Structure Prediction of Ionic Epitaxial Interfaces with Ogre Demonstrated for Colloidal Heterostructures of Lead Halide Perovskites.

Colloidal epitaxial heterostructures are nanoparticles composed of two different materials connected at an interface, which can exhibit properties different from those of their individual components. Combining dissimilar materials offers exciting opportunities to create a wide variety of functional heterostructures. However, assessing structural compatibility─the main prerequisite for epitaxial growth─is challenging when pairing complex materials with different lattice parameters and crystal structures. This complicates both the selection of target heterostructures for synthesis and the assignment of interface models when new heterostructures are obtained. Here, we demonstrate Ogre as a powerful tool to accelerate the design and characterization of colloidal heterostructures. To this end, we implemented developments tailored for the high-efficiency prediction of epitaxial interfaces between ionic/polar materials, which encompass most colloidal semiconductors. These include the use of pre-screening candidate models based on charge balance at the interface and the use of a classical potential for fast energy evaluations, with parameters automatically calculated based on the input bulk structures. These developments are validated for perovskite-based CsPbBr/PbSBr heterostructures, where Ogre produces interface models in excellent agreement with density functional theory and experiments. Furthermore, we use Ogre to rationalize the templating effect of CsPbCl on the growth of lead sulfochlorides, where perovskite seeds induce the formation of PbSCl rather than PbSCl due to better epitaxial compatibility. Finally, combining Ogre simulations with experimental data enables us to unravel the structure and composition of the hitherto unsolved CsPbBr/BiPbS interface, and to assign a structure to several other reported metal halide- and oxide-based interfaces. The Ogre package is available on GitHub or via the desktop application, available for Windows, Linux, and Mac.