Highly efficient charge separation in model Z-scheme TiO₂/TiSi₂/Si photoanode by micropatterned titanium silicide interlayer

Atomic layer deposited (ALD) TiO₂ is an attractive material for improving the photoactivity and chemical stability of semiconductor electrodes in artificial photosynthesis. Using photoelectrochemical (PEC) measurements, we show that an interfacial, topographically microstructured TiSi₂ layer inside the TiO₂/Si heterojunction improves the charge carrier separation and shifts the water dissociation onset potential to more negative values. These observations are correlated with the X-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS) measurements, which reveal an increased band bending due to the TiSi₂ interlayer. Combined with the UV–Vis absorption results, the photoelectron spectroscopy measurements allow the reconstruction of the complete energy band diagram for the TiO₂/TiSi₂/Si heterojunction and the calculation of the valence and conduction band offsets. The energy band alignment and improvements in PEC results reveal that the charge transfer across the heterojunction follows a Z-scheme model, where the metal-like TiSi₂ islands act as recombination centers at the interface.