Analysis of the Inhomogeneous Growth of Sputtered Black TiO₂ Thin Films

Black titanium dioxide (B-TiO₂) is a highly active photoelectrochemical material compared to pure titanium dioxide due to its increased light absorption properties. Recently, we presented the deposition of thin-film B-TiO₂ using an asymmetric bipolar reactive magnetron sputter process. The resulting samples exhibit excellent photoelectrochemical properties, which can be fine-tuned by varying the process parameters. In this article, results of morphological, electrical, and photoelectrochemical measurements are discussed to better understand the surprisingly high electrochemical activity of the films. In order to study the influence of the dynamic process on film formation, we use static sputtering with a fixed substrate covering the entire chamber area in front of the two targets. This allows the material composition of the sputtered film to be analyzed depending on its relative position to the targets. The results lead to the conclusion that the asymmetric bipolar sputtering mainly produces two phases, a transparent, nonconductive crystalline phase and a black, conductive amorphous phase. As a consequence, the dynamically sputtered samples are multilayers of these two materials. We discuss that the significantly better electrical and photoelectrochemical properties emerge from the inhomogeneous nature of the laminates, like also found in core-shell nanoparticles of B-TiO₂.