Energy-loss Near-edge Structure Research Articles

Energy-Loss Near-Edge Structures and Low-Loss Structures of Polymers in a Solid Electrolyte Interface Formed from Fluoroethylene Carbonate on a Si Anode Clarified by DFT Calculations

To shed light on the polymer bonding structure and inorganic/polymer nanocomposite structures in fluoroethylene carbonate (FEC)-based solid electrolyte interfaces (SEIs), high-energy-resolution ene...

A primordial 15N-depleted organic component detected within the carbonaceous chondrite Maribo

We report on the detection of primordial organic matter within the carbonaceous chondrite Maribo that is distinct from the majority of organics found in extraterrestrial samples. We have applied high-spatial resolution techniques to obtain C-N isotopic compositions, chemical, and structural information of this material. The organic matter is depleted in 15N relative to the terrestrial value at around δ15N ~ -200‰, close to compositions in the local interstellar medium. Morphological investigations by electron microscopy revealed that the material consists of µm- to sub-µm-sized diffuse particles dispersed within the meteorite matrix. Electron energy loss and synchrotron X-ray absorption near-edge structure spectroscopies show that the carbon functional chemistry is dominated by aromatic and C=O bonding environments similar to primordial organics from other carbonaceous chondrites. The nitrogen functional chemistry is characterized by C-N double and triple bonding environments distinct from what is usually found in 15N-enriched organics from aqueously altered carbonaceous chondrites. Our investigations demonstrate that Maribo represents one of the least altered CM chondrite breccias found to date and contains primordial organic matter, probably originating in the interstellar medium.

Electronic structure of LiOsO3: Electron energy-loss spectroscopy and first-principles study

Electronic structure of LiOsO3 were investigated by using first-principle calculations and electron energy loss spectroscopy (EELS). According to the calculated densities of states, the interband transitions from valence band (VB) to conduction band (CB) to the low energy loss spectrum were assigned. The hybridization of O 2p with Os 5d was critical to the coexistence of metal and ferroelectricity in LiOsO3. From the simulation of the energy loss near-edge structure (ELNES), the fine structure of O K-edge was in good agreement with the experimental spectrum, while the core hole effect and spin-orbital coupling had little effect on the spectra.

Extraction of the local coordination and electronic structures of FeO6 octahedra using crystal field multiplet calculations combined with STEM-EELS

The material properties of metal oxides are sensitive to even low levels of cation doping, and the local atomic structures around such trace elements in a crystal will differ from the bulk structure due to the different ionic size and electron configuration. The present work explores the extraction of the local structure of a minority component contained in an atomic column by analyzing the Fe L2,3 energy-loss near-edge structure of atomic-resolution monochromated electron energy-loss spectra, using crystal field multiplet calculations. The crystal field splitting of the Fe 3d state and the local coordination structure of FeO6 octahedra in iron oxides in real space with known structures were determined. The results closely agreed with structures obtained from neutron diffraction and the Fe 3d DOS generated by density functional theory calculations. The previously unknown local structure of FeO6 octahedra present at octahedral sites as a minor component (14.4%) in the brownmillerite structure of Ca2Fe1.07Mn0.93O5 was determined. This structure was found to be unique and differed from the results obtained using neutron diffraction, which reflect those of mainly MnO6 octahedra. The present method is evidently an effective means of investigating the local structures around trace elements.

Core hole screened electron energy loss calculations of beam damaged lithium fluoride

A method of calculating the magnitude of the core hole screening of lithium materials is implemented for the simulation of Energy Loss Near Edge Structure (ELNES). ELNES is calculated for a range of lithium materials resulting in improved agreement between calculation and experiment. The technique uses linear response theory to relate the electron density to the core hole shielding contribution from the valence electrons in a crystal. This contribution is then implemented via a non-integer core hole in final state rule calculations.

A hyperspectral unmixing framework for energy-loss near-edge structure analysis

Extracting different spectral components and their corresponding concentrations from spectrum images is one of the key challenges for electron energy-loss spectroscopy analysis due to the large amount of data, differing spectral features and low signal-to-noise ratio. Here, an open-source software framework of hyperspectral unmixing for energy-loss near-edge fine structure analysis is proposed. This software determines the number of independent spectral components, the signature of each spectral component and the abundance of each spectral component in each pixel, without reference spectrum or prior knowledge of the datasets. This approach should be suitable for automated materials and chemical analysis.

