Differential phase contrast (DPC) mapping electric fields: Optimising experimental conditions.

DPC in Scanning Transmission Electron Microscopy (STEM) is a valuable method for mapping the electric fields in semiconductor materials. However, optimising the experimental conditions can be challenging. In this paper, we test and compare critical experimental parameters, including the convergence angle, camera length, acceleration voltage, sample configuration, and orientation using a four-quadrant segmented detector and a Si specimen containing layers of different As concentrations. The DPC measurements show a roughly linear correlation with the estimated electric fields, until the field gets close to the detection limitation, which is ∼0.5 mV/nm with a sample thickness of ∼145 nm. These results can help inform which technique to use for different user cases: When the electric field at a planar junction is above ∼0.5 mV/nm, DPC with a segmented detector is practical for electric field mapping. With a planar junction, the DPC signal-to-noise ratio can be increased by increasing the specimen thickness. However, for semiconductor devices with electric fields smaller than ∼0.5 mV/nm, or for devices containing curved junctions, DPC is unreliable and techniques with higher sensitivity will need to be explored, such as 4D STEM using a pixelated detector.

Electron Beam Effects on Oxide Thin Films-Structure and Electrical Property Correlations.

In situ transmission electron microscope (TEM) characterization techniques provide valuable information on structure-property correlations to understand the behavior of materials at the nanoscale. However, understanding nanoscale structures and their interaction with the electron beam is pivotal for the reliable interpretation of in situ/ex situ TEM studies. Here, we report that oxides commonly used in nanoelectronic applications, such as transistor gate oxides or memristive devices, are prone to electron beam induced damage that causes small structural changes even under very low dose conditions, eventually changing their electrical properties as examined via in situ measurements. In this work, silicon, titanium, and niobium oxide thin films are used for in situ TEM electrical characterization studies. The electron beam induced reduction of the oxides turns these insulators into conductors. The conductivity change is reversible by exposure to air, supporting the idea of electron beam reduction of oxides as primary damage mechanism. Through these measurements we propose a limit for the critical dose to be considered for in situ scanning electron microscopy and TEM characterization studies.

VOCl as a Cathode for Rechargeable Chloride Ion Batteries.

A novel room temperature rechargeable battery with VOCl cathode, lithium anode, and chloride ion transporting liquid electrolyte is described. The cell is based on the reversible transfer of chloride ions between the two electrodes. The VOCl cathode delivered an initial discharge capacity of 189 mAh g(-1) . A reversible capacity of 113 mAh g(-1) was retained even after 100 cycles when cycled at a high current density of 522 mA g(-1) . Such high cycling stability was achieved in chloride ion batteries for the first time, demonstrating the practicality of the system beyond a proof of concept model. The electrochemical reaction mechanism of the VOCl electrode in the chloride ion cell was investigated in detail by ex situ X-ray diffraction (XRD), infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The results confirm reversible deintercalation-intercalation of chloride ions in the VOCl electrode.

Investigating hybridization schemes of coupled split-ring resonators by electron impacts.

We present a comprehensive theoretical and experimental investigation of the plasmon hybridization of coupled split-ring resonators by means of the electron energy-loss spectroscopy. Split-ring resonator is a key element in design of negative refractive index metamaterials, and has been therefore intensively studied in the literature. Here, our aim is the study of hybridization effects for higher-order non-dipolar modes, which have been not investigated beforehand. We provide a complete scheme of the multimodal distribution of the coupled and single-element split-ring resonators, with a precise attention to the hybridization of those modes according to the induced moments. Our study suggests a clear dominance of electric and magnetic dipole moments over higher-order modes in the far-field radiation spectrum.

Lithium potential variations for metastable materials: case study of nanocrystalline and amorphous LiFePO4.

Much attention has been paid to metastable materials in the lithium battery field, especially to nanocrystalline and amorphous materials. Nonetheless, fundamental issues such as lithium potential variations have not been pertinently addressed. Using LiFePO4 as a model system, we inspect such lithium potential variations for various lithium storage modes and evaluate them thermodynamically. The conclusions of this work are essential for an adequate understanding of the behavior of electrode materials and even helpful in the search for new energy materials.

