Effects of Size and Shape on the Tolerances for Misalignment and Probabilities for Successful Oriented Attachment of Nanoparticles.

Oriented attachment (OA) of nanoparticles is an important pathway of crystal growth, but there is a lack of tools to model OA. Here, we present several simple models that relate the probability of achieving OA to basic geometric parameters, such as particle size, shape, and lattice periodicity. A Moiré-domain model is applied to understand twist misorientations between parallel surfaces, and it predicts that the range of twist angles yielding perfect OA is inversely related to the width of the contact area. This idea is explored further through a surface functional model, which investigates how patterns of crystallographic registration can drive the emergence of complex orientational energy landscapes. The energy landscapes are predicted to possess multiple local minima that can trap particles in imperfect alignments, and these local minima become deeper and more numerous as the contact area increases, which makes OA more challenging for large particles. A second set of models is presented to understand the sequence of events by which two crystallographic faces become coplanar after the collision. We use a central force approximation to predict the odds that two particle faces will attain coalignment when the particles collide with random misalignments, and we show that in the absence of special biasing forces, the probability of attaining alignment on a given face is roughly proportional to its solid angle as viewed from the center of the particle. The model thus predicts that OA is most favorable between well-faceted particles and becomes exceedingly unlikely for large spherical particles that express many microfacets.