Artificial Solids by Design: Assembly and Electron Microscopy Study of Nanosheet-Derived Heterostructures

Two-dimensional materials do not only attract interest owing to their anisotropic properties and quantum confinement effects but also lend themselves as well-defined building blocks for the rational design of 3D materials with custom-made structures and, hence, properties. Here, we present the bottom-up fabrication of an artificial superlattice derived from positively charged layered double hydroxide (LDH) and negatively charged perovskite layers sequentially assembled by electrostatic layer-by-layer deposition. In contrast to previously employed bulk methods averaging out the elemental distribution within such stacks, we use a combination of HRTEM, STEM, and EEL spectroscopy to elucidate the structure and composition of the multilayer stack with a high spatial resolution on the subnanometer scale. Atomic column resolved STEM coupled with EELS line scans confirms the periodic arrangement of individual nanosheets by evaluation of the Ca-L 2,3 and Mn-L 2,3 edges. Furthermore, HRTEM confirms the formation of up to 100 double layer thick films, thus demonstrating the transition from ultrathin nanosheet assemblies to artificial bulk solids with engineered structures and property profiles. We ascertain the formation of densely packed stacks with a well-ordered layered morphology, while nonidealities such as lack of in-plane layer registry, layer terminations, sheet bending, and contamination by residual ligands are side effects of the solution-based deposition process. In addition, we demonstrate that the packing density of the multilayer system can be tuned by changing the LDH dispersing agent from formamide to water, resulting in porous stacks containing about eight times less LDH and featuring significantly increased interlayer distances.