandems due to their signifi cant promise for high internal quantum effi ciency (IQE) and broad spectral coverage. However, CHJ devices thus far have also exhibited poor fi ll factor (FF), resulting in minimal enhancements (or even decreases) in power conversion effi ciency (PCE) when compared with single heterojunction (SHJ) cells. In this study, the major variables controlling the CHJ maximum power point and FF are determined using a combinatorial approach. By matching the maximum power point voltage (V MPP) of the constituent parallel-connected heterojunctions (subjunctions) and minimizing the injection barriers intrinsic to CHJs, high FF and PCE can be achieved. Optimized CHJ devices are demonstrated with >99% IQE in the interlayer and a 46% increase in PCE compared to a SHJ reference (4.1% versus 2.8%). Devices with a transparent exciton dissociation layer (EDL)/interlayer/acceptor structure are employed, such that each CHJ has absorption effi ciency identical to its interlayer/acceptor SHJ counterpart. Using these results, a clear map of performance as a function of material parameters is developed, providing straightforward, universal design rules to guide future engineering of molecules and layer architectures for CHJ organic photovoltaic devices.

Regioregular poly(3-hexylthiophene) (RR-P3HT) is a widely used donor material for bulk heterojunction polymer solar cells. While much is known about the structure and properties of RR-P3HT films, important questions regarding hole mobilities in this material remain unresolved. Measurements of the out-of-plane hole mobilities, μ, of RR-P3HT films have been restricted to films in the thickness regime on the order of micrometers, beyond that generally used in solar cells, where the film thicknesses are typically 100 to 200 nm. Studies of in-plane carrier mobilities have been conducted in thinner films, in the thickness range 100-200 nm. However, the in-plane and out-of-plane hole mobilities in RR-P3HT can be significantly different. We show here that the out-of-plane hole mobilities in neat RR-P3HT films increase by an order of magnitude, from 10(-4) cm(2)/V·s, for a 80 nm thick film, to a value of 10(-3) cm(2)/V·s for films thicker than 700 nm. Through a combination of morphological characterization and simulations, we show that the thickness dependent mobilities are not only associated with the differences between the average morphologies of thick films and thin films, but specifically associated with changes in the local morphology of films as a function of distance from the interfaces.

We show that due to a substrate-induced orientation of the local morphology of thin supported conjugated polymer films of poly[4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl-alt-4-(2-ethylhexan-1-one)thieno[3,4-b]thiophene-2,6-diyl] (PBDTTT-C), the out-of-plane hole mobility, μ, increased with increasing film thickness h, becoming independent of h for h > 110 nm. The temperature and electric field dependencies of μ are in agreement with predictions of the well-known Gaussian Disorder Model (GDM), developed to describe charge transport in materials possessing positional and energetic disorder. Room temperature studies reveal a negative dependence of μ on the electric field E, with a strength quantified by the parameter β. The largest magnitude of β was measured in the thinnest films, indicative of the strongest dependence of μ on the electric field E; β decreased monotonically with increasing film thickness. The thickness dependencies of μ and β manifest an increase of the average anisotropy of the films with decreasing film thickness, corroborated by UV–vis spectroscopy and spectroscopic ellipsometry measurements.

A larger interfacial area between the copolymer and fullerene is obtained with the gradient copolymer relative to the block architecture. This is correlated with two orders of magnitude higher initial carrier density.