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 superlattices1-9. However, the interfacial vibrations that affect the phonon-mediated properties, such as thermal conductivity10,11, are measured using macroscopic techniques that lack spatial resolution. Although it is accepted that intrinsic phonons change near boundaries12,13, the physical mechanisms and length scales through which interfacial effects influence materials remain unclear. Here we demonstrate the localized vibrational response of interfaces in strontium titanate-calcium titanate superlattices by combining advanced scanning transmission electron microscopy imaging and spectroscopy, density functional theory calculations and ultrafast optical spectroscopy. Structurally diffuse interfaces that bridge the bounding materials are observed and this local structure creates phonon modes that determine the global response of the superlattice once the spacing of the interfaces approaches the phonon spatial extent. Our results provide direct visualization of the progression of the local atomic structure and interface vibrations as they come to determine the vibrational response of an entire superlattice. Direct observation of such local atomic and vibrational phenomena demonstrates that their spatial extent needs to be quantified to understand macroscopic behaviour. Tailoring interfaces, and knowing their local vibrational response, provides a means of pursuing designer solids with emergent infrared and thermal responses.

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. Here we demonstrate that, with improved instrument stability and sensitivity, the specific vibrational signals of the same substitutional impurity and the neighbouring carbon atoms in monolayer graphene with different chemical-bonding configurations are clearly resolved, complementary with density functional theory calculations. The present work opens the door to the direct observation of local phonon modes with chemical-bonding sensitivity, and provides more insights into the defect-induced physics in graphene.

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. The SS wavelength and stability can be tuned by doping and uniaxial strain. The SS-state band gap is larger by 0.6 eV compared to the gap of both the ferromagnetic and antiferromagnetic state, enabling bandgap tuning and possibly an unusual formation of quantum wells in a single material via magnetic-field manipulation. The SS-induced out-of-plane ferroelectricity enables switching of the SS chirality by an electric field. Finally, forming heterostructures, for example, with graphene or boron nitride, maintains SS ordering and provides another method of modulation and a potential for magnetoelectric devices.

Effects of Ion Energy and Density on the Plasma Etching-Induced Surface Area, Edge Electrical Field, and Multivacancies in MoSe2 Nanosheets for Enhancement of the Hydrogen Evolution Reaction.

Plasma functionalization can increase the efficiency of MoSe2 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 MoSe2 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-2 and Tafel slope of 51.6 mV dec-1 after the plasma treatment using a power of 20 W. The interactions between the plasma and catalyst during etching and vacancies generation are evaluated by plasma simulation. Finite element and first-principles density functional theory calculations are also conducted and the results are consistent with the experimental results, indicating that the improved HER catalytic activity stems from the enhanced electric field and more active sites on the catalyst, and reduced bandgap and adsorption energy arising from the etched through-holes and vacancies, respectively. The results convey new fundamental knowledge about the plasma effects and means to enhance the efficiency of catalysts in water splitting as well insights into the design of high-performance HER catalysts.

Spontaneous Formation of 1D Pattern in Monolayer VSe2 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. Here we report the spontaneous formation of long-range, well-ordered 1D patterns in monolayer vanadium diselenide (VSe2) by a single annealing stage during growth. Atomic-resolution images in real space combined with density-functional-theory (DFT) calculations reveal the 1D features of patterned VSe2. Further experimental characterization of the intermediate states in the growth process confirm the spontaneous formation of the 1D pattern by annealing-induced Se-deficient linear defects. The 1D pattern can be reversibly transformed to homogenous VSe2 monolayer by reintroducing Se atoms. Moreover, additional experiments demonstrate that a dispersive deposition of Pt atoms along the 1D structures of patterned VSe2 is achieved, while DFT calculations find that their catalytic activity for hydrogen evolution reaction (HER) is as good as that of Pt surfaces. The formation of long-range, well-ordered 1D patterns not only demonstrates an effective way of dimension modulation in 2D materials but also enriches the potential of intrinsically patterned 2D materials for promising catalytic activities.

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. Here, we analyze experimental spectra of single organic molecules on metal surfaces at ∼4 K, which often exhibit a pronounced dip. We show that measurements on iron(II) [tetra-(pentafluorophenyl)]porphyrin resolve this single dip at 4 K into a series of step-shaped inelastic excitations at 0.4 K. Via extensive spectral maps under applied magnetic fields and corresponding theoretical analysis we find that the dip is due to ultralow-energy vibrations of the molecular frame, typically in the range below 20 meV. The result indicates that ultralow energy vibrations in organic molecules are much more common than currently thought and may be all-pervasive for molecules above a certain size.

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-C3 and Si-C4, to examine atom-projected phonon densities of states and display the atomic-displacement patterns for select modes that are dominated by impurity displacements. The vortices are driven by large displacements of the impurities, and reflect local symmetries. Similar vortices are found at phosphorus impurities in hexagonal boron nitride, suggesting that they may be a feature of heavy impurities in crystalline materials. Phonon vortices at defects are expected to play a role in thermal conductivity and other properties.

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. Interfaces play an important role in the vibrational properties of materials, where interface states enhance thermal conductivity and can generate unique infrared-optical activity. The nonequivalence of the corresponding interface atomic vibrations, however, is not investigated so far due to a lack of experimental techniques with both high spatial and high spectral resolution. Herein, the nonequivalence of AlN-(Al0.65Ga0.35)N and (Al0.65Ga0.35)N-AlN interface vibrations is experimentally demonstrated using monochromated electron energy-loss spectroscopy in the scanning transmission electron microscope (STEM-EELS) and density-functional-theory (DFT) calculations are employed to gain insights in the physical origins of observations. It is demonstrated that STEM-EELS possesses sensitivity to the displacement vector of the vibrational modes as well as the frequency, which is as critical to understanding vibrations as polarization in optical spectroscopies. The combination enables direct mapping of the nonequivalent interface phonons between materials with different phonon polarizations. The results demonstrate the capacity to carefully assess the vibrational properties of complex heterostructures where interface states dominate the functional properties.