Colloidal inorganic nanocrystals are versatile nanoscale building blocks. Advances in their synthesis have yielded nanocrystals with various morphologies including spheres, polyhedra, rods, disks, sheets, wires, and a wide range of branched shapes. Recent developments in chemical methods have allowed the synthesis of colloidal nanocrystals made of sections of different inorganic materials connected together. Many research groups are investigating these nanocrystals’ structural and photophysical properties experimentally and theoretically, and many have examined their prospects for commercial applications. Branched nanocrystals, in particular, are gaining attention, in part for their potential applications in solar cells or electronic devices. In this Account, we review recent developments in synthesis and controlled assembly of colloidal branched nanocrystals.
Synthesis of branched nanocrystals builds on previous work with spherical nanocrystals and nanorods, but a unique factor is the need to control the branching event. Multiple arms can branch from a nucleus, or secondary branches can form from a growing arm. Branching can be governed by mechanisms including twinning, crystal splitting, polymorphism, oriented attachment, and others. One of the most relevant parameters is the choice of appropriate surfactant molecules, which can bind selectively to certain crystal facets or can even promote specific crystallographic phases during nucleation and growth. Also, seeded growth approaches recently have allowed great progress in the synthesis of nanocrystals with elaborate shapes. In this approach, nanocrystals with a specified chemical composition, size, shape, crystalline habit, and phase act as seeds on which multiple branches of a second material nucleate and grow. These approaches yield nanostructures with improved homogeneity in distribution of branch length and cross section. Ion exchange reactions allow further manipulation of branched nanocrystals by transforming crystals of one material into crystals with the same size, shape, and anion sublattice but with a new cation. Combining seeded growth with ion exchange provides a method for greatly expanding the library of branched nanocrystals.
Assembly of morphologically complex nanocrystals is evolving in parallel to developments in chemical synthesis. While researchers have made many advances in the past decade in controlled assembly of nanocrystals with simple polyhedral shapes, modeling and experimental realization of ordered superstructures of branched nanocrystals are still in their infancy. In the only case of ordered superstructure reported so far, the assembly proceeds by steps in a hierarchical fashion, in analogy to several examples of assembly found in nature. Meanwhile, disordered assemblies of branched nanocrystals are also interesting and may find applications in various fields.