Iodinated Al^III-based phthalocyanines are promising sensitizers for dye-sensitized solar cells; A theoretical comparison between Zn ^II, Mg^II, and Al^III-based phthalocyanine sensitizers

To design efficient dyes for dye-sensitized solar cells (DSSCs), using a Zn-coordinated phthalocyanine (TT7) as the prototype, a series of phthalocyanine dyes (Pcs) with different metal ions and peripheral/axial groups have been investigated by means of density functional theory (DFT) and time-dependent DFT (TDDFT) methods. Computational results show that the iodinated Al-based dye with a peripheral amino group (Al-I-NH₂-Pc) exhibits the largest redshift in the maximum absorbance (λ_max). In addition, Al-based dyes have appropriate energy-level arrangements of frontier orbitals to keep excellent balance between electron injection and regeneration of oxidized dyes. Further, it has been found that the intermolecular π-staking interaction in Al-I-Pc molecules is weaker than the other metal-based Pcs, which may effectively reduce dye aggregation on the semi-conductor surface. All these results suggest iodinated Al-based Pcs (Al-I-Pcs) to be potentially promising sensitizers in DSSCs.