Defect‐Enhanced Charge Separation and Transfer within Protection Layer/Semiconductor Structure of Photoanodes

Silicon (Si) requires a protection layer to maintain stable and long‐time photoanodic reaction. However, poor charge separation and transfer are key constraint factors in protection layer/Si photoanodes that reduce their water‐splitting efficiency. Here, a simultaneous enhancement of charge separation and transfer in Nb‐doped NiO x /Ni/black‐Si photoanodes induced by plasma treatment is reported. The optimized photoanodes yield the highest charge‐separation efficiency (η sep ) of ≈81% at 1.23 V versus reversible hydrogen electrode, corresponding to the photocurrent density of ≈29.1 mA cm −2 . On the basis of detailed characterizations, the concentration and species of oxygen defects in the NiO x ‐based layer are adjusted by synergistic effect of Nb doping and plasma treatment, which are the dominating factors for forming suitable band structure and providing a favorable hole‐migration channel. This work elucidates the important role of oxygen defects on charge separation and transfer in the protection layer/Si‐based photoelectrochemical systems and is encouraging for application of this synergistic strategy to other candidate photoanodes.