Proceedings of 6th International Conference on Hybrid and Organic Photovoltaics (HOPV14)
Publication date: 1st March 2014
Electrons accumulated in the mesoporous semiconductor electrodes are thought to be charge compensated by cations in surrounding electrolyte, but it is unclear whether these ions are adsorbed at the semiconductor surface or free in the electrolyte. Here we will present a study where a combination of techniques is used to investigate the charge compensation mechanism.
When electrons are present in the mesoporous semiconductor, the charge-compensating cations are adsorbed at the interface, or in solution. The position of the cations will affect the electric field across adsorbed dye molecules, see Figure 1. This will lead to differences in the absorption spectrum of the dye due to a Stark shift.1 Adsorbed dye molecules are thought to be, at least partially, located within the Helmholtz double layer at the semiconductor / electrolyte interface. Electroabsorption techniques can thus be used to determine the mechanism of charge compensation of electrons in these electrodes. We will present new experimental data that will give new insights into the charge compensation mechanism in dye-sensitized solar cells.
Ref 1: Cappel, U. B.; Feldt, S. M.; Schöneboom, J.; Hagfeldt A.; Boschloo, G.The Influence of Local Electric Fields on Photoinduced Absorption in Dye-Sensitized Solar Cells J. Am. Chem. Soc.2010,132 (26), 9096–9101
Figure 1: Charge compensation at the semiconductor / dye /electrolyte interface. (a)The counter charge for the electron in TiO2 is a solvated cation outside the densely packed dye monolayer (red). Dye molecules are inside the Helmholtz double layer (indicated with a dotted line) and will experience an electric field. (b)If solvation ions can penetrate the dye layer, the HH layer will be thinner (about 5 Å, defined by the radius of the solvated cation). Dye molecules are partially in the HH layer and will experience some electric field. (c) The counter charge is an adsorbed cation (without solvation shell). The dye molecules will not experience an electric field from the electron–cation pair.
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