Electrolyte/Dye/TiO₂ Interfacial Structures of Dye-Sensitized Solar Cells Revealed by In Situ Neutron Reflectometry...

The nature of an interfacial structure buried within a device assembly is often critical to its function. For example, the dye/TiO₂ interfacial structure that comprises the working electrode of a dye-sensitized solar cell (DSC) governs its photovoltaic output. These structures have been determined outside of the DSC device, using ex situ characterization methods; yet, they really should be probed while held within a DSC since they are modulated by the device environment. Dye/TiO₂ structures will be particularly influenced by a layer of electrolyte ions that lies above the dye self-assembly. We show that electrolyte/dye/TiO₂ interfacial structures can be resolved using in situ neutron reflectometry with contrast matching. We find that electrolyte constituents ingress into the self-assembled monolayer of dye molecules that anchor onto TiO₂. Some dye/TiO₂ anchoring configurations are modulated by the formation of electrolyte/dye intermolecular interactions. These electrolyte-influencing structural changes will affect dye-regeneration and electron-injection DSC operational processes. This underpins the importance of this in situ structural determination of electrolyte/dye/TiO₂ interfaces within representative DSC device environments.