Time-Resolved Indirect Nanoplasmonic Sensing Spectroscopy of Dye Molecule Interactions with Dense and Mesoporous TiO₂ Films

Indirect nanoplasmonic sensing (INPS) is an experimental platform exploiting localized surface plasmon resonance (LSPR) detection of processes in nanomaterials, molecular assemblies, and films at the nanoscale. Here we have for the first time applied INPS to study dye molecule adsorption/impregnation of two types of TiO₂ materials: thick (10 μm) mesoporous films of the kind used as photoanode in dye-sensitized solar cells (DSCs), with particle/pore size in the range of 20 nm, and thin (12–70 nm), dense, and flat films. For the thick-film experiments plasmonic Au nanoparticles were placed at the hidden, internal interface between the sensor surface and the mesoporous TiO₂. This approach provides a unique opportunity to selectively follow dye adsorption locally in the hidden interface region inside the material and inspires a generic and new type of nanoplasmonic hidden interface spectroscopy. The specific DSC measurement revealed a time constant of thousands of seconds before the dye impregnation front (the diffusion front) reaches the hidden interface. In contrast, dye adsorption on the dense, thin TiO₂ films exhibited much faster, Langmuir-like monolayer formation kinetics with saturation on a time scale of order 100 s. This new type of INPS measurement provides a powerful tool to measure and optimize dye impregnation kinetics of DSCs and, from a more general point of view, offers a generic experimental platform to measure adsorption/desorption and diffusion phenomena in solid and mesoporous systems and at internal hidden interfaces