Epitaxy: Programmable Atom Equivalents Versus Atoms

The programmability of DNA makes it an attractive structure-directing ligand for the assembly of nanoparticle superlattices in a manner that mimics many aspects of atomic crystallization. However, the synthesis of multilayer single crystals of defined size remains a challenge. Though previous studies considered lattice mismatch as the major limiting factor for multilayer assembly, thin film growth depends on many interlinked variables. Here, a more comprehensive approach is taken to study fundamental elements, such as the growth temperature and the thermodynamics of interfacial energetics, to achieve epitaxial growth of nanoparticle thin films. Under optimized equilibrium conditions, single crystal, multilayer thin films can be synthesized over 500 × 500 μm2 areas on lithographically patterned templates. Importantly, these superlattices follow the same patterns of crystal growth demonstrated in thin film atomic deposition, allowing for these processes to be understood in the context of well-studied atomic epitaxy, and potentially enabling a nanoscale model to study fundamental crystallization processes.