Dynamic Characteristics of Aggregation Effects of Organic Dyes in Dye-Sensitized Solar Cells

Two organic dyes (LS-1 and IQ4) containing identical electron donor and acceptor units but distinct π units result in significantly different power conversion efficiency of the corresponding dye-sensitized solar cells (DSSCs): LS-1, 4.4%, and IQ4, 9.2%. Herein, we combine first-principle calculations and molecular dynamics to explore the aggregation effects of LS-1 and IQ4 by comparing their optical properties and intermolecular electronic couplings. The calculated absorption spectra are in good agreement with the experimental observations and reveal them to be evidently affected by the dimerization. Furthermore, molecular dynamics simulations show that steric hindrance induced by the diphenylquinoxaline unit in IQ4 can elongate the distances between intermolecular π units or electron donors, which are responsible for the fact that the intermolecular electronic coupling of LS-1 is about 10 times larger than that of IQ4. More importantly, the aggregated IQ4 remains almost perpendicular to the TiO2 surface, whereas LS-1 gradually tilts during the dynamic simulation, impacting electron injection and recombination in several ways, which clarifies why IQ4 leads to larger photocurrent and higher conversion efficiency. The deep understanding of the dye aggregation effects sheds new light on the complex factors determining DSSC function and paves the way for rational design of high-efficiency self-anti-aggregation sensitizers.