Applications of Large-Area Nanopatterning to Energy Generation & Storage Devices

Abstract

This dissertation encompasses the creation and testing of nanostructured, electrochemically-active energy generation and storage devices, and development of the associated fabrication techniques. The fabricated devices include nanopatterned, plasmonically-active, TiO2+Au thin films for Photocatalytic Water Splitting (PCW), TiO2-based Dye-Sensitized Solar Cells (DSSCs) incorporating nanopatterned, plasmonically-active metallic front electrodes, and Si nanopillar anodes for Li-ion batteries. Techniques were also developed for encapsulation and removal of wet-etched Si nanowires from their mother substrates.

TiO2 was the first material to be widely used for PCW. Its use is hampered by its large bandgap (~3.2eV), and poor recombination lifetimes. Au nanoparticles (NPs) have been previously used to improve recombination lifetimes in TiO2 by separating photogenerated carriers near the NP edges, and to increase photocurrents by injecting plasmonically-excited hot electrons into the TiO2 conduction band. Using nanostructured TiO2+Au electrodes, we aim to increase the PCW efficiency of TiO2-based electrodes.

Dye-sensitized solar cells (DSSCs) employ visible-absorbing dyes anchored to a high-surface-area semiconducting scaffold. The front transparent conducting electrode (TCE) is typically ITO, a scarce and expensive material. We aim to increase the efficiency of thin-film DSSCs and eliminate the use of ITO by using a metallic subwavelength array (MESH) of nanoholes as the front TCE.

Silicon holds promise as a high-capacity anode material for Li-ion batteries, as it can store ~10x the Li of graphite, the current leading anode material (3569 vs. 372 mAh/g). However, Si undergoes dramatic (>300%) volume expansion upon “lithiation”, pulverizing any structure with non-nanoscopic dimensions (>250nm). We created large-area arrays of “nanopillars” with sub-100nm diameters, using roll-to-roll-compatible flexible-mold NIL on commercially-available metal substrates.

Ordered nanopatterning by NIL combined with Metal-Assisted Chemical Etching (MACE) techniques is ideal for creating large-area arrays of high aspect-ratio nanowires, for use in solar cells or battery anodes. We introduce a polymer encapsulation technique that allows separation of the nanowire array from the mother substrate, while leaving the array structure, and original metal nanopattern, intact.