Electron Energy Loss Spectroscopy Research Articles

Transmission electron microscopic study on rutile-type GeO2 film on TiO2 (001) substrate

Rutile-type GeO2 (r-GeO2) with an ultrawide bandgap of ∼4.7 eV has emerged as a promising material for next-generation power-electronic and optoelectronic devices. We performed transmission electron microscopy (TEM) observation to analyze the structural properties of r-GeO2 film on r-TiO2 (001) substrate at an atomic level. The r-GeO2 film exhibits a threading dislocation density of 3.6 × 109 cm−2 and there exist edge-, screw-, and mixed-type dislocations in the film as demonstrated by two-beam TEM. The edge-type dislocations have Burgers vectors of [100] and/or [110]. The bandgap of the r-GeO2 film is 4.74 ± 0.01 eV as determined by electron energy loss spectroscopy.

Scalable bottom-up synthesis of Co-Ni-doped graphene.

Introducing heteroatoms into graphene is a powerful strategy to modulate its catalytic, electronic, and magnetic properties. At variance with the cases of nitrogen (N)- and boron (B)-doped graphene, a scalable method for incorporating transition metal atoms in the carbon (C) mesh is currently lacking, limiting the applicative interest of model system studies. This work presents a during-growth synthesis enabling the incorporation of cobalt (Co) alongside nickel (Ni) atoms in graphene on a Ni(111) substrate. Single atoms are covalently stabilized within graphene double vacancies, with a Co load ranging from 0.07 to 0.22% relative to C atoms, controllable by synthesis parameters. Structural characterization involves variable-temperature scanning tunneling microscopy and ab initio calculations. The Co- and Ni-codoped layer is transferred onto a transmission electron microscopy grid, confirming stability through scanning transmission electron microscopy and electron energy loss spectroscopy. This method holds promise for applications in spintronics, gas sensing, electrochemistry and catalysis, and potential extension to graphene incorporation of similar metals.

Direct Three-Dimensional Observation of the Plasmonic Near-Fields of a Nanoparticle with Circular Dichroism.

Characterizing the spatial distribution of the electromagnetic fields of a plasmonic nanoparticle is crucial for exploiting its strong light-matter interaction for optoelectronic and catalytic applications. However, observing the near-fields in three dimensions with a high spatial resolution is still challenging. To realize efficient three-dimensional (3D) nanoscale mapping of the plasmonic fields of nanoparticles with complex shapes, this work established autoencoder-embedded electron energy loss spectroscopy (EELS) tomography. A 432-symmetric chiral gold nanoparticle, a nanoparticle with a high optical dissymmetry factor, was analyzed to relate its geometrical features to its exotic optical properties. Our deep-learning-based feature extraction method discriminated plasmons with different energies in the EEL spectra of the nanoparticle in which signals from multiple plasmons were intermixed; this component was key for acceptable 3D visualization of each plasmonic field separately using EELS tomography. With this methodology, the electric field of the plasmon that induces far-field circular dichroism was observed in 3D. The field linked to this chiroptical property was strong along the swirling edges of the particle, as predicted by a numerical calculation. This study provides insight into the correlation between structural and optical chiralities through direct 3D observation of the plasmonic fields. Furthermore, the strategy of implementing an autoencoder for EELS tomography can be generalized to achieve competent 3D analysis of other features, including the optical properties of the dielectrics and chemical states.

Characterization of fuel cladding chemical interaction on a high burnup U-10Zr metallic fuel via electron energy loss spectroscopy enhanced by machine learning

