Density functional theory study of new azo dyes with different π-spacers for dye-sensitized solar cells.

Some of new azo-based metal-free dyes with different π-conjugation spacers, such as carbazole, fluorene, pyrrole, thiophene, furan and thiazole, have been investigated with density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. Theoretical calculations allow us to quantify factors such as light harvesting efficiency (LHE), electron injection driving force (ΔG(inject)) and the weight of the LUMO orbital on the carboxylic group (QLUMO) related to the short-circuit photocurrent density (Jsc), and to evaluate both charge recombination between the semiconductor conduction band electrons and the oxidized dyes and/or electrolyte, and also the shift of the conduction band of the semiconductor as a result of the adsorption of the dyes onto the semiconductor surface, associated with the open-circuit photovoltage (Voc). According to the results, we could predict that how the π-conjugation spacers influence the Jsc as well as the Voc of DSSCs. Among these dyes, the carbazole and fluorene-based dyes (dyes 1 and 2) show the highest LHE, ΔG(inject), QLUMO, and the slowest recombination rate. Consequently, the obtained results show that the carbazole and fluorene-based dyes could have the better Jsc and Voc compared to the other dyes.