Impact of Donor–Acceptor Interaction and Solvent Additive on the Vertical Composition Distribution of Bulk Heterojunction Polymer Solar Cells

The vertical composition distribution of a bulk heterojunction (BHJ) photoactive layer is known to have dramatic effects on photovoltaic performance in polymer solar cells. However, the vertical composition distribution evolution rules of BHJ films are still elusive. In this contribution, three BHJ film systems, composed of polymer donor PBDB-T, and three different classes of acceptor (fullerene acceptor PCBM, small-molecule acceptor ITIC, and polymer acceptor N2200) are systematically investigated using neutron reflectometry to examine how donor–acceptor interaction and solvent additive impact the vertical composition distribution. Our results show that those three BHJ films possess homogeneous vertical composition distributions across the bulk of the film, while very different composition accumulations near the top and bottom surface were observed, which could be attributed to different repulsion, miscibility, and phase separation between the donor and acceptor components as approved by the measurement of the donor–acceptor Flory–Huggins interaction parameter χ. Moreover, the solvent additive 1,8-diiodooctane (DIO) can induce more distinct vertical composition distribution especially in nonfullerene acceptor-based BHJ films. Thus, higher power conversion efficiencies were achieved in inverted solar cells because of facilitated charge transport in the active layer, improved carrier collection at electrodes, and suppressed charge recombination in BHJ solar cells.