Electron energy loss spectra from silica glass optical fibers

AbstractTo investigate the possible structural differences between silica glass fibers and bulk silica glasses, electron energy loss spectroscopy (EELS) has been used to study the short‐range and medium‐range structures of both forms of silica glasses. The short‐range structure of silica glass, such as the coordination and symmetry, was investigated by the energy loss near edge structure (ELNES) of Si L2,3‐edges. The ordering structure in the medium‐range was analyzed by the exponential optical absorption edge also known as the Urbach edge of the glasses. The optical absorption data were obtained from the low energy loss spectrum of EELS through Kramers‐Kronig analysis. The results show that silica fiber has the same short‐range structure as the bulk specimen, but is significantly more disordered than the bulk glasses.

Quantitative Analysis Method for Nitrogen Electron Energy-Loss Near-Edge Structures in Nanocarbons Based on Density Functional Theory Calculations and Linear Regression

Nonmetallic heteroatoms found in carbon nanomaterials act as active sites and exhibit excellent catalytic performance. Owing to structural complexity and the limitations of characterization technology, the identification of active sites in nanocarbon is challenging and controversial. Electron energy-loss spectroscopy is an electron microscope technique with high spatial resolution and a powerful tool for identifying the arrangement of heteroatoms. However, structural information regarding the configuration and distribution of heteroatoms is difficult to obtain using existing analytical methods. Herein, we have developed a method for the quantitative analysis of electron energy-loss near-edge structures to identify accurately nitrogen species in nanocarbon. Based on this approach, the relative amounts of nitrogen species were obtained from linear regression with calculated spectra. The concentration distribution of nanocarbon obtained by this method was consistent with the result of X-ray photoelectron spectroscopy analysis at different depths. Therefore, this fitting method can be used for the quantitative analysis of nitrogen K-edge structures. This provides a new strategy for studying the structure–activity relationships of carbon-based materials and the further design of custom nanocarbon catalysts with high active site densities.

Study of C K-Edge High Energy Resolution Energy-Loss Near-Edge Structures of Copper Phthalocyanine and Its Chlorinated Molecular Crystals by First-Principles Band Structure Calculations.

High energy resolution energy-loss near-edge structures (ELNES) at the carbon K-edge of copper phthalocyanine (CuPc) and its chlorinated molecular crystals were observed using electron energy-loss spectroscopy combined with a scanning transmission electron microscope equipped with a monochromator. The ELNES spectra were investigated using first-principles band structure calculations with a core-hole introduced into the 1s orbitals of the nonequivalent C atoms. The calculated spectra including half a core-hole were consistent with the experimental spectra. The spectral features could be interpreted in terms of the different contributions of the partial density of states (PDOS) of nonequivalent C atoms with different transition energies depending on the site. The core-hole effects were also discussed using the spatial distribution of unoccupied states and PDOSs, which revealed site-dependent core-hole effects, where a C atom with a strong spatial distribution intensity of the unoccupied states in the ground state (GS) are susceptible to the core-hole effects. The spectral changes due to chlorination of the CuPc molecule were mainly attributed to an increase of the threshold energy of the C atoms bonded to chlorine, and the influence of the change in the PDOS by chlorination was not significantly large.

Electron Energy Loss Structures of Terminated Scandium and Hafnium MXene Monolayers from First-Principles Calculations

In this study, the energy loss near edge structure (ELNES) of two-dimensional transition metal carbides and nitrides, namely ‘MXenes’, has been calculated in the density functional theory using the full-potential linearized augmented plane wave method. Calculations of band structure demonstrate that, in agreement with other studies, although MAX phases (bulks) and pristine MXenes (monolayers) are all metallic, some functionalized MXenes are semiconductors. For the first time, we have calculated the ELNES spectra of carbon and nitrogen K-edges in MAX M2AlX phases, pristine M2X MXenes and functionalized MXenes M2XT2 (M = Sc, Hf; X = C, N; T = F, OH, O) at magic angle conditions. Compared to the M2AlX bulks, the differences of energy between the main peaks in carbon and nitrogen K edges of M2X monolayers increase due to the slightly smaller bond lengths that can be used as a fingerprint for monolayers. The structures in ELNES spectra are sensitive to the chemical nature and the location of the T groups on the MXene surface. The energy position of the first main peak and the separation between the main peaks in the ELNES spectra of M2XT2 increase from T = O to T = OH and to T = F surface groups, respectivelyshows that the M-X bond length decreases from T = O to T = OH and to T = F. This short bond in M2XF2 leads to enhanced M-X interaction. The main features in carbon and nitrogen K edges correspond to the peaks in the unoccupied densities of states (DOS), namely σ* and π* states; however, the contribution of σ* states is dominant. Furthermore, for accurate insight into the excitonic effects (electron–hole coupling) in core edges, we have used the solving of the equation of motion of the two-particle Green’s function, the Bethe–Salpeter equation (BSE) to determine these effects on the K x-ray absorption near edge structure (XANES) of semiconductors Sc2CF2, Sc2C(OH)2, Sc2CO2 and Hf2CO2 MXenes. Calculations have been performed in two different levels of theory, with and without considering the excitonic effects. The excitonic effects considerably result in shifting the spectral features to the lower energies and changing in the intensity and overall shapes of the absorption spectra.

