The Winner Takes It All: Carbon Supersedes Hexagonal Boron Nitride with Graphene on Transition Metals at High Temperatures.

The production of high-quality hexagonal boron nitride (h-BN) is essential for the ultimate performance of 2D materials-based devices, since it is the key 2D encapsulation material. Here, a decisive guideline is reported for fabricating high-quality h-BN on transition metals. It is crucial to exclude carbon from the h-BN related process, otherwise carbon prevails over boron and nitrogen due to its larger binding energy, thereupon forming graphene on metals after high-temperature annealing. The surface reaction-assisted conversion from h-BN to graphene with high-temperature treatments is demonstrated. The pyrolysis temperature Tp is an important quality indicator for h-BN/metals. When the temperature is lower than Tp , the quality of the h-BN layer is improved upon annealing. While the annealing temperature is above Tp , in case of carbon-free conditions, the h-BN disintegrates and nitrogen desorbs from the surface more easily than boron, eventually leading to clean metal surfaces. However, once the h-BN layer is exposed to carbon, graphene forms on Pt(111) in the high-temperature regime. This not only provides an indispensable principle (avoid carbon) for fabricating high-quality h-BN materials on transition metals, but also offers a straightforward method for the surface reaction-assisted conversion from h-BN to graphene on Pt(111).

High-Quality Hexagonal Boron Nitride from 2D Distillation.

The production of high-quality two-dimensional (2D) materials is essential for the ultimate performance of single layers and their hybrids. Hexagonal boron nitride (h-BN) is foreseen to become the key 2D hybrid and packaging material since it is insulating, impermeable, flat, transparent, and chemically inert, though it is difficult to attain in ultimate quality. Here, a scheme is reported for producing single layer h-BN that shows higher quality in view of mosaicity and strain variations than material from chemical vapor deposition (CVD). We delaminate CVD h-BN from Rh(111) and transfer it to a clean metal surface. The twisting angle between BN and the second substrate yields metastable moiré structures. Annealing above 1000 K leads to 2D distillation, i.e., catalyst-assisted BN sublimation from the edges of the transferred layer and subsequent condensation into superior quality h-BN. This provides a way for 2D material production remote from CVD instrumentation.

Catalyst Proximity-Induced Functionalization of h-BN with Quat Derivatives.

Inert single-layer boron nitride (h-BN) grown on a catalytic metal may be functionalized with quaternary ammonium compounds (quats) that are widely used as nonreactive electrolytes. We observe that the quat treatment, which facilitates the electrochemical transfer of two-dimensional materials, involves a decomposition of quat ions and leads to covalently bound quat derivatives on top of the 2D layer. Applying tetraoctylammonium and h-BN on rhodium, the reaction product is top-alkylized h-BN as identified with high-resolution X-ray photoelectron spectroscopy. The alkyl chains are homogeneously distributed across the surface, and the properties thereof are well-tunable by the choice of different quats. The functionalization further weakens the 2D material-substrate interaction and promotes easy transfer. Therefore, the functionalization scheme that is presented enables the design of 2D materials with tailored properties and with the freedom to position and orient them as required. The mechanism of this functionalization route is investigated with density functional theory calculations, and we identify the proximity of the catalytic metal substrate to alter the chemical reactivity of otherwise inert h-BN layers.

Centimeter-Sized Single-Orientation Monolayer Hexagonal Boron Nitride With or Without Nanovoids.

Large-area hexagonal boron nitride (h-BN) promises many new applications of two-dimensional materials, such as the protective packing of reactive surfaces or as membranes in liquids. However, scalable production beyond exfoliation from bulk single crystals remained a major challenge. Single-orientation monolayer h-BN nanomesh is grown on 4 in. wafer single crystalline rhodium films and transferred on arbitrary substrates such as SiO2, germanium, or transmission electron microscopy grids. The transfer process involves application of tetraoctylammonium bromide before electrochemical hydrogen delamination. The material performance is demonstrated with two applications. First, protective sealing of h-BN is shown by preserving germanium from oxidation in air at high temperatures. Second, the membrane functionality of the single h-BN layer is demonstrated in aqueous solutions. Here, we employ a growth substrate intrinsic preparation scheme to create regular 2 nm holes that serve as ion channels in liquids.

Two-nanometer voids in single-layer hexagonal boron nitride: formation via the "can-opener" effect and annihilation by self-healing.

