Analyses of hydrogen local environments in metals and intermetallic compounds using inelastic neutron scattering calculations based on first-principles hydrogen adiabatic potentials.

This study re-evaluates the theoretical approach to analyzing inelastic neutron spectra of hydrogen-containing metals and intermetallic compounds. Previously, these analyses utilized hydrogen quantum nuclear states, modeled as solutions to the Schrödinger equation. The potential surfaces in these models were approximated from the total energies derived from first-principles electronic structure calculations. The current study improves upon this method by employing more efficient and accurate treatments for sampling the potential surface. It utilizes symmetrically irreducible sampling points arranged on densely populated mesh grids for the first-principles calculations. A comparative analysis of the theoretical predictions with experimental spectra for hydrides of Ti2Sb and Ti3Sb, as well as a LaNi5hydrogen primary solid solution, demonstrates that this approach is promising for elucidating the unknown local environments of hydrogen atoms in systems where the approximate potential well describes the hydrogen quantum states.

Optimization and inference of bin widths for histogramming inelastic neutron scattering spectra.

A data-driven bin-width optimization for the histograms of measured data sets based on inhomogeneous Poisson processes was developed in a neurophysiology study [Shimazaki & Shinomoto (2007). Neural Comput. 19, 1503-1527], and a subsequent study [Muto, Sakamoto, Matsuura, Arima & Okada (2019). J. Phys. Soc. Jpn, 88, 044002] proposed its application to inelastic neutron scattering (INS) data. In the present study, the results of the method on experimental INS time-of-flight data collected under different measurement conditions from a copper single crystal are validated. The extrapolation of the statistics on a given data set to other data sets with different total counts precisely infers the optimal bin widths on the latter. The histograms with the optimized bin widths statistically verify two fine-spectral-feature examples in the energy and momentum transfer cross sections: (i) the existence of phonon band gaps; and (ii) the number of plural phonon branches located close to each other. This indicates that the applied method helps in the efficient and rigorous observation of spectral structures important in physics and materials science like novel forms of magnetic excitation and phonon states correlated to thermal conductivities.

Proposal for Measuring Magnetism with Patterned Apertures in a Transmission Electron Microscope.

We propose a magnetic measurement method utilizing a patterned postsample aperture in a transmission electron microscope. While utilizing electron magnetic circular dichroism, the method circumvents previous needs to shape the electron probe to an electron vortex beam or astigmatic beam. The method can be implemented in standard scanning transmission electron microscopes by replacing the spectrometer entrance aperture with a specially shaped aperture, hereafter called a ventilator aperture. The proposed setup is expected to work across the whole range of beam sizes-from wide parallel beams down to atomic resolution magnetic spectrum imaging.

Detection of local chemical states of lithium and their spatial mapping by scanning transmission electron microscopy, electron energy-loss spectroscopy and hyperspectral image analysis.

Advancements in the field of renewable energy resources have led to a growing demand for the analysis of light elements at the nanometer scale. Detection of lithium is one of the key issues to be resolved for providing guiding principles for the synthesis of cathode active materials, and degradation analysis after repeated use of those materials. We have reviewed the different techniques currently used for the characterization of light elements such as high-resolution transmission electron microscopy, scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). In the present study, we have introduced a methodology to detect lithium in solid materials, particularly for cathode active materials used in lithium-ion battery. The chemical states of lithium were isolated and analyzed from the overlapping multiple spectral profiles, using a suite of STEM, EELS and hyperspectral image analysis. The method was successfully applied in the chemical state analyses of hetero-phases near the surface and grain boundary regions of the active material particles formed by chemical reactions between the electrolyte and the active materials.

Magnetic measurements with atomic-plane resolution.

Rapid development of magnetic nanotechnologies calls for experimental techniques capable of providing magnetic information with subnanometre spatial resolution. Available probes of magnetism either detect only surface properties, such as spin-polarized scanning tunnelling microscopy, magnetic force microscopy or spin-polarized low-energy electron microscopy, or they are bulk probes with limited spatial resolution or quantitativeness, such as X-ray magnetic circular dichroism or classical electron magnetic circular dichroism (EMCD). Atomic resolution EMCD methods have been proposed, although not yet experimentally realized. Here, we demonstrate an EMCD technique with an atomic size electron probe utilizing a probe-corrected scanning transmission electron microscope in its standard operation mode. The crucial element of the method is a ramp in the phase of the electron beam wavefunction, introduced by a controlled beam displacement. We detect EMCD signals with atomic-plane resolution, thereby bringing near-atomic resolution magnetic circular dichroism spectroscopy to hundreds of laboratories worldwide.

