Nitroxide Radicals for Highly Efficient Redox Mediation in Dye-sensitized Solar Cells

A robust nitroxide radical, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and its 4-subsituted derivatives (R-TEMPO) exhibit electrochemically reversible redox properties with tunable half-wave potentials (E-1/2) based on the substituent effect. Dye-sensitized solar cells using R-TEMPO as mediators with electron-withdrawing R groups showed significantly enhanced photovoltages compared with those obtained using iodides. The linearity between the open-circuit voltage (V-oc) and E-1/2 revealed that V-oc dominated by the energy gap between the Fermi level of TiO2 and the SOMO level of R-TEMPO.