Owing to several important properties, BiVO4 is the
promising photoanode material for the photoelectrochemical (PEC) water
oxidation reaction; however, the poor charge transfer and transport
and slow surface catalytic activity limit to achieve the expected
high theoretical efficiency. In the present investigation, thin films
of TiO2 have been formed over the BiVO4 photoanode
surface using the atomic layer deposition technique (ALD). Films are
formed at 5, 50, and 150 nm thicknesses, and the PEC performances
have been evaluated. Enhancement in the performance has been observed
upon inclusion of the ALD/TiO2 films over BiVO4. The performance has been observed to be higher in the case of 50
nm ALD/TiO2 films. The ALD/TiO2 films have several
important roles in the enhancement in the PEC efficiency other than
only the enhancement of stability through retardation of the photocorrosion
process. The intensity modulated photocurrent spectroscopy measurements
have been carried out for the selective evaluation of the different
modes of charge transfer processes upon excitation of the photoanode
materials on photoexcitation. The enhancement in the charge transfer
rate constant (k
t) over the relative retardation
of the charge recombination rate constant (k
r) indicated the specific roles of modulation of the surface
states. The investigation revealed the significant scopes of the modifications
of surfaces using ALD techniques to selectively modulate the surface
electronic states of materials in enhancing catalytic efficiency.