DFT/TD-DFT study of novel T shaped phenothiazine-based organic dyes for dye-sensitized solar cells applications

Five novel T shaped phenothiazine-based organic dyes DTTP1~5 with different spacers at N (10) position were designed. The geometries, electronic structures, absorption spectra, electron transfer and injection properties of these isolated dyes and dye/(TiO₂)₉ systems were investigated via density functional theory (DFT) and time dependent density functional theory (TD-DFT) calculation. The optimized geometries indicate that these T shaped dyes show non-planar conformations, which are helpful in suppressing the close intermolecular π-π aggregation in device and enhancing thermal stability. The calculated results indicate that type of π-conjugated spacers can affect the molecular absorption spectra. Introduction of thiophene-benzothiadizole-thiophene unit as π-conjugated spacer can most effectively shift the light absorption to near infrared region and enhance the light harvesting efficiency (LHE). Moreover, it is found that these dyes show a good performance of electron injection and dye regeneration owing to the proper electron injection driving force (ΔG_inject) and dye regeneration driving force (ΔG_reg). The theoretical results reveal that these dyes could be used as potential sensitizers for DSSCs, and DTTP4 would be the most plausible sensitizer for high-efficiency DSSCs due to the narrow HOMO-LUMO energy gap (Δ_H-L), broad absorption spectrum, high LHE value, and large dipole moment (μ_normal).