Morphology, structural and optical properties of iron oxide thin film photoanodes in photoelectrochemical cell: Effect of electrochemical oxidation

Hematite (α-Fe2O3) is a promising semiconductor as photoanode in solar hydrogen production from photoelectrolysis of water due to its appropriate band gap, low cost and high electrochemical stability in aqueous caustic electrolytes. Operation of such photoanode in a biased photoelectrochemical cell constitutes an anodization with consequent redox reactions at the electrode surface. α-Fe2O3 thin film photoanodes were prepared by simple and inexpensive dip coating method on fluorine doped tin oxide (FTO) glass substrate, annealed in air at 500 °C for 2 h, then electrochemically oxidized (anodized) in 1 M KOH at 500 mV for 1 min in dark and light conditions. Changes in structural properties and morphology of α-Fe2O3 nanoparticles films were investigated by XRD, Raman spectroscopy and a high resolution FE-SEM. The average grain size was observed to increase from ~57 nm for pristine samples to 73 and 77 nm for anodized samples in dark and light respectively. Broadening and red shift in Raman spectra in anodized samples may be attributed to lattice expansion upon oxidation. The UV–visible measurements revealed enhanced absorption in the photoanodes after the treatment. The findings suggest that the anodization of the photoelectrode in a biased cell causes not only changes of the molecular structure at the surface, but also changes in the crystallographic structure which can be detected with x-ray diffractometry.