Nonequivalent Atomic Vibrations at Interfaces in a Polar Superlattice.

In heterostructures made from polar materials, e.g., AlN-GaN-AlN, the nonequivalence of the two interfaces is long recognized as a critical aspect of their electronic properties; in that, they host different 2D carrier gases.

Phonon vortices at heavy impurities in two-dimensional materials.

The advent of monochromated electron energy-loss spectroscopy has enabled atomic-resolution vibrational spectroscopy, which triggered interest in spatially localized or quasi-localized vibrational modes in materials. Here we report the discovery of phonon vortices at heavy impurities in two-dimensional materials. We use density-functional-theory calculations for two configurations of Si impurities in graphene, Si-C and Si-C, to examine atom-projected phonon densities of states and display the atomic-displacement patterns for select modes that are dominated by impurity displacements.

Single-atom vibrational spectroscopy with chemical-bonding sensitivity.

Correlation of lattice vibrational properties with local atomic configurations in materials is essential for elucidating functionalities that involve phonon transport in solids. Recent developments in vibrational spectroscopy in a scanning transmission electron microscope have enabled direct measurements of local phonon modes at defects and interfaces by combining high spatial and energy resolution. However, pushing the ultimate limit of vibrational spectroscopy in a scanning transmission electron microscope to reveal the impact of chemical bonding on local phonon modes requires extreme sensitivity of the experiment at the chemical-bond level.

Twisted bilayer zigzag-graphene nanoribbon junctions with tunable edge states.

Stacking two-dimensional layered materials such as graphene and transitional metal dichalcogenides with nonzero interlayer twist angles has recently become attractive because of the emergence of novel physical properties. Stacking of one-dimensional nanomaterials offers the lateral stacking offset as an additional parameter for modulating the resulting material properties. Here, we report that the edge states of twisted bilayer zigzag graphene nanoribbons (TBZGNRs) can be tuned with both the twist angle and the stacking offset.

Direct Visualization of Localized Vibrations at Complex Grain Boundaries.

Grain boundaries (GBs) are a prolific microstructural feature that dominates the functionality of a wide class of materials. The functionality at a GB results from the unique atomic arrangements, different from those in the grain, that have driven extensive experimental and theoretical studies correlating atomic-scale GB structures to macroscopic electronic, infrared optical, and thermal properties. In this work, a SrTiO GB is examined using atomic-resolution aberration-corrected scanning transmission electron microscopy and ultrahigh-energy-resolution monochromated electron energy-loss spectroscopy, in conjunction with density functional theory.

Tunable, Ferroelectricity-Inducing, Spin-Spiral Magnetic Ordering in Monolayer FeOCl.

Spin spirals (SS) are a special case of noncollinear magnetism, where the magnetic-moment direction rotates along an axis. They have generated interest for novel phenomena, spintronics applications, and their potential formation in monolayers, but the search for monolayers exhibiting SS has not been particularly fruitful. Here, we employ density functional theory calculations to demonstrate that SS form in a recently synthesized monolayer, FeOCl.

Emergent interface vibrational structure of oxide superlattices.

As the length scales of materials decrease, the heterogeneities associated with interfaces become almost as important as the surrounding materials. This has led to extensive studies of emergent electronic and magnetic interface properties in superlattices. However, the interfacial vibrations that affect the phonon-mediated properties, such as thermal conductivity, are measured using macroscopic techniques that lack spatial resolution.

Controllable fabrication and photocatalytic performance of nanoscale single-layer MoSe islands with substantial edges on an Ag(111) substrate.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) are emerging as new electrocatalysts and photocatalysts. The edge sites of 2D TMDs show high catalytic activity and are thus favored at the catalyst surface over TMD inert basal planes. However, 2D TMDs that predominantly expose edges are thermodynamically unfavorable, limiting the number of edge sites at the surface.

On-surface synthesis of size- and shape-controlled two-dimensional Au nanoclusters using a flexible fullerene molecular template.

Synthesizing nano-clusters with a well-defined size, shape, and composition is an important and challenging goal in nanotechnology. Here we report the application of a single layer C60 molecule as an effective molecular template for the synthesis of size- and shape-selected two-dimensional gold clusters (Aun) on a graphite substrate. This molecular template facilitates the preferential formation of Au19 clusters with a selectivity as high as 90%.

Effects of Ion Energy and Density on the Plasma Etching-Induced Surface Area, Edge Electrical Field, and Multivacancies in MoSe Nanosheets for Enhancement of the Hydrogen Evolution Reaction.

Plasma functionalization can increase the efficiency of MoSe in the hydrogen evolution reaction (HER) by providing multiple species but the interactions between the plasma and catalyst are not well understood. In this work, the effects of the ion energy and plasma density on the catalytic properties of MoSe nanosheets are studied. The through-holes resulting from plasma etching and multi-vacancies induced by plasma-induced damage enhance the HER efficiency as exemplified by a small overpotential of 148 mV at 10 mA cm and Tafel slope of 51.

