Excitonic Effects in Energy-Loss Spectra of Freestanding Graphene.

In this work, we perform electron energy-loss spectroscopy (EELS) of freestanding graphene with high energy and momentum resolution to disentangle the quasielastic scattering from the excitation gap of Dirac electrons close to the optical limit. We show the importance of many-body effects on electronic excitations at finite transferred momentum by comparing measured EELS to ab initio calculations at increasing levels of theory. Quasi-particle corrections and excitonic effects are addressed within the GW approximation and the Bethe-Salpeter equation, respectively. Both effects are essential in the description of the EEL spectra to obtain a quantitative agreement with experiments, with the position, dispersion, and shape of both the excitation gap and the π plasmon being significantly affected by excitonic effects.

Direct Observation of Locally Modified Excitonic Effects within a Moiré Unit Cell in Twisted Bilayer Graphene.

Bilayer graphene, which forms moiré superlattices, possesses distinct electronic and optical properties owing to its hybridized energy band and the emergence of van Hove singularities depending on its twist angle. Extensive research has been conducted on the global characteristics of moiré superlattices induced by their long-range periodicity. However, the local properties, which differ owing to the variations in the three-dimensional atomic arrangement, within a moiré unit cell have been rarely explored. In this study, we demonstrate the highly localized excitation of carbon 1s electrons to unoccupied van Hove singularities in twisted bilayer graphene by electron energy loss spectroscopy using a monochromated transmission electron microscope. The core-level excitations associated with the van Hove singularities exhibit a systematic twist-angle dependence analogous to optical excitations. Furthermore, local variations in the core-level van Hove singularity peaks, which can originate from the core-exciton lifetimes and band modifications corresponding to the local stacking geometry within a moiré unit cell, are unambiguously corroborated.

Imaging of isotope diffusion using atomic-scale vibrational spectroscopy.

The spatial resolutions of even the most sensitive isotope analysis techniques based on light or ion probes are limited to a few hundred nanometres. Although vibrational spectroscopy using electron probes has achieved higher spatial resolution1-3, the detection of isotopes at the atomic level4 has been challenging so far. Here we show the unambiguous isotopic imaging of 12C carbon atoms embedded in 13C graphene and the monitoring of their self-diffusion via atomic-level vibrational spectroscopy. We first grow a domain of 12C carbon atoms in a pre-existing crack of 13C graphene, which is then annealed at 600 degrees Celsius for several hours. Using scanning transmission electron microscopy-electron energy loss spectroscopy, we obtain an isotope map that confirms the segregation of 12C atoms that diffused rapidly. The map also indicates that the graphene layer becomes isotopically homogeneous over 100-nanometre regions after 2 hours. Our results demonstrate the high mobility of carbon atoms during growth and annealing via self-diffusion. This imaging technique can provide a fundamental methodology for nanoisotope engineering and monitoring, which will aid in the creation of isotope labels and tracing at the nanoscale.

Deciphering the Intense Postgap Absorptions of Monolayer Transition Metal Dichalcogenides.

Rich valleytronics and diverse defect-induced or interlayer pre-bandgap excitonics have been extensively studied in transition metal dichalcogenides (TMDCs), a system with fascinating optical physics. However, more intense high-energy absorption peaks (∼3 eV) above the bandgaps used to be long ignored and their underlying physical origin remains to be unveiled. Here, we employ momentum resolved electron energy loss spectroscopy to measure the dispersive behaviors of the valley excitons and intense higher-energy peaks at finite momenta. Combined with accurate Bethe-Salpeter equation calculations, non-band-nesting transitions at the Q valley and at the midpoint of KM are found to be responsible for the high-energy broad absorption peaks in tungsten dichalcogenides and present spin polarizations similar to A excitons, in contrast with the band-nesting mechanism in molybdenum dichalcogenides. Our experiment-theory joint research will offer insights into the physical origins and manipulation of the intense high-energy excitons in TMDC-based optoelectronic devices.

