Direct Visualization of Photomorphic Reaction Dynamics of Plasmonic Nanoparticles in Liquid by Four-Dimensional Electron Microscopy.

Liquid-cell electron microscopy (LC-EM) provides a unique approach for in situ imaging of morphology changes of nanocrystals in liquids under electron beam irradiation. However, nanoscale real-time imaging of chemical and physical reaction processes in liquids under optical stimulus is still challenging. Here, we report direct observation of photomorphic reaction dynamics of gold nanoparticles (AuNPs) in water by liquid-cell four-dimensional electron microscopy (4D-EM) with high spatiotemporal resolution. The photoinduced agglomeration, coalescence, and fusion dynamics of AuNPs at different temperatures are studied. At low laser fluences, the AuNPs show a continuous aggregation in several seconds, and the aggregate size decreases with increasing fluence. At higher fluences close to the melting threshold of AuNPs, the aggregates further coalesced into nanoplates. While at fluences far above the melting threshold, the aggregates fully fuse into bigger NPs, which is completed within tens of nanoseconds. This liquid-cell 4D-EM would also permit study of other numerical physical and chemical reaction processes in their native environments.