Proceedings of nanoGe Fall Meeting 2018 (NFM18)
Publication date: 6th July 2018
The n-type semiconductor bismuth vanadate (BiVO4) has recently gained a lot of attention as photoanode material for visible-light induced water oxidation. Its absorption in the visible domain (band gap energy of 2.4 eV), its suitable band edge positions compared to the OER half reaction, its stability against photo-corrosion as well as its low cost, make BiVO4 one of the most interesting ternary oxide materials for light-induced oxygen evolution from water. One major drawback for BiVO4 is its poor bulk electronic conductivity; problem, which for instance can be can be overcome by efficient doping strategies.
In contrast to well-known cation doping, we present the novel approach of anion substitution in BiVO4 powder samples and thin film electrodes.
A new solid-vapor reaction method for the treatment of powdered BiVO4 with HF(g) at ambient pressure and in inert gas atmosphere was developed to reproducibly substitute oxygen by fluorine. Obtained F:BiVO4 powder samples were characterized extensively by means of chemical and structural analysis. Additionally, DFT calculations were carried out to verify the experimentally determined defect model caused by F-introduction into the structure. After an electrode preparation step, the F:BiVO4 powder samples were investigated by means of photoelectrochemistry regarding the light-induced water oxidation reaction. It is demonstrated, that higher photocurrents were obtained for F:BiVO4 compared to its pristine counterpart.
The developed fluorine incorporation methods were further applied to well-functioning BiVO4 thin film photoanodes. The fluorination procedure can also yield F‑containing BiVO4 thin film photoanodes. It is shown, that photoelectrochemical performance of F:BiVO4 thin film photoanodes is also enhanced compared to its non-fluorinated analogue.
Our results demonstrate the widely unapplied field of anion doping to be a viable tool to optimize photoanode properties with respect to photoelectrochemical applications.
This work was funded by the DFG SPP1613 program.
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