The application of bismuth vanadate BiVO4 photoelectrodes for solar water splitting is hindered by the poor carrier transport. To overcome this, multiple donor doping strategies e.g. dual doping, gradient doping have been explored. Here, we show for the first time the successful introduction of calcium Ca as an acceptor type dopant into BiVO4 photoelectrodes. Interestingly, instead of generating cathodic photocurrents, the Ca doped BiVO4 photoelectrodes show anodic photocurrents with an enhanced carrier separation efficiency. Hard X ray photoelectron spectroscopy HAXPES shows that this enhancement is caused by out diffusion of Ca during the deposition process, which spontaneously creates a p n junction within the BiVO4 layer. Overall, a significant two fold improvement of the AM1.5 photocurrent is obtained upon Ca doping. This study highlights the importance of controlled doping beyond simply modifying carrier concentration and may enable new device architectures in photoelectrode material
