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

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 TiO₂ . 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 D₁ -D_sq , D_sq -D_sq were systematically designed and synthesized. The photophysical and electrochemical properties were evaluated and the E_HOMO and E_LUMO levels were determined; these energy levels determines the electron injection from E_LUMO of the dye to E_CB of TiO₂ and regeneration of oxidized dye by the electrolyte, respectively. The absorption spectra of D_sq -D_sq , D₁ -D_sq were broadened in solution compared to model dye D_sq ; this indicates that the dye-dye interaction is prominent in solution. In D₁ -D_sq excitation energy transfer between photoexcited D₁ and D_sq was explained by using Förster resonance energy transfer (FRET). The homodimeric dye showed a device performace of 2.8 % (V_oc 0.607, J_sc 6.62 mA/cm² , ff 69.3 %),whereas the heterodimeric dye D₁ -D_sq showed a device performance of 3.9 % (V_oc 0.652 V, J_sc 8.89 mA/cm² , ff 68.8 %). The increased photocurrent for D₁ -D_sq is due to the panchromatic IPCE response compared to D_sq -D_sq . The increased V_oc is due to the effective passivation of the TiO₂ surface by the spirolinker, and the effective dipole moment that shifts the conduction band on TiO₂ . Hence, the open circuit potential, V_oc , for the devices prepared from D_sq , D₁ -D_sq and D_sq -D_sq were systematically modulated by controlling the intermolecular π-π and intramolecular dipole-dipole interactions of the dimeric dyes.