Photoelectrochemical (PEC) water dissociation into hydrogen and oxygen at a semiconductor-liquid interface offers an
environmentally benign approach to hydrogen production. We have developed an integrated PEC device using
hydrogenated amorphous silicon carbide (a-SiC or a-SiC:H) material as photoelectrode in conjunction with an
amorphous silicon (a-Si) tandem photovoltaic device. Such a "hybrid PV/a-SiC" PEC cell produces photocurrent of
about 1.3 mA/cm2 in a short-circuit configuration and is durable in a pH2 electrolyte. On the other hand, the
aforementioned structure finished with ITO contacts and measured as a solid-state device features a current density of 5
mA/cm2, indicating a potential solar-to-hydrogen (STH) conversion efficiency of about 6% in the hybrid PV/a-SiC PEC
cell. The much lower photocurrent measured in the hybrid PEC cell suggests that there exists an interfacial barrier
between the a-SiC and electrolyte, which hinders the photocurrent extraction. In order to mitigate against the interfacial
barrier and hence improve the photo-generated charge carrier transport through the a-SiC/electrolyte interface, we have
explored several surface modification techniques, namely the use of metallic nano-particles (such as platinum or
palladium) and the growth of an additional thin layer (a-SiNx, carbon-rich a-SiC, a-SiF, etc.) on the top of a-SiC by
PECVD. In the latter case, it is observed that the addition of a thin PECVD-fabricated layer does not significantly
improve the photocurrent, presumably due to a poor band alignment at the a-SiC/electrolyte interface. The use of lower
work function nanoparticles like titanium has led to promising results in terms of photocurrent enhancement and an
a nodic shift in the onset potential.
Photoelectrochemical (PEC) water splitting at a semiconductor-electrolyte interface using sunlight is of considerable interest as it offers a clean approach to hydrogen production. PEC cells require semiconductor photoelectrode materials fulfilling a number of important requirements, such as band-edge alignment, corrosion resistance to electrolyte, and adequate current generation. We report the development of RF-PECVD-deposited hydrogenated amorphous silicon
carbide (a-SiC:H) photoelectrodes with improved durability, which, when combined with a-Si:H tandem photovoltaic devices, should produce hydrogen directly from water under sunlight. The a-SiC:H is commonly grown with a bandgap in excess of 2.0 eV and completes the PEC device by providing contact with the electrolyte, proper band-edge alignment,
and acts as a buffer for the a-Si:H tandem structure. Effects of the pH of electrolyte, type of substrates, and a platinum nanoparticle coating on the durability of a-SiC photoelectrodes will be presented. From these studies we surmise that corrosion or damage mechanism occurring on a-SiC:H layer could be divided into different aspects of physical and chemical. From the physical point of view, defects associated with spikes in textured TCO substrates, roughness of
stainless steel, or other sources of pinholes may initiate delamination as confirmed by SEM (Scanning Electron Microscopy) and EDS (Energy-Dispersive X-ray Spectroscopy) studies. Chemically, the production of hydrogen involves reactions that may etch the electrode, especially when physical defects are involved. We observe that reducing the acidity of the electrolyte (increasing the pH from 0 to 2) significantly reduces corrosion while the useful photocurrent
output of the a-SiC:H p/i structure is unaffected.
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