Strong interactions in dye-sensitized interfaces

Phthalocyanines (Pcs) are capable of converting sunlight into electric energy when adsorbed on TiO2 in a dye-sensitized solar cell. Of special interest in this type of cell is the energy level alignment as well as how molecules adsorb on the surface as it determines the output of the cell. We investigated the FePc-TiO2(110) interface using scanning tunneling microscopy, synchrotron-based photoelectron spectroscopy, and X-ray absorption spectroscopy. We found a strong coupling of the first-layer FePc to the substrate resulting in an alteration of the electronic structure and charge transfer from the molecules. The FePc in the second layer is not severely affected by the bonding to the surface and has bulk-like electronic properties. The growth of FePc thin films proceeds in a layer plus island mode, and the molecular plane is parallel to the surface. The energy level alignment at the interface is determined, and the lowest unoccupied molecular orbital is found above the conduction band minimum of the oxide substrate.