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.

Accelerated ageing tests on large numbers of nanocrystalline dye‐sensitised solar cells (nc‐DSC) show that, to first order, separation between the effects of the stresses of visible light soaking, UV illumination and thermal treatment on long‐term stability is possible. The corresponding mechanisms are electrochemical, photochemical and purely chemical in nature. It was found that visible light soaking alone is not a dominant stress factor. A dramatic improvement in UV stability has been achieved by using MgI2 as additive to the electrolyte. Thermal stress appears to be one of the most critical factors determining the long‐term stability of nc‐DSC and is strongly related to the chemical composition of electrolyte solvents and additives. Encouraging stability results have been obtained for cells based on pure nitrile‐based solvents: (1) A minor decrease in performance of initially 5.5% solar efficient cells has been found after 2000 h at 60°C without light soaking; (2) After 900 h ageing at 85°C, a decrease of 30% in maximum power has been observed; (3) After 3400 h of combined thermal stress and continuous light soaking (45°C, 1 sun equivalent) good stability with 15% decrease in maximum power can be demonstrated. It should be noted that such good thermal stability has not been reported previously for dye‐sensitised solar cells so far. Copyright © 2001 John Wiley & Sons, Ltd.