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Boron nitride nanotubes (BNNTs) are an emerging class of molecular container offering new functionalities and possibilities for studying molecules at the nanoscale. Herein, BNNTs are demonstrated as highly effective nanocontainers for polyoxometalate (POM) molecules. The encapsulation of POMs within BNNTs occurs spontaneously at room temperature from an aqueous solution, leading to the self-assembly of a POM@BNNT host-guest system. Analysis of the interactions between the hostnanotube and guest-molecule indicate that Lewis acid-base interactions between W=O groups of the POM (base) and B atoms of the BNNT lattice (acid) likely play a major role in driving POM encapsulation, with photoactivated electron transfer from BNNTs to POMs in solution also contributing to the process. The transparent nature of the BNNT nanocontainer allows extensive investigation of the guest-molecules by photoluminescence, Raman, UV-vis absorption, and EPR spectroscopies. These studies revealed considerable energy and electron transfer processes between BNNTs and POMs, likely mediated via defect energy states of the BNNTs and resulting in the quenching of BNNT photoluminescence at room temperature, the emergence of new photoluminescence emissions at cryogenic temperatures (<100 K), a photochromic response, and paramagnetic signals from guest-POMs. These phenomena offer a fresh perspective on host-guest interactions at the nanoscale and open pathways for harvesting the functional properties of these hybrid systems.

Magnon diffuse scattering (MDS) signals could, in principle, be studied with high spatial resolution in scanning transmission electron microscopy (STEM), thanks to recent technological progress in electron energy-loss spectroscopy. However, detecting MDS signals in STEM is technically challenging due to their overlap with the much stronger thermal diffuse scattering (TDS) signals. In bcc Fe at 300 K, MDS signals greater than or comparable to TDS signals have been predicted to occur under the central Bragg disk, well into a currently inaccessible energy-loss region. Therefore, to successfully detect MDS in STEM, it is necessary to identify conditions in which TDS and MDS signals can be distinguished from one another in regions outside the central Bragg disk. Temperature may be a key factor due to the distinct thermal signatures of magnon and phonon signals. In this work, we present a study on the effects of temperature on MDS and TDS in bcc Fe-considering a detector outside the central Bragg disk and a fixed convergent electron probe-using the frozen phonon and frozen magnon multislice methods. Our study reveals that neglecting the effects of atomic vibrations causes the MDS signal to grow approximately linearly up to the Curie temperature of Fe, after which it exhibits less variation. The MDS signal displays an alternating behavior due to dynamical diffraction, instead of increasing monotonically as a function of thickness. The inclusion of the effects of atomic vibrations through a complex atomic electrostatic potential causes the linear growth of the MDS signal to change to a nonlinear behavior that exhibits a predominant peak for a sample of thickness 16.072 nm at 1100 K. In contrast, the TDS signal grows more linearly than the MDS signal through the studied temperature range but still exhibits appreciable dynamical diffraction effects. An analysis of the signal-to-noise ratio (SNR) shows that the MDS signal can be a statistically significant contribution to the

The microstructural evolution of Cu(In,Ga)Se₂ absorber layers during a three-stage-type co-evaporation process was studied to elucidate the effect of a Cu-rich stage on the formation of extended structural defects. Defect densities for two Cu-poor samples, one interrupted before and one after this crucial Cu-rich composition stage, were investigated by scanning transmission electron microscopy (STEM) imaging. The structure and chemical nature of individual defects were investigated by aberration-corrected high-resolution STEM in combination with electron energy-loss spectroscopy on the atomic-scale. In spite of the different defect densities between the two samples, most of the individual defects exhibited similar chemistry. In particular, the elemental distributions of atomic columns at {112} twin planes, which are very frequent in Cu(In,Ga)Se₂ thin films, were found to be the same as in the defect-free grain interiors. In contrast, within grain boundaries, dislocation cores, and other structurally more complex defects, elemental redistributions of Cu and In were observed.

