Dye-sensitized composite semiconductor nanostructures

Understanding of the charge transport and recombination mechanisms of dye-sensitized solar cells based on semiconductor nanostructures is essential for the improvement of their performance. A great deal of information on these systems have been obtained from studies on a single material (mostly TiO2 and to a lesser extent ZnO and SnO2). We have conducted extensive measurements on composite dye-sensitized nanosturctures and found that the composite systems possess unusual properties. Dye-sensitized photoelectrochemical cells made from nanocrystalline films of some materials (e.g., SnO2) yield comparatively small open-circuit voltages and energy and quantum conversion efficiencies, despite excellent dye-semiconductor interaction. However, on deposition of ultra-thin shells of insulators or high band gap semiconductors on the crystallites, a dramatic increase in the above parameters is observed. Outer shells were found to have insignificant or in most cases a negative effect on TiO2 films. We explain the above findings on the basis of vast differences in the leakage rates of trapped electrons in different materials which is sensitive to the effective electron mass. Electrons injected to the conduction band in dye-sensitization enter into shallow traps from which they get thermally reemitted to the conduction band. The building up of the electron quasi-fermi level and transport depends on this process. The spread of the hydrogenic wave function of a trapped electron increases inverse exponentially with the effective mass so that the electron leakage and their recombination with acceptors ‘outside’ become severe when the crystallite size is comparable to the Bohr radius of the trapped electron. Such recombinations are effectively suppressed by deposition of thin films on the crystallites. Excited dye molecules anchored to the outer shell injects electrons to the conduction band via tunneling.