Toward Confined Carbyne with Tailored Properties.

Confining carbyne to a space that allows for stability and controlled reactivity is a very appealing approach to have access to materials with tunable optical and electronic properties without rival. Here, we show how controlling the diameter of single-walled carbon nanotubes opens the possibility to grow a confined carbyne with a defined and tunable band gap. The metallicity of the tubes has a minimal influence on the formation of the carbyne, whereas the diameter plays a major role in the growth. It has been found that the properties of confined carbyne can be tailored independently from its length and how these are mostly determined by its interaction with the carbon nanotube. Molecular dynamics simulations have been performed to interpret these findings. Furthermore, the choice of a single-walled carbon nanotube host has been proven crucial even to synthesize an enriched carbyne with the smallest energy gap currently reported and with remarkable homogeneity.

Probing Exciton Dispersions of Freestanding Monolayer WSe_{2} by Momentum-Resolved Electron Energy-Loss Spectroscopy.

Excitons, as bound electron-hole paired quasiparticle, play an essential role in the energy transport in the optical-electric properties of semiconductors. Their momentum-energy dispersion relation is a fundamental physical property of great significance to understand exciton dynamics. However, this dispersion is seldom explored especially in two-dimensional transition metal dichalcogenides with rich valleytronic properties. In this work, momentum resolved electron energy-loss spectroscopy was used to measure the dispersions of excitons in freestanding monolayer WSe_{2}. Besides the parabolically dispersed valley excitons, a subgap dispersive exciton was observed at nonzero momenta for the first time, which can be introduced by the prolific Se vacancies. Our work provides a paradigm to directly probe exciton dispersions in 2D semiconductors and could be generalized to many low-dimensional systems.

Position and momentum mapping of vibrations in graphene nanostructures.

Propagating atomic vibrational waves-phonons-determine important thermal, mechanical, optoelectronic and transport characteristics of materials. Thus a knowledge of phonon dispersion (that is, the dependence of vibrational energy on momentum) is a key part of our understanding and optimization of a material's behaviour. However, the phonon dispersion of a free-standing monolayer of a two-dimensional material such as graphene, and its local variations, have remained elusive for the past decade because of the experimental limitations of vibrational spectroscopy. Even though electron energy loss spectroscopy (EELS) in transmission has recently been shown to probe local vibrational charge responses1-4, such studies are still limited by momentum space integration due to the focused beam geometry; they are also restricted to polar materials such as boron nitride or oxides1-4, in which huge signals induced by strong dipole moments are present. On the other hand, measurements on graphene performed by inelastic X-ray (neutron) scattering spectroscopy5-7 or EELS in reflection8,9 do not have any spatial resolution and require large microcrystals. Here we provide a new pathway to determine phonon dispersions down to the scale of an individual free-standing graphene monolayer by mapping the distinct vibrational modes for a large momentum transfer. The measured scattering intensities are accurately reproduced and interpreted with density functional perturbation theory10. Additionally, a nanometre-scale mapping of selected momentum-resolved vibrational modes using graphene nanoribbon structures has enabled us to spatially disentangle bulk, edge and surface vibrations. Our results are a proof-of-principle demonstration of the feasibility of studying local vibrational modes in two-dimensional monolayer materials at the nanometre scale.

Layer Rotation-Angle-Dependent Excitonic Absorption in van der Waals Heterostructures Revealed by Electron Energy Loss Spectroscopy.

