Novel Carbazole-Phenothiazine Dyads for Dye-Sensitized Solar Cells: A Combined Experimental and Theoretical Study

We report a joint experimental and computational work on new organic donor-acceptor dye sensitizers in which a carbazole (CZ) and a phenothiazine (PTZ) units are linked together by an alkyl C6H13, while two different anchoring groups are employed: the cyanoacrylic acid (CS1A, CSORG1) and the rhodanine-3-acetic acid (CS4A, CSORG4). The CZ moiety has multiple roles of (i) acting as an extra-electron donor portion, providing more electron density on the PTZ; (ii) suppressing the back-electron transfer from TiO2 to the electrolyte by forming a compact insulating dye layer; (iii) modulating dye aggregation on the semiconductor surface; and (iv) acting as an antenna, collecting photons and, through long-range energy transfer, redirecting the captured energy to the dye sensitizer. We show that the introduction of the CZ donor remarkably enhances the photovoltaic performances of the rhodanine-based dye, compared to the corresponding simple PTZ dye, with more than a two-fold increase in the overall efficiencies, while it does not bring beneficial effects in the case of the cyanoacrylic-based sensitizer. Based on quantum mechanical calculations and experimental measurements, we show that, in addition to a favored long-range energy transfer, which increases the light absorption in the blue region of the spectrum, the presence of the CZ unit in the CSORG4 dye effectively induces a beneficial aggregation pattern on the semiconductor surface, yielding a broadened and red-shifted light absorption, accounting for the two-fold increase in the generated photocurrent.