The high concentration of electrolyte ions permeating the nanoporous films
of dye sensitized solar cells eliminates all but nanoscopic electric fields
in the solution and in the TiO2. The only substantial electric field is ex
pected to occur at the TiO2/solution interface, and it is primarily across
this interface that the photopotential drops in operating cells. In the dar
k, the low conductivity of the TiO2, and the high conductivity of the solut
ion ensure that applied potentials drop over only a small fraction of the n
anoporous TiO2 film near the substrate electrode. Therefore, measurements i
n the dark cannot be directly compared to measurements under illumination b
ecause the latter access most or all of the TiO2 film. The sensitizing dye
is located partially inside the electrochemical double layer at the TiO2/so
lution interface and so its redox potential is not fixed relative to either
the TiO2 or the solution. If the dye is mostly inside the double layer, it
s potential will tend to follow that of the TiO2; if it is mostly outside,
it will be almost independent of the TiO2. Different photovoltage-limiting
kinetic steps can result in these two cases. The narrow absorption spectra
of many dyes provides the dye cells with a natural advantage over conventio
nal solar cells in applications such as photoelectrochromic windows and pow
er windows.