Fuel cladding chemical interaction (FCCI) is one of the limiting factors for metallic fuels in nuclear application. A comprehensive analysis of chemical elements in FCCI is the basis for understanding the phenomena and developing potential mitigating strategies. The detection of low atomic number elements (Z < 11) and lanthanide fission products is challenging for energy dispersive x-ray spectroscopy (EDS). This work used scanning transmission electron microscopy (STEM) based electron energy loss spectroscopy (EELS) to study the distribution of carbon and lanthanides in the FCCI region of a solid U-10Zr (wt%) fuel irradiated to 13.2 at. % burnup at fast flux testing facility. Processing the EELS data involved three major steps: 1) enhancing the signal to noise ratio by denoising the spectrum using principal component analysis methods; 2) identification of chemical elements with core energy loss edges; 3) microstructural phase segmentation based on raw EELS spectrums using the K-means clustering method. EELS analysis revealed the formation of zirconium carbide, a rind-like microstructural phase in FCCI region between fuel and cladding. This rind appeared to be intact at this burnup. The study also revealed the shift of plasmon peak between zirconium and zirconium carbide. The EELS mapping also indicated a different distribution of Ce from other lanthanide elements, such as La, Pr, and Nd, suggesting the lanthanides should be separately investigated. The use of the K-means clustering method on the EELS data of FCCI region revealed different phases, especially Fe-Ce and Zr-C, that concurred with the findings from EDS and STEM-EELS elemental mappings.

Detailed study of interphase degradation in SiC/BN/SiC ceramic matrix composites after elevated temperature tensile testing

Ceramic matrix composites of silicon carbide fibres in a silicon carbide matrix with boron nitride interphase are promising candidates for replacing superalloys in the hottest part of aerospace engines, reducing the need for cooling and increasing the fuel efficiency. This needs a thorough understanding of how these materials degrade under high levels of stress combined with high temperatures in an oxidative environment. This work presents a detailed investigation of the degradation in the interphase and surrounding interfaces. Advanced electron microscopy and electron energy loss spectroscopy are used to extract information on the degradation process. It was found that silica and boria form along with a migration of silica into the interphase. At 1000 °C the degradation along the surface leads to early fracture at the surface and eventually complete fracture of the composite, lower temperature allows for the oxidation to reach the centre of the sample before complete failure.

On the structural and bandgap properties of mist-CVD-grown κ-Ga2O3 post continuous temperature annealing

We investigate the continuous annealing of orthorhombic κ-Ga2O3 films on AlN/c-plane sapphire templates grown by Mist Chemical Vapor Deposition (mist-CVD) using in situ high-temperature x-ray diffraction (HT-XRD). Increasing the annealing temperature from 400 to 1100 °C in both vacuum and ambient air reveals a phase transition onset at 825 °C. High-resolution transmission electron microscopy and XRD demonstrated that annealing within the stability window of 650 to 775 °C effectively improves the crystal quality of the κ-Ga2O3 thin film. Optical transmittance and low-loss electron energy loss spectroscopy (EELS) show the pristine film’s bandgaps to be 4.96 and 4.67 eV, respectively, with reduced bandgaps in annealed films due to increased defect density. EELS-derived optical joint density of states indicates that air-annealing fosters sub-bandgap radiative processes, while vacuum annealing suppresses them, qualitatively correlated with the observed photoluminescence intensity variations. The results of this comprehensive high-temperature annealing study offer crucial insight into the influence of annealing ambient conditions on the crystallographic properties of κ-Ga2O3 films and the associated evolution of extended sub-bandgap states.

ZIF-derived non-bonding Cu/Zn catalysts-driven peroxymonosulfate activation via selective generation of surface-bound radicals for efficient water purification

The peroxymonosulfate-based advanced oxidation processes (PMS-AOPs) have been extensively studied in wastewater treatment due to their ability to generate various reactive oxygen species. However, the ultra-short half-lives of free radical species limit their effective transfer from the catalyst surfaces to the target organic contaminants for efficient decontamination. Thus, directed production of reactive species with longer lifetimes is challenging but belong with significant demand. In this study, a catalyst with neighboring Cu and Zn heteroatoms pairs anchored on the surface of zeolitic imidazolate framework (Cu/Zn-ZIF) was designed to selectively and sustainably generate radicals via PMS activation. Electron energy-loss spectroscopy (EELS) demonstrated the formation of non-bonding Cu-Zn heteroatom pairs. Owing to the synergistic effect of the Cu and Zn heteroatoms, the Cu/Zn-ZIF/PMS system achieved 99.5 % removal rate of bisphenol A (BPA) within 60 min. Therein, PMS was stabilized by the strongly adsorptive Cu/Zn-ZIF and activated within the nanoscale confinement of Cu sites, resulting in the directional generation of surface-bound •OH and SO4•− radicals with longer lifetimes, which facilitated the efficient removal of BPA. Significantly, it also demonstrated robust resilience against disruptions caused by intricate aquatic environments, including freshwater bodies and ionic species. These findings provide reference for theoretical research on the design of functional MOFs materials and the practical application of surface-bound radicals in AOPs

