A Model System for Photocatalysis: Ti-Doped α-Fe2O3(1(1)over-bar02) Single-Crystalline Films

Hematite (alpha-Fe2O3) is one of the most investigated anode materials for photoelectrochemical water splitting. Its efficiency improves by doping with Ti, but the underlying mechanisms are not understood. One hurdle is separating the influence of doping on conductivity, surface states, and morphology, which all affect performance. To address this complexity, one needs well-defined model systems. We build such a model system by growing single-crystalline, atomically flat Ti-doped alpha-Fe2O3(1 (1) over bar 02) films by pulsed laser deposition (PLD). We characterize their surfaces, combining in situ scanning tunneling microscopy (STM) with density functional theory (DFT), and reveal how dilute Ti impurities modify the atomic-scale structure of the surface as a function of the oxygen chemical potential and Ti content. Ti preferentially substitutes subsurface Fe and causes a local restructuring of the topmost surface layers. Based on the experimental quantification of Ti-induced surface modifications and the structural model we have established, we propose a strategy that can be used to separate the effects of Ti-induced modifications to the surface atomic and electronic structures and bulk conductivity on the reactivity of Ti-doped hematite.