Atomic layer deposition of metastable β-Fe₂O₃ via isomorphic epitaxy for photoassisted water oxidation.

We report the growth and photoelectrochemical (PEC) characterization of the uncommon bibyite phase of iron(III) oxide (β-Fe2O3) epitaxially stabilized via atomic layer deposition on an conductive, transparent, and isomorphic template (Sn-doped In2O3). As a photoanode, unoptimized β-Fe2O3 ultrathin films perform similarly to their ubiquitous α-phase (hematite) counterpart, but reveal a more ideal bandgap (1.8 eV), a ∼0.1 V improved photocurrent onset potential, and longer wavelength (>600 nm) spectral response. Stable operation under basic water oxidation justifies further exploration of this atypical phase and motivates the investigation of other unexplored metastable phases as new PEC materials.