Effects of the terminal donor unit in dyes with D–D–π–A architecture on the regeneration mechanism in DSSCs: a computational study

Abstract

This theoretical study on dye-sensitized solar cells (DSSCs) includes design strategies for dye donor units to improve the efficiency of DSSCs, and further illuminates the organic dye regeneration mechanism. We have designed a series of new organic sensitizers based on a D–D–π–A architecture to exhibit easy electron transfer and to have remarkable light harvesting properties in the visible region by density functional theory (DFT) and time-dependent (TD)-DFT calculations. Furthermore, the interaction of the organic sensitizers with the conventional redox electrolyte using the triiodide/iodide couple (I₃⁻/I⁻) is investigated. Our calculations indicate that incorporation of strong electron-donating groups remarkably improves the charge transfer characteristics, optoelectronic properties and rapid dye regeneration as compared to less electron donating substituents. In addition, our study demonstrates the possibility of second electron injection from the oxidized dye complex to the semiconductor surface, which further confirms our recently proposed dye regeneration mechanism.