Substrate Dependent Water Splitting with Ultrathin
α‑Fe<sub>2</sub>O<sub>3</sub> Electrodes
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Abstract
Thin films of hematite (α-Fe<sub>2</sub>O<sub>3</sub>) were
deposited by atomic layer deposition (ALD), and the effects of metal
oxide underlayers on the photocatalytic water oxidation performance
were investigated. It was found that a Ga<sub>2</sub>O<sub>3</sub> underlayer dramatically enhances the water oxidation performance
of the thinnest hematite films. The performance enhancement is attributed
to the increased crystallinity of the ultrathin films induced by the
oxide underlayers. The degree of crystallinity was examined by Raman
line shape analysis of the characteristic hematite phonon modes. It
was found that multiple metal oxide underlayers, including Nb<sub>2</sub>O<sub>5</sub>, ITO, and WO<sub>3</sub>, increase the film
crystallinity compared to hematite deposited on bare FTO. The increased
crystallite size was also clearly evident from the high resolution
SEM images. The degree of crystallinity was found to correlate with
absorbance and the photocatalytic water oxidation performance. These
findings shed light on the origin of the dead layer at the interface
of the FTO substrate and ultrathin hematite films and elucidate strategies
at overcoming it