Vertically Aligned CdO-Decked α-Fe₂O₃ Nanorod Arrays by a Radio Frequency Sputtering Method for Enhanced...

Green hydrogen production is one of the most desirable sustainable goals of the United Nations. Thus, for that purpose, we developed hematite (α-Fe₂O₃), an n-type semiconductor, a desirable candidate for photoelectrochemical (PEC) water splitting, enabling hydrogen evolution. High recombination losses, low efficiency, and large-scale production hinder its potential. To address these issues, we have fabricated optimized bare and cadmium oxide (CdO)-decorated hematite thin film nanorod arrays using a throughput radio frequency (RF) sputtering with efficient water splitting behavior. To the best of our knowledge, no work has been done so far on the synthesis of CdO/α-Fe₂O₃ via RF sputtering for PEC application. Bare α-Fe₂O₃ samples, with a morphology of vertically aligned nanorods, were fabricated with optimized parameters such as as-deposited 70 nm of Fe, an angle of deposition of 70°, and an annealing temperature of 600 °C, which showed a photocurrent density of 0.38 mA/cm² at 1.65 V vs reversible hydrogen electrode (RHE). Characterizations depicted that this unique morphology with high crystallinity directly enhanced the performance of hematite photoanodes. Further, deposition of 30 nm of cadmium (CdO) on the α-Fe₂O₃ nanorods produced a corn-like morphology with CdO nanoparticles (∼2 nm), resulting in 4-times enhancement of the PEC performance (1.2 mA/cm² at 1.65 V vs RHE). CdO acted as a co-catalyst, responsible for satisfactory suppression of recombination and facilitating the hole transfer, directly enhancing the overall photocurrent density. This photoanode showed an extremely stable behavior over a period of 26 h when kept under constant illumination. Furthermore, the CdO-modified photoanode showed a better dye degradation (98% in 40 min) than the bare hematite (60% in 40 min), proving to be an efficient photoanode.