Single-layered ultrasmall nanoplates of MoS2 embedded in carbon nanofibers with excellent electrochemical performance for lithium and sodium storage.

The preparation and electrochemical storage behavior of MoS2 nanodots--more precisely single-layered ultrasmall nanoplates--embedded in carbon nanowires has been studied. The preparation is achieved by an electrospinning process that can be easily scaled up. The rate performance and cycling stability of both lithium and sodium storage were found to be outstanding. The storage behavior is, moreover, highly exciting from a fundamental point of view, as the differences between the usual storage modes--insertion, conversion, interfacial storage--are beneficially blurred. The restriction to ultrasmall reaction domains allows for an almost diffusion-less and nucleation-free "conversion", thereby resulting in a high capacity and a remarkable cycling performance.

An FeF(3)·0.5H2O polytype: a microporous framework compound with intersecting tunnels for Li and Na batteries.

To improve the energy/power density of energy storage materials, numerous efforts have focused on the exploration of new structure prototypes, in particular metal-organic fameworks, Prussian blue analogues, open-framework oxides, and polyanion salts. Here we report a novel pyrochlore phase that appears to be useful as a high-capacity cathode for Li and Na batteries. It is an iron fluoride polymorph characterized by an intersecting tunnel structure, providing the space for accommodation and transport of Li and Na ions. It is prepared using hydrolyzable ionic liquids, which serve as reaction educts and structure-directing agents not only as far as the chemical structure is concerned but also in terms of morphology (shape, defect structure, electrode network structure). A capacity higher than 220 mA h g(-1) (for Li and Na storage) and a lifetime of at least 300 cycles (for Li storage) are demonstrated.

Direct Observation of Quadrupolar Strain Fields forming a Shear Band in Metallic Glasses.

For decades, scanning/transmission electron microscopy (S/TEM) techniques have been employed to analyze shear bands in metallic glasses and understand their formation in order to improve the mechanical properties of metallic glasses. However, due to a lack of direct information in reciprocal space, conventional S/TEM cannot characterize the local strain and atomic structure of amorphous materials, which are key to describe the deformation of glasses. For this work, 4-dimensional-STEM (4D-STEM) is applied to map and directly correlate the local strain and the atomic structure at the nanometer scale in deformed metallic glasses. Residual strain fields are observed with quadrupolar symmetry concentrated at dilated Eshelby inclusions. The strain fields percolate in a vortex-like manner building up the shear band. This provides a new understanding of the formation of shear bands in metallic glass.

Synergy of cations in high entropy oxide lithium ion battery anode.

High entropy oxides (HEOs) with chemically disordered multi-cation structure attract intensive interest as negative electrode materials for battery applications. The outstanding electrochemical performance has been attributed to the high-entropy stabilization and the so-called 'cocktail effect'. However, the configurational entropy of the HEO, which is thermodynamically only metastable at room-temperature, is insufficient to drive the structural reversibility during conversion-type battery reaction, and the 'cocktail effect' has not been explained thus far. This work unveils the multi-cations synergy of the HEO Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O at atomic and nanoscale during electrochemical reaction and explains the 'cocktail effect'. The more electronegative elements form an electrochemically inert 3-dimensional metallic nano-network enabling electron transport. The electrochemical inactive cation stabilizes an oxide nanophase, which is semi-coherent with the metallic phase and accommodates Li+ ions. This self-assembled nanostructure enables stable cycling of micron-sized particles, which bypasses the need for nanoscale pre-modification required for conventional metal oxides in battery applications. This demonstrates elemental diversity is the key for optimizing multi-cation electrode materials.

Microstructural Study of MgB2 in the LiBH4-MgH2 Composite by Using TEM.