Single-atom catalytic sites may have existed in all supported transition metal catalysts since their first application. Yet, interest in the design of single-atom heterogeneous catalysts (SACs) only really grew when advances in transmission electron microscopy (TEM) permitted direct confirmation of metal site isolation. While atomic-resolution imaging remains a central characterization tool, poor statistical significance, reproducibility, and interoperability limit its scope for deriving robust characteristics about these frontier catalytic materials. Here, we introduce a customized deep-learning method for automated atom detection in image analysis, a rate-limiting step toward high-throughput TEM. Platinum atoms stabilized on a functionalized carbon support with a challenging irregular three-dimensional morphology serve as a practically relevant test system with promising scope in thermo- and electrochemical applications. The model detects over 20,000 atomic positions for the statistical analysis of important properties for establishing structure–performance relations over nanostructured catalysts, like the surface density, proximity, clustering extent, and dispersion uniformity of supported metal species. Good performance obtained on direct application of the model to an iron SAC based on carbon nitride demonstrates its generalizability for single-atom detection on carbon-related materials. The approach establishes a route to integrate artificial intelligence into routine TEM workflows. It accelerates image processing times by orders of magnitude and reduces human bias by providing an uncertainty analysis that is not readily quantifiable in manual atom identification, improving standardization and scalability., S.M., D.F.A., J.P.-R., and N.L. acknowledge funding from NCCR Catalysis (180544), a National Centre of Competence in Research funded by the Swiss National Science Foundation. S.M.C. acknowledges support from a University Academic Fellowship at the University of Leeds and the Diamond Light Source, U.K. for access and support in the use of the electron Physical Science Imaging Centre (EM17997). SuperSTEM is the U.K. National Research Facility for Advanced Electron Microscopy, supported by the Engineering and Physical Sciences Research Council., Peer Reviewed, Postprint (author's final draft)

Ultrananocrystalline diamond (UNCD) film is a crystalline diamond film consisting of 3-5 nm randomly oriented diamond crystallites surrounded by 0.2-0.3 nm wide grain. These films possess exemplary mechanical, electronic and optical properties. Under normal process conditions, these UNCD films are highly electrically insulating, but they can become highly conducting when Ar is substituted in the synthesis gas with some N2. In this contribution, we have revisited, using aberration corrected microscopes and combining HR(S)TEM and EELS, the structure and local composition of these n-type UNCD films. n-type UNCD films are composed of elongated diamond nanocrystals (called nanowires (NWs)). The formation of these NWs is initiated when the N2 content in the gas phase reaches about 10% in volume. From these studies, we concluded that the insulator-metal transition of these films is strongly correlated with the formation of these diamond NWs. Indeed, these NWs are enveloped by a sp2-based carbon layer that seems to provide the conductive path for electrons. Thus, here we will present the atomic structure studies and local EELS analyses developed on these complex films. These results show where the nitrogen is located into these nanostructures and provide insights into their atomic configuration. These aspects provide very important information about the role played by nitrogen in the formation of such nano-objects. In summary, these studies elucidate crucial questions concerning the local composition (atomic configuration) of these materials. This detailed knowledge is essential for better understanding the outstanding properties of such materials as well as for shedding light on their growth mechanism.

The role of local chemical environments in the electron energy loss spectra of complex multiferroic oxides was studied using computational and experimental techniques. The evolution of the O K-edge across an interface between bismuth ferrite (BFO) and lanthanum strontium manganate (LSMO) was considered through spectral averaging over crystallographically equivalent positions to capture the periodicity of the local O environments. Computational techniques were used to investigate the contribution of individual atomic environments to the overall spectrum, and the role of doping and strain was considered. Chemical variation, even at the low level, was found to have a major impact on the spectral features, whereas strain only induced a small chemical shift to the edge onset energy. Through a combination of these methods, it was possible to explain experimentally observed effects such as spectral flattening near the interface as the combination of spectral responses from multiple local atomic environments., Peer Reviewed, Postprint (published version)

