Epitaxial attachment of quantum dots into ordered superlattices enables the synthesis of quasi-two-dimensional materials that theoretically exhibit features such as Dirac cones and topological states, and have major potential for unprecedented optoelectronic devices. Initial studies found that disorder in these structures causes localization of electrons within a few lattice constants, and highlight the critical need for precise structural characterization and systematic assessment of the effects of disorder on transport. Here we fabricated superlattices with the quantum dots registered to within a single atomic bond length (limited by the polydispersity of the quantum dot building blocks), but missing a fraction (20%) of the epitaxial connections. Calculations of the electronic structure including the measured disorder account for the electron localization inferred from transport measurements. The calculations also show that improvement of the epitaxial connections will lead to completely delocalized electrons and may enable the observation of the remarkable properties predicted for these materials.

Confined-but-connected quantum dot solids (QDS) combine the advantages of tunable, quantum-confined energy levels with efficient charge transport through enhanced electronic interdot coupling. We report the fabrication of QDS by treating self-assembled films of colloidal PbSe quantum dots with polar nonsolvents. Treatment with dimethylformamide balances the rates of self-assembly and ligand displacement to yield confined-but-connected QDS structures with cubic ordering and quasi-epitaxial interdot connections through facets of neighboring dots. The QDS structure was analyzed by a combination of transmission electron microscopy and wide-angle and small-angle X-ray scattering. Excitonic absorption signatures in optical spectroscopy confirm that quantum confinement is preserved. Transport measurements show significantly enhanced conductivity in treated films.

Epitaxially connected superlattices of self-assembled colloidal quantum dots present a promising route toward exquisite control of electronic structure through precise hierarchical structuring across multiple length scales. Here, we uncover propagation of disorder as an essential feature in these systems, which intimately connects order at the atomic, superlattice, and grain scales. Accessing theoretically predicted exotic electronic states and highly tunable minibands will therefore require detailed understanding of the subtle interplay between local and long-range structure. To that end, we developed analytical methods to quantitatively characterize the propagating disorder in terms of a real paracrystal model and directly observe the dramatic impact of angstrom scale translational disorder on structural correlations at hundreds of nanometers. Using this framework, we discover improved order accompanies increasing sample thickness and identify the substantial effect of small fractions of missing epitaxial bonds on statistical disorder. These results have significant experimental and theoretical implications for the elusive goals of long-range carrier delocalization and true miniband formation.

The formation of epitaxially connected quantum dot solids involves a complex interplay of interfacial assembly, surface chemistry, and irreversible-directed attachment. We describe the basic mechanism in the context of a coherent phase transition with distinct nucleation and propagation steps. The proposed mechanism explains how defects in the preassembled structure influence nucleation and how basic geometric relationships govern the transformation from hexagonal assemblies of isolated dots to interconnected solids with square symmetry. We anticipate that new mechanistic insights will guide future advances in the formation of high-fidelity quantum dot solids with enhanced grain size, interconnectivity, and control over polymorph structures.

The combination of self-assembly and directed attachment of colloidal nanocrystals at fluid interfaces presents a scientifically interesting and technologically important research challenge. Remarkable strides have been made in the synthesis of polyhedral nanocrystals with precisely defined shapes and their self-assembly into highly ordered superstructures. We discuss the interplay of entropic and enthalpic driving forces and the kinetic aspects of interfacial selfassembly and attachment. We present in situ parallel smallangle X-ray scattering measurements and emerging insights into the complex choreography of interfacial transport processes involved in the formation of highly ordered epitaxially connected nanocrystal solids. New understanding emerging from in situ measurements provides process control and design principles for the selective formation of specific superlattice polymorphs. We discuss outstanding challenges that must be resolved to translate know-how from controlled assembly and attachment in the laboratory to scalable integration for emerging technological applications.