Understanding Charge Transport and Selectivitiy in Ionically Functionalized Fullerenes for Electron-Selective Interfacial Layers
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Significant improvements in power conversion efficiency (>10%) of emerging thin-film photovoltaics have been achieved in the last 5 years. High efficiencies would not be possible without the development of new selective interfacial layers. However, a complete understanding of how interfacial layers function to improve the selectivity of charge extracting contacts in thin-film photovoltaics is still being sought. The goal of this work is to contribute to the understanding of the operation of selective interfacial layers based on the study of ionically functionalized fullerenes. Just as other ionically functionalized materials have shown promise as electron-selective interfacial layers in organic photovoltaics and mixed organic-inorganic halide perovskites, Chapter II demonstrates the utility of ionically functionalized fullerenes. High performing solar cells necessitate the use of conductive interfacial layers; anomalously high conductivity in ionically functionalized materials, which have been used as interfacial layers, has been ascribed to self-doping. This work demonstrates that less than 1% of an ionically functionalized fullerene is reduced in its highly conductive pristine state and is concurrent with the presence of distinct chemical species. These studies describe how the chemical origin of the high conductivity of ionically functionalized fullerenes does not require the invocation of direct anion reduction or significant chemical transformations such as Hofmann-like elimination reactions occurring to a stoichiometric degree. This work also addresses the question of how the selectivity of a charge extracting contact is improved by the presence of an interfacial layer. The quantification of energy barrier reduction, which is often discussed in terms of work function modification or energy-level alignment, is demonstrated using metal|semiconductor junctions modified with an ionically functionalized fullerene. The barrier height of high work function electrodes was reduced significantly, by as much as 0.45 V, and was correlated to thin (2–5 nm) portions of the film rather than fullerene aggregates. The studies that comprise this work form a coherent model for understanding the key factors that have resulted in the continued use of ionically functionalized interfacial layers, their high conductivity, and energy barrier modification of the charge extracting electrodes. This dissertation contains coauthored, previously published, and unpublished work.