Interfacial Energy Gradients Drive Coalescence of Supported Nanoparticles

TL;DR

This study reveals that interfacial energy gradients on heterogeneous substrates can direct nanoparticle migration and coalescence, offering new ways to control nanomaterial assembly beyond traditional stochastic models.

Contribution

It demonstrates that substrate-induced interfacial energy gradients can govern nanoparticle movement and coalescence, providing a novel mechanism for directed nanoparticle assembly.

Findings

Pt nanoparticles transform into Pt$_3$Si on Si nanodomains.

Directed migration of Pt$_3$Si nanoparticles driven by energy gradients.

Substrate heterogeneity influences nanoparticle coalescence pathways.

Abstract

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 (SiN$_x$) substrates where localized crystalline silicon (Si) nanodomains are deliberately formed via electron beam irradiation at $800^\circ$C. We observe that Pt nanoparticles in contact with these Si pads transform into a more mobile platinum silicide (Pt$_3$Si) phase. Strikingly, these Pt$_3$Si 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 substrate heterogeneity can be used to direct nanoparticle behavior, challenging conventional coalescence models and offering pathways for the rational design of supported nanomaterials.