Synthesis and characterization of semiconductor thin films for photoelectrochemical energy conversion

The field of solar energy conversion has experienced resurgence in recent years due to mounting concerns related to fossil fuel consumption. The sheer quantity of available solar energy and corresponding opportunity for technological improvement has motivated extensive study of novel light-absorbing semiconductors for solar energy conversion. Often, these studies have focused on new ways of synthesizing and altering thin film semiconductor materials with unique compositions and morphologies in order to optimize them for higher conversion efficiencies. In this dissertation, we discuss the synthesis and electrochemical characterization of a variety of candidate semiconductor materials exhibiting promising characteristics for photoelectrochemical solar energy conversion. Three specific methods of thin film deposition are detailed. The first is a physical vapor deposition technique used to independently tune the morphology and composition of hematite (α-Fe2O3) based materials. Because of hematite’s poor electronic properties, these modifications were able to significantly improve its performance as a photoanode for water oxidation. The second technique is electrodeposition, which was employed to deposit the novel ternary metal oxide, CuBi2O4. The study of these films, along with those prepared by physical vapor deposition, provided insight into the factors limiting the ability of this photo-active material to function as a photocathode for hydrogen evolution from water. The third technique is chemical spray pyrolysis, which was employed to deposit and optimize films of the bismuth chalco-halides BiOI and BiSI. These studies were used to obtain previously unknown properties of these materials relevant to their utilization in photoelectrochemical cells. The manipulation of deposition temperature had significant effects on these properties and dictated the films’ overall photoconversion performance.