Copper Oxide Thin Films through Solution Based Methods for Electrical Energy Conversion and Storage

of “Copper Oxide Thin Films through Solution Based Methods for Electrical Energy Conversion and Storage”, by Changqiong Zhu, Ph.D., Tufts University, November 2015. Copper oxides (Cu2O and CuO), composed of non-toxic and earth abundant elements, are promising materials for electrical energy generation and storage devices. Solution based techniques for creating thin films of these materials, such as electrodeposition, are important to understand and develop because of their potential for realizing substantial energy savings compared to traditional fabrication methods. Cuprous oxide (Cu2O), with its direct band gap, is a p-type semiconductor that is well suited for creating solution-processed photovoltaic devices (solar cells); several key advancements made toward this application are the primary focus of this thesis. Electrodeposition of single-phase, crystalline Cu2O thin films is demonstrated using previously unexplored, acidic lactate/Cu solutions, which has provided additional understanding of the impacts of growth solution chemistry on film formation. The influence of pH on the resulting Cu2O thin film properties is revealed by using the same ligand (sodium lactate) at various solution pH values. Cu2O films grown from acidic lactate solutions can exhibit a distinctive flowerlike, dendritic morphology, in contrast to the faceted, dense films obtained using alkaline lactate solutions. Relative speciation distributions of the various metal complex ions present under different growth conditions are calculated using reported equilibrium association constants and experimentally supported by UV-Visible absorption spectroscopy. Dependence of thin film morphology on the lactate/Cu molar ratio and applied potential is described. Cu2O/eutectic gallium-indium Schottky junction devices are formed and devices are tested under monochromatic green LED illumination. Further surface examination of the Cu2O films using X-ray photoelectron spectroscopy (XPS) reveals the fact that films grown from acidic lactate solution with a small lactate/Cu molar ratio, which exhibit improved photovoltaic performance compared to films grown from basic lactate solution with a large lactate/Cu molar ratio, are sodium-free. This finding stands in contrast to the observation that films grown in basic solution contain a significant amount of sodium impurity at their top surfaces. Therefore, it is concluded that the sodium impurities present in films grown from basic lactate solutions are detrimental to overall photovoltaic device performance by introducing interface traps and recombination centers for charge carriers, which suggests that removing these impurities may be a promising strategy for improving Cu2O based solar cells. It has been found that impurities at the surface of electrodeposited p-Cu2O films can be efficiently removed through the use of concentrated aqueous ammonia solution as a wet etching agent. The performance of Cu2O homojunction photovoltaic devices incorporating etched p-Cu2O as the bottom layer is higher compared to devices with as-deposited p-Cu2O layers due to an improvement of the homojunction interface quality. Reducing the density of defect states that act as carrier recombination centers