Homo- and Heterodimeric Dyes for Dye-Sensitized Solar Cells: Panchromatic Light Absorption and Modulated Open Circuit Potential.

The design of dyes for panchromatic light absorption has attracted much attention in the field of dye-sensitized solar cells (DSSCs). An approach to enhance panchromatic light absorption utilizes mixtures of complementary light-absorbing dyes as well as dyes with specific anchoring groups that facilitate interfacial charge transfer with TiO . Dipole-dipole interactions between the dye molecules on the surface broaden the spectrum, which results in decreased DSSC device performance. However, controlled aggregation of dyes results in broadening the spectral profile along with enhanced photocurrent generation. To control the dye-dye interaction, dimeric dyes with different dipole lengths D -D , D -D were systematically designed and synthesized. The photophysical and electrochemical properties were evaluated and the E and E levels were determined; these energy levels determines the electron injection from E of the dye to E of TiO and regeneration of oxidized dye by the electrolyte, respectively. The absorption spectra of D -D , D -D were broadened in solution compared to model dye D ; this indicates that the dye-dye interaction is prominent in solution. In D -D excitation energy transfer between photoexcited D and D was explained by using Förster resonance energy transfer (FRET). The homodimeric dye showed a device performace of 2.8 % (V 0.607, J 6.62 mA/cm , ff 69.3 %),whereas the heterodimeric dye D -D showed a device performance of 3.9 % (V 0.652 V, J 8.89 mA/cm , ff 68.8 %). The increased photocurrent for D -D is due to the panchromatic IPCE response compared to D -D . The increased V is due to the effective passivation of the TiO surface by the spirolinker, and the effective dipole moment that shifts the conduction band on TiO . Hence, the open circuit potential, V , for the devices prepared from D , D -D and D -D were systematically modulated by controlling the intermolecular π-π and intramolecular dipole-dipole interactions of the dimeric dyes.