In Situ Atomic‐Scale Observation of Kinetic Pathways of Sublimation in Silver Nanoparticles

Uncovering kinetics of sublimation atomically is critical to understanding both natural phenomena and advanced manufacturing technologies. Here, direct in situ atomic‐scale observations to understand the effects of size, surface, and defects in the sublimation process of supported silver nanoparticles upon heating within an aberration‐corrected transmission electron microscopy are conducted. Atomic‐scale evidence to sublimation and atomic rearrangement in small Ag nanoparticles during heating is provided, and it is demonstrated that the sublimation‐induced stable surfaces in the particles with a size smaller than ≈30 nm are {111} and {100} planes. The role of surface energy and defects in the uniform and nonuniform sublimation pathways at the atomic scale is also revealed, and it is found that the nanoparticles with low surface energy tend to undergo a uniform sublimation pathway, while those with high surface energy or five‐fold twin grain boundary proceed via a nonuniform sublimation pathway. Further dynamic analysis unravels a critical size of ≈8 nm for the transformation from linear to nonlinear sublimation rates in the two pathways. These findings demonstrate that the size, shape, and defects are of paramount importance for the sublimation dynamics in the first‐order phase transformation, helping to advance the general understanding of many technological applications.