Experimental and first-principles theoretical studies on Ag-doped cuprous oxide as photocathode in photoelectrochemical splitting of water

Nanostructured thin films of undoped and Ag-doped cuprous oxide were deposited on indium tin oxide-coated glass substrate using simple spray pyrolysis method for their use as photocathode in photoelectrochemical (PEC) cell for solar energy based water splitting. Combination of experiments and first-principles density functional theory based calculations was used to determine and understand the effect of Ag substitution on electronic structure and PEC performance. Thin films were characterized using XRD, FE-SEM, UV–Vis spectroscopy and PEC measurements. The results of DFT calculations show that the top of valence band and bottom of conduction band of undoped Cu2O lie at Г point of brillouin zone, respectively, suggesting that pure Cu2O is a direct band gap material. Minimal changes appear in the band gap and band gap energies in the Ag-doped Cu2O system, keeping it still a direct band gap material. A defect band appearance can be seen between −4 and −5 eV in the valence band consisting mainly of Ag 4d states and can be explained by a stronger interaction between the Ag 4d and O 2p, due to the larger Ag size. Ag-doped samples exhibit improved conductivity and fourfold increase in photocurrent density with respect to undoped samples.