Theoretical Exploration of the Effects of Conjugated Side Chains on the Photoelectric Properties of Y6-Based Nonfullerene Acceptors

With the application of nonfullerene acceptors (NFAs) Y6 and its derivatives, the power conversion efficiencies (PCEs) of single-junction organic solar cells (OSCs) have exceeded 20%. Side-chain engineering has proven to be an important strategy for optimizing Y6-based NFAs. However, studies on the incorporation of conjugated side chains into Y6-based NFAs are still rare, and the corresponding underlying mechanisms are still not well understood. In this article, we systematically designed eight molecules based on modifications to the conjugated side chains of two reported Y6-based NFAs, involving alterations of branched alkyl chains at different positions on the thiophene, benzene, bithiophene, and benzene-thiophene moieties that serve as conjugated side chains. Using reliable density functional theory (DFT) and time-dependent DFT calculations, we obtained key photovoltaic parameters such as molecular planarity, dipole moments, electrostatic potential and corresponding fluctuations, frontier molecular orbitals, exciton binding energy (Eb), singlet–triplet energy differences (ΔEST), and UV–vis absorption spectra of these newly designed NFAs. The results show that the side conjugated rings and the positions of lateral alkyl chains attached to these rings exert noticeable influences on their photoelectric properties. Notably, compared to the prototype T3EH, 2T2EH, 2T3EH, PT2EH, PT3EH, and P2EH exhibit enhanced absorption (manifesting as increased total oscillator strength) and smaller Eb and ΔEST values, hinting at their promising potential as novel NFAs.