Heterostructures comprising van der Waals (vdW) stacked transition metal dichalcogenide (TMDC) monolayers are a fascinating class of two-dimensional (2D) materials. The presence of interlayer excitons, where the electron and the hole remain spatially separated in the two layers due to ultrafast charge transfer, is an intriguing feature of these heterostructures. The optoelectronic functionality of 2D heterostructure devices is critically dependent on the relative rotation angle of the layers. However, the role of the relative rotation angle of the constituent layers on intralayer absorption is not clear yet. Here, we investigate MoS2/WSe2 vdW heterostructures using monochromated low-loss electron energy loss (EEL) spectroscopy combined with aberration-corrected scanning transmission electron microscopy and report that momentum conservation is a critical factor in the intralayer absorption of TMDC vdW heterostructures. The evolution of the intralayer excitonic low-loss EEL spectroscopy peak broadenings as a function of the rotation angle reveals that the interlayer charge transfer rate can be about an order of magnitude faster in the aligned (or anti-aligned) case than in the misaligned cases. These results provide a deeper insight into the role of momentum conservation, one of the fundamental principles governing charge transfer dynamics in 2D vdW heterostructures.

Direct Proof of a Defect-Modulated Gap Transition in Semiconducting Nanotubes.

Measurements of optical properties at a nanometer level are of central importance for the characterization of optoelectronic devices. It is, however, difficult to use conventional light-probe measurements to determine the local optical properties from a single quantum object with nanometrical inhomogeneity. Here, we successfully measured the optical gap transitions of an individual semiconducting carbon nanotube with defects by using a monochromated electron source as a probe. The optical conductivity extracted from an electron energy-loss spectrum for a certain type of defect presents a characteristic modification near the lowest excitation peak ( E11), where excitons and nonradiative transitions, as well as phonon-coupled excitations, are strongly involved. Detailed line-shape analysis of the E11 peak clearly shows different degrees of exciton lifetime shortening and electronic state modification according to the defect type.

Cation-mixing stabilized layered oxide cathodes for sodium-ion batteries.

Sodium-ion batteries are promising for large-scale energy storage due to sodium's low cost and infinite abundance. The most popular cathodes for sodium-ion batteries, i.e., the layered sodium-containing oxides, usually exhibit reversible host rearrangement between P-type and O-type stacking upon charge/discharge. Herein we demonstrate that such host rearrangement is unfavorable and can be suppressed by introducing transition-metal ions into sodium layers. The electrode with stabilized P3-type stacking delivers superior rate capability, high energy efficiency, and excellent cycling performance. Owing to the cation-mixing nature, it performs the lowest lattice strain among all reported cathodes for sodium-ion batteries. Our findings highlight the significance of a stable host for sodium-ion storage and moreover underline the fundamental distinction in material design strategy between lithium- and sodium-ion batteries.

Structural Distortions and Charge Density Waves in Iodine Chains Encapsulated inside Carbon Nanotubes.

Atomic chains are perfect systems for getting fundamental insights into the electron dynamics and coupling between the electronic and ionic degrees of freedom in one-dimensional metals. Depending on the band filling, they can exhibit Peierls instabilities (or charge density waves), where equally spaced chain of atoms with partially filled band is inherently unstable, exhibiting spontaneous distortion of the lattice that further leads to metal-insulator transition in the system. Here, using high-resolution scanning transmission electron microscopy, we directly image the atomic structures of a chain of iodine atoms confined inside carbon nanotubes. In addition to long equidistant chains, the ones consisting of iodine dimers and trimers were also observed, as well as transitions between them. First-principles calculations reproduce the experimentally observed bond lengths and lattice constants, showing that the ionic movement is largely unconstrained in the longitudinal direction, while naturally confined by the nanotube in the lateral directions. Moreover, the trimerized chain bears the hallmarks of a charge density wave. The transition is driven by changes in the charge transfer between the chain and the nanotube and is enabled by the charge compensation and additional screening provided by the nanotube.

Single-atom detection of light elements: Imaging or spectroscopy?