Zinc phosphide (Zn3P2) nanowires constitute prospective building blocks for next generation solar cells due to the combination of suitable optoelectronic properties and an abundance of the constituting elements in the Earth's crust. The generation of periodic superstructures along the nanowire axis could provide an additional mechanism to tune their functional properties. Here we present the vapour–liquid–solid growth of zinc phosphide superlattices driven by periodic heterotwins. This uncommon planar defect involves the exchange of Zn by In at the twinning boundary. We find that the zigzag superlattice formation is driven by reduction of the total surface energy of the liquid droplet. The chemical variation across the heterotwin does not affect the homogeneity of the optical properties, as measured by cathodoluminescence. The basic understanding provided here brings new propsects on the use of II–V semiconductors in nanowire technology.

We present a theory and a simulation of diffuse scattering due to the excitation of magnons in scanning transmission electron microscopy. The calculations indicate that magnons can present atomic contrast when detected by electron energy-loss spectroscopy using atomic-size electron beams. The results presented here indicate that the intensity of the magnon diffuse scattering in bcc iron at 300 K is 4 orders of magnitude weaker than the intensity of thermal diffuse scattering arising from atomic vibrations.

Layered metal/dielectric hyperbolic metamaterials (HMMs) support a wide landscape of plasmon polariton excitations. In addition to surface plasmon polaritons, coupled Bloch-like gap-plasmon polaritons with high modal confinement inside the multilayer are supported. Photons can excite only a subset of these polaritonic modes, typically with a limited energy and momentum range in respect to the wide set of high-K modes supported by hyperbolic dispersion media, and coupling with gratings or local excitation is necessary. Strikingly, electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope allows nm-scale local excitation and mapping of the spatial field distribution of all the modes supported by a photonic or plasmonic structure, both bright and dark, and also all other inelastic interactions of the beam, including phonons and interband transitions. Herein, experimental evidence of the spatial distribution of plasmon polaritons in multilayered type II HMM nanostructures is acquired with an aloof electron beam adjacent to structures of current interest. HMM pillars are useful for their separation and adjustability of optical scattering and absorption, while HMM slot cavities can be used as waveguides with high field confinement. The nature of the modes is confirmed with corresponding simulations of EEL and optical spectra and near-field intensities.

The growth of compound semiconductors on silicon has been widely sought after for decades, but reliable methods for defect-free combination of these materials have remained elusive. Recently, interconnected GaAs nanoscale membranes have been used as templates for the scalable integration of nanowire networks on III-V substrates. Here, we demonstrate how GaAs nanoscale membranes can be seamlessly integrated on silicon by controlling the density of nuclei in the initial stages of growth. We also correlate the absence or presence of defects with the existence of a single or multiple nucleation regime for the single membranes. Certain defects exhibit well-differentiated spectroscopic features that we identify with cathodoluminescence and micro-photoluminescence techniques. Overall, this work presents a new approach for the seamless integration of compound semiconductors on silicon.

The nature of the liquid–solid interface determines the characteristics of a variety of physical phenomena, including catalysis, electrochemistry, lubrication, and crystal growth. Most of the established models for crystal growth are based on macroscopic thermodynamics, neglecting the atomistic nature of the liquid–solid interface. Here, experimental observations and molecular dynamics simulations are employed to identify the 3D nature of an atomic‐scale ordering of liquid Ga in contact with solid GaAs in a nanowire growth configuration. An interplay between the liquid ordering and the formation of a new bilayer is revealed, which, contrary to the established theories, suggests that the preference for a certain polarity and polytypism is influenced by the atomic structure of the interface. The conclusions of this work open new avenues for the understanding of crystal growth, as well as other processes and systems involving a liquid–solid interface.