Electron-Beam Writing of Atomic-Scale Reconstructions at Oxide Interfaces.

The epitaxial growth of complex oxides enables the production of high-quality films, yet substrate choice is restricted to certain symmetry and lattice parameters, thereby limiting the technological applications of epitaxial oxides. In comparison, the development of free-standing oxide membranes gives opportunities to create novel heterostructures by nonepitaxial stacking of membranes, opening new possibilities for materials design. Here, we introduce a method for writing, with atomic precision, ionically bonded crystalline materials across the gap between an oxide membrane and a carrier substrate. The process involves a thermal pretreatment, followed by localized exposure to the raster scan of a scanning transmission electron microscopy (STEM) beam. STEM imaging and electron energy-loss spectroscopy show that we achieve atomically sharp interface reconstructions between a 30-nm-thick SrTiO3 membrane and a niobium-doped SrTiO3(001)-oriented carrier substrate. These findings indicate new strategies for fabricating synthetic heterostructures with novel structural and electronic properties.

Layer Resolved Cr Oxidation State Modulation in Epitaxial SrFe0.67Cr0.33O3-δ Thin Films.

Understanding how doping influences physicochemical properties of ABO3 perovskite oxides is critical for tailoring their functionalities. In this study, SrFe0.67Cr0.33O3-δ epitaxial thin films were used to examine the effects of Fe and Cr competition on structure and B-site cation oxidation states. The films exhibit a perovskite-like structure near the film/substrate interface, while a brownmillerite-like structure with horizontal oxygen vacancy channels predominates near the surface. Electron energy loss spectroscopy shows Fe remains Fe3+, while Cr varies from ∼Cr3+ (tetrahedral layers) to ∼Cr4+ (octahedral layers) within brownmillerite phases and becomes ∼Cr4.5+ in perovskite-like phases. Theoretical simulations indicate that Cr-O bond arrangements and the way oxygen vacancies interact with Cr and Fe drive Cr charge disproportionation. High-valent Cr cations introduce additional densities of states near the Fermi level, reducing the optical bandgap from ∼2.0 eV (SrFeO2.5) to ∼1.7 eV (SrFe0.67Cr0.33O3-δ). These findings offer insights into B-site cation doping in the perovskite oxide framework.

Phonon modes and electron-phonon coupling at the FeSe/SrTiO3 interface.

The remarkable increase in superconducting transition temperature (Tc) observed at the interface of one-unit-cell FeSe films on SrTiO3 substrates (1 uc FeSe/STO)1 has attracted considerable research into the interface effects2-6. Although this high Tc is thought to be associated with electron-phonon coupling (EPC)2, the microscopic coupling mechanism and its role in the superconductivity remain elusive. Here we use momentum-selective high-resolution electron energy loss spectroscopy to atomically resolve the phonons at the FeSe/STO interface. We uncover new optical phonon modes, coupling strongly with electrons, in the energy range of 75-99 meV. These modes are characterized by out-of-plane vibrations of oxygen atoms in the interfacial double-TiOx layer and the apical oxygens in STO. Our results also demonstrate that the EPC strength and superconducting gap of 1 uc FeSe/STO are closely related to the interlayer spacing between FeSe and the TiOx terminated STO. These findings shed light on the microscopic origin of the interfacial EPC and provide insights into achieving large and consistent Tc enhancement in FeSe/STO and potentially other superconducting systems.

