Multiscale Design of Interaction-Driven Superlattice Assembly in Nanocomposite Tectons

Abstract

Understanding how molecular-scale interactions govern the assembly and processing of nanocomposite tectons (NCTs) is essential for the design of functional nanoparticle superlattices. Here, we present a multiscale simulation framework that connects explicit microscale descriptions of polymer-grafted, supramolecularly functionalized NCTs to mesoscale predictions of superlattice formation and cold sintering. Potentials of mean force (PMFs) extracted from microscale simulations show that the graft length and nanoparticle diameter tune both the depth and range of effective attraction through the interplay of hydrogen bond-mediated association, brush entropy, and core curvature. These interactions predict the emergence of body-centered-cubic order during annealing, with a clear crossover from disordered aggregation to crystallization as the attractions strengthen. Slower annealing and higher concentration both promote larger, more ordered crystallites, whereas an excessive graft length frustrates long-range order. Simulated cold sintering further reveals how compression merges crystalline grains into continuous networks while introducing structural defects. By directly linking NCT chemistry to assembly kinetics and final microstructure, this framework provides mechanistic insights and quantitative guidance for engineering nanoparticle superlattices with tailored order and connectivity.