Abstract

Nanoscale phase separation plays a critical role in achieving high photovoltaic performance in bulk-heterojunction organic solar cells, which is limited by solubility, crystallinity, and the compatibility of the donors and acceptors. However, these limits can be overcome by new applications of the traditional planar heterojunction structure. Herein, we demonstrate quasi-orthogonal solvents for a wide-band-gap donor (P2F-EHp) and a highly crystalline non-fullerene acceptor (M4–4F) to overcome the over-agglomeration and enabled the fabrication of a planar heterojunction device with a favorable power conversion efficiency of 14.2% (compared with 12.7% in bulk-heterojunction device), which is among one of the highest efficiencies of planar heterojunction devices to date. Detailed studies based on cross-sectional transmittance electron microscopy, grazing incidence wide-angle X-ray scattering at various incident angles, and resonance soft X-ray scattering measurements confirmed the formation of optimal nanoscale morphology. Further transient absorption measurements also proved that the exciton dissociation and free-carrier generation efficiency are not limited by the small mixed-phase area and large pure domains. These findings show insights into the intrinsic morphological changes and charge transfer process in bulk-heterojunction and planar heterojunction structures, providing a novel method for matching donors and acceptors with relatively poor compatibility. • Comparing absorption, morphology, and charge carrier dynamics of BHJ and PHJ devices. • Introducing an effective approach to construct OSCs using poorly compatible donors and acceptors. • Demonstrating the possibility of obviating the need for bulk-heterojunction structure.

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