Atom-thin transition metal dichalcogenides (TMDs) have emerged as fascinating materials and key structures for electrocatalysis. So far, their edges, dopant heteroatoms and defects have been intensively explored as active sites for the hydrogen evolution reaction (HER) to split water. However, grain boundaries (GBs), a key type of defects in TMDs, have been overlooked due to their low density and large structural variations. Here, we demonstrate the synthesis of wafer-size atom-thin TMD films with an ultra-high-density of GBs, up to ~1012 cm−2. We propose a climb and drive 0D/2D interaction to explain the underlying growth mechanism. The electrocatalytic activity of the nanograin film is comprehensively examined by micro-electrochemical measurements, showing an excellent hydrogen-evolution performance (onset potential: −25 mV and Tafel slope: 54 mV dec−1), thus indicating an intrinsically high activation of the TMD GBs.

Single-atom B or N substitutional doping in single-layer suspended graphene, realized by low-energy ion implantation, is shown to induce a dampening or enhancement of the characteristic interband π plasmon of graphene through a high-resolution electron energy loss spectroscopy study using scanning transmission electron microscopy. A relative 16% decrease or 20% increase in the π plasmon quality factor is attributed to the presence of a single substitutional B or N atom dopant, respectively. This modification is in both cases shown to be relatively localized, with data suggesting the plasmonic response tailoring can no longer be detected within experimental uncertainties beyond a distance of approximately 1 nm from the dopant. Ab initio calculations confirm the trends observed experimentally. Our results directly confirm the possibility of tailoring the plasmonic properties of graphene in the ultraviolet waveband at the atomic scale, a crucial step in the quest for utilizing graphene's properties toward the development of plasmonic and optoelectronic devices operating at ultraviolet frequencies.

peer-reviewed, Formic acid is a valuable chemical derived from biomass, as it has a high hydrogen-storage capacity and appears to be an attractive source of hydrogen for various applications. Hydrogen production via formic acid decomposition is often based on using supported catalysts with Pt-group metal nanoparticles. In the present paper, we show that the decomposition of the acid proceeds more rapidly on single metal atoms (by up to 1 order of magnitude). These atoms can be obtained by rather simple means through anchoring Pt-group metals onto mesoporous N-functionalized carbon nanofibers. A thorough evaluation of the structure of the active site by aberration-corrected scanning transmission electron microscopy (ac-STEM) in high-angle annular dark field (HAADF) mode and by CO chemisorption, X-ray photoelectron spectroscopy (XPS), and quantum chemical calculations reveals that the metal atom is coordinated by a pair of pyridinic nitrogen atoms at the edge of graphene sheets. The chelate binding provides an ionic/electron-deficient state of these atoms that prevents their aggregation and thereby leads to an excellent stability under the reaction conditions. Catalysts with single atoms have also shown very high selectivity. Evidently, the findings can be extended to hydrogen production from other chemicals and can be helpful for improving other energy-related and environmentally benign catalytic processes., ACCEPTED, peer-reviewed

Excitons and plasmons are the two most fundamental types of collectiveelectronic excitations occurring in solids. Traditionally, they have beenstudied separately using bulk techniques that probe their average energeticstructure over large spatial regions. However, as the dimensions of materialsand devices continue to shrink, it becomes crucial to understand how theseexcitations depend on local variations in the crystal- and chemical structureon the atomic scale. Here we use monochromated low-lossscanning-transmission-electron-microscopy electron-energy-loss (LL-STEM-EEL)spectroscopy, providing the best simultaneous energy and spatial resolutionachieved to-date to unravel the full set of electronic excitations in few-layerMoS2 nanosheets over a wide energy range. Using first-principles many-bodycalculations we confirm the excitonic nature of the peaks at ~2eV and ~3eV inthe experimental EEL spectrum and the plasmonic nature of higher energy-losspeaks. We also rationalise the non-trivial dependence of the EEL spectrum onbeam and sample geometry such as the number of atomic layers and distance tosteps and edges. Moreover, we show that the excitonic features are dominated bythe long wavelength (q=0) components of the probing field, while the plasmonicfeatures are sensitive to a much broader range of q-vectors, indicating aqualitative difference in the spatial character of the two types of collectiveexcitations. Our work provides a template protocol for mapping the local natureof electronic excitations that open new possibilities for studyingphoto-absorption and energy transfer processes on a nanometer scale.