The hampered kinetics of reactive hydride composites (RHCs) in hydrogen storage and release, which limits their use for extensive applications in hydrogen storage S1and energy conversion, can be improved using additives. However, the mechanism of the kinetic restriction and the additive effect on promoting the kinetics have remained unclear. These uncertainties are addressed by utilizing versatile transmission electron microscopy (TEM) on the LiBH4-MgH2 composite under the influence of the 3TiCl3·AlCl3 additives. The formation of the MgB2 phase, as the rate-limiting step, is emphatically studied. According to the observations, the heterogeneous nucleation of MgB2 relies on different nucleation centers (Mg or TiB2 and AlB2). The varied nucleation and growth of MgB2 are related to the in-plane strain energy density at the interface, resulting from the atomic misfit between MgB2 and its nucleation centers. This leads to distinct MgB2 morphologies (bars and platelets) and different performances in the dehydrogenation kinetics of LiBH4-MgH2. It was found that the formation of numerous MgB2 platelets is regarded as the origin of the kinetic improvement. Therefore, to promote dehydrogenation kinetics in comparable RHC systems for hydrogen storage, it is suggested to select additives delivering a small atomic misfit.

Structural evolution of magnesium difluoride: from an amorphous deposit to a new polymorph.

The structural evolution of magnesium difluoride from an amorphous deposit has been investigated by in situ powder X-ray diffraction (XRPD) and transmission electron microscopy (TEM). Crystalline MgF(2) was evaporated at different temperatures, which define the vapor pressures in the range from 4.7 × 10(-3) to 1.6 × 10(-1) mbar, and deposited onto various substrates. The temperature of the substrate was systematically varied from -228 to 25 °C. Magnesium difluoride was obtained as an amorphous sample when deposited on a substrate kept at a temperature below -100 °C. Upon warming, the deposit transforms via the CaCl(2) type of structure (ß-MgF(2), at 70 °C) into the stable rutile type (α-MgF(2), 250 °C) by a displacive order-disorder phase transition. The new ß-MgF(2) polymorph was refined assuming the orthorhombic CaCl(2) type of structure (Pnnm, No. 58) with the lattice constants a = 4.592(1) Å, b = 4.938(3) Å, and c = 2.959(3) Å. When deposited above -50 °C, samples crystallize directly in the rutile structure.

Direct Atomic-Scale Structure and Electric Field Imaging of Triazine-Based Crystalline Carbon Nitride.

Crystalline carbon nitrides (CNs) have recently attracted considerable attention owing to their superior photocatalytic activity. However, the electron-beam-sensitive nature of crystalline CNs hinders atomic-resolution imaging of their local structures by conventional (scanning) transmission electron microscopy ((S)TEM) techniques. Here, the atomic structure of a triazine-based crystalline CN, poly(triazine imide) (PTI) incorporated with lithium and chloride ions, is unambiguously revealed using the emerging imaging technique of differential phase contrast STEM under a low dose. The lightest-element Li/H configuration is resolved within framework cavities of PTI and significantly affects the electronic structure for photoabsorption. The atomic electric field of PTI crystal directly determined in real space provides a fundamental evidence for the chemical bonding of Li ions and adjacent atoms for the migration of photogenerated carriers. These results facilitate the comprehension on local atomic configuration and chemical bonding state of crystalline CNs and can lead to a deeper understanding of the photocatalytic mechanism.

New Insight into Desodiation/Sodiation Mechanism of MoS2: Sodium Insertion in Amorphous Mo-S Clusters.

Molybdenum disulfide (MoS2) is a promising anode material for sodium batteries due to its high theoretical capacity. While significantly improved electrochemical performance has been achieved, the reaction mechanism is still equivocal. Herein, we applied electron pair distribution function and X-ray absorption spectroscopy to investigate the desodiation/sodiation mechanism of MoS2 electrodes. The results reveal that Mo-S bonds are well preserved and dominant in the sodiation product matrix but do not convert to metallic Mo and Na2S even at deep sodiation. The MoS2 multilayer sheets break into disordered MoSx clusters with modified octahedral symmetry during discharging. The long-range order was not rebuilt during subsequent charging but with partial recovery of the Mo-S coordination symmetry. The mechanism of the reaction is independent of the carbon matrix, although it prevents the MoSx clusters from leaching into the electrolyte and thus contributes to an extended cycle life. This work refreshes the fundamental understanding of the desodiation/sodiation mechanism of MoS2 materials.

