Anisotropic Cracking of Nanocrystal Superlattices

The synthesis colloidal nanocrystals in nonpolar organic solvents has led to exceptional size- and shape-control, enabling the formation of nanocrystal superlattices isostructural to atomic lattices built with nanocrystals rather than atoms. The long aliphatic ligands (e.g., oleic acid) used to achieve this control separate nanocrystals too far in the solid state for most charge-transporting devices. Solid-state ligand exchange, which brings particles closer together and enhances conductivity, necessitates large changes in the total volume of the solid (compressive stress), which leads to film cracking. In this work, truncate octahedral lead selenide nanocrystals are shown to self-assemble into body-centered cubic superlattices in which the atomic axes of the individual nanocrystals are coaligned with the crystal axes of the superlattice. Due to this coalignment, upon ligand exchange of the superlattices, cracking is preferentially observed on ⟨011⟩ superlattice directions. This observation is related to differences in the ligand binding to exposed {100} and {111} planes of the PbSe nanocrystal surfaces. This result has implications for binary and more complex structures in which differential reactivity of the constituent elements can lead to disruption of the desired structure. In addition, cracks in PbSe superlattices occur in a semiregular spacings inversely related to the superlattice domain size and strongly influenced by the presence of twin boundaries, which serve as both emission centers and propagation barriers for fractures. This work shows that defects, similar to behavior in nanotwinned metals, could be used to engineer enhanced mechanical strength and electrical conductivity in nanocrystal superlattices.