Mapping the energy-momentum dispersion of hBN excitons and hybrid plasmons in hBN-WSe2 heterostructures

Heterostructures obtained by combining two-dimensional (2D) sheets are widely investigated as a platform for designing new materials with customised characteristics. Transition metal dichalcogenides (TMDCs) are often combined with hexagonal boron nitride (hBN) to enhance their excitonic resonances. However, little is known about how stacking affects excitons and plasmons in TMDCs or their mutual interactions. Here, we combine momentum-resolved electron energy-loss spectroscopy with first-principles calculations to study the energy-momentum dispersion of plasmons in multi-layer WSe2-hBN heterostructures as well as in their isolated components. The dispersion of the high-momentum excitons of hBN, alone and in combination with WSe2, is mapped across the entire Brillouin zone. Signatures of hybridisation in the plasmon resonances and some of the excitons suggest that the contribution of hBN cannot be neglected when interpreting the response of such a heterostructure. The consequences of using hBN as an encapsulant for TMDCs are also discussed.

Elemental mapping in single-particle reconstructions by reconstructed electron energy-loss analysis.

For macromolecular structures determined by cryogenic electron microscopy, no technique currently exists for mapping elements to defined locations, leading to errors in the assignment of metals and other ions, cofactors, substrates, inhibitors and lipids that play essential roles in activity and regulation. Elemental mapping in the electron microscope is well established for dose-tolerant samples but is challenging for biological samples, especially in a cryo-preserved state. Here we combine electron energy-loss spectroscopy with single-particle image processing to allow elemental mapping in cryo-preserved macromolecular complexes. Proof-of-principle data show that our method, reconstructed electron energy-loss (REEL) analysis, allows a three-dimensional reconstruction of electron energy-loss spectroscopy data, such that a high total electron dose is accumulated across many copies of a complex. Working with two test samples, we demonstrate that we can reliably localize abundant elements. We discuss the current limitations of the method and potential future developments.

Atomic-scale visualization of defect-induced localized vibrations in GaN.

Phonon engineering is crucial for thermal management in GaN-based power devices, where phonon-defect interactions limit performance. However, detecting nanoscale phonon transport constrained by III-nitride defects is challenging due to limited spatial resolution. Here, we used advanced scanning transmission electron microscopy and electron energy loss spectroscopy to examine vibrational modes in a prismatic stacking fault in GaN. By comparing experimental results with ab initio calculations, we identified three types of defect-derived modes: localized defect modes, a confined bulk mode, and a fully extended mode. Additionally, the PSF exhibits a smaller phonon energy gap and lower acoustic sound speeds than defect-free GaN, suggesting reduced thermal conductivity. Our study elucidates the vibrational behavior of a GaN defect via advanced characterization methods and highlights properties that may affect thermal behavior.

Investigating the expansion behavior of silicon nitride nanopores

Nanopores are a single-molecule detection platform that has attracted more and more researchers’ attention, but so far there is still a lack of systematic research on their stability. In this study, we investigated the mechanism behind the expansion behavior of solid-state nanopores and its effect on the electrical properties of nanopores. Through the analysis of electron energy loss spectroscopy, it was found that the expansion process of nanopores is accompanied by the loss of silicon elements. Three nanopore expansion models can well explain the differential impact of silicon element loss in different regions on the electrical properties of nanopores. Molecular dynamics simulations analyzed the differences in nanopore conductivity and expansion rate corresponding to different expansion models from the perspective of single-atom loss. Finally, we demonstrated that chemical modification can isolate direct contact between the nanopore wall and the solution, thereby greatly delaying the expansion behavior of solid-state nanopores.

MXene Electrodes for All Strain-Free Solid-State Batteries.

