PNNL

Abstract

Solution crystallization of materials ranging from simple salts to complex supramolecular assemblies has long been viewed through the lens of classical nucleation and growth theories in which monomeric building blocks assemble into ordered structures through inherent thermal fluctuations that overcome a free energy barrier and comntinue to grow by addition of such units to atomic steps. However, recent observations have revealed a rich set of hierarchical pathways during both nucleaton and growth involving of higher order than monomers. While many studies have investigated and deduced mechanisms underlying hierarchical nucleation pathways, much less research has been directed towards development of a mechanistic picture of growth by assembly of more complex units. Here we review recent investigstions into crystal growth by particle attachment with an emphasis on oriented attachment. We discuss the relationship between interfacial structure, interparticle forces, and attachment dynamics, discuss the consequences of size dependent phase stability, and examine the impact of ligand-functionalization of primary particles.