Structural Properties and ELNES of Polycrystalline and Nanoporous Mg3N2.

Nanoporous, high-purity magnesium nitride (Mg3N2) was synthesized with a liquid ammonia-based process, for potential applications in optoelectronics, gas separation and catalysis, since these applications require high material purity and crystallinity, which has seldom been demonstrated in the past. One way to evaluate the degree of crystalline near-range order and atomic environment is electron energy-loss spectroscopy (EELS) in a transmission electron microscope. However, there are hardly any data on Mg3N2, which makes identification of electron energy-loss near-edge structure (ELNES) features difficult. Therefore, we have studied nanoporous Mg3N2 with EELS in detail in comparison to EELS spectra of bulk Mg3N2, which was analyzed as a reference material. The N-K and Mg-K edges of both materials are similar. Despite having the same crystal structure, however, there are differences in fine-structural features, such as shifts and absences of peaks in the N-K and Mg-K edges of nanoporous Mg3N2. These differences in ELNES are attributed to coordination changes in nanoporous Mg3N2 caused by the significantly smaller crystallite size of 2-6 nm compared to the larger (25-125 nm) crystal size in a bulk material.

Experimental quantification of the Fe-valence state at amosite-asbestos boundaries using acSTEM dual-electron energy-loss spectroscopy

Abstract Determination of the oxidation state and coordination geometry of iron in Fe-bearing minerals expands our knowledge obtained by standard mineralogical characterization. It provides information that is crucial in assessing the potential of minerals to interact with their surrounding environment and to generate reactive oxygen species, which can disrupt the normal function of living organisms. Aberration-corrected scanning transmission electron microscopy dual-electron energy-loss spectroscopy (acSTEM Dual-EELS) has only rarely been applied in environmental and medical mineralogy, but it can yield data that are essential for the description of near-surface and surface mechanisms involved in many environmental and health-related processes. In this study, we have applied the energy loss near-edge structure (ELNES) and L2,3 white-line intensity-ratio methods using both the universal curve and progressively larger integrating windows to verify their effectiveness in satisfactorily describing the valence state of iron at amosite grain boundaries, and, at the same time, to estimate thickness in the same region of interest. The average valence state obtained from acSTEM Dual-EELS and from a simplified geometrical model were in good agreement, and within the range defined by the bulk and the measured surface-valence states. In the specific case presented here, the use of the universal curve was most suitable in defining the valence state of iron at amosite grain boundaries. The study of ELNES revealed an excellent correspondence with the valence state determined by the L2,3 white-line intensity-ratio method through the use of the universal curve, and it seems that the spectra carry some information regarding the coordination geometry of Fe. The combination of visual examination, reconstruction of the grain boundaries through a simple geometrical model, and Dual-EELS investigation is a powerful tool for characterizing the grain boundaries of hazardous minerals and foreseeing their potential activity in an organism, with the possibility to describe toxic mechanisms in a stepwise fashion.

