Proceedings of September Meeting 2016 (NFM16)
Publication date: 14th June 2016
Photoelectrochemical (PEC) water-splitting cells, a promising way to convert solar energy into storable hydrogen fuel, typically consist of semiconductor photoelectrode and electrocatalyst (EC). Although noble metal such as Pt, Ir, and Ru have been used prevalently as EC, their scarcity compelled to investigate earth abundant material based EC with high catalytic activity for cost effective water splitting systems. Here in, we demonstrated integration of electrolyte-permeable porous NiOx thin film on SiO2 grown n-Si photoanode for efficient water oxidation reaction. In comparison with the dense NiOx, the porous NiOx is found to have a relatively high PEC performance because the electrolyte-permeability improves the charge transfer kinetics by enlarged catalytic active area as well as thermodynamic open circuit potential (Voc) by abnormal interfacial energetics. The entire layer of porous NiOx is oxidized and its Fermi-level is found to be engineered in-situ during the oxidation reaction, which makes the porous NiOx/Si junction to exhibits effective change of built in potential. This enables the Voc decoupled from the photovoltage (Vph), while the conventional dense NiOx/n-Si junction, where the built in potential is fixed, has Voc limited by the Vph. As a result, we achieved Voc of 1.03 V vs. reversible hydrogen electrode with porous NiOx, which is 0.5 V better than with dense NiOx.