Core-loss Electron Energy-loss Spectroscopy Research Articles

Discovering invariant spatial features in electron energy loss spectroscopy images on the mesoscopic and atomic levels

Over the last two decades, Electron Energy Loss Spectroscopy (EELS) imaging with a scanning transmission electron microscope has emerged as a technique of choice for visualizing complex chemical, electronic, plasmonic, and phononic phenomena in complex materials and structures. The availability of the EELS data necessitates the development of methods to analyze multidimensional data sets with complex spatial and energy structures. Traditionally, the analysis of these data sets has been based on analysis of individual spectra, one at a time, whereas the spatial structure and correlations between individual spatial pixels containing the relevant information of the physics of underpinning processes have generally been ignored and analyzed only via the visualization as 2D maps. Here, we develop a machine learning-based approach and workflows for the analysis of spatial structures in 3D EELS data sets using a combination of dimensionality reduction and multichannel rotationally invariant variational autoencoders. This approach is illustrated for the analysis of both the plasmonic phenomena in a system of nanowires and in the core excitations in functional oxides using low loss and core-loss EELS, respectively. The code developed in this manuscript is open sourced and freely available and provided as a Jupyter notebook for the interested reader.

Synthesis, characterization, and preliminary insights of ZnFe2O4 nanoparticles into potential applications, with a focus on gas sensing

This work presents a hydrothermal-based facile method for synthesizing ZnFe2O4, whose size can be controlled with the concentration of sodium acetate used as a fuel and its physical changes at nanoscales when exposed to two different gases. The structural, morphological, compositional, and electronic properties of the synthesized samples are also presented in this paper. The crystal structure of the synthesized samples was determined using an X-ray Diffractometer (XRD). The results revealed fluctuations in the size, lattice parameter, and strain in the nanoparticles with increasing the concentration of sodium acetate. Field-Emission Scanning Electron Microscopy (FESEM) was used to determine synthesized materials’ morphology and particle size. It revealed that the particles possessed approximately spherical morphology whose size decreased significantly with the increasing amount of sodium acetate. Transmission Electron Microscopy (TEM) was utilized to determine the structure, morphology, and elemental distributions in particles at the nanoscale, and it confirmed the findings of XRD and FESEM analyses. The high-resolution TEM (HRTEM) imaging analysis of the nanoparticles in our studied samples revealed that the particles predominantly possessed (001) type facets. X-ray photoelectron spectroscopy (XPS) and core-loss electron energy loss spectroscopy (EELS) showed an increasing fraction of Fe2+ with the decreasing size of the particles in samples. The Brunauer, Emmett, and Tellers (BET) analysis of samples revealed a higher surface area as the particle size decreases. In addition, the determined surface area and pore size values are compared with the literature, and it was found that the synthesized materials are promising for gas-sensing applications. The ab initio calculations of the Density of States (DOS) and Band structure of (001) surface terminating ZnFe2O4 were carried out using Quantum Espresso software to determine the bandgap of the synthesized samples. They were compared to their corresponding experimentally determined bandgap values and showed close agreement. Finally, in-situ TEM measurement was carried out on one of the four studied samples with robust properties using Ar and CO2 as reference and target gases, respectively. It is concluded from the presented study that the size reduction of the ZnFe2O4 nanoparticles (NPs) tunes the bandgap and provides more active sites due to a higher concentration of oxygen vacancies. The in-situ TEM showed us a nanoscale observation of the change in one of the crystal structure parameters. The d spacing of ZnFe2O4 NPs showed a noticeable fluctuation, reaching more than 5% upon exposure to CO2 and Ar gases.

Identifying and imaging polymer functionality at high spatial resolution with core-loss EELS

Electron energy loss spectroscopy (EELS) is a proven tool for probing materials chemistry at high spatial resolution. Core-loss EELS fine structure should allow measurement of local polymer chemistry. For organic materials, sensitivity to radiolysis is expected to limit the resolution achievable with EELS: but core-loss EELS has proven difficult at any resolution, yielding inconsistent spectra that compare unfavorably with theoretically analogous x-ray absorption spectra. Many of the previously identified shortcomings should not be limiting factors on modern equipment. This study establishes that EELS can generate identifiable carbon K-edge spectra for a range of common polymer types and chemistry, and demonstrates fine structure features matching prior x-ray absorption spectra. EELS fine structure features broaden intuitively with the instrument's energy resolution, and beam-induced features are readily differentiated by collecting spectra at a series of doses. The results are demonstrated with spectrum images of a model polymer blend, and used to estimate practical pixel sizes that can be used for mapping core-loss EELS as a function of electron dose.

