Evidence for an Electronic State at the Interface between the SnO₂ Core and the TiO₂ Shell in Mesoporous SnO₂/TiO₂ Thin Films

A comparative spectroelectrochemical study of micron thick mesoporous thin films composed of TiO 2 and SnO 2 nanocrystallites was undertaken to identify the location and identity of electronic state(s) in core/shell SnO 2 /TiO 2 films that have emerging applications in energy science. The mesoporous TiO 2 and SnO 2 films were synthesized by sol–gel techniques, and the core/shell material was created by atomic layer deposition of a TiO 2 shell on a SnO 2 core. Electrochemical reduction of these materials in aqueous electrolytes resulted in a blue shift of the fundamental VB → CB absorbance as well as a broad absorbance across the visible region. For SnO 2, three unique spectra were required to model the potential dependent data while only one unique spectrum was needed to model the corresponding data for SnO 2 /TiO 2 and TiO 2 . Significantly, standard addition of the spectra measured for SnO 2 and TiO 2 did not model that for SnO 2 /TiO 2 . In other words, upon reduction of SnO 2 /TiO 2 there was no spectroscopic evidence for electrons residing in the SnO 2 core or in the TiO 2 shell. Instead, the appearance of a single potential-independent absorption spectrum was observed and attributed to electrons present within an interfacial region between the core and the shell. The charge extraction technique was used to determine that the density of SnO 2 /TiO 2 states was more similar to that of TiO 2 than SnO 2 . The potential onset followed the trend SnO 2 /TiO 2 > SnO 2 > TiO 2, with TiO 2 closest to the vacuum level and SnO 2 /TiO 2 the furthest away. The implications of these results for solar energy conversion are discussed.