Theoretical design of porphyrin sensitizers with different acceptors for application in dye-sensitized solar cells

Using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, three porphyrin dyes with different acceptors, such as carboxylic acid, cyanoacrylic acid, and 2-cyano-N-hydroxyacrylamide, have been designed. Compared to the best sensitizer (YD2-o-C8) so far, these designed dyes have small highest occupied orbital to lowest unoccupied orbital (HOMO–LUMO) band gaps, and wide absorptions with large oscillator strength at porphyrin Q bands. And the designed Dye1 is similar to YD2-o-C8 in electronic coupling with TiO2, while improved Dye2 and Dye3 are better than YD2-o-C8, thus, Dye2 and Dye3 will be much faster for electron injection in dye-sensitized solar cell systems based on their long-term stable and efficient anchor groups. All these features show that our designed dyes, especially Dye2 and Dye3, have better absorption performance and faster electron injection. In addition, our results point out that 2-cyano-N-hydroxyacrylamide is a new promising acceptor. This study is expected to assist the molecular design of new efficient dyes for the advancement of dye-sensitized solar cells.