Atomic-Resolution Mapping of Localized Phonon Modes at Grain Boundaries.

Phonon scattering at grain boundaries (GBs) is significant in controlling the nanoscale device thermal conductivity. However, GBs could also act as waveguides for selected modes. To measure localized GB phonon modes, milli-electron volt (meV) energy resolution is needed with subnanometer spatial resolution. Using monochromated electron energy loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM) we have mapped the 60 meV optic mode across GBs in silicon at atomic resolution and compared it to calculated phonon densities of states (DOS). The intensity is strongly reduced at GBs characterized by the presence of 5- and 7-fold rings where bond angles differ from the bulk. The excellent agreement between theory and experiment strongly supports the existence of localized phonon modes and thus of GBs acting as waveguides.

Can Copper Nanostructures Sustain High-Quality Plasmons?

Silver, king among plasmonic materials, features low inelastic absorption in the visible-infrared (vis-IR) spectral region compared to other metals. In contrast, copper is commonly regarded as too lossy for actual applications. Here, we demonstrate vis-IR plasmons with quality factors >60 in long copper nanowires (NWs), as determined by electron energy-loss spectroscopy. We explain this result by noticing that most of the electromagnetic energy in these plasmons lies outside the metal, thus becoming less sensitive to inelastic absorption. Measurements for silver and copper NWs of different diameters allow us to elucidate the relative importance of radiative and nonradiative losses in plasmons spanning a wide spectral range down to <20 meV. Thermal population of such low-energy modes becomes significant and generates electron energy gains associated with plasmon absorption, rendering an experimental determination of the NW temperature. Copper is therefore emerging as an attractive, cheap, abundant material platform for high-quality plasmonics in elongated nanostructures.

Protein secondary structure signatures from energy loss spectra recorded in the electron microscope.

Infrared spectroscopy is a powerful technique for characterising protein structure. It is now possible to record energy losses corresponding to the infrared region in the electron microscope and to avoid damage by positioning the probe in the region adjacent to the structure being studied. Spectra from bacteriorhodopsin, a protein that is predominately a α helix, and OmpF porin, a protein that is mainly ß sheet show significant differences over a spectral range from ∼0.1 to 0.25 eV (∼1000 to 1800 cm-1 ). Although the energy resolution equivalent to 60 cm-1 is inferior to Fourier Transform InfraRed Spectroscopy (FTIR) the spectra are very sensitive to molecular orientation. Polar bonds aligned parallel to the specimen grid make particularly strong contributions to the energy loss spectra. Ultra-high-resolution energy loss spectroscopy in the electron microscope can potentially add useful information to imaging and diffraction for determining the secondary structure misfolding believed to be responsible for dementia diseases such as Alzheimer's.

Proteins are long linear molecular chains that when folded into complex three-dimensional shapes enable them to perform their biological functions. Infrared spectroscopy is a powerful technique for characterising protein folds, especially the proportions of helices and sheets that are significant building blocks in the overall structure. Traditionally, it was only possible to record infrared spectra from large amounts of material. In this paper, we show that it is possible to record the equivalent of the infrared spectrum from regions much smaller than a cell using a high-performance spectrometer coupled to electron microscopy. One great advantage is that the spectroscopic measurements can be combined with the standard high-resolution imaging and other characterisation techniques available in the electron microscope. We believe expansion of this method will impact diseases such as Alzheimer's, which are believed to be the results of an incorrect folding process. Our technique, where we combine infrared spectroscopic measurements with electron microscopy, could be invaluable in characterising the critical early stages of protein misfolding and/or assembly. This information will be invaluable in disease prognosis and the search for potential therapies.

Properties of Dipole-Mode Vibrational Energy Losses Recorded From a TEM Specimen.

The authors discuss the dipole vibrational modes that predominate in the energy-loss spectra of ionic materials below 1 eV, concentrating on thin-film specimens of typical transmission electron microscopy (TEM) thickness. The thickness dependence of the intensity is shown to be a useful guide to the bulk or surface character of vibrational peaks. The lateral and depth resolution of the energy-loss signal is investigated with the aid of finite-element calculations.

Direct Evidence of Lithium Ion Migration in Resistive Switching of Lithium Cobalt Oxide Nanobatteries.

Lithium cobalt oxide nanobatteries offer exciting prospects in the field of nonvolatile memories and neuromorphic circuits. However, the precise underlying resistive switching (RS) mechanism remains a matter of debate in two-terminal cells. Herein, intriguing results, obtained by secondary ion mass spectroscopy (SIMS) 3D imaging, clearly demonstrate that the RS mechanism corresponds to lithium migration toward the outside of the Lix CoO2 layer. These observations are very well correlated with the observed insulator-to-metal transition of the oxide. Besides, smaller device area experimentally yields much faster switching kinetics, which is qualitatively well accounted for by a simple numerical simulation. Write/erase endurance is also highly improved with downscaling - much further than the present cycling life of usual lithium-ion batteries. Hence very attractive possibilities can be envisaged for this class of materials in nanoelectronics.

