Wafer-Scale Programmed Assembly of One-Atom-Thick Crystals.

Crystalline films offer various physical properties based on the modulation of their thicknesses and atomic structures. The layer-by-layer assembly of atomically thin crystals provides a powerful means to arbitrarily design films at the atomic level, which are unattainable with existing growth technologies. However, atomically clean assembly of the materials with high scalability and reproducibility remains challenging. We report programmed crystal assembly of graphene and monolayer hexagonal boron nitride, assisted by van der Waals interactions, to form wafer-scale films of pristine interfaces with near-unity yield. The atomic configurations of the films are tailored with layer-resolved compositions and in-plane crystalline orientations. We demonstrate batch-fabricated tunnel device arrays with modulation of the resistance over orders of magnitude by thickness control of the hexagonal boron nitride barrier with single-atom precision and large-scale, twisted multilayer graphene with programmable electronic band structures and crystal symmetries. Our results constitute an important development in the artificial design of large-scale films.

Crystal Phase Transition Creates a Highly Active and Stable RuCX Nanosurface for Hydrogen Evolution Reaction in Alkaline Media.

Although metastable crystal structures have received much attention owing to their utilization in various fields, their phase-transition to a thermodynamic structure has attracted comparably little interest. In the case of nanoscale crystals, such an exothermic phase-transition releases high energy within a confined surface area and reconstructs surface atomic arrangement in a short time. Thus, this high-energy nanosurface may create novel crystal structures when some elements are supplied. In this work, the creation of a ruthenium carbide (RuCX , X < 1) phase on the surface of the Ru nanocrystal is discovered during phase-transition from cubic-close-packed to hexagonal-close-packed structure. When the electrocatalytic hydrogen evolution reaction (HER) is tested in alkaline media, the RuCX exhibits a much lower overpotential and good stability relative to the counterpart Ru-based catalysts and the state-of-the-art Pt/C catalyst. Density functional theory calculations predict that the local heterogeneity of the outermost RuCX surface promotes the bifunctional HER mechanism by providing catalytic sites for both H adsorption and facile water dissociation.