Zero Cu valence and superconductivity in high-quality CuxBi2Se3 crystal

In this work, the role of Cu dopants in the development of superconductivity in $\mathrm{B}{\mathrm{i}}_{2}\mathrm{S}{\mathrm{e}}_{3}$ is investigated. A series of $\mathrm{C}{\mathrm{u}}_{x}\mathrm{B}{\mathrm{i}}_{2}\mathrm{S}{\mathrm{e}}_{3}$ ($x=0--0.3$) crystals is grown using the Bridgman method and electrochemical techniques. Based on the observable lattice increases along the $c$ axis, the existence of Cu atoms intercalated in the van der Waals (vdW) gaps in $\mathrm{B}{\mathrm{i}}_{2}\mathrm{S}{\mathrm{e}}_{3}$ is verified by x-ray diffraction, scanning electron microsopy--energy dispersive spectroscopy, and transmission electron microscopy analysis. Furthermore, the chemical state of the Cu is found to be zero valence by characterization of the x-ray photoelectron and Auger electron spectra. The absence of $\mathrm{C}{\mathrm{u}}^{1+}$ and $\mathrm{C}{\mathrm{u}}^{2+}$ in the electron energy-loss spectroscopy near-edge fine structure is confirmed as well. Meanwhile, our Raman data also show the same result: the intercalation of Cu in the vdW gap which weakens the binding of the quintuple layers in the $\mathrm{C}{\mathrm{u}}_{0.1}\mathrm{B}{\mathrm{i}}_{2}\mathrm{S}{\mathrm{e}}_{3}$ crystal. The electric resistance and magnetic susceptibility show a superconducting transition near 3--3.4 K in the series of Cu-doped $\mathrm{B}{\mathrm{i}}_{2}\mathrm{S}{\mathrm{e}}_{3}$. A sharp superconducting transition with the highest value of ${T}_{C}=3.4\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ and the largest magnetic shielding fraction of 84% is observed in the optimized 10% Cu-doped $\mathrm{B}{\mathrm{i}}_{2}\mathrm{S}{\mathrm{e}}_{3}$. These results imply that the formation of superconducting quasiparticles is not related to the charge transfer of Cu, but is supported by the internal stress of Cu intercalated in the van der Waals gap. The superconducting transition observed in the specific heat implies that the superconductivity in $\mathrm{C}{\mathrm{u}}_{x}\mathrm{B}{\mathrm{i}}_{2}\mathrm{S}{\mathrm{e}}_{3}$ is unconventional.

Investigations on electronic structure of YMnO3 by electron energy loss spectra and first-principle calculations

Crystal structure and electronic structure of YMnO3 were investigated by X-ray diffraction and transmission electron microscopy related techniques. According to the density of states (DOS), the individual interband transitions to energy loss peaks in the low energy loss spectrum were assigned. The hybridization of O 2p with Mn 3d and Y 4d analyzed by the partial DOS was critical to the ferroelectric nature of YMnO3. From the simulation of the energy loss near-edge structure, the fine structure of O K-edge was in good agreement with the experimental spectrum. The valence state of Mn (+3) in YMnO3 was determined by a comparison between experiment and calculations.

Combined study of the ground and excited states in the transformation of nanodiamonds into carbon onions by electron energy-loss spectroscopy

The electron momentum density and sp2/sp3 ratio of carbon materials in the thermal transformation of detonation nanodiamonds (ND) into carbon nano-onions are systematically studied by electron energy-loss spectroscopy (EELS). Electron energy-loss near-edge structures of the carbon K-ionization in the electron energy-loss spectroscopy are measured to determine the sp2 content of the ND-derived samples. We use the method developed by Titantah and Lamoen, which is based on the ability to isolate the π* spectrum and has been shown to give reliable and accurate results. Compton profiles (CPs) of the ND-derived carbon materials are obtained by performing EELS on the electron Compton scattering region. The amplitude of the CPs at zero momentum increases with increasing annealing temperature above 500 °C. The dramatic changes occur in the temperature range of 900–1300 °C, which indicates that the graphitization process mainly occurs in this annealing temperature region. Our results complement the previous work on the thermal transformation of ND-derived carbon onions and provide deeper insight into the evolution of the electronic properties in the graphitization process.

Electronic structure of multiferroic BiFeO3: Electron energy-loss spectroscopy and first-principles study

The electronic structure of BiFeO3 has been investigated by using electron energy loss spectrum and first-principle calculations. Assignments of the individual interband transitions have been accomplished by comparing the interband transition energy with the calculated PDOS. The DOS is mainly divided into two regions, the hybridized region of O 2p with Fe 3p in the valence band and that of O 2p hybridized with Bi 6p in the conduction band. From the simulation of high energy-loss near-edge structure, the core-hole effect is believed to be more significant. The feature groups for the experimental spectra of O K-edge and Fe L2,3-edge are consistent with simulation results.

