Spin Coating Promotes the Epitaxial Growth of AgCN Microwires on 2D Materials.

Epitaxial growth of inorganic crystals on 2D materials is expected to greatly advance nanodevices and nanocomposites. However, because pristine surfaces of 2D materials are chemically inert, it is difficult to grow inorganic crystals epitaxially on 2D materials. Previously, successful results were achieved only by vapor-phase deposition at high temperature, and solution-based deposition including spin coating made the epitaxial growth unaligned, sparse, or nonuniform on 2D materials. Here, we show that solvent-controlled spin coating can uniformly deposit a dense layer of epitaxial AgCN microwires onto various 2D materials. Adding ethanol to an aqueous AgCN solution facilitates uniform formation of the thin supersaturated solution layer during spin coating, which promotes heterogeneous crystal nucleation on 2D material surfaces over homogeneous nucleation in the bulk solution. Microscopic analysis confirms highly aligned, uniform, and dense growth of epitaxial AgCN microwires on graphene, MoS2, hBN, WS2, and WSe2. The epitaxial microwires, which are optically observable and chemically removable, enable crystallographic mapping of grains in millimeter-sized polycrystalline graphene as well as precise control of twist angles (<∼1°) in van der Waals heterostructures. In addition to these practical applications, our study demonstrates the potential of 2D materials as epitaxial templates even in spin coating of inorganic crystals.

Epitaxial Growth of Diamond-Shaped Au1/2Ag1/2CN Nanocrystals on Graphene.

Epitaxial synthesis of inorganic nanomaterials on pristine 2D materials is of interest in the development of nanostructured devices and nanocomposite materials, but is quite difficult because pristine surfaces of 2D materials are chemically inert. Previous studies found a few exceptions including AuCN, AgCN, CuCN, and Cu0.5Au0.5CN, which can be preferentially synthesized and epitaxially aligned onto various 2D materials. Here, we discover that Au1/2Ag1/2CN forms diamond-shaped nanocrystals epitaxially grown on pristine graphene surfaces. The nanocrystals synthesized by a simple drop-casting method are crystallographically aligned to lattice structures of the underlying graphene. Our experimental investigations on 3D structures and the synthesis conditions of the nanocrystals imply that the rhombic 2D geometries originate from different growth rates depending on orientations along and perpendicular to 1D molecular chains of Au1/2Ag1/2CN. We also perform in situ TEM observations showing that Au1/2Ag1/2CN nanocrystals are decomposed to Au and Ag alloy nanocrystals under electron beam irradiation. Our experimental results provide an additional example of 1D cyanide chain families that form ordered nanocrystals epitaxially aligned on 2D materials, and reveal basic physical characteristics of this rarely investigated nanomaterial.

A Transformative Gold Patterning through Selective Laser Refining of Cyanide.

Gold is an essential noble metal for electronics, and its application area is increasing continuously through the introduction of gold nanoparticle ink that enables rapid prototyping and direct writing of gold electrodes on versatile substrates at a low temperature. However, the synthesis of gold nanoparticles has certain limitations involving high cost, long synthesis time, large waste of material, and frequent use of chemicals. In this study, we suggest simultaneous laser refining of gold cyanide and selective fabrication of gold electrodes directly on the substrate without a separate synthesis step. Gold cyanide is commonly the first product of gold from the primitive ore, and the gold can be extracted directly from the rapid photothermal decomposition of gold cyanide by the laser. It was confirmed that laser-induced thermocapillary force plays an important role in creating the continuous gold patterns by aligning the refined gold. The resultant gold electrodes exhibited a low resistivity analogous to the conventional direct writing method using nanoparticles, and the facile repair process of a damaged electrode was demonstrated as the proof-of-concept. The proposed transformative approach for gold patterning, distinguished from the previous top-down and bottom-up approaches, has the potential to replace the well-known techniques and provide a new branch of electrode manufacturing scheme.

Reversible disorder-order transitions in atomic crystal nucleation.

Nucleation in atomic crystallization remains poorly understood, despite advances in classical nucleation theory. The nucleation process has been described to involve a nonclassical mechanism that includes a spontaneous transition from disordered to crystalline states, but a detailed understanding of dynamics requires further investigation. In situ electron microscopy of heterogeneous nucleation of individual gold nanocrystals with millisecond temporal resolution shows that the early stage of atomic crystallization proceeds through dynamic structural fluctuations between disordered and crystalline states, rather than through a single irreversible transition. Our experimental and theoretical analyses support the idea that structural fluctuations originate from size-dependent thermodynamic stability of the two states in atomic clusters. These findings, based on dynamics in a real atomic system, reshape and improve our understanding of nucleation mechanisms in atomic crystallization.