Atomic Layer Deposition of Ru and RuO2: New Process Development, Fabrication of Heterostructured Nanoelectrodes, and Applications in Energy Storage

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The ability to fabricate heterostructured nanomaterials with each layer of the structure having some specific function, i.e. energy storage, charge collection, etc., has recently attracted great interest. Of the techniques capable of this type of process, atomic layer deposition (ALD) remains unique due to its monolayer thickness control, extreme conformality, and wide variety of available materials. This work aims at using ALD to fabricate fully integrated heterostructured nanomaterials.

To that end, two ALD processes, using a new and novel precursor, bis(2,6,6-trimethyl-cyclohexadienyl)ruthenium, were developed for Ru and RuO2 showing stable growth rates of 0.5 Å/cycle and 0.4 Å/cycle respectively. Both process are discussed and compared to similar processes reported in the literature. The Ru process is shown to have significantly lower nucleation while the RuO2 is the first fully characterized ALD process known.

Using the fully developed RuO2 ALD process, thin film batteries were fabricated and tested in standard coin cell configurations. These cells showed high first cycle gravimetric capacities of ~1400 mAh/g, which significantly degraded after ~40 cycles. Rate performance was also studied and showed a decrease in 1st cycle capacity as a function of increased rate. These results represent the first reports of any RuO2 battery studied beyond 3 cycles.

To understand the degradation mechanisms witnessed in the thin film studies in-situ TEM experiments were conducted. Single crystal RuO2 nanowires were grown using a vapor transport method. These nanowires were cycled inside a TEM using Li2O as an electrolyte and showed a ~95% volume expansion after lithiation, ~26% of which was irreversible. Furthermore, a chemical irreversibility was also witnessed, where the reaction products Ru and Li2O remain even after full delithiation.

With these mechanisms in mind heterostructured nanowires were fabricated in an attempt to improve the cycling performance. Core/shell TiN/RuO2 and MWCNT/RuO2 structures were fabricating using the ALD process developed in this work. While the TiN/RuO2 structures did not show improved cycling performance due to connection issues, the MWCNT/RuO2 structure showed a stable areal capacity of ~600 μAh/cm2 after ~20 cycles and were easily cycled 100 times.