Feature-specific Correlation of Structural, Optical, and Chemical Properties in the Transmission Electron Microscope with Hypermodal Data Fusion

AbstractModern transmission electron microscopy instrumentation can probe a wide range of structural, optical, and chemical properties with unprecedented resolution. However, each of these properties must be recorded in independent datasets using different detector modes with no unifying framework currently available for quantitatively mapping their relationships onto chemically distinct features, particularly in complex morphologies. Here, we tackle this challenge by proposing a data acquisition and analysis workflow called “hypermodal data fusion,” describing how to directly couple an arbitrary number of highly disparate detector modes including spectroscopy and scanning diffraction and jointly analyze them for correlations. We demonstrate this concept on a random collection of anatase and rutile nanoparticles, first detailing how to use core-loss electron energy-loss spectroscopy to unmix the different polymorphs despite three-dimensional overlap along the beam direction and then showing how this can be used to extract polymorph-specific composition, bandgaps, and crystal structure. We conclude with a discussion on the applicability of this workflow for a broad range of materials systems.

Probing the structure of vanadium tetracyanoethylene using electron energy-loss spectroscopy

The molecule-based ferrimagnetic semiconductor vanadium tetracyanoethylene (V[TCNE]x, x ≈ 2) has garnered interest from the quantum information community due to its excellent coherent magnonic properties and ease of on-chip integration. Despite these attractive properties, a detailed understanding of the electronic structure and mechanism for long-range magnetic ordering have remained elusive due to a lack of detailed atomic and electronic structural information. Previous studies via x-ray absorption near edge spectroscopy and the extended x-ray absorption fine structure have led to various proposed structures, and in general, V[TCNE]x is believed to be a three-dimensional network of octahedrally coordinated V2+, each bonded to six TCNE molecules. Here, we elucidate the electronic structure, structural ordering, and degradation pathways of V[TCNE]x films by correlating calculations of density functional theory (DFT) with scanning transmission electron microscopy and electron energy-loss spectroscopy (EELS) of V[TCNE]x films. Low-loss EELS measurements reveal a bandgap and an excited state structure that agree quantitatively with DFT modeling, including an energy splitting between apical and equatorial TCNE ligands within the structure, providing experimental results directly backed by theoretical descriptions of the electronic structure driving the robust magnetic ordering in these films. Core-loss EELS confirms the presence of octahedrally coordinated V+2 atoms. Upon oxidation, changes in the C1s-π* peak indicate that C=C of TCNE is preferentially attacked. Furthermore, we identify a relaxation of the structural ordering as the films age. These results lay the foundation for a more comprehensive and fundamental understanding of magnetic ordering and dynamics in these classes of metal–ligand compounds.

Strategies for EELS Data Analysis. Introducing UMAP and HDBSCAN for Dimensionality Reduction and Clustering.

Hierarchical density-based spatial clustering of applications with noise (HDBSCAN) and uniform manifold approximation and projection (UMAP), two new state-of-the-art algorithms for clustering analysis, and dimensionality reduction, respectively, are proposed for the segmentation of core-loss electron energy loss spectroscopy (EELS) spectrum images. The performances of UMAP and HDBSCAN are systematically compared to the other clustering analysis approaches used in EELS in the literature using a known synthetic dataset. Better results are found for these new approaches. Furthermore, UMAP and HDBSCAN are showcased in a real experimental dataset from a core–shell nanoparticle of iron and manganese oxides, as well as the triple combination nonnegative matrix factorization–UMAP–HDBSCAN. The results obtained indicate how the complementary use of different combinations may be beneficial in a real-case scenario to attain a complete picture, as different algorithms highlight different aspects of the dataset studied.

Combined study of the ground and excited states of carbon onions by electron energy-loss spectroscopy: Comparison with highly ordered pyrolytic graphite

Herein, an extensive electron energy loss spectroscopy (EELS) study presents the electronic structure properties of carbon nano-onions (CNOs) and graphite under same acquisition conditions, respectively. The low-loss and core-loss EELS spectra were recorded at the so-called “magic angle” on the optic axis in a transmission electron microscope. Through the “three-Gaussian” method we found the second peak in the core-loss spectrum of CNOs is markedly different from that of graphite. Valence Compton profiles were obtained by recording the EELS at a large scattering angle. The CNOs and graphite Compton profile difference indicates stronger electron localization in CNOs. From this comparison, we are able to conclude that the electronic structure properties of the ground and excited states of CNOs are quite different from those of graphite.

