Preferentially oriented TiO2 nanotube arrays on non-native substrates and their improved performance as electron transporting layer in halide perovskite solar cells

Anodically formed TiO2 nanotube arrays (TNTAs) constitute an optoelectronic platform that is being studied for use as a photoanode in photoelectrocatalytic cells, as an electron transport layer (ETL) in solar cells and photodetectors, and as an active layer for chemiresistive and microwave sensors. For optimal transport of charge carriers in these one-dimensional polycrystalline ordered structures, it is desirable to introduce a preferential texture with the grains constituting the nanotube walls aligned along the transport direction. Through X-ray diffraction analysis, we demonstrate that choosing the right water content in the anodization electrolyte and the use of a post-anodization zinc ion treatment can introduce a preferential texture in sub-micron length transparent TNTAs formed on non-native substrates. The incorporation of 1.5 atom% of Zn in TiO2 nanotubes prior to annealing, was found to consistently result in the strongest preferential orientation along the [001] direction. [001] oriented, Zn-doped TNTAs exhibited a responsivity of 523 A/W at a bias of 2 V for 365 nm photons, which is among the highest reported performance values for ultraviolet photodetection using titania nanotubes. Furthermore, the textured nanotubes without a Zn2+ treatment showed a significantly enhanced performance in halide perovskite solar cells that used TNTAs as the ETL.