Different types of ALD Ru films, including as-deposited, annealed Ru, without and with a subsequent CMP step, were used for wet etching study. With respect to the as-deposited Ru, the etching rate of the annealed Ru film in metal-free chemical mixtures (pH = 7-9) was found to decrease substantially. X-ray photoelectron spectroscopy characterization indicated that this behavior could be explained by the presence of the formation of RuOx (x = 2,3) caused by the anneal. A short CMP step applied to the annealed Ru wafer removed the surface RuOx, at least partially, resulting in a significant increase of the etching rate. The change in surface roughness was quantified using atomic force microscopy.
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