Unveiling the Local Atomic Arrangements in the Shear Band Regions of Metallic Glass.

The prospective applications of metallic glasses are limited by their lack of ductility, attributed to shear banding inducing catastrophic failure. A concise depiction of the local atomic arrangement (local atomic packing and chemical short-range order), induced by shear banding, is quintessential to understand the deformation mechanism, however still not clear. An explicit view of the complex interplay of local atomic structure and chemical environment is presented by mapping the atomic arrangements in shear bands (SBs) and in their vicinity in a deformed Vitreloy 105 metallic glass, using the scanning electron diffraction pair distribution function and atom probe tomography. The results experimentally prove that plastic deformation causes a reduction of geometrically favored polyhedral motifs. Localized motifs variations and antisymmetric (bond and chemical) segregation extend for several hundred nanometers from the SB, forming the shear band affected zones. Moreover, the variations within the SB are found both perpendicular and parallel to the SB plane, also observable in the oxidation activity. The knowledge of the structural-chemical changes provides a deeper understanding of the plastic deformation of metallic glasses especially for their functional applications and future improvements.

Quantifying the performance of a hybrid pixel detector with GaAs:Cr sensor for transmission electron microscopy.

Hybrid pixel detectors (HPDs) have been shown to be highly effective for diffraction-based and time-resolved studies in transmission electron microscopy, but their performance is limited by the fact that high-energy electrons scatter over long distances in their thick Si sensors. An advantage of HPDs compared to monolithic active pixel sensors is that their sensors do not need to be fabricated from Si. We have compared the performance of the Medipix3 HPD with a Si sensor and a GaAs:Cr sensor using primary electrons in the energy range of 60-300 keV. We describe the measurement and calculation of the detectors' modulation transfer function (MTF) and detective quantum efficiency (DQE), which show that the performance of the GaAs:Cr device is markedly superior to that of the Si device for high-energy electrons.

First-time synthesis of a magnetoelectric core-shell composite via conventional solid-state reaction.

In recent years, multiferroics and magnetoelectrics have demonstrated their potential for a variety of applications. However, no magnetoelectric material has been translated to a real application yet. Here, we report for the first time that a magnetoelectric core-shell ceramic, is synthesized via a conventional solid-state reaction, where core-shell grains form during a single sintering step. The core consists of ferrimagnetic CoFe2O4, which is surrounded by a ferroelectric shell consisting of (BiFeO3)x-(Bi1/2K1/2TiO3)1-x. We establish the core-shell nature of these grains by transmission-electron microscopy (TEM) and find an epitaxial crystallographic relation between core and shell, with a lattice mismatch of 6 ± 0.7%. The core-shell grains exhibit exceptional magnetoelectric coupling effects that we attribute to the epitaxial connection between the magnetic and ferroelectric phase, which also leads to magnetic exchange coupling as demonstrated by neutron diffraction. Apparently, ferrimagnetic CoFe2O4 cores undergo a non-centrosymmetric distortion of the crystal structure upon epitaxial strain from the shell, which leads to simultaneous ferrimagnetism and piezoelectricity. We conclude that in situ core-shell ceramics offer a number of advantages over other magnetoelectric composites, such as lower leakage current, higher density and absence of substrate clamping effects. At the same time, the material is predestined for application, since its preparation is cost-effective and only requires a single sintering step. This discovery adds a promising new perspective for the application of magnetoelectric materials.

Mapping structure and morphology of amorphous organic thin films by 4D-STEM pair distribution function analysis.

