We demonstrate tandem and triple-junction polymer solar cells with power conversion efficiencies of 8.9% and 9.6% that use a newly designed, high molecular weight, small band gap semiconducting polymer and a matching wide band gap polymer.

Diketopyrrolopyrrole-based conjugated polymers bridged with thiazole units and different donors have been designed for polymer solar cells. Quantum efficiencies above 50% have been achieved with energy loss between optical band gap and open-circuit voltage below 0.6 eV.

For a series of six diketopyrrolopyrrole (DPP)-based conjugated polymers, we establish a direct correlation between their external quantum efficiencies (EQE) in organic solar cells and the fibrillar microstructure in the blend. The polymers consist of electron-deficient DPP units, carrying long branched 2'-decyltetradecyl (DT) side chains for solubility, that alternate along the main chain with electron-rich aromatic segments comprising benzene, thiophene, or fused aromatic rings. The high molecular weight DT-DPP polymers were incorporated in bulk heterojunction solar cells with [6,6]-phenyl-C71-butyric acid methyl ester ([70]PCBM) as acceptor. The morphology of the DT-DPP:[70]PCBM blends is characterized by a semicrystalline fibrillar microstructure with fibril widths between 4.5 and 30 nm as evidenced from transmission electron microscopy. A clear correlation is found between the widths of the fibrils and the EQE for photon to electron conversion. The highest EQEs (60%) and power conversion efficiencies (7.1%) are obtained for polymers with fibril widths less than 12 nm. For blends with fibrils wider than 12 nm, the EQE is low because exciton diffusion becomes limiting for charge generation. Interestingly, the correlation found here matches with previous data on related DPP-based polymers. This suggests that for this class of materials the relation between fiber width and EQE is universal. The fiber width is largely correlated with the solubility of the polymers, with less soluble DPP-based polymers giving narrower fibrils.

The nature of the solubilizing alkyl side chains has a strong effect on the performance of semiconducting diketopyrrolopyrrole polymers in organic solar cells with fullerene acceptors. The effect relates to the width of semicrystalline polymer fibrils that form in these blends. If the width of the fibril is wider than the exciton diffusion length, fewer charges form and the efficiency drops.

Solution processed polymer tandem solar cells that combine wide and small bandgap absorber layers reach a power conversion efficiency of 7% in a series configuration. This represents a 20% increase compared to the best single junction cells made with the individual active layers and shows that the tandem configuration reduces transmission and thermalization losses in converting sunlight.