Growth and Characterization of Transition Metal Oxide Semiconductors for the Photoelectrochemical Oxidation of Water Using Visible Light
The first chapter in this thesis presents an introduction and background motivation for artificial photosynthesis using transition metal oxide semiconductors. Also included is a section on some fundamental concepts of electrochemistry with semiconductors for the reader that may be unfamiliar with this research area. The second and third chapters are devoted to copper tungstate (CuWO4), an n-type semiconductor with a band gap of 2.0 eV that exhibits great promise as the photoanode in a z-scheme water-splitting device. The second chapter is in regards to CuWO4 thin films deposited via reactive-ion co-sputtering, while the third chapter presents a novel technique for the preparation of nanostructured CuWO4 with the aim of addressing some fundamental limitations when using 3rd-row transition metal oxide materials. In the second chapter, a detailed systematic study into the co-sputter growth conditions of CuWO4 will be presented with the aim of understanding the optimal growth parameters for photoelectrochemical applications. Structural and electronic characterization of the thin films will be presented to demonstrate the quality of the growth process. A thickness series was performed to determine the optimal thickness for maximizing photocurrent density. The photocurrent density reported in this thesis is the highest current density thus reported in the literature for CuWO4 at the thermodynamic water oxidation potential. A two-electrode experiment was performed in order to determine the feasibility of utilizing CuWO4 in a z-scheme device. A number of oxygen evolution reaction catalysts were deposited onto the surface of CuWO4 thin films and their effect on the overall current density will be discussed. Long-duration potentiostatic measurements were carried out over a wide range of pH values to ascertain the stability of the material, and a discussion into possible degradation mechanisms will be discussed. Finally, the efficacy of CuWO4 as a water oxidation catalyst will be demonstrated and discussed.
The third chapter in this thesis shall discuss two novel approaches for the formation of nanostructured CuWO4 with the aim of overcoming the inherently poor minority carrier mobility that has thus far slowed limited photoelectrochemical applications of the material. In the first approach, anodic aluminum oxide nanotemplates were utilized in an attempt to electrochemically deposit CuWO4 nanowires into the pores. In the second approach, a novel nitric acid treatment on tungsten thin films was utilized to develop a nanostructured surface followed by incorporation of copper using an combined physical vapor deposition and subsequent annealing process. The overall results of both techniques will be discussed. The fourth and final chapter in this thesis is a report on the growth and characterization of a nickel iron oxide alloy material to serve as a photoanode. Thin films were grown via reactive-ion co-sputtering of nickel and iron metal targets in the presence of oxygen. Optical, structural, electronic, and photoelectrochemical characterization was performed and the results shall be discussed.
Two appendices complete the work. The first appendix is a list of characterization and deposition instruments utilized throughout this body of work. The second appendix is a collection of Mathematica® programs developed during the course of the author's Ph.D. studies in order to aid in data collection and analysis.