Combined Electron Energy Loss Spectroscopy Research Articles

Pentatwinned AuAg Nanorattles with Tailored Plasmonic Properties for Near-Infrared Applications.

Noble metal nanoparticles, particularly gold and silver nanoparticles, have garnered significant attention due to their ability to manipulate light at the nanoscale through their localized surface plasmon resonance (LSPR). While their LSPRs below 1100 nm were extensively exploited in a wide range of applications, their potential in the near-infrared (NIR) region, crucial for optical communication and sensing, remains relatively underexplored. One primary reason is likely the limited strategies available to obtain highly stable plasmonic nanoparticles with tailored optical properties in the NIR region. Herein, we synthesized AuAg nanorattles (NRTs) with tailored and narrow plasmonic responses ranging from 1000 to 3000 nm. Additionally, we performed comprehensive characterization, employing advanced electron microscopy and various spectroscopic techniques, coupled with finite difference time domain (FDTD) simulations, to elucidate their optical properties. Notably, we unveiled the main external and internal LSPR modes by combining electron energy-loss spectroscopy (EELS) with surface-enhanced Raman scattering (SERS). Furthermore, we demonstrated through surface-enhanced infrared absorption spectroscopy (SEIRA) that the NRTs can significantly enhance the infrared signals of a model molecule. This study not only reports the synthesis of plasmonic NRTs with tunable LSPRs over the entire NIR range but also demonstrates their potential for NIR sensing and optical communication.

Thermal near-field tuning of silicon Mie nanoparticles

Abstract Tunable high-refractive-index nanostructures are highly desired for realizing photonic devices with a compact footprint. By harnessing