The Influence of Local Electric Fields on Photoinduced Absorption in Dye-sensitized Solar Cells

The dye-sensitized solar cell (DSC) challenges conventional photovoltaics with its potential for low-cost production and its flexibility in terms of color and design. Transient absorption spectroscopy is widely used to unravel the working mechanism of DSCs. A surprising, unexplained feature observed in these studies is an apparent bleach of the ground-state absorption of the dye, under conditions where the dye is in the ground state. Here, we demonstrate that this feature can be attributed to a change of the local electric field affecting the absorption spectrum of the dye, an effect related to the Stark effect first reported in 1913. We present a method for measuring the effect of an externally applied electric field on the absorption of dye monolayers adsorbed on flat TiO(2) substrates. The measured signal has the shape of the first derivative of the absorption spectra of the dyes and reverses sign along with the reversion of the direction of the change in dipole moment upon excitation relative to the TiO(2) surface. A very similar signal is observed in photoinduced absorption spectra of dye-sensitized TiO(2) electrodes under solar cell conditions, demonstrating that the electric field across the dye molecules changes upon illumination. This result has important implications for the analysis of transient absorption spectra of DSCs and other molecular optoelectronic devices and challenges the interpretation of many previously published results.