Sparse modeling of EELS and EDX spectral imaging data by nonnegative matrix factorization.

Advances in scanning transmission electron microscopy (STEM) techniques have enabled us to automatically obtain electron energy-loss (EELS)/energy-dispersive X-ray (EDX) spectral datasets from a specified region of interest (ROI) at an arbitrary step width, called spectral imaging (SI). Instead of manually identifying the potential constituent chemical components from the ROI and determining the chemical state of each spectral component from the SI data stored in a huge three-dimensional matrix, it is more effective and efficient to use a statistical approach for the automatic resolution and extraction of the underlying chemical components. Among many different statistical approaches, we adopt a non-negative matrix factorization (NMF) technique, mainly because of the natural assumption of non-negative values in the spectra and cardinalities of chemical components, which are always positive in actual data. This paper proposes a new NMF model with two penalty terms: (i) an automatic relevance determination (ARD) prior, which optimizes the number of components, and (ii) a soft orthogonal constraint, which clearly resolves each spectrum component. For the factorization, we further propose a fast optimization algorithm based on hierarchical alternating least-squares. Numerical experiments using both phantom and real STEM-EDX/EELS SI datasets demonstrate that the ARD prior successfully identifies the correct number of physically meaningful components. The soft orthogonal constraint is also shown to be effective, particularly for STEM-EELS SI data, where neither the spatial nor spectral entries in the matrices are sparse.

Quantitative analysis of cation mixing and local valence states in LiNixMn2-xO4 using concurrent HARECXS and HARECES measurements.

Cation mixing in positive electrode materials for rechargeable lithium ion batteries, LiNixMn2-xO4 (x = 0, 0.2, 0.5) and Li0.21Ni0.7Mn1.64O4-δ (denoted as x = 0.7), is analyzed by high-angular-resolution electron-channeling X-ray/electron spectroscopy (HARECXS/HARECES) techniques, using energy-dispersive X-ray spectroscopy and electron energy-loss spectroscopy. Mixing between the tetrahedral lithium sites and the octahedral transition metal sites is quantified, and the site-dependent valence states of the transition metals are examined. In the non-doped (x = 0) sample, Mn was found to occupy only octahedral sites as either Mn(3+) or Mn(4+) For x = 0.2-0.7, some of the nickel ions (6-13% depending on x) occupy tetrahedral anti-sites. All the nickel ions are in the divalent state, regardless of the occupation site. For x = 0.2 and 0.7, manganese ions occupy both octahedral and tetrahedral sites; those in the octahedral sites are tetravalent, while the tetrahedral sites contain a mixture of divalent and trivalent ions. For x = 0.5, manganese occupies only the octahedral sites, with all ions determined to be in the tetravalent state (within experimental accuracy). All the samples substantially satisfied the local charge neutrality conditions. This study demonstrates the feasibility of using HARECXS/HARECES for quantitative analysis of the atomic configuration and valence states in lithium manganese oxide spinel materials.

Quantitative determination of occupation sites of trace Co substituted for multiple Fe sites in M-type hexagonal ferrite using statistical beam-rocking TEM-EDXS analysis.

The occupation sites and the occupancies of trace dopants in La/Co co-doped Sr-M-type ferrite, SrFe12O19, were quantitatively and precisely determined by beam-rocking energy-dispersive X-ray spectroscopy (EDXS) on the basis of electron-channeling effects. Because the Co atoms, in particular, should be partially substituted for the five crystallographically inequivalent sites, which could be key parameters in improving the magneto-crystalline anisotropy, it is difficult yet intriguing to discover their occupation sites and occupancies without using the methods of large-scale facilities, such as neutron diffraction and synchrotron radiation. In the present study, we tackled this problem by applying an extended statistical atom location by channeling enhanced microanalysis method, using conventional transmission electron microscopy, EDXS and dynamical electron elastic/inelastic scattering theories. The results show that the key occupation sites of Co were the 2a, 4f1 and 12k sites. The quantified occupancies of Co were consistent with those of the previous study, which involved a combination of neutron diffraction and extended X-ray absorption fine structure analysis, as well as energetics considerations based on by first-principles calculations.

