High efficiency co-sensitized solar cell based on luminescent lanthanide complexes with pyridine-2,6-dicarboxylic acid ligands

Abstract

Two lanthanide complexes, Ln(HPDA)₃·4EtOH (Ln = Tb, Dy) (H₂PDA = pyridine-2,6-dicarboxylic acid, EtOH = ethanol), have been successfully synthesized using hydrothermal or solvothermal methods, and their crystal structures were analyzed by single crystal XRD. Both crystals have orthorhombic symmetry with space group Pbcn, exhibiting three-dimensional (3D) supramolecular architecture through hydrogen bonding interactions. The metal center was coordinated to nine atoms by three pyridine-2,6-dicarboxylic acid ligands. The nine-coordinated lanthanide metal complexes were assembled onto a nanocrystalline TiO₂ film to form co-sensitized photoelectrodes with N719 for dye-sensitized solar cells, and their photoelectrochemical performance was studied. In the tandem structure of composite electrodes, the energy levels of lanthanide metal complexes are reorganized in their single-crystal form, as verified by ab initio calculations. The co-sensitized systems are far superior for electron-injection and hole-recovery compared with single N719-sensitized systems. Luminescence properties were measured and electrochemical analysis was also performed on these complexes.