Molybdenum-doped BiVO thin films were uniformly coated on indium-doped tin oxide (ITO) substrates via a facile modified hot spin coating (HSC) technique. The prepared layers were used as photoanode in a photoelectrochemical (PEC) cell. Different percentage of Mo dopant was examined to maximize the photo-current density (J) of the layers. The highest J value (872 ± 8 μA/cm) was obtained by 5 atomic% of Mo doping. After that, the surface topographies of these samples were changed by varying the initial precursor concentration from 27 to 80 mM. The relation between surface topographies and the PEC activity of Mo-doped BiVO thin films was investigated from microscopic point of view by calculating the surface roughness exponent of α, and a mechanism for the PEC activity of Mo-doped BiVO photoanodes was proposed accordingly. The sample with a small roughness exponent provided a surface with jagged microscopic fluctuations which may trap the air molecules between the electrolyte and sample surface, hindering the fine atomic interaction for photo-generated electron-hole transition. Therefore, the layer with the highest roughness exponent (2α = 0.48 ± 0.03), which means the smoother microscopic surface and better interfacial contact with the electrolyte, exhibited the best PEC activity.
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