A Deep Learning Framework Discovers Compositional Order and Self-Assembly Pathways in Binary Colloidal Mixtures

[Image: see text] Binary colloidal superlattices (BSLs) have demonstrated enormous potential for the design of advanced multifunctional materials that can be synthesized via colloidal self-assembly. However, mechanistic understanding of the three-dimensional self-assembly of BSLs is largely limited due to a lack of tractable strategies for characterizing the many two-component structures that can appear during the self-assembly process. To address this gap, we present a framework for colloidal crystal structure characterization that uses branched graphlet decomposition with deep learning to systematically and quantitatively describe the self-assembly of BSLs at the single-particle level. Branched graphlet decomposition is used to evaluate local structure via high-dimensional neighborhood graphs that quantify both structural order (e.g., body-centered-cubic vs face-centered-cubic) and compositional order (e.g., substitutional defects) of each individual particle. Deep autoencoders are then used to efficiently translate these neighborhood graphs into low-dimensional manifolds from which relationships among neighborhood graphs can be more easily inferred. We demonstrate the framework on in silico systems of DNA-functionalized particles, in which two well-recognized design parameters, particle size ratio and interparticle potential well depth can be adjusted independently. The framework reveals that binary colloidal mixtures with small interparticle size disparities (i.e., A- and B-type particle radius ratios of r(A)/r(B) = 0.8 to r(A)/r(B) = 0.95) can promote the self-assembly of defect-free BSLs much more effectively than systems of identically sized particles, as nearly defect-free BCC-CsCl, FCC-CuAu, and IrV crystals are observed in the former case. The framework additionally reveals that size-disparate colloidal mixtures can undergo nonclassical nucleation pathways where BSLs evolve from dense amorphous precursors, instead of directly nucleating from dilute solution. These findings illustrate that the presented characterization framework can assist in enhancing mechanistic understanding of the self-assembly of binary colloidal mixtures, which in turn can pave the way for engineering the growth of defect-free BSLs.