Photoelectrochemical performance of W-doped BiVO4 thin films deposited by spray pyrolysis

The effects of tungsten doping and hydrogen annealing on the photoelectrochemical (PEC) performance of bismuth vanadate (BiVO4) photoanodes for solar water splitting were studied. Thin films of BiVO4 were deposited on indium tin oxide-coated glass slides by ultrasonic spray pyrolysis of an aqueous solution containing bismuth nitrate and vanadium oxysulfate. Tungsten doping was achieved by adding either silicotungstic acid (STA) or ammonium metatungstate (AMT) to the precursor. The 1.7- to 2.2-μm-thick films exhibited a highly porous microstructure. Undoped films that were reduced at 375°C in 3% H2 exhibited the largest photocurrent densities under 0.1 W cm−2 AM1.5 illumination, where photocurrent densities of up to 1.3 mA cm−2 at 0.5 V with respect to Ag/AgCl were achieved. Films doped with 1% or 5% (atomic percent) tungsten from either STA or AMT exhibited reduced PEC performance and greater sample-to-sample performance variations. Powder x-ray diffraction data indicated that the films continue to crystallize in the monoclinic polymorph at low doping levels but crystallize in the tetragonal scheelite structure at higher doping. It is surmised that the phase and morphology differences promoted by the addition of W during the deposition process reduced the PEC performance as measured by photovoltammetry.