Extending donor size in D-A-π-A organic dye for dye sensitized solar cells: Anti-aggregation and improving electron injection

We have theoretically designed two D-A-π-A dyes 3 and 4 based on the efficient references 1 and 2 by introducing an extra electron donor unit (D2). Via calculating the electronic structures of isolated dyes, we obtain that dyes 3 and 4 possess stronger light-harvesting efficiency imparted by the fluorescence energy transfer of D2 part, maintain comparable lifetime of excited states, and shorten the electron injection time significantly with regard to 1 and 2. Meanwhile, dye 3 positively shifts the edge of virtual states of TiO₂ in a larger extent compared to its counterparts. Then after considering the alignment morphology of multiple dyes adsorbed on TiO₂ surface, we find that dyes 3 and 4 manifest the capability of anti-aggregation obviously, which is evidenced by the smaller quantity of intermolecular electronic coupling compared to that of dyes 1 and 2, definitively illustrating the prominent performance of novel dyes with the bulky D2 moiety. Finally, dye 3 is screened out as the potential candidate for future application.