The vacancy ordering behavior of an A-site deficient perovskite system, Ca1-xLa2x/3TiO3, was studied using atomic resolution scanning transmission electron microscopy (STEM) in conjunction with electron energy-loss spectroscopy (EELS), with the aim of determining the role of A-site composition changes. At low La content (x = 0.2), adopting Pbnm symmetry, there was no indication of long-range ordering. Domains, with clear boundaries, were observed in bright-field (BF) imaging, but were not immediately visible in the corresponding high-angle annular dark-field (HAADF) image. These boundaries, with the aid of displacement maps from A-site cations in the HAADF signal, are shown to be tilt boundaries. At the La-rich end of the composition (x = 0.9), adopting Cmmm symmetry, long-range ordering of vacancies and La3+ ions was observed, with alternating La-rich and La-poor layers on (001)p planes, creating a double perovskite lattice along the c axis. These highly ordered domains can be found isolated within a random distribution of vacancies/La3+, or within a large population, encompassing a large volume. In regions with a high number density of double perovskite domains, these highly ordered domains were separated by twin boundaries, with 90° or 180° lattice rotations across boundaries. The occurrence and characteristics of these ordered structures are discussed and compared with similar perovskite systems.

peer-reviewed, Supporting information for this article can be found on second file., Herein, we report the formation of multisegment Si-Ge axial heterostructure nanowires in a wet chemical synthetic approach. These nanowires are grown by the liquid injection of the respective silicon and germanium precursors into the vapor phase of an organic solvent in which a tin-coated stainless steel substrate is placed. The Si-Ge transition is obtained by sequential injection with the more difficult Ge-Si transition enabled by inclusion of a quench sequence in the reaction. This approach allows for alternating between pure Si and pure Ge segments along the entire nanowire length with good control of the respective segment dimensions. The multisegment heterostructure nanowires presented are Ge Si, Si Ge Si, Ge-Si-Ge, Si-Ge-Si-Ge, and Si-Ge-Si-Ge-Si-Ge. The interfacial abruptness of the Ge to Si interface is also determined through the use of aberration corrected scanning transmission electron microscopy and electron energy loss spectroscopy., ACCEPTED, peer-reviewed

Although Li- and Mn-rich transition metal oxides have been extensively studied as high-capacity cathode materials for Li-ion batteries, the crystal structure of these materials in their pristine state is not yet fully understood. Here we apply complementary electron microscopy and spectroscopy techniques at multi-length scale on well-formed Li1.2(Ni0.13Mn0.54Co0.13)O2 crystals with two different morphologies as well as two commercially available materials with similar compositions, and unambiguously describe the structural make-up of these samples. Systematically observing the entire primary particles along multiple zone axes reveals that they are consistently made up of a single phase, save for rare localized defects and a thin surface layer on certain crystallographic facets. More specifically, we show the bulk of the oxides can be described as an aperiodic crystal consisting of randomly stacked domains that correspond to three variants of monoclinic structure, while the surface is composed of a Co- and/or Ni-rich spinel with antisite defects.

Thin-film oxide heterostructures show great potential for use in spintronic memories, where electronic charge and spin are coupled to transport information. Here we use a La0.7Sr0.3MnO3 (LSMO)/PbZr0.2Ti0.8O3 (PZT) model system to explore how local variations in electronic and magnetic phases mediate this coupling. We present direct, local measurements of valence, ferroelectric polarization and magnetization, from which we map the phases at the LSMO/PZT interface. We combine these experimental results with electronic structure calculations to elucidate the microscopic interactions governing the interfacial response of this system. We observe a magnetic asymmetry at the LSMO/PZT interface that depends on the local PZT polarization and gives rise to gradients in local magnetic moments; this is associated with a metal-insulator transition at the interface, which results in significantly different charge-transfer screening lengths. This study establishes a framework to understand the fundamental asymmetries of magnetoelectric coupling in oxide heterostructures.

