Interfacial Modification of Photoanode|Electrolyte Interface Using Oleic Acid Enhancing the Efficiency of...

Dye-sensitized solar cells (DSSCs) are useful devices in converting renewable solar energy into electrical energy. In DSSCs, the triiodide reduction at the surface of TiO₂ is one of the detrimental processes that limit the realization of high efficiencies of the device. To alleviate the active sites available on the semiconductor surface for this detrimental process, the interfacial modification of the dye-adsorbed TiO₂|electrolyte interface has been attempted by coadsorption of oleic acid (OA) over the TiO₂ surface. Thus, the modified cell exhibited a higher efficiency (η) of 12.9% under one sun illumination when compared with that of the unmodified cell (η = 11.1%). To provide an insight into the OA anchoring and dynamics of electron transport at the photoanode|electrolyte interface, molecular spectroscopic and electrochemical impedance spectroscopic analyses were carried out. A red shift in the optical absorption spectrum was observed after the addition of OA to dye-adsorbed TiO₂. The binding of OA to TiO₂ surface was found to be through bridging bidentate type. Mott-Schottky analyses of the DSSCs under dark conditions were made to probe the shift in the Fermi level of TiO₂ upon OA modification. In addition, the Förster resonance energy transfer (FRET) has been found between OA and N719 dye. Thus, the red shift in the optical absorption, enhanced electron-transfer kinetics, and FRET contributes to the observed enhancement in the efficiency of the device containing OA-modified photoanode.