The frequency-dependent photocurrent response of dye-sensitized TiO2 cells to modulated illumination is analyzed. Analytical expressions are derived that describe generation, collection, and recombination of electrons in a thin layer nanocrystalline solar cell under conditions of steady illumination and with a superimposed small amplitude modulation. The analysis considers illumination from the contact side and from the counter electrode side, and characteristic differences in the intensity-modulated photocurrent response are predicted for the two cases. The attenuation of the ac photocurrent by the RC time constant of the cell is also considered. The theoretical analysis shows that intensity modulated photocurrent spectroscopy (IMPS) can provide new insight into the dynamics of electron transport and collection in the dye-sensitized solar cell. Experimental IMPS data measured for high-efficiency dye-sensitized cells are fitted to the theoretical model using Bode plots in order to derive values of the lifetime (2 × 10-2 s) and diffusion coefficient (5 × 10-5 cm2 s-1) of photoinjected electrons.

The lifetime τ n and diffusion coefficient D n of photoinjected electrons have been measured in a dye-sensitized nanocrystalline TiO2 solar cell over 5 orders of magnitude of illumination intensity using intensity-modulated photovoltage and photocurrent spectroscopies. τ n was found to be inversely proportional to the square root of the steady-state light intensity, I 0, whereas D n varied with I 0 0.68. The intensity dependence of τ n is interpreted as evidence that the back reaction of electrons with I3 - may be second order in electron density. The intensity dependence of D n is attributed to an exponential trap density distribution of the form N t(E) ∝ exp[−β(E − E c)/(k B T)] with β ≈ 0.6. Since τ n and D n vary with intensity in opposite senses, the calculated electron diffusion length L n = (D n τ n )1/2 falls by less than a factor of 5 when the intensity is reduced by 5 orders of magnitude. The incident photon to current efficiency (IPCE) is predicted to decrease by less than 10% over the same range of illumination intensity, and the experimental results confirm this prediction.