Molecular engineering of the fused azacycle donors in the D-A-π-A metal-free organic dyes for efficient dye-sensitized solar cells

Abstract Four novel D-A-π-A metal-free organic sensitizers QL1–4 with the fused azacycle units as donors have been designed and synthesized to investigate the relationship between both the sizes and conjugations of azacycle and performances of dye-sensitized solar cells systematically. QL1 with the five-membered azacycle, i.e., with carbazole (Cz) as donor, exhibits the smallest molar extinction coefficients (e). QL2 and QL3 with the seven-membered azacycle, i.e. with N-phenyl-iminostilbene (ISB) and N-phenyl-iminodibenzyl (IDB) as donors, respectively, show the red-shifted absorption spectra and higher e compared to QL1. However, QL2 and QL3 with an only distinction in a single or double bond, display distinctive PCEs. QL4 with the six-membered azacycle, i.e., 9,9,10-triphenyl-9,10-dihydroacridine (TDD), exhibits a blue-shifted absorption spectrum due to a big dihedral angle, resulting in a lower photovoltaic performance. Especially, QL3 with the ISB donor is conducive to achieving a PCE of 6.22%, which is higher than QL2, due to its better planar structure and more conjugation. When co-adsorbed with CDCA, QL3 exhibits the highest PCE of 7.14% among all dyes, and up to 8.26% by co-sensitizing with dye WL5, which surpasses that of the reference dye N719 (7.75%). The results indicate that the size and conjugation of the fused azacycle donors may affect the photovoltaic performance significantly, and the ISB unit is demonstrated as a promising donor for efficient organic dyes.