Impact of <i>meta</i>- and <i>para</i>-Direction External Side Chains in Y-Series Acceptors on the Molecular Packing and Charge Carrier Dynamics of Organic Photovoltaics

Abstract

The side-chain directions in nonfullerene acceptors (NFAs) strongly influence the intermolecular interactions in NFAs; however, the influence of these side chains on the morphologies and charge carrier dynamics of Y6-based acceptors remains underexplored. In this study, we synthesize four distinct Y6-based acceptors, i.e., meta-HOP-Y6-F (mF), meta-HOP-Y6-Cl (mCl), para-HOP-Y6-F (pF), and para-HOP-Y6-Cl (pCl), with outer side chains of alkoxy-2-ethylhexyl attached at the meta or para positions. Devices containing the meta-position acceptors blended with the polymer donor PM6 achieve power conversion efficiencies (PCEs) at least 1.27-fold higher than those of devices containing para-position acceptors. The enhanced performance can be attributed to the formation of donor-acceptor domains that are advantageous for charge carrier generation, transport, and collection. This is due to variations in phase aggregation that result from steric hindrance effects at the meta- and para-position acceptors. As a result, meta-position acceptors with lower steric hindrance improved pi-pi and lamellar stacking, whereas the para-position acceptors encountered excessive steric hindrance, reducing their photovoltaic efficiencies. Additionally, the meta-position acceptors demonstrate long charge carrier lifetimes, which suppress recombination in the charge transfer state and promote efficient charge separation. These results underline the critical role of side-chain direction in optimizing Y6-based acceptors for improving photovoltaic performance.