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Photoactive bismuth vanadate (BiVO) thin films were deposited by reactive co-magnetron sputtering from metallic Bi and V targets. The effects of the V-to-Bi ratio, molybdenumdoping and post-annealing on the crystallographic and photoelectrochemical (PEC) properties of the BiVOfilms were investigated. Phase-pure monoclinic BiVOfilms, which are more photoactive than the tetragonal BiVO phase, were obtained under slightly vanadium-rich conditions. After annealing of the Mo-doped BiVOfilms, the photocurrent increased 2.6 times compared to undoped films. After optimization of the BiVOfilm thickness, the photocurrent densities (without a catalyst or a blocking layer or a hole scavenger) exceeded 1.2 mA/cm2 at a potential of 1.23 V under solar AM1.5 irradiation. The surprisingly high injection efficiency of holes into the electrolyte is attributed to the highly porous film morphology. This co-magnetron sputtering preparation route for photoactive BiVOfilms opens new possibilities for the fabrication of large-scale devices for water splitting.


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