An EELS signal-from-background separation algorithm for spectral line-scan/image quantification

Background removal is an important step in the quantitative analysis of electron energy-loss structure. Existing methods usually require an energy-loss region outside the fine structure in order to estimate the background. This paper describes a method for signal-from-background separation that is based on subspace division. The linear space is divided into two subspaces. The signal is recovered from a linear subspace containing no background information, and the other subspace containing the background is discarded. This method does not rely on any signal outside the energy-loss range of interest and should be very helpful for multiple linear least-squares (MLLS) regression analysis on experimental signals with little or no available smooth pre-edge region or with overlapping pre-edge features. Use of the algorithm is demonstrated with several practical applications, including closely overlapping core-loss spectra and zero-loss peak removal. Tests based on experimental data indicate that the algorithm has similar or better performance relative to conventional pre-edge power-law fitting methods in applications such as MLLS regression for electron energy-loss near-edge structure.

Imaging the atomic structure and local chemistry of platelets in natural type Ia diamond.

In the past decades, many efforts have been devoted to characterizing {001} platelet defects in type Ia diamond. It is known that N is concentrated at the defect core. However, an accurate description of the atomic structure of the defect and the role that N plays in it is still unknown. Here, by using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy we have determined the atomic arrangement within platelet defects in a natural type Ia diamond and matched it to a prevalent theoretical model. The platelet has an anisotropic atomic structure with a zigzag ordering of defect pairs along the defect line. The electron energy-loss near-edge fine structure of both carbon K- and nitrogen K-edges obtained from the platelet core is consistent with a trigonal bonding arrangement at interstitial sites. The experimental observations support an interstitial aggregate mode of formation for platelet defects in natural diamond.

Behaviour of Fe4O5–Mg2Fe2O5 solid solutions and their relation to coexisting Mg–Fe silicates and oxide phases

Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe4O5–Mg2Fe2O5 solid solutions and (2) to explore the phase relations involving (Mg,Fe)2Fe2O5 (denoted as O5-phase) and Mg–Fe silicates. Multi-anvil experiments were performed at 11–20 GPa and 1100–1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O5-phase coexists with Fe2O3, hp-(Mg,Fe)Fe2O4, (Mg,Fe)3Fe4O9 or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O5-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe3+-bearing phase B. However, (Mg,Fe)2Fe2O5 does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe2+ and Fe3+ (at least ~ 1.0 cations Fe per formula unit). Fe-L2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe3+/Fetot = ~ 0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si4+ + [6]Mg2+ = 2Fe3+. The ability to accommodate Fe2+ and Fe3+ makes this potential “water-storing” mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg2Fe2O5 have been refined, yielding H°1bar,298 = − 1981.5 kJ mol− 1. Solid solution is complete across the Fe4O5–Mg2Fe2O5 binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe2+ with silicates indicates that (Mg,Fe)2Fe2O5 has a strong preference for Fe2+. Modelling of partitioning with olivine is consistent with the O5-phase exhibiting ideal mixing behaviour. Mg–Fe2+ partitioning between (Mg,Fe)2Fe2O5 and ringwoodite or wadsleyite is influenced by the presence of Fe3+ and OH incorporation in the silicate phases.

Systematic analysis of electron energy-loss near-edge structures in Li-ion battery materials.

Electrical conductivity, state of charge and chemical stability of Li-ion battery materials all depend on the electronic states of their component atoms, and tools for measuring these reliably are needed for advanced materials analysis and design. Here we report a systematic investigation of electron energy-loss near-edge structures (ELNES) of Li-K and O-K edges for ten representative Li-ion battery electrodes and solid-state electrolytes obtained by performing transmission electron microscopy with a Wien-filter monochromator-equipped microscope. While the peaks of Li-K edges are positioned at about 62 eV for most of the materials examined, the peak positions of O-K edges vary within a range of about 530 to 540 eV, and the peaks can be categorised into three groups based on their characteristic edge shapes: (i) double peaks, (ii) single sharp peaks, and (iii) single broad peaks. The double peaks of group (i) are attributable to the d0 electronic configuration of their transition metal ions bonded to O atoms. The origin of the different peak shapes of groups (ii) and (iii) is more subtle but insights are gained using density functional theory methods to simulate O-K ELNES edges of group (ii) material LiCoO2 and group (iii) material LiFePO4. Comparison of their densities of states reveals that in LiCoO2 the Co-O hybrid orbitals are separated from Li-O hybrid orbitals, resulting in a sharp peak in the O-K edge, while Fe-O, Li-O and P-O hybrid orbitals in LiFePO4 partially overlap each other and produce a broad peak.