Reducing Voltage Losses in Cascade Organic Solar Cells while Maintaining High External Quantum Efficiencies

High photon energy losses limit the open‐circuit voltage ( V OC ) and power conversion efficiency of organic solar cells (OSCs). In this work, an optimization route is presented which increases the V OC by reducing the interfacial area between donor (D) and acceptor (A). This optimization route concerns a cascade device architecture in which the introduction of discontinuous interlayers between alpha‐sexithiophene (α‐6T) (D) and chloroboron subnaphthalocyanine (SubNc) (A) increases the V OC of an α‐6T/SubNc/SubPc fullerene‐free cascade OSC from 0.98 V to 1.16 V. This increase of 0.18 V is attributed solely to the suppression of nonradiative recombination at the D–A interface. By accurately measuring the optical gap ( E opt ) and the energy of the charge‐transfer state ( E CT ) of the studied OSC, a detailed analysis of the overall voltage losses is performed. E opt – qV OC losses of 0.58 eV, which are among the lowest observed for OSCs, are obtained. Most importantly, for the V OC ‐optimized devices, the low‐energy (700 nm) external quantum efficiency (EQE) peak remains high at 79%, despite a minimal driving force for charge separation of less than 10 meV. This work shows that low‐voltage losses can be combined with a high EQE in organic photovoltaic devices.