Imaging the phase distribution of amorphous or partially crystalline organic materials at the nanoscale and analyzing the local atomic structure of individual phases has been a long-time challenge. We propose a new approach for imaging the phase distribution and for analyzing the local structure of organic materials based on scanning transmission electron diffraction (4D-STEM) pair distribution function analysis (PDF). We show that electron diffraction based PDF analysis can be used to characterize the short- and medium-range order in aperiodically packed organic molecules. Moreover, we show that 4D-STEM-PDF does not only provide local structural information with a resolution of a few nanometers, but can also be used to image the phase distribution of organic composites. The distinct and thickness independent contrast of the phase image is generated by utilizing the structural difference between the different types of molecules and taking advantage of the dose efficiency due to use of the full scattering signal. Therefore, this approach is particularly interesting for imaging unstained organic or polymer composites without distinct valence states for electron energy loss spectroscopy. We explore the possibilities of this new approach using [6,6]-phenyl-C61- butyric acid methyl ester (PC61BM) and poly(3-hexylthiophene-2,5-diyl) (P3HT) as the archetypical and best-investigated semiconductor blend used in organic solar cells, compare our phase distribution with virtual dark-field analysis and validate our approach by electron energy loss spectroscopy.

Towards quantitative treatment of electron pair distribution function.

The pair distribution function (PDF) is a versatile tool to describe the structure of disordered and amorphous materials. Electron PDF (ePDF) uses the advantage of strong scattering of electrons, thus allowing small volumes to be probed and providing unique information on structure variations at the nano-scale. The spectrum of ePDF applications is rather broad: from ceramic to metallic glasses and mineralogical to organic samples. The quantitative interpretation of ePDF relies on knowledge of how structural and instrumental effects contribute to the experimental data. Here, a broad overview is given on the development of ePDF as a structure analysis method and its applications to diverse materials. Then the physical meaning of the PDF is explained and its use is demonstrated with several examples. Special features of electron scattering regarding the PDF calculations are discussed. A quantitative approach to ePDF data treatment is demonstrated using different refinement software programs for a nanocrystalline anatase sample. Finally, a list of available software packages for ePDF calculation is provided.

Revealing the Dual Surface Reactions on a HE-NCM Li-Ion Battery Cathode and Their Impact on the Surface Chemistry of the Counter Electrode.

The understanding of surface reactions at the electrode-electrolyte interfaces has been a longstanding challenge in Li-ion batteries. X-ray photoemission electron microscopy is used to throw light on the disputed aspects of the surface reactivity of high-energy Li-rich Li1+ x(Ni aCo bMn1- a-b)1- xO2 (HE-NCM) cycled in an aprotic electrolyte against Li4Ti5O12 (LTO). Despite the highly oxidative potential of 5.1 V vs Li+/Li, there is no formation of a layer of oxidized electrolyte byproducts on any of the cathode particles; instead, a homogeneous organic-inorganic layer builds up across the particles of the LTO anode due to the electrolyte and poly(vinylidene fluoride) binder decomposition on HE-NCM. In addition, such a layer incorporates, already from the first charge, micrometer-sized agglomerates of transition metals (TMs). The presence of TMs on the anode is explained by the instability of the reduced Mn, Co, and Ni formed at the surface of HE-NCM mainly during delithiation. The reduced TMs are unstable and prone to be transported to the LTO, where they get further reduced to metallic-like clusters. These results demonstrate that a dual reaction takes place at the HE-NCM-electrolyte interface if subject to high potential, namely, degradation of the surface structure and decomposition of the electrolyte, affecting directly the anode surface through the migration-diffusion processes.

Fast kinetics of multivalent intercalation chemistry enabled by solvated magnesium-ions into self-established metallic layered materials.

Rechargeable magnesium batteries are one of the most promising candidates for next-generation battery technologies. Despite recent significant progress in the development of efficient electrolytes, an on-going challenge for realization of rechargeable magnesium batteries remains to overcome the sluggish kinetics caused by the strong interaction between double charged magnesium-ions and the intercalation host. Herein, we report that a magnesium battery chemistry with fast intercalation kinetics in the layered molybdenum disulfide structures can be enabled by using solvated magnesium-ions ([Mg(DME)x]2+). Our study demonstrates that the high charge density of magnesium-ion may be mitigated through dimethoxyethane solvation, which avoids the sluggish desolvation process at the cathode-electrolyte interfaces and reduces the trapping force of the cathode lattice to the cations, facilitating magnesium-ion diffusion. The concept of using solvation effect could be a general and effective route to tackle the sluggish intercalation kinetics of magnesium-ions, which can potentially be extended to other host structures.