Discovery of the last remaining binary platinum-group pernitride RuN2.

The last remaining marcasite-type RuN2 was successfully synthesized by direct chemical reaction between ruthenium and molecular nitrogen above the pressure of 32 GPa. For the first time, we found that Ru 4d is weakly hybridized with N 2p in the structure by using transmission electron microscopy equipped with electron-energy-loss spectroscopy. Our finding give important knowledge about the platinum-group pernitride with respect to the chemical bonding between platinum-group element and nitrogen.

Signal enhancement of electron magnetic circular dichroism by ultra-high-voltage TEM, toward quantitative nano-magnetism measurements.

Electron magnetic circular dichroism (EMCD) has been known as the transmission electron microscopy (TEM) counterpart of X-ray magnetic circular dichroism (XMCD). XMCD is already widely used for the characterization of magnetic materials with synchrotron radiation. There have been common difficulties encountered in quantitative analysis of the EMCD signal measured by medium-voltage TEMs, such as a small signal fraction and the low signal-to-noise ratio of the EMCD signal. Theoretical calculations of EMCD considering many-beam dynamical diffraction effects showed improved net magnetic signal fractions at an accelerating voltage of 1 MV compared with 200 kV, which is in agreement with the present experiment.

Quantitative characterization of nanoscale polycrystalline magnets with electron magnetic circular dichroism.

Electron magnetic circular dichroism (EMCD) allows the quantitative, element-selective determination of spin and orbital magnetic moments, similar to its well-established X-ray counterpart, X-ray magnetic circular dichroism (XMCD). As an advantage over XMCD, EMCD measurements are made using transmission electron microscopes, which are routinely operated at sub-nanometre resolution, thereby potentially allowing nanometre magnetic characterization. However, because of the low intensity of the EMCD signal, it has not yet been possible to obtain quantitative information from EMCD signals at the nanoscale. Here we demonstrate a new approach to EMCD measurements that considerably enhances the outreach of the technique. The statistical analysis introduced here yields robust quantitative EMCD signals. Moreover, we demonstrate that quantitative magnetic information can be routinely obtained using electron beams of only a few nanometres in diameter without imposing any restriction regarding the crystalline order of the specimen.

Energy loss by channeled electrons: a quantitative study on transition metal oxides.

Electron energy-loss spectroscopy (EELS) attached to current transmission electron microscopes can probe not only element-selective chemical information, but also site-selective information that depends on the position that a specific element occupies in a crystal lattice. The latter information is exploited by utilizing the Bloch waves symmetry in the crystal, which changes with its orientation with respect to the incident electron wave (electron channeling). We demonstrate the orientation dependence of the cross-section of the electron energy-loss near-edge structure for particular crystalline sites of spinel ferrites, by quantitatively taking into account the dynamical diffraction effects with a large number of the diffracted beams. The theoretical results are consistent with a set of experiments in which the transition metal sites in spinel crystal structures are selectively excited. A new measurement scheme for site-selective EELS using a two-dimensional position-sensitive detector is proposed and validated by theoretical predictions and trial experiments.

New algorithm for efficient Bloch-waves calculations of orientation-sensitive ELNES.

We discuss in detail the Bloch waves method for the calculation of energy and orientation dependent scattering cross-section for inelastic scattering of electrons on crystals. Convergence properties are investigated and a new algorithm with superior timing and accuracy is described. The new method is applied to calculations of intensity of weakly excited spots, maps of magnetic signal, and tilt series from zone axis orientation towards three-beam orientation.

Chemical Bonding of AlH3 Hydride by Al-L2,3 Electron Energy-Loss Spectra and First-Principles Calculations.

In a previous study, we used transmission electron microscopy and electron energy-loss (EEL) spectroscopy to investigate dehydrogenation of AlH3 particles. In the present study, we systematically examine differences in the chemical bonding states of Al-containing compounds (including AlH3) by comparing their Al-L2,3 EEL spectra. The spectral chemical shift and the fine peak structure of the spectra were consistent with the degree of covalent bonding of Al. This finding will be useful for future nanoscale analysis of AlH3 dehydrogenation toward the cell.

