Unraveling the Morphology in Solution-Processed Pseudo-Bilayer Planar Heterojunction Organic Solar Cells

The conventional bulk heterojunction (BHJ) structure is widely used for fabricating high-performance organic solar cells (OSCs) due to the nanometer-scale phase separation of the donor/acceptor component. However, the elaborate control of the BHJ morphology is difficult to carry out because the morphology evolution is such a complicated process. The compatibility requirement of materials in the same solvent restricts the structural diversity of the molecules to some extent. Meanwhile, the nanoscopic interpenetrating donor/acceptor domains reduce their crystallinity. The bilayer planar heterojunction (PHJ), by contrast, possesses complementary advantages that can make it an alternative candidate to achieve device fabrication and produce different vertical stratification in heterojunction films. However, the flat contact area limits the charge separation and transmission efficiency. The sequential solution processed approach was used to facilitate material diffusion in layers. Also, solvent additives were employed to further enhance the diffusion and thus the device performance. Nevertheless, the morphology of the formed pseudo-bilayer planar heterojunction (PPHJ) has not been fully revealed yet. Here, we carefully study the morphology of the nonfullerene-based PPHJ device in three dimensions. High hole mobility of 2.09 × 10^-4 cm² V^-1 s^-1 and electron mobility of 7.91 × 10^-5 cm² V^-1 s^-1 were obtained in the solution-processed PPHJ device. Meanwhile, a distinct phase separation size with a vertical rearrangement of donor and acceptor was observed, which enable the pseudo-bilayer devices to be equipped with a comparable spectral response to the BHJ devices. We demonstrate that a unique device architecture (ITO/ZnO/PBDB-T/ITIC/MoO₃/Ag) with a power conversion efficiency of 7% can be obtained from a larger molecular weight of PBDB-T without using extra additives. The solution-processed PPHJ films have much in common with the BHJ films. The results proposed that with appropriate molecular design and vertical phase separation optimization, the performance of the solution-processed PPHJ-based OSCs can be further improved.