A series of self-assembled WO3–BiVO4 nanostructured thin films with 17, 25, 50, 67, and 100 mol% WO3 were grown on the (001) yttria-stabilized zirconia (YSZ) substrate by pulsed laser deposition method. The microstructures including crystalline phases, epitaxial relationship, interface structures, and chemical composition distributions were investigated by a combination of various electron microscopy techniques including scanning electron microscopy, transmission electron microscopy, and X-ray energy dispersive spectroscopy. The monoclinic BiVO4 formed the matrix, in which WO3 nanopillars were embedded with specific epitaxial relationships. In BiVO4-rich sample, orthorhombic Bi2WO6 was formed. However, metastable hexagonal WO3 phase and orthorhombic WO3 phase coexisted in other composite samples. The thin amorphous layer at the film/substrate interface indicated that the mismatch strain between films and substrate is released. The hydrostatic tensile strain due to thermal expansion mismatch between BiVO4 and WO3 as well as the diffusion of Bi into the WO3 stabilized the metastable h-WO3. A WO3–BiVO4 pseudobinary phase diagram was proposed based on the magnitude of the thermal expansion mismatch and the distance of Bi diffusion, which can be applied to design the microstructures of WO3–BiVO4 heterojunctions and optimize their photoelectrochemical properties.

Hematite (α-Fe2O3) photoanodes are widely studied as candidates for water splitting photoelectrochemical (PEC) cells. To speed up the development of high efficiency hematite photoanodes, systematic investigations of the effect of material properties such as dopants and microstructure on PEC properties that determine the photoanode performance are crucial. Toward this end, this work presents a route for reproducible fabrication of thin film hematite photoanodes with reproducible microstructure and PEC properties. Hematite thin (50 nm) films are deposited by pulsed laser deposition from a Ti-doped (1 cation%) Fe2O3 target onto cleaned transparent conducting substrates (fluorinated tin oxide, FTO, coated glass substrates). Special attention is paid to rigorous cleaning of the substrates prior to the hematite deposition, which is found to be crucial for achieving highly reproducible results. Specimens prepared by this route display homogenous conformal coating with very little spread in PEC properties between different specimens, meeting the necessary prerequisite for systematic investigation of hematite photoanodes.

We report on non-particulate titania photoelectrodes with a unique highly-ordered nanotube-array architecture prepared by an anodization process that enables precise control over array dimensions. Under 320–400 nm illumination titania nanotube-array photoanodes, pore size 110 nm, wall thickness 20 nm, and 6 μm length, generate hydrogen by water photoelectrolysis at a normalized rate of 80 mL/W•hr, to date the most efficient titania-based photoelectrochemical device, with a conversion efficiency of 12.25%. The highly-ordered nanotubular architecture allows for superior charge separation and charge transport, with a calculated quantum efficiency of nearly 100% for incident photons with energies larger than the titania bandgap.