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The photoelectrochemical behavior of a planar 1 cm2 thick Ti-doped hematitefilm deposited on F:SnO2 coated glass was studied with both front and backillumination. Despite low quantum efficiency, photocurrent was observed uponback illumination with low wavelengths, indicating that some photogeneratedholes are able to traverse at least 700 nm across the hematite film andeffectively oxidize water. This cannot be accounted for using the commonlyaccepted hole collection length of hematite based on fitting to the Gartnermodel. Furthermore, under back illumination, 450 nm excitation resulted inincreased photocurrent as compared to 530 nm excitation despite most of thelight being absorbed further away from the surface. These results demonstratethat the photocurrent is strongly dependent on the optical excitationwavelength, and related to both delocalized holes with long lifetime andlocalized excitations rather than only being dependent on the proximity of theabsorption to the surface.

Wavelength Dependent Photocurrent of Hematite Photoanodes: Reassessing the Hole Collection Length