Interfacial Energy Gradients Drive Coalescence of Supported Nanoparticles.

Understanding and controlling nanoparticle coalescence is crucial for applications ranging from catalysis to nanodevice fabrication, yet the behavior of nanoparticles on dynamically evolving, heterogeneous substrates remains poorly understood. Here, we employ in situ transmission electron microscopy to investigate platinum (Pt) nanoparticle dynamics on silicon nitride (SiNx) substrates where localized crystalline silicon (Si) nanodomains are deliberately formed via electron beam irradiation at 800 °C. We observe that Pt nanoparticles in contact with these Si pads transform into a more mobile platinum silicide (Pt3Si) phase. Strikingly, these Pt3Si nanoparticles exhibit pronounced directional migration away from the Si pads, driven by interfacial energy gradients, rather than undergoing stochastic Brownian motion. This directed movement fundamentally dictates coalescence pathways, leading to either enhanced sintering when particles are channeled together or inhibited coalescence when Si pads act as repulsive barriers. Our findings reveal that local substrate chemistry and the resulting interfacial energy landscapes can dominate over initial particle size or proximity in controlling solid-state nanoparticle migration and assembly. This work provides insights into how emergent substrate heterogeneity biases nanoparticle behavior by guiding precontact migration pathways, thereby challenging conventional coalescence models that assume random particle motion, and suggesting a route toward the rational design of supported nanomaterials.