On the Design of Oxide Films, Nanomaterials, and Heterostructures for Solar Water Oxidation Photoanodes
Photoelectrochemistry and its associated technologies show unique potential to facilitate the large-scale production of solar fuels - those energy-rich chemicals obtained through conversion processes driven by solar energy, mimicking the photosynthetic process of green plants. The critical component of photoelectrochemical devices designed for this purpose is the semiconductor photoelectrode, which must be optically absorptive, chemically stable, and possess the required electronic band alignment with respect to the redox couple of the electrolyte to drive the relevant electrochemical reactions. After many decades of investigation, the primary technological obstacle remains the development of photoelectrode structures capable of efficient and stable conversion of light with visible frequencies, which is abundant in the solar spectrum. Metal oxides represent one of the few material classes that can be made photoactive and remain stable to perform the required functions. The unique range of functional properties of oxides, and especially the oxides of transition metals, relates to their associated diversity of cation oxidation states, cation electronic configurations, and crystal structures.
In this dissertation, the use of metal oxide films, nanomaterials, and heterostructures in photoelectrodes enabling the solar-driven oxidation of water and generation of hydrogen fuel is examined. A range of transition- and post-transition-metal oxide material systems and nanoscale architectures is presented. The first chapters present results related to electrodes based on alpha-phase iron(III) oxide, a promising visible-light-active material widely investigated for this application. Studies of porous films fabricated by physical vapor deposition reveal the importance of structural quality, as determined by the deposition substrate temperature, on photoelectrochemical performance. Heterostructures with nanoscale feature dimensionality are explored and reviewed in a later chapter, which describes the methodologies to combine the unique and complimentary functional properties of dissimilar oxides to optimize the water photo-oxidation process Experimental results based on an iron(III) oxide-tungsten(VI) oxide system show enhancements associated with the heterostructure, which may indicate the presence of unexpected minority carrier dynamics, as observed additionally by ultrafast transient absorption spectroscopy.
Next, a new conceptual framework for the design of solar water oxidation photoelectrodes based on the spatially inhomogeneous doping of wide-bandgap metal oxide nanostructures is introduced and experimentally verified. It is found that optical absorption and electronic conduction can be decoupled and optimized by spatially segregating the functional impurity species that facilitate their associated physical processes. In the final chapters of this dissertation the electronic structures of key oxide-oxide interfaces, relevant to the operation of efficient photoanodes, are examined using synchrotron-based soft x-ray spectroscopy. These studies indicate that the interfacial regions of electrodes possess distinct electronic structures, which deviate in terms of orbital character and occupancy from those of their constituent bulk oxides. These observations inform methodology to address certain operational deficiencies associated with the use of metal oxides for solar energy conversion applications.