Characterization and understanding of the tilt-dependence of core-loss spectra for hexagonal boron nitride

Despite great interest in the thermo-mechanical, optical, and electronic features of layered materials, the complete nature of anisotropy and its effect on their spectroscopic properties remains poorly understood due to the difficulty in characterizing the chemical bonding in different crystal orientations. Here, we use electron energy loss spectroscopy (EELS) to evaluate the tilt-dependent bonding characterization of hexagonal boron nitride (hBN), a promising layered van der Waals material, by tilting the specimen and studying the changing core-loss spectra. Our experimentally calculated values match well with the theoretically obtained curve of tilt versus relative peak intensities of the core-loss EELS spectra, which illustrates the scope for precise quantitative analysis of layered materials using EELS.

Accurate EELS background subtraction – an adaptable method in MATLAB

• Electron energy loss spectroscopy (EELS) requires background fitting and removal. • Scripts for background subtraction have been written in MATLAB. • The scripts can be applied to core, low, and ultra-low loss EELS. • Statistical information on the goodness-of-fit is given. • Several examples of background subtraction are presented in the main text. Electron energy-loss spectroscopy (EELS) is a technique that can give useful information on elemental composition and bonding environments. However in practice, the complexity of the background contributions, which can arise from multiple sources, can hamper the interpretation of the spectra. As a result, background removal is both an essential and difficult part of EELS analysis, especially during quantification of elemental composition. Typically, a power law is used to fit the background but this is often not suitable for many spectra such as in the low-loss region (< 50 eV) and when there are overlapping EELS edges. In this article, we present a series of scripts written in MATLAB v. R2019b that aims to provide statistical information on the model used to fit the background, allowing the user to determine the accuracy of background subtraction. The scripts were written for background subtraction of vibrational EELS in the ultralow-loss region near the zero-loss peak but can also be applied to other kinds of EEL spectra. The scripts can use a range of models for fitting, provided by the Curve Fitting Toolbox of MATLAB, and the user is able to precisely define the window for fitting as well as for edge integration. We demonstrate the advantages of using these scripts by comparing their background subtraction of example spectra to the most commonly used software, Gatan Microscopy Suite 3. The example spectra include those containing multiple scattering, multiple overlapping peaks, as well as vibrational EELS. Additionally, a comprehensive guide to using the scripts has been included in the Supplementary Information.

Direct Measurement of Electronic Band Structures at Oxide Grain Boundaries.

Grain boundaries (GBs) modulate the macroscopic properties in polycrystalline materials because they have different atomic and electronic structures from the bulk. Despite the progress on the understanding of GB atomic structures, knowledge of the localized electronic band structures is still lacking. Here, we experimentally characterized the atomic structures and the band gaps of four typical GBs in α-Al2O3 by scanning transmission electron microscopy and valence electron energy-loss spectroscopy (EELS). It was found that the band gaps of the GBs are narrowed by 0.5-2.1 eV compared with that of 8.8 eV in the bulk. By combing core-loss EELS with first-principles calculations, we elucidated that the band gap reductions directly correlate with the decrease of the coordination numbers of Al and O ions at the GBs. These results provide in-depth understanding between the local atomic and electronic band structures for GBs and demonstrate a novel electronic-structure analysis for crystalline defects.

Sol-gel synthesis of nanoporous LaFeO3 powders for solar applications

In the present study, we report on the synthesis of nano-porous perovskite-type lanthanum iron oxide, LaFeO3, using the ascorbic-acid assisted sol-gel method. The as-synthesized powders are characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), electron energy-loss spectroscopy (EELS), and ultra-violet visible (UV–Vis) spectrophotometry. Experimental results are systematically discussed by Density Functional Theory modeling analysis. Our XRD findings show that the as-synthesized powders have an excellent crystallinity. These powders are found to be composed of particles around 60 nm in size, as revealed by TEM results, inside which there exist a high density of pores. Each nanoparticle exhibits a good chemical homogeneity as determined from core-loss EELS mapping analysis. Our low-loss EELS analysis, in addition, shows that the optical bandgap as measured on a single particle is close to 2.38 eV, which is larger than that of its bulk counterpart (2.1 eV). This result is also confirmed with the help of UV–Vis McLean analysis on a macroscopic scale, where the inter-pore spacing (22 nm) is found to be responsible for the observed increase in the bandgap. We believe that this increase in the bandgap, combined with the fine inter-particles porosity, make our as-synthesize nanoporous LaFeO3 powders a promising candidate for solar photocatalytic activities.

