Kinetically Trapped Nanocrystals with Symmetry-Preserving Shapes

Abstract

The shape of nanocrystals is crucial in determining their surface area, reactivity, optical properties, mechanical strength, and self-assembly behavior. Traditionally, shape control has been achieved through empirical methods, highlighting the need for a more refined theoretical framework. A comprehensive model should account for the kinetic factors at distinct stages of the shape-formation process to identify the key determinants of nanocrystal morphology. By modulating kinetics at terraces, ledges, and kinks, we reveal that the primary factors are the adatom nucleation energies and the geometry of growth islands. Transient sites dominate the growth process, leading to kinetically trapped, metastable shapes. We illustrate these concepts with face-centered cubic nanocrystals, demonstrating diverse shape evolutions, including surface roughening and the preservation of crystal symmetry in cubes, octahedra, rhombic dodecahedra, and their truncated variants. This study reveals the mechanisms driving the formation of cubic nanocrystal shapes and offers guidance for their precise synthesis.