Magnetoelectric oxide heterostructures are proposed active layers for spintronic memory and logic devices, where information is conveyed through spin transport in the solid state. Incomplete theories of the coupling between local strain, charge, and magnetic order have limited their deployment into new information and communication technologies. In this study, we report direct, local measurements of strain- and charge-mediated magnetization changes in the La0.7Sr0.3MnO3/PbZr0.2Ti0.8O3 system using spatially resolved characterization techniques in both real and reciprocal space. Polarized neutron reflectometry reveals a graded magnetization that results from both local structural distortions and interfacial screening of bound surface charge from the adjacent ferroelectric. Density functional theory calculations support the experimental observation that strain locally suppresses the magnetization through a change in the Mn-eg orbital polarization. We suggest that this local coupling and magnetization suppression may be tuned by controlling the manganite and ferroelectric layer thicknesses, with direct implications for device applications.

We investigated the structure of the tungsten bronze barium neodymium titanates Ba6-3nNd8+2nTi18O54, which are exploited as microwave dielectric ceramics. They form a complex nanostructure, which resembles a nanofilm with stacking layers of ∼12 Å thickness. The synthesized samples of Ba6-3nNd8+2nTi18O54 (n = 0, 0.3, 0.4, 0.5) are characterized by pentagonal and tetragonal columns, where the A cations are distributed in three symmetrically inequivalent sites. Synchrotron X-ray diffraction and electron energy loss spectroscopy allowed for quantitative analysis of the site occupancy, which determines the defect distribution. This is corroborated by density functional theory calculations. Pentagonal columns are dominated by Ba, and tetragonal columns are dominated by Nd, although specific Nd sites exhibit significant concentrations of Ba. The data indicated significant elongation of the Ba columns in the pentagonal positions and of the Nd columns in tetragonal positions involving a zigzag arrangement of atoms along the b lattice direction. We found that the preferred Ba substitution occurs at Nd[3]/[4] followed by Nd[2] and Nd[1]/[5] sites, which is significantly different to that proposed in earlier studies. Our results on the Ba6-3nNd8+2nTi18O54 "perovskite" superstructure and its defect distribution are particularly valuable in those applications where the optimization of material properties of oxides is imperative; these include not only microwave ceramics but also thermoelectric materials, where the nanostructure and the distribution of the dopants will reduce the thermal conductivity.

peer-reviewed, Herein, we report a novel approach to form axial heterostructure nanowires composed of linearly distinct Ni silicide (Ni2Si) and Si segments via a one-pot solution synthesis method. Initially, Si nanowires are grown using Au seeds deposited on a Ni substrate with the Si delivery in the solution phase using a liquid phenylsilane precursor. Ni silicide then forms axially along the wires through progressive Ni diffusion from the growth substrate, with a distinct transition between the silicide and pure Si segments. The interfacial abruptness and chemical composition of the heterostructure nanowires was analysed through transmission electron microscopy, electron diffraction, energy dispersive X-ray spectroscopy, aberration corrected scanning transmission electron microscopy and atomically resolved electron energy loss spectroscopy. The method represents a versatile approach for the formation of complex axial NW heterostructures and could be extended to other metal silicide or analogous metal germanide systems.

The origin of photoluminescence in copper indium sulfide (CIS) quantum dots (Qdots) has previously been ascribed to a donor–acceptor pair (DAP) recombination, with a crystal lattice defect implicated as the origin of the donor state. In this study, electron energy-loss spectroscopy (EELS) was used to observe defect-rich compositional domains within individual CIS Qdots, supporting a model of defect-state-mediated photoluminescence for these particles, and identifying them as an ideal model system for future study of lattice defects on Qdot properties.