The influence of surfaces and interfaces on high spatial resolution vibrational EELS from SiO2.

High-resolution monochromated electron energy-loss spectroscopy has the potential to map vibrational modes at nanometer resolution. Using the SiO2/Si interface as a test case, we observe an initial drop in the SiO2 vibrational signal when the electron probe is 200 nm from the Si due to long-range nature of the Coulomb interaction. However, the distance from the interface at which the SiO2 integrated signal intensity drops to half its maximum value is 5 nm. We show that nanometer resolution is possible when selecting the SiO2/Si interface signal which is at a different energy position than the bulk signal. Calculations also show that, at 60 kV, the signal in the SiO2 can be treated non-relativistically (no retardation) while the signal in the Si, not surprisingly, is dominated by relativistic effects. For typical transmission electron microscope specimen thicknesses, surface coupling effects must also be considered.

Controlling Structural Anisotropy of Anisotropic 2D Layers in Pseudo-1D/2D Material Heterojunctions.

Chemical vapor deposition and growth dynamics of highly anisotropic 2D lateral heterojunctions between pseudo-1D ReS2 and isotropic WS2 monolayers are reported for the first time. Constituent ReS2 and WS2 layers have vastly different atomic structure, crystallizing in anisotropic 1T' and isotropic 2H phases, respectively. Through high-resolution scanning transmission electron microscopy, electron energy loss spectroscopy, and angle-resolved Raman spectroscopy, this study is able to provide the very first atomic look at intimate interfaces between these dissimilar 2D materials. Surprisingly, the results reveal that ReS2 lateral heterojunctions to WS2 produce well-oriented (highly anisotropic) Re-chains perpendicular to WS2 edges. When vertically stacked, Re-chains orient themselves along the WS2 zigzag direction, and consequently, Re-chains exhibit six-fold rotation, resulting in loss of macroscopic scale anisotropy. The degree of anisotropy of ReS2 on WS2 largely depends on the domain size, and decreases for increasing domain size due to randomization of Re-chains and formation of ReS2 subdomains. Present work establishes the growth dynamics of atomic junctions between novel anisotropic/isotropic 2D materials, and overall results mark the very first demonstration of control over anisotropy direction, which is a significant leap forward for large-scale nanomanufacturing of anisotropic systems.

Nanoscale probing of bandgap states on oxide particles using electron energy-loss spectroscopy.

Surface and near-surface electronic states were probed with nanometer spatial resolution in MgO and TiO2 anatase nanoparticles using ultra-high energy resolution electron energy-loss spectroscopy (EELS) coupled to a scanning transmission electron microscope (STEM). This combination allows the surface electronic structure determined with spectroscopy to be correlated with nanoparticle size, morphology, facet etc. By acquiring the spectra in aloof beam mode, radiation damage to the surface can be significantly reduced while maintaining the nanometer spatial resolution. MgO and TiO2 showed very different bandgap features associated with the surface/sub-surface layer of the nanoparticles. Spectral simulations based on dielectric theory and density of states models showed that a plateau feature found in the pre-bandgap region in the spectra from (100) surfaces of 60nm MgO nanocubes is consistent with a thin hydroxide surface layer. The spectroscopy shows that this hydroxide species gives rise to a broad filled surface state at 1.1eV above the MgO valence band. At the surfaces of TiO2 nanoparticles, pronounced peaks were observed in the bandgap region, which could not be well fitted to defect states. In this case, the high refractive index and large particle size may make Cherenkov or guided light modes the likely causes of the peaks.

Damage-free vibrational spectroscopy of biological materials in the electron microscope.

Vibrational spectroscopy in the electron microscope would be transformative in the study of biological samples, provided that radiation damage could be prevented. However, electron beams typically create high-energy excitations that severely accelerate sample degradation. Here this major difficulty is overcome using an 'aloof' electron beam, positioned tens of nanometres away from the sample: high-energy excitations are suppressed, while vibrational modes of energies <1 eV can be 'safely' investigated. To demonstrate the potential of aloof spectroscopy, we record electron energy loss spectra from biogenic guanine crystals in their native state, resolving their characteristic C-H, N-H and C=O vibrational signatures with no observable radiation damage. The technique opens up the possibility of non-damaging compositional analyses of organic functional groups, including non-crystalline biological materials, at a spatial resolution of ∼10 nm, simultaneously combined with imaging in the electron microscope.

Controlled Living Nanowire Growth: Precise Control over the Morphology and Optical Properties of AgAuAg Bimetallic Nanowires.

