Efficiency of Interfacial Electron Transfer from Zn-Porphyrin Dyes into TiO₂ Correlated to the Linker Single Molecule Conductance

High performance dye-sensitized solar cells (DSSCs) rely upon molecular linkers that allow efficient electron transport from the photoexcited dye into the conduction band of the semiconductor host substrate. We have studied photoinduced electron injection efficiencies from modular assemblies of a Zn-porphyrin dye and a series of linker molecules which are axially bound to the Zn-porphyrin complex and covalently bound to TiO₂ nanoparticles. Experimental measurements based on terahertz spectroscopy are compared to the calculated molecular conductance of the linker molecules. We find a linear relationship between measured electron injection efficiency and calculated single-molecule conductance of the linker employed. Since the same chromophore is used in all cases, variations in the absorptivities of the adsorbate complexes are quite small and cannot account for the large variations in observed injection efficiencies. These results suggest that the linker single-molecule conductance is a key factor that should be optimized for maximum electron injection efficiencies in DSSCs. In addition, our findings demonstrate for the first time the possibility of inferring values of single molecule conductance for bridging molecules at semiconductor interfaces by using time-resolved THz spectroscopy