Exploring the Potential of Linear π-Bridge Structures in a D-π-A Organic Photosensitizer for Improved Open-Circuit Voltage.

We present the design, synthesis, and evaluation of novel metal-free photosensitizers based on D-π-A structures featuring tri-arylamine as an electron donor, cyanoacrylic acid as an anchoring group, and substituted derivative π-bridges including 9,9-dimethyl-9H-fluorene, benzo[ b ]thiophene, or naphtho [1,2- b :4,3- b ']dithiophene. The aim of the current research is to unravel the relationship between chemical structure and photovoltaic performance in solar cell applications by investigating the properties of these organic sensitizers. The newly developed photosensitizers displayed variations in HOMO-LUMO energy gaps and photovoltaic performances due to their distinct π-bridge structures and exhibited diverse spectral responses ranging from 343 to 490 nm. The t-shaped and short linear photosensitizers demonstrated interesting behaviors in dye-sensitized solar cells, such as the effect of the molecular size in electron recombination. The study showed that a t-shaped photosensitizer with a bulky structure reduced electron recombination, while short linear photosensitizers with a smaller molecular size resulted in a higher open-circuit voltage value and enhanced photovoltaic performance. Impedance analysis further supported the findings, highlighting the influence of dye loading and I 3 - ion surface passivation on the overall performance of solar cells. The molecular design methodology proposed in this study enables promising photovoltaic performance in solar cells, addressing the demand for highly efficient, metal-free organic photosensitizers.