Metal oxide thin films by chemical vapor deposition for photocatalytic water splitting

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Date
2016
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Publisher
University of Alabama Libraries
Abstract

Photoelectrochemical cells (PEC) are devices which convert solar energy into consumable chemical energy by splitting water into oxygen and hydrogen. Photocatalytic activity at a semiconductor oxide surface forms the backbone of the PEC and thus the quest for high activity oxide materials and improving the cells efficiency is a widely explored field of research. Metal oxide semiconductors with band gaps in the visible spectrum are actively sought as photocatalytic electrode materials. The major advantages are that oxides are nontoxic, stable, and inexpensive. However, their overall efficiency is usually limited by short carrier diffusion length due to structural defects, limited light absorptivity and sluggish kinetics at the interface. To overcome these limitations crystalline semiconductor oxides synthesized by high temperature techniques are desired. A direct liquid injection chemical vapor deposition technique has been employed to synthesize films of Fe2O3 (hematite) and BiVO4 (bismuth vanadate) for use as photocatalysts. The high temperature synthesis technique is optimized to obtain good quality crystalline smooth films on fluorine doped tin oxide substrates and their photoelectrochemical characteristics have been studied. It is observed that the interlayer oxide material used for growth of the Fe2O3 and BiVO4 has a significant role in their photoactivity.The interlayer oxide serves as an efficient electron transport layer and also influences the grain characteristics of the film. For hematite it is observed that a n-type metal oxide interlayer (e.g. Nb2O5 or TiO2) helps improve the photoactivity as compared to a p-type oxide (NiO). BiVO4 has a poor electron diffusion length, and a WO3 interlayer improves the photocurrent in BiVO4 films by improving the charge collection efficiency. The low absorption coefficient of hematite requires a dense electrode for greater light absorption; however, the electrode thickness is limited by the poor hole diffusion length (~4 nm). Plasmonic metal nanostructures of gold (Au), silver (Ag), and copper (Cu), which are known to concentrate and scatter broad range wavelengths of incident light, are promising for enhancing the light absorption cross-section of a semiconducting material. Gold nanoparticles embedded in hematite films have been synthesized. About three times higher light absorption and photocurrent enhancement are obtained. A thickness-dependent study of photoactivity indicates a greater enhancement of gold-embedded hematite thin films compared to thicker films due to reduced charge transport distance and optimal local field enhancement effect. The embedded structure also has the advantage of consistent performance and protection of plasmonic nanostructures from electrochemical corrosion, resulting in long cycles of operation.

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Electronic Thesis or Dissertation
Keywords
Chemistry, Materials science, Physical chemistry
Citation