DyeTiO2 interfacial structure of dye-sensitised solar cell working electrodes buried under a solution of I-/I3- redox electrolyte.

Dye-sensitised solar cells (DSCs) have niche prospects for electricity-generating windows that could equip buildings for energy-sustainable future cities. However, this 'smart window' technology is being held back by a lack of understanding in how the dye interacts with its device environment at the molecular level. A better appreciation of the dyeTiO2 interfacial structure of the DSC working electrodes would be particularly valuable since associated structure-function relationships could be established; these rules would provide a 'toolkit' for the molecular engineering of more suitable DSC dyes via rational design. Previous materials characterisation efforts have been limited to determining this interfacial structure within an environment exposed to air or situated in a solvent medium. This study is the first to reveal the structure of this buried interface within the functional device environment, and represents the first application of in situ neutron reflectometry to DSC research. By incorporating the electrolyte into the structural model of this buried interface, we reveal how lithium cations from the electrolyte constituents influence the dyeTiO2 binding configuration of an organic sensitiser, MK-44, via Li+ complexation to the cyanoacrylate group. This dye is the molecular congener of the high-performance MK-2 DSC dye, whose hexa-alkyl chains appear to stabilise it from Li+ complexation. Our in situ neutron reflectometry findings are built up from auxiliary structural models derived from ex situ X-ray reflectometry and corroborated via density functional theory and UV/vis absorption spectroscopy. Significant differences between the in situ and ex situ dyeTiO2 interfacial structures are found, highlighting the need to characterise the molecular structure of DSC working electrodes while in a fully assembled device.

Preferred Molecular Orientation of Coumarin 343 on TiO2 Surfaces: Application to Dye-Sensitized Solar Cells.

The dye···TiO2 interfacial structure in working electrodes of dye-sensitized solar cells (DSCs) is known to influence its photovoltaic device performance. Despite this, direct and quantitative reports of such structure remain sparse. This case study presents the application of X-ray reflectometry to determine the preferred structural orientation and molecular packing of the organic dye, Coumarin 343, adsorbed onto amorphous TiO2. Results show that the dye molecules are, on average, tilted by 61.1° relative to the TiO2 surface, and are separated from each other by 8.2 Å. These findings emulate the molecular packing arrangement of a monolayer of Coumarin 343 within its crystal structure. This suggests that the dye adsorbs onto TiO2 in one of its lowest energy configurations; that is, dye···TiO2 self-assembly is driven more by thermodynamic rather than kinetic means. Complementary DSC device tests illustrate that this interfacial structure compromises photovoltaic performance, unless a suitably sized coadsorbant is interdispersed between the Coumarin 343 chromophores on the TiO2 surface.