Control over material structure and morphology during electrodeposition is necessary for material synthesis and energy applications. One approach to guide crystallite formation is to take advantage of epitaxy on a current collector to facilitate crystallographic control. Single-layer graphene on metal foils can promote "remote epitaxy" during Cu and Zn electrodeposition, resulting in growth of metal that is crystallographically aligned to the substrate beneath graphene. However, the substrate-graphene-deposit interactions that allow for epitaxial electrodeposition are not well understood. Here, we investigate how different graphene layer thicknesses (monolayer, bilayer, trilayer, and graphite) influence the electrodeposition of Zn and Cu. Scanning transmission electron microscopy and electron backscatter diffraction are leveraged to understand metal morphology and structure, demonstrating that remote epitaxy occurs on mono- and bilayer graphene but not trilayer or thicker. Density functional theory (DFT) simulations reveal the spatial electronic interactions through thin graphene that promote remote epitaxy. This work advances our understanding of electrochemical remote epitaxy and provides strategies for improving control over electrodeposition.
It is critical to understand the transformation mechanisms in layered metal chalcogenides to enable controlled synthesis and processing. Here, we develop an alumina encapsulation layer-based in situ transmission electron microscopy (TEM) setup that enables the investigation of melting, crystallization, and alloying of nanoscale bismuth telluride platelets while limiting sublimation in the high-vacuum TEM environment. Heating alumina-encapsulated platelets to 700 °C in situ resulted in melting that initiated at edge planes and proceeded via the movement of a sharp interface. The encapsulated melt was then cooled to induce solidification, with individual nuclei growing to form single crystals with the same basal plane orientation as the original platelet and nonequilibrium crystal shapes imposed by the encapsulation layer. Finally, heating platelets in the presence of antimony caused alloying and lattice strain, along with heterogeneous phase formation. These findings provide new insight into important transformation processes in layered metal chalcogenide materials.