Quantification of Charge Transfer at the Interfaces of Oxide Thin Films.

The interfacial electronic distribution in transition-metal oxide thin films is crucial to their interfacial physical or chemical behaviors. Core-loss electron energy-loss spectroscopy (EELS) may potentially give valuable information of local electronic density of state at high spatial resolution. Here, we studied the electronic properties at the interface of Pb(Zr0.2Ti0.8)O3 (PZT)/4.8 nm La0.8Sr0.2MnO3 (LSMO)/SrTiO3 (STO) using valance-EELS with a scanning transmission electron microscope. Modeled with dielectric function theory, the charge transfer in the vicinity of the interfaces of PZT/LSMO and LSMO/STO was determined from the shifts of plasma peaks of valence EELS (VEELS), agreeing with theoretical prediction. Our work demonstrates that the VEELS method enables a high-efficient quantification of the charge transfer at interfaces, shedding light on the charge-transfer issues at heterogenous interfaces in physical and chemical devices.

Measuring the areal density of nanomaterials by electron energy-loss spectroscopy

Thickness measurements of nanomaterials are usually performed using transmission electron microscopy (TEM) techniques such as convergent beam electron diffraction (CBED) patterns analysis and the log-ratio method based on electron energy-loss spectroscopy (EELS) spectrum. However, it is challenging to obtain both the thickness and elemental information, especially in non-crystalline materials or for very thin samples. In this work, we establish a series of procedures to calculate the areal density of the material by directly measuring the inelastic scattering probability in a thin sample. Core-loss EELS are fit with a quantitative model to extract atomic areal density. Knowledge of one of the parameters (volume density or sample thickness) allows a measurement of the other. The absolute error between the known thicknesses and those measured was less than 4% using two-dimensional materials with a well-defined thickness as test samples, which is much better than the log-ratio method for very thin samples. One promising advantage of this method is the thickness/areal density determination in mixed phase/element systems. We use Ag-Co bimetallic triangles and black rutile as examples to calculate the thickness map in mixture systems in different cases. We also demonstrate this technique can be applied to measure the argon gas density in spherical cavities. This allows a temperature vs pressure curve to be obtained and illustrates the unique capability of this technique.

Assessing Oxygen Vacancies in Bismuth Oxide through EELS Measurements and DFT Simulations

Pioneering electron energy loss spectroscopy (EELS) measurements of α-Bi2O3 are performed on three samples obtained through different synthesis methods. Experimental low-loss and core-loss EELS spectra are acquired. By combining them with detailed structural characterization and Density Functional Theory (DFT) simulations, we are able to detect and evaluate the presence of oxygen vacancies in the samples. This type of information has not been accessed previously from EELS data in bismuth oxide, because high-resolution EELS spectra or how vacancies reflect in Bi2O3 spectra were unreported. This novel measurement is further validated through comparison with photoluminescence data. Therefore, the technique has the ability to probe oxygen vacancies in Bi2O3 at an unprecedented resolution, which might allow solving material science and technological issues related to this material.

High efficiency core-loss EELS analyzing from the viewpoint of chemometrics

Electron energy–loss spectroscopy (EELS) equipped on a modern scanning transmission electron microscope is a powerful high resolution elemental analysis technique. However, the conventional method of extracting elemental information quantitatively from EELS spectra is non-trivial. In this article we tried to interpret EELS data from the viewpoint of chemometrics. An EELS spectrum image collected from a vicinal SiC/SiO2 interface was employed as an example. By analyzing the EELS data with sophisticated chemometrics methods, chemical components and elemental ratios of C/Si and O/Si across the interface were derived. Compared with conventional EELS analysis, the chemometrics methods gave more reliable and accurate results with higher calculation efficiency. The chemometrics analysis confirmed that the transition from SiC to SiO2 was chemically sharp, and the transition layer in the vicinal interface was a linear combination of SiC and SiO2. Chemometrics analysis can be a fast and robust complementary method for EELS analysis.