Air-Stable Monolayer Cu Se Exhibits a Purely Thermal Structural Phase Transition.

Materials possessing structural phase transformations exhibit a rich set of physical and chemical properties that can be used for a variety of applications. In 2D materials, structural transformations have so far been induced by strain, lasers, electron injection, electron/ion beams, thermal loss of stoichiometry, and chemical treatments or by a combination of such approaches and annealing. However, stoichiometry-preserving, purely thermal, reversible phase transitions, which are fundamental in physics and can be easily induced, have not been observed.

Direct Visualization of Hydrogen-Transfer Intermediate States by Scanning Tunneling Microscopy.

Hydrogen atoms bonded within molecular cavities often undergo tunneling or thermal-transfer processes that play major roles in diverse physical phenomena. Such transfers may or may not entail intermediate states. The existence of such fleeting states is typically determined by indirect means, while their direct visualization has not been achieved, largely because their concentrations under equilibrium conditions are negligible.

Atomically precise, custom-design origami graphene nanostructures.

The construction of atomically precise carbon nanostructures holds promise for developing materials for scientific study and nanotechnology applications. Here, we show that graphene origami is an efficient way to convert graphene into atomically precise, complex nanostructures. By scanning tunneling microscope manipulation at low temperature, we repeatedly fold and unfold graphene nanoislands (GNIs) along an arbitrarily chosen direction.

Spontaneous Formation of 1D Pattern in Monolayer VSe with Dispersive Adsorption of Pt Atoms for HER Catalysis.

Creation of functional patterns in two-dimensional (2D) materials provides opportunities to extend their potential for applications. Transition-metal dichalcogenides (TMDCs) are suitable 2D materials for pattern generation because of properties including alterable polymorphic phases, easy chalcogen-vacancy formation, metal-atom insertion, and alloying. Such patterning can be used for selective functionalization.

Symmetry breakdown of 4,4″-diamino-p-terphenyl on a Cu(111) surface by lattice mismatch.

Site-selective functionalization of only one of two identical chemical groups within one molecule is highly challenging, which hinders the production of complex organic macromolecules. Here we demonstrate that adsorption of 4,4″-diamino-p-terphenyl on a metal surface leads to a dissymmetric binding affinity. With low temperature atomic force microscopy, using CO-tip functionalization, we reveal the asymmetric adsorption geometries of 4,4″-diamino-p-terphenyl on Cu(111), while on Au(111) the symmetry is retained.

Fabrication of Millimeter-Scale, Single-Crystal One-Third-Hydrogenated Graphene with Anisotropic Electronic Properties.

Periodically hydrogenated graphene is predicted to form new kinds of crystalline 2D materials such as graphane, graphone, and 2D C H , which exhibit unique electronic properties. Controlled synthesis of periodically hydrogenated graphene is needed for fundamental research and possible electronic applications. Only small patches of such materials have been grown so far, while the experimental fabrication of large-scale, periodically hydrogenated graphene has remained challenging.

Tip-triggered Thermal Cascade Manipulation of Magic Number Gold-Fullerene Clusters in the Scanning Tunnelling Microscope.

We demonstrate cascade manipulation between magic number gold-fullerene hybrid clusters by channelling thermal energy into a specific reaction pathway with a trigger from the tip of a scanning tunnelling microscope (STM). The (C)-Au clusters, formed via self-assembly on the Au(111) surface, consist of n Au atoms and m C molecules; the three smallest stable clusters are (C)-Au, (C)-Au, and (C)-Au. The manipulation cascade was initiated by driving the STM tip into the cluster followed by tip retraction.

Evidence for Ultralow-Energy Vibrations in Large Organic Molecules.

The quantum efficiency or the rate of conversion of incident photon to free electron in photosynthesis is known to be extremely high. It has long been thought that the origin of this efficiency are molecular vibrations leading to a very fast separation of electrons and holes within the involved molecules. However, molecular vibrations are commonly in the range above 100 meV, which is too high for excitations in an ambient environment.

Identifying and Visualizing the Edge Terminations of Single-Layer MoSe Island Epitaxially Grown on Au(111).

Recently, single-layer transition-metal dichalcogenides have drawn significant attention due to their remarkable physical properties in the monolayer as well as at the edges. Here, we constructed high-quality, single-layer MoSe islands on the Au(111) surfaces in ultrahigh vacuum by molecular beam epitaxy. All of the islands have hexagonal or triangular shapes with two kinds of well-defined edges.

Construction of Two-Dimensional Chiral Networks through Atomic Bromine on Surfaces.

Using atomic bromine and 2,6-diphenylanthracene (DPA), we successfully constructed and characterized the large-area 2D chiral networks on Ag(111) and Cu(111) surfaces by combining molecular beam epitaxy with scanning tunneling microscopy. The Br atoms distribute themselves periodically in the network with the maximum number of -C-H···Br hydrogen bonds. Density functional theory calculations demonstrate that the hydrogen bonds contribute to the stability of the Br-organic networks.