A fundamental understanding of the processes that occur during early stages of corrosion is traditionally limited by the dearth of techniques that probe the liquid-solid interface with both high spatial resolution and microstructural detail such as grain size and orientation. Here, we demonstrate that with a microfluidic liquid flow cell holder, we can track the progress of corrosion in situ in Al thin films with transmission electron microscopy (TEM). To mitigate the loss of resolution caused by imaging through liquid, we developed a method in which the liquid is temporarily de-wetted from the entire windowed area by switching the liquid stream from pure water to a mixture of ethanol and water. In the de-wetted region, we then collected images of the film microstructure with high spatial resolution over regular intervals while maintaining a low electron flux over the imaged area to minimize beam-induced effects. For as-deposited films, we find that the corrosion progresses in a fractal manner, consistent with reported behavior for films studied in water with low iron and chloride concentrations. For films that were subjected to rapid thermal annealing, we observe a higher density of pitting events, which we attribute to defects created by thermal stress in the oxide film. Furthermore, we observe that the pits can form at multiple locations in a single grain and are not confined to grain boundaries.
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