Open-circuit voltage exceeding the outermost HOMO-LUMO offset in cascade organic solar cells

•A four-layer cascade organic solar cell structure is presented.•The open-circuit voltage (Voc) exceeds the outermost HOMO-LUMO offset.•The turn-on voltage exceeds the outermost HOMO-LUMO offset.•The lowest energy offset at the individual heterojunctions determines Voc.

We demonstrate a planar organic solar cell with a four-layer cascade architecture that exhibits an open-circuit voltage (Voc) greater than the offset in energy between the highest occupied molecular orbital (HOMO) of the outermost donor and the lowest unoccupied molecular orbital (LUMO) of the outermost acceptor. The device consists of a subphthalocyanine (SubPc)/fullerene (C60) heterojunction that is modified by inserting one or two additional donor layers between SubPc and the anode. We find that two-, three- and four-layer structures yield similar Voc (1.0 V, 0.91 V and 0.94 V, respectively), even though the outermost HOMO-LUMO offset decreases from 1.4 eV to 1.10 eV, and to 0.9 eV, respectively. Analysis of the turn-on voltage in dark provides further evidence that open-circuit voltage is not limited by the outermost HOMO-LUMO offset.

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