Density functional theory characterization and design of high-performance diarylamine-fluorene dyes with different π spacers for dye-sensitized solar cells

To rationalize the marked difference in the energy conversion efficiency of dye sensitized solar cells (DSSCs) based on organic dyes 1 and 2 different only in their pi spacer, density functional theory (DFT) and time-dependent DFT calculations of the geometries, electronic structures and absorption spectra of the organic dyes before and after binding to titanium oxide were carried out. These enable us to determine factors such as dipole moments associated with the open-circuit photovoltage (V-oc), and to quantify parameters such as the light harvesting efficiency, the electron injection efficiency associated with the short-circuit photocurrent density (J(sc)). The results reveal that compared to 2 with a thiazole spacer, 1 with a thiophene spacer could cause a red shift of the absorption spectrum, increase the oscillator strength and improve the driving force for electron injection, thus leading to the larger J(sc), in good agreement with experimental data. As for V-oc, our results stress that apart from the generally emphasized vertical dipole moment of the dyes pointing outward from the semiconductor surface, the number of photoinjected electrons from the dye to the semiconductor is also crucial to obtain high performance dyes with high V-oc. After justifying the reliability of the quantum-chemical methods, we designed another four dyes with different pi spacers to screen more efficient organic dyes. Fortunately, taking 1 as reference, we find that dye 4 with a thienothiophene spacer displays an enhanced J(sc) and V-oc, indicating that it will be a more efficient diarylamine-fluorene-based organic dye used in DSSCs, which will play a theoretical guiding role in the design and synthesis of new organic dyes.