All-solid-state batteries with nonflammable inorganic solid electrolytes are the key to addressing the safety issues of lithium-ion batteries with flammable organic liquid electrolytes. However, conventional electrode materials suffer from substantial volume changes during Li+ (de)intercalation, leading to mechanical failure of interfaces between electrode materials and solid electrolytes and then severe performance degradation. In this study, we report strain-free charge storage via the interfaces between transition metal carbides (MXenes) and solid electrolytes, where MXene shows negligible structural changes during Li+ (de)intercalation. Operando scanning electron transmission microscopy with electron energy-loss spectroscopy reveals the pillar effect of trapped Li+ in the interlayer spaces of MXene to achieve the strain-free features. An all strain-free solid-state battery, which consists of a strain-free Ti3C2Tx negative electrode and a strain-free disordered rocksalt Li8/7Ti2/7V4/7O2 positive electrode, demonstrates long-term stable operation while preserving the interfacial contact between electrode materials and solid electrolytes.

Size-Dependent Core-Shell Fine Structures and Oxygen Evolution Activity of Electrochemical IrOx Nanoparticles Revealed by Cryogenic Electron Microscopy.

Electrochemically oxidized amorphous iridium oxides (IrOx) offer significantly improved electrocatalytic activities on the oxygen evolution reaction (OER) compared to crystalline IrO2, yet the origin of their decent activity and their size-dependent properties have not been fully understood. An important argument is the formation of deprotonated oxygen species not only at the topmost surface but also at the near surface, which creates an electrophilic character that activates the OER electrocatalysis. However, high spatial resolution identification of the electrophilic oxygen species remains unachieved. We address this hitherto-unresolved problem on size-selected electrochemical IrOx nanoparticles (NPs) by using cryogenic scanning transmission electron microscopy combined with electron energy loss spectroscopy, which enables simultaneous atomic detection of the near surface compositional and electronic structures with minimal damage that are further correlated with their size-dependent OER activities. Depending on the particle size, the electrochemical IrOx NPs showed distinctly different core-shell fine structures ranging from amorphous and hydrous IrOxHy NPs to a "metallic Ir core/sub-stoichiometric IrOx interlayer/amorphous IrOxHy shell" NP structure. Moreover, the formation of deprotonated, electrophilic oxygen is directly identified at the substoichiometric IrOx interface layer. These features account for a previously unestablished particle size effect of the electrochemical IrOx NPs, showing increasing water oxidation reactivity with an increasing nanoparticle size. Our results provide important insights into how subsurface oxygen chemistry controls the surface reactivity in the nanoscale Ir-based OER electrocatalysts.

Effect of pure (ligand-free) nanoparticles of magnetite in sodium chloride matrix on hematological indicators, blood gases, electrolytes and serum iron

AbstractOne of the physical methods for obtaining magnetite nanoparticles (NPs) is electron beam physical vapor deposition (EB PVD), which requires complex equipment, but allows obtaining a significant amount of pure (ligand-free) NPs. The biomedical application of such NPs is less studied than materials from other synthesis methods. The objective is to study the effect of pure magnetite NPs in the NaCl matrix obtained by EB PVD on hematological indicators, gases, electrolytes and parameters of iron metabolism in the blood of intact animals. The physical characteristics of NPs were studied using high-resolution transmission electron microscopy, scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy mapping, electron energy-loss spectroscopy, selected area electron diffraction and fast Fourier transform. In vivo experiments were conducted on albino male rats, which were injected with solution of magnetite-sodium chloride NPs (1.35 mg Fe/kg). After 3 and 72 h, hematological parameters, blood gases, electrolytes, and serum iron were determined. The synthesized NPs had an average size of 11 nm. They were identified as magnetite, where polycrystals and single crystals were present. The absence of contamination in crystal boundaries, clear orientation and orderliness of atoms in crystals were established. The administration of NPs in the sodium chloride matrix to animals was characterized by a transient increase in the main indicators of red blood accompanied by an increase in the saturation of erythrocytes with hemoglobin and their mean volume after 3 h. It did not worsen blood gases and pH, but decreased blood Na+ content after 72 h. The investigated NPs caused changes in the parameters of serum iron characteristic to iron preparations, which after 3 h were smaller compared to the reference iron drug, and after 72 h—similar to it. More intense rapid effects on hematological parameters at lower serum iron indicate greater activity of the studied pure magnetite NPs obtained by EB PVD syntesis compared to the reference iron preparation.