Inspired by the concept of living polymerization reaction, we are able to produce silver-gold-silver nanowires with a precise control over their total length and plasmonic properties by establishing a constant silver deposition rate on the tips of penta-twinned gold nanorods used as seed cores. Consequently, the length of the wires increases linearly in time. Starting with ∼210 nm × 32 nm gold cores, we produce nanowire lengths up to several microns in a highly controlled manner, with a small self-limited increase in thickness of ∼4 nm, corresponding to aspect ratios above 100, whereas the low polydispersity of the product allows us to detect up to nine distinguishable plasmonic resonances in a single colloidal solution. We analyze the spatial distribution and the nature of the plasmons by electron energy loss spectroscopy and obtain excellent agreement between measurements and electromagnetic simulations, clearly demonstrating that the presence of the gold core plays a marginal role, except for relatively short wires or high-energy modes.

Depth profiling charge accumulation from a ferroelectric into a doped Mott insulator.

The electric field control of functional properties is a crucial goal in oxide-based electronics. Nonvolatile switching between different resistivity or magnetic states in an oxide channel can be achieved through charge accumulation or depletion from an adjacent ferroelectric. However, the way in which charge distributes near the interface between the ferroelectric and the oxide remains poorly known, which limits our understanding of such switching effects. Here, we use a first-of-a-kind combination of scanning transmission electron microscopy with electron energy loss spectroscopy, near-total-reflection hard X-ray photoemission spectroscopy, and ab initio theory to address this issue. We achieve a direct, quantitative, atomic-scale characterization of the polarization-induced charge density changes at the interface between the ferroelectric BiFeO3 and the doped Mott insulator Ca(1-x)Ce(x)MnO3, thus providing insight on how interface-engineering can enhance these switching effects.

Atomic configuration of nitrogen-doped single-walled carbon nanotubes.

Having access to the chemical environment at the atomic level of a dopant in a nanostructure is crucial for the understanding of its properties. We have performed atomically resolved electron energy-loss spectroscopy to detect individual nitrogen dopants in single-walled carbon nanotubes and compared with first-principles calculations. We demonstrate that nitrogen doping occurs as single atoms in different bonding configurations: graphitic-like and pyrrolic-like substitutional nitrogen neighboring local lattice distortion such as Stone-Thrower-Wales defects. We also show that the largest fraction of nitrogen amount is found in poly aromatic species that are adsorbed on the surface of the nanotube walls. The stability under the electron beam of these nanotubes has been studied in two different cases of nitrogen incorporation content and configuration. These findings provide key information for the applications of these nanostructures.

Atomic and electronic structure of the BaTiO3/Fe interface in multiferroic tunnel junctions.

Artificial multiferroic tunnel junctions combining a ferroelectric tunnel barrier of BaTiO(3) with magnetic electrodes display a tunnel magnetoresistance whose intensity can be controlled by the ferroelectric polarization of the barrier. This effect, called tunnel electromagnetoresistance (TEMR), and the corollary magnetoelectric coupling mechanisms at the BaTiO(3)/Fe interface were recently reported through macroscopic techniques. Here, we use advanced spectromicroscopy techniques by means of aberration-corrected scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) to probe locally the nanoscale structural and electronic modifications at the ferroelectric/ferromagnetic interface. Atomically resolved real-space spectroscopic techniques reveal the presence of a single FeO layer between BaTiO(3) and Fe. Based on this accurate description of the studied interface, we propose an atomistic model of the ferroelectric/ferromagnetic interface further validated by comparing experimental and simulated STEM images with atomic resolution. Density functional theory calculations allow us to interpret the electronic and magnetic properties of these interfaces and to understand better their key role in the physics of multiferroics nanostructures.

Nanometer scale spectral imaging of quantum emitters in nanowires and its correlation to their atomically resolved structure.

We report the spectral imaging in the UV to visible range with nanometer scale resolution of closely packed GaN/AlN quantum disks in individual nanowires using an improved custom-made cathodoluminescence system. We demonstrate the possibility to measure full spectral features of individual quantum emitters as small as 1 nm and separated from each other by only a few nanometers and the ability to correlate their optical properties to their size, measured with atomic resolution. The direct correlation between the quantum disk size and emission wavelength provides evidence of the quantum confined Stark effect leading to an emission below the bulk GaN band gap for disks thicker than 2.6 nm. With the help of simulations, we show that the internal electric field in the studied quantum disks is smaller than what is expected in the quantum well case. We show evidence of a clear dispersion of the emission wavelengths of different quantum disks of identical size but different positions along the wire. This dispersion is systematically correlated to a change of the diameter of the AlN shell coating the wire and is thus attributed to the related strain variations along the wire. The present work opens the way both to fundamental studies of quantum confinement in closely packed quantum emitters and to characterizations of optoelectronic devices presenting carrier localization on the nanometer scale.