Investigation of phase separation in InGaN alloys by plasmon loss spectroscopy in a TEM

ABSTRACTPhase separation of InxGa1-xN alloys into Ga-rich and In-rich regions was observed by a number of research groups for samples grown with high indium content, x. Due to the radiation sensitivity of InGaN to beam damage by fast electrons, high-resolution imaging in transmission electron microscopy (TEM) or core-loss electron energy-loss spectroscopy (EELS) may lead to erroneous results. Low-loss EELS can yield spectra of the plasmon loss regions at much lower electron fluxes. Unfortunately, due to their delayed edge onset, the low energetic core losses of Ga and In partially overlap with the plasmon peaks, all of which shift with indium content.Here we demonstrate a method to quantify phase separation in InGaN thin films from the low-loss region in EELS by simultaneously fitting both plasmon and core losses over the energy range of 13-30eV. Phase separation is shown to lead to a broadening of the plasmon peak and the overlapping core losses, resulting in an unreliable determination of the indium concentration from analyzing the plasmon peak position alone if phase separation is present. For x=0.3 and x=0.59, the relative contributions of the binary compounds are negligibly small and indicate random alloys. For xnom.=0.62 we observed strong broadening, indicating phase separation.

High-Resolution Imaging and Spectroscopy at High Pressure: A Novel Liquid Cell for the Transmission Electron Microscope.

We demonstrate quantitative core-loss electron energy-loss spectroscopy of iron oxide nanoparticles and imaging resolution of Ag nanoparticles in liquid down to 0.24 nm, in both transmission and scanning transmission modes, in a novel, monolithic liquid cell developed for the transmission electron microscope (TEM). At typical SiN membrane thicknesses of 50 nm the liquid-layer thickness has a maximum change of only 30 nm for the entire TEM viewing area of 200×200 µm.

Interplay of strain and indium incorporation in InGaN/GaN dot-in-a-wire nanostructures by scanning transmission electron microscopy

The interplay between strain and composition is at the basis of heterostructure design to engineer new properties. The influence of the strain distribution on the incorporation of indium during the formation of multiple InGaN/GaN quantum dots (QDs) in nanowire (NW) heterostructures has been investigated, using the combined techniques of geometric phase analysis of atomic-resolution images and quantitative elemental mapping from core-loss electron energy-loss spectroscopy within scanning transmission electron microscopy. The variation in In-content between successive QDs within individual NWs shows a dependence on the magnitude of compressive strain along the growth direction within the underlying GaN barrier layer, which affects the incorporation of In-atoms to minimize the local effective strain energy. Observations suggest that the interfacial misfit between InGaN/GaN within the embedded QDs is mitigated by strain partitioning into both materials, and results in normal stresses inflicted by the presence of the surrounding GaN shell. These experimental measurements are linked to the local piezoelectric polarization fields for individual QDs, and are discussed in terms of the photoluminescence from an ensemble of NWs.

Theoretical study of core-loss electron energy-loss spectroscopy at graphene nanoribbon edges

A systematic study of simulated atomic-resolution electronic energy-loss spectroscopy (EELS) for different graphene nanoribbons (GNRs) is presented. The results of ab initio studies of carbon core-loss EELS on GNRs with different ribbon edge structures and different hydrogen terminations show that theoretical core-loss EELS can distinguish key structural features at the atomic scale. In addition, the combination of polarized core-loss EELS with symmetry resolved electronic partial density of states calculations can be used to identify the origins of all the primary features in the spectra. For example, the nature of the GNR edge structure (armchair, zigzag, etc) can be identified, along with the degree of hydrogenation. Hence it is possible to use the combination of ab initio calculations with high resolution, high energy transmission core-loss EELS experiments to determine the local atomic arrangement and chemical bonding states (i.e. a structural fingerprint) in GNRs, which is essential for future practical applications of graphene.

Probing the Chemical Structure in Diamond-Based Materials Using Combined Low-Loss and Core-Loss Electron Energy-Loss spectroscopy

We report the analysis of the changes in local carbon structure and chemistry caused by the self-implantation of carbon into diamond via electron energy-loss spectroscopy (EELS) plasmon energy shifts and core-edge fine structure fingerprinting. These two very different EELS energy and intensity ranges of the spectrum can be acquired under identical experimental conditions and nearly simultaneously using specially designed deflectors and energy offset devices known as "DualEELS." In this way, it is possible to take full advantage of the unique and complementary information that is present in the low- and core-loss regions of the EELS spectrum. We find that self-implanted carbon under the implantation conditions used for the material investigated in this paper creates an amorphous region with significant sp 2 content that varies across the interface.