A mechanistic understanding of the growth of multiply twinned nanoparticles (MTPs), such as decahedra (Dh) and icosahedra (Ih), is crucial for precisely controlled syntheses and applications. Despite previous successes, no consensus has been reached regarding the multiple competing growth pathways for MTPs proposed thus far, in part due to the lack of information about their nucleation and growth dynamics. Here, we used decahedral and icosahedral gold nanoparticles as a model system in conjunction with in situ liquid cell transmission electron microscopy (LCTEM) to investigate the nucleation and growth dynamics of MTPs in aqueous solution; two growth pathways were successfully identified: (A) nucleation-based layer-by-layer growth from a rounded multiply twinned seed and (B) the successive twinning and growth of tetrahedra. The LCTEM results enabled us to directly and conclusively identify the growth behaviors of intermediate products. The internal strain relaxation mechanisms and growth kinetics differ for the two pathways: in pathway A, a MTP grew by the opening and closing of re-entrant grooves at the twin boundaries, which was not found in pathway B. We also analyzed different MTP growth pathways from an energetic perspective and discussed how the preferred pathway (A or B) is related to factors, such as the initial seed yield and the size- and morphology-dependent formation of MTPs. Our results contextualize the current understanding of MTP formation mechanisms and provide insightful guidance for the precisely controlled synthesis of MTPs for practical applications.
Keywords: Au decahedral/icosahedral nanostructures; growth kinetics; liquid cell TEM; multiply twinned nanoparticle; nucleation-based growth; strain relaxation; successive twinning growth.