The exposure of hexagonal boron nitride single layers to low energy ions leads to the formation of vacancy defects that are mobile at elevated temperatures. For the case of h-BN on rhodium, a superhoneycomb surface with 3 nm lattice constant (nanomesh), a concerted self-assembly of these defects is observed, where the "can-opener" effect leads to the cut-out of 2 nm "lids" and stable voids in the h-BN layer. These clean-cut voids repel each other, which enables the formation of arrays with a nearest neighbor distance down to about 8 nm. The density of voids depends on the Ar ion dose, and can reach 10(12) cm(-2). If the structures are annealed above 1000 K, the voids disappear and pristine h-BN nanomesh with larger holes is recovered. The results are obtained by scanning tunneling microscopy and density functional theory calculations.

Implantation length and thermal stability of interstitial ar atoms in boron nitride nanotents.

Hyperthermal atoms may be implanted beneath single layers of graphene or hexagonal boron nitride (h-BN) on a substrate. For the case of h-BN on rhodium, which is a corrugated honeycomb superstructure with a periodicity of 3.2 nm, Ar atoms are implanted at distinct interstitial sites within the supercell, where the h-BN is weakly bound to the substrate. These peculiar structures are reminiscent of "nanotents" with an ultimately thin "rainfly". Here we explore the implantation length (i.e., the distance the atoms move before they come to rest as interstitial defects) and the thermal stability of these atomic agglomerates above room temperature. The results are obtained by variable-temperature scanning tunneling microscopy and density functional theory calculations.

Immobilizing individual atoms beneath a corrugated single layer of boron nitride.

Single atoms, and in particular the least reactive noble gases, are difficult to immobilize at room temperature. Ion implantation into a crystal lattice has this capability, but the randomness of the involved processes does not permit much control over their distribution within the solid. Here we demonstrate that the boron nitride nanomesh, a corrugated single layer of hexagonal boron nitride (h-BN) with a 3.2 nm honeycomb superstructure formed on a Rh(111) surface, can trap individual argon atoms at distinct subsurface sites at room temperature. A kinetic energy window for implantation is identified where the argon ions can penetrate the h-BN layer but not enter the Rh lattice. Scanning tunneling microscopy and photoemission data show the presence of argon atoms at two distinct sites within the nanomesh unit cell, confirmed also by density functional theory calculations. The single atom implants are stable in air. Annealing of implanted structures to 900 K induces the formation of highly regular holes of 2 nm diameter in the h-BN layer with adjacent flakes of the same size found on top of the layer. We explain this "can-opener" effect by the presence of a vacancy defect, generated during the penetration of the Ar ion through the h-BN lattice, and propagating along the rim of a nanomesh pore where the h-BN lattice is highly bent. The reported effects are also observed in graphene on ruthenium and for neon atoms.

Tuning structural and mechanical properties of two-dimensional molecular crystals: the roles of carbon side chains.

A key requirement for the future applicability of molecular electronics devices is a resilience of their properties to mechanical deformation. At present, however, there is no fundamental understanding of the origins of mechanical properties of molecular films. Here we use quinacridone, which possesses flexible carbon side chains, as a model molecular system to address this issue. Eight molecular configurations with different molecular coverage are identified by scanning tunneling microscopy. Theoretical calculations reveal quantitatively the roles of different molecule-molecule and molecule-substrate interactions and predict the observed sequence of configurations. Remarkably, we find that a single Young's modulus applies for all configurations, the magnitude of which is controlled by side chain length, suggesting a versatile avenue for tuning not only the physical and chemical properties of molecular films but also their elastic properties.

Direct observation of enantiospecific substitution in a two-dimensional chiral phase transition.

Initial stages of a chiral phase transition in the monolayer of a quinacridone derivative on the Au(111) surface were investigated by scanning tunneling microscopy at submolecular resolution. The prochiral molecules form a homochiral lamella phase at low coverages upon adsorption. A transition to a racemate lattice is observed with increasing coverage. Enantiomers of a homochiral lamella line become specifically substituted by opposite enantiomers such that a heterochiral structure evolves. Due to the higher density, lateral alkyl chains are bent away from the surface. Our findings are significant for the understanding and control of chiral phase transitions in related molecular systems like liquid crystals.

Homochiral recognition among organic molecules on copper(110).

The adsorption of a prochiral quinacridone derivative (QA16C) with two alkyl chains of 16 carbon atoms on a Cu(110) surface was investigated with variable-temperature scanning tunneling microscopy. QA16C molecules prefer to assemble at 150 K into short homochiral molecular lines with two enantiomorphous orientations in which the lateral alkyl chains exhibit partial disorder. With increasing sample temperatures, the QA16C lines form larger well-ordered homochiral domains. As a reason for the homochiral recognition, we identify a rigid alignment of the molecule due to the interaction with the substrate. In addition, lateral intermolecular interactions in the form of hydrogen bonding and van der Waals interactions are identified.