Influence of electrical potential distribution, charge transport, and recombination on the photopotential and photocurrent conversion efficiency of dye-sensitized nanocrystalline TiO2 solar cells: A study by electrical impedance and optical modulation techniques

The role of electrical potential, charge transport, and rt combination in d etermining the photopotential and photocurrent conversion efficiency (IPCE) of dye-sensitized nanocrystalline solar cells was studied. Electrostatic a rguments and electrical impedance spectroscopy (EIS) are used to obtain inf ormation on the electrical and electrochemical potential distribution in th e cell. It is shown that on the macroscopic level, no significant electrica l potential drop exists within the porous TiO2 when it contacts the electro lyte and that the electrical potential drop at the transparent conducting o xide substrate (TCO)/TiO2 interface occurs over a narrow region, one or two layers of TiO2. Analyses of EIS and other data indicate that both the phot opotential of the cell and the decrease of the electrical potential drop ac ross the TCO/TiO2 interface are caused by the buildup of photoinjected elec trons in the TiO2 film. The time constants for the recombination and collec tion of the photoinjected electrons are measured by EIS and intensity-modul ated photocurrent spectroscopy (IMPS). As the applied bias is varied from s hort-circuit to open-circuit conditions at 1 sun light intensity, recombina tion becomes faster, the collection of electrons becomes slower, and the IP CE decreases. The decrease of IPCE correlates directly with the decline of the charge-collection efficiency eta(cc) which is obtained from the time co nstants for the recombination and collection of the photoinjected electrons . Significantly, at open circuit, eta(cc) is only 45% of its short-circuit value, indicating that the dye-sensitized nanocrystalline TiO2 solar cell b ehaves as a nonideal photodiode.