Local electronic structure analysis by site-selective ELNES using electron channeling and first-principles calculations.

In this paper, we review our recent analyses of electron energy loss near edge structure (ELNES) of particular crystalline sites, exploiting dynamical electron diffraction effects, or electron channeling, whereby the excitation weights of the Bloch waves propagating in a crystal can be controlled systematically by adjusting the diffraction conditions. A state-of-the-art data processing technique, multivariate curve resolution (MCR), can restore purely site-specific spectral profiles and their compositions from the experimental data set. Another technique, the Pixon deconvolution method, effectively removes the statistical noise, which enables us to compare the spectral fine structures with those calculated by first principles and discuss the site-specific local atomic and electronic structures. We demonstrate typical case studies in model materials and then an advanced chemical state analysis in a real material. Finally, some remarks toward further refinement of the method are made.

Spectral restoration and energy resolution improvement of electron energy-loss spectra by Pixon reconstruction: II. Application to practical ELNES analysis of low SNR.

We applied Pixon deconvolution as introduced in Part I to several practical, examples of low signal-to-noise ratio (SNR), electron energy-loss spectra with a goal toward restoring their fine spectral features and/or improving the energy resolution. We demonstrate that by directly fitting the two-dimensional spectral data recorded on the CCD; the method enables us to reveal fine spectral structures. Consequently, Pixon reconstruction extends the ability to probe electronic states in very spatially localized areas, a capability currently unique to our method.

Spectral restoration and energy resolution improvement of electron energy-loss spectra by Pixon reconstruction: I. Principle and test examples.

We explore the use of the Pixon method, one of the highest performance image reconstruction methods available today, for the analysis of electron energy loss spectra (EELS). The method takes particular advantage of two-dimensional (2-D) CCD data, in which the data are blurred by a PRF (point-response-function as measured by the low-loss spectrum) both in the direction of energy dispersion and in the cross-dispersion direction. The Pixon method is used to simultaneously (i) deconvolve the PRF, increasing the spectral resolution, and (ii) fit the data in the cross-dispersion direction which efficiently combines the signal into a single parent spectrum. Relative to 1-D methods, we demonstrate that our 2-D treatment (i) more effectively detects weak features and (ii) allows EELS methods to be applied to much lower signal-to-noise ratio data. Both of these advantages are critical to the future development of EELS analysis.

Peak assignments of ELNES and XANES using overlap population diagrams.

The usefulness of overlap population (OP) diagrams for peak assignments of an electron energy loss near-edge structure (ELNES) and an X-ray absorption near-edge structure (XANES) is demonstrated. Mg-K, L(2,3), and O-K edges of MgO are taken as examples. Theoretical calculations are performed using a first-principles orthogonalized linear combination of atomic orbitals (OLCAO) method. A core-hole is included explicitly, and a large supercell is used to minimize artificial interactions among the core-holes in adjacent cells. All experimental spectra are quantitatively reproduced by the calculations. The OP diagrams for a selected pair of atomic orbitals are computed in order to provide proper assignments for each peak in ELNES and XANES. They are interpreted in terms of interactions among Mg-Mg and Mg-O bonds. Results are found to be consistent to our previous conclusion, which was obtained using a cluster method [T. Mizoguchi, et al., Phys. Rev. B 61 (2000) 2180]. The powerful combination of the OP diagram and a high-energy resolution ELNES to obtain fine electronic structures is also demonstrated.

Site-specific electronic structure analysis by channeling EELS and first-principles calculations.

Site-specific electronic structures were investigated by electron energy loss spectroscopy (EELS) under electron channeling conditions. The Al-K and Mn-L(2,3) electron energy loss near-edge structure (ELNES) of, respectively, NiAl2O4 and Mn3O4 were measured. Deconvolution of the raw spectra with the instrumental resolution function restored the blunt and hidden fine features, which allowed us to interpret the experimental spectral features by comparing with theoretical spectra obtained by first-principles calculations. The present method successfully revealed the electronic structures specific to the differently coordinated cationic sites.