Mechanistic Insights into Superlattice Transformation at a Single Nanocrystal Level Using Nanobeam Electron Diffraction.

Understanding the mechanism and ultimately directing nanocrystal (NC) superlattice assembly and attachment have important implications on future advances in this emerging field. Here, we use 4D-STEM to investigate a monolayer of PbS NCs at various stages of the transformation from a hexatic assembly to a nonconnected square-like superlattice over large fields of view. Maps of nanobeam electron diffraction patterns acquired with an electron microscope pixel array detector (EMPAD) offer unprecedented detail into the 3D crystallographic alignment of the polyhedral NCs. Our analysis reveals that superlattice transformation is dominated by translation of prealigned NCs strongly coupled along the <11n>AL direction and occurs stochastically and gradually throughout single grains. We validate the generality of the proposed mechanism by examining the structure of analogous PbSe NC assemblies using conventional transmission electron microscopy and selected area electron diffraction. The experimental results presented here provide new mechanistic insights into NC self-assembly and oriented attachment.

Successive Ionic Layer Absorption and Reaction for Postassembly Control over Inorganic Interdot Bonds in Long-Range Ordered Nanocrystal Films.

Epitaxially connected assemblies of nanocrystals (NCs) present an interesting new class of nanomaterial in which confinement of charge carriers is intermediate between that of a quantum dot and a quantum well. Despite impressive advances in the formation of high-fidelity assemblies, predicted collective properties have not yet emerged. A critical knowledge gap toward realizing these properties is the current lack of understanding of and control over the formation of epitaxial interdot bonds connecting the NCs within the assemblies. In this work we demonstrate successive ionic layer absorption and reaction (SILAR) to enhance the interdot bonding within the NC assembly. SILAR treatment improved the fraction of interdot bonds from 82% to 91% and increased their width from 3.1 to 4.0 nm. Absorption spectra and charge transport measurements indicate that the effect of postassembly growth on quantum confinement in this system depends on the composition of the SILAR shell material. Increased NC film conductance following SILAR processing indicates that building and strengthening interdot bonds lead to increased electronic coupling and doping in the assemblies. The postassembly film growth detailed here presents an opportunity to repair structural defects and to tailor the balance of quantum confinement and interdot coupling in epitaxially connected NC assemblies.