Single-atom imaging and spectroscopy at a lower accelerating voltage (~60kV) has been largely facilitated by the development of aberration correctors for transmission electron microscopy (TEM)/ scanning TEM (STEM). Such an STEM condition will reduce beam damage and has therefore been demonstrated capable of detecting individual atoms of light elements including B, C, and N in mono-layered materials. However, other light elements such as Li, O, or F are still difficult to visualise as individual atoms by using conventional STEM/TEM imaging because their extremely weak contrast can be often smeared out by the other atoms nearby. In this paper, we demonstrate the successful detection of these 'hardly visible' atoms in the spectroscopy mode.

Electron Spectroscopy of Single Quantum Objects To Directly Correlate the Local Structure to Their Electronic Transport and Optical Properties.

Physical property of a single quantum object is governed by its precise atomic arrangement. The direct correlation of localized physical properties with the atomic structures has been therefore strongly desired but still limited in the theoretical studies. Here, we have successfully examined the localized electronic properties of individual carbon nanotubes by means of high-resolution electron energy-loss spectroscopy combined with high-resolution transmission electron microscopy. Well-separated sharp peaks at the carbon K(1s) absorption edge and in the valence-loss spectra are obtained from a single freestanding carbon nanotube with the local chiral index and unambiguously identified as the transitions between the van Hove singularities. The spectra features clearly vary upon the different areas even in the individual carbon nanotube. Variations in interband transitions, plasmonic behaviors, and unoccupied electronic structures are clearly attributed to the local irregular atomic arrangement such as topological defect and/or elastic bond stretching.

Single-atom electron energy loss spectroscopy of light elements.

Light elements such as alkali metal (lithium, sodium) or halogen (fluorine, chlorine) are present in various substances and indeed play significant roles in our life. Although atomic behaviours of these elements are often a key to resolve chemical or biological activities, they are hardly visible in transmission electron microscope because of their smaller scattering power and higher knock-on probability. Here we propose a concept for detecting light atoms encaged in a nanospace by means of electron energy loss spectroscopy using inelastically scattered electrons. In this method, we demonstrate the single-atom detection of lithium, fluorine, sodium and chlorine with near-atomic precision, which is limited by the incident probe size, signal delocalization and atomic movement in nanospace. Moreover, chemical shifts of lithium K-edge have been successfully identified with various atomic configurations in one-dimensional lithium compounds.

Atomic structure and dynamic behaviour of truly one-dimensional ionic chains inside carbon nanotubes.

Materials with reduced dimensionality have attracted much interest in various fields of fundamental and applied science. True one-dimensional (1D) crystals with single-atom thickness have been realized only for few elemental metals (Au, Ag) or carbon, all of which showed very short lifetimes under ambient conditions. We demonstrate here a successful synthesis of stable 1D ionic crystals in which two chemical elements, one being a cation and the other an anion, align alternately inside carbon nanotubes. Unusual dynamical behaviours for different atoms in the 1D lattice are experimentally corroborated and suggest substantial interactions of the atoms with the nanotube sheath. Our theoretical studies indicate that the 1D ionic crystals have optical properties distinct from those of their bulk counterparts and that the properties can be engineered by introducing atomic defects into the chains.

Thermal/electron irradiation assisted coalescence of Sc3N@C80 fullerene in carbon nanotube and evidence of charge transfer between pristine/coalesced fullerenes and nanotubes.

Sc3N@C80 fullerenes are inserted inside carbon nanotubes (CNTs). The results show that the thermal stability of Sc3N@C80 fullerenes is around 1200 °C for the fullerenes resting on the wall of CNTs. Internal fullerenes show stability up to 1300 °C, which portrays them as one of most stable types of fullerenes. Electron irradiation of the peapods at 90 kV leads to the formation of capsules inside the CNTs at 5 × 10(9) e nm(-2) electron dosage. This value is an order of magnitude higher than the threshold of electron-induced damage in C60 molecules. Electron energy loss spectroscopy confirms the presence of Sc atoms in capsules. Encapsulation of fullerenes and capsule formation changes the oxidation state of Sc atoms from +2.5 towards +3. This is an evidence of charge transfer between the fullerene/capsule cage and CNT walls.