Epitaxial growth and band offsets of β -(ScxGa1− x)2O3 thin films grown on (100) β -Ga2O3 substrate

β-(ScxGa1−x)2O3 (x = 0–0.36) thin films were epitaxially grown on (100) β-Ga2O3 substrates by oxygen-radical-assisted pulsed-laser deposition. β-(ScxGa1−x)2O3 epilayers were coherently strained up to x = 0.30, although the presence of a structural disorder was implied when x &amp;gt; 0.2. The bandgap energies measured by reflection electron energy loss spectroscopy increased from 4.56 to 5.25 eV with increasing Sc content. In β-(ScxGa1−x)2O3 epilayers, a slightly negative bandgap bowing behavior with a bowing parameter of −0.4 eV was observed, resulting in a larger bandgap increase than in β-(AlxGa1−x)2O3 epilayers with identical x. X-ray photoemission spectroscopy measurement revealed that the valence-band and conduction-band offsets of β-(Sc0.17Ga0.83)2O3 epilayer with respect to β-Ga2O3 were 0.0 and 0.3 eV, respectively.

Microstructural evolution of diamond thin film grown on a silicon substrate via a surface-wave plasma system: Identification of intermediated phase

Diamond thin films are promising for diverse applications because of their exceptional properties. Understanding the interface between diamond films and substrates is crucial for optimizing the film quality and functionality. In this study, a diamond thin film was grown on a Si(100) substrate using a microwave-based surface-wave plasma system and subjected to transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS). The formation of a SiC interlayer was identified at the interface between the diamond thin film and Si substrate through cross-sectional TEM and EELS. Analysis of the atomic structure and crystalline properties indicated that the interlayer was β-SiC and that the orientation relationships [110]β-SiC//[110]Si and (111)β-SiC//(111)Si existed at the β-SiC/Si interface. The β-SiC interlayer exhibited the {111} extra half-planes, because they were more easily formed by the {111} planes than the {110} extra half-planes generated on {001} planes through 60° misfit dislocations. Many stacking faults and microtwins were observed in the diamond grains; such planar defects were likely attributed to strain behavior and complex contrasts at the nanoscale.

TEM-EELS analysis reveals the W-atom mediated radiation-induced amorphization in M23C6

To gain a mechanistic understanding of the phase stability of M23C6 upon irradiation, the bulk W-doped M23C6 (Cr-W-C system) in the range of 0–12 at.% W concentration was prepared and subjected to helium beam irradiation, following with a thorough electron energy loss spectroscopy (EELS) analysis. Radiation-induced amorphization (RIA) was observed only at the 4 W sample with a W concentration of ∼12 at.%. Analysis of the low-loss spectrum showed that the inelastic mean free path (λ) could be applied an effective indicator of the presence of an amorphous phase. The white line ratio of the carbon K-edge spectrum showed that the chemical bonding state in the crystalline state is mainly 2p3/2 bonding, and it changes to dominantly 2p1/2 bonding accompanying with the crystal-to-amorphous (c-a) transition. Discussion on the relationship between the change in λ (Δλ) and the lattice parameter (Δa) due to irradiation reveals that Δa is not dependent on Δλ, indicating that Δλ is mainly caused by the volume expansion due to the c-a transition. In addition, a crystalline state is remained even after a lattice parameter change of ∼1.5 % in 0 W and 1W-samples, whereas, a lattice expansion of ∼0.2 % would trigger the occurrence of crystal-to-amorphous transition in the 4W-sample. The detailed EELS analysis demonstrated that the constitutional W atoms play an important role in facilitating the occurrence of RIA in M23C6, that is, the phase instability accompanying the lattice expansion due to irradiation was emphasized by the addition of W in M23C6. The insights obtained here suggest that a higher W concentration in M23C6 is more susceptible to RIA, and therefore the resistance to amorphization is achievable by decreasing the W concentration in the steels.