Donor Polymer Can Assist Electron Transport in Bulk Heterojunction Blends with Small Energetic Offsets.

Conventional organic solar cell (OSC) systems have significant energy offsets between the donor and acceptor both at the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels. Because of this, in a bulk heterojunction (BHJ) system, electrons typically transport in acceptors, whereas holes typically transport in donors. It is not favorable for electrons to hop back and forth between the donor and acceptor because the hopping is energetically disfavored. In such conventional OSC systems, the addition of donor polymer to acceptor films should typically reduce the electron mobility. In this study, a surprisingly large increase (up to 30×) in electron mobility is observed in an OSC blend when introducing a polymer donor into small molecular acceptor. By ruling out morphology reasons, it is shown that the donor polymer can assist the electron transport by providing "bridges" or a "shortcut" for electron transport across the domains of small molecular acceptors. This can happen because, for these systems, the LUMO offset is small. The study shows the benefits of donor-assisted electron transport in BHJ systems with small energetic offsets. This finding could be also applied to other fields to tune the optimized charge transport property of organic materials or slush blends.

Tweaking the Molecular Geometry of a Tetraperylenediimide Acceptor.

Partial flattening of the spatially extended molecular scaffold has been employed as an effective tactic to improve the device performance of a perylenediimide (PDI)-based small-molecule acceptor because the less twisted yet not completely planar molecular geometry is anticipated to improve the molecular packing and thereby attain a more suitable balance between the carrier transport ability and phase domain size. A small-molecule acceptor BF-PDI comprising four α-substituted PDI units attached around a 9,9'-bifluorenylidene (BF) central moiety is designed and studied in polymer solar cells. The BF group is deemed a ring-fused analogue of the tetraphenylethylene (TPE) unit. Due to the less twisted and better conjugated BF skeleton, BF-PDI displays more delocalized lowest unoccupied molecular orbital. By virtue of both the electronic and steric effects, BF-PDI is suggested to bring about superior intermolecular stacking and donor-acceptor phase separation morphology in blend films. Indeed, the experimental results show that BF-PDI displays improved charge transport ability and a higher power-conversion efficiency of 8.05% than that of TPE-PDI. Grazing-incidence wide-angle X-ray diffraction and resonant soft X-ray scattering confirm the more compact and ordered molecular packing as well as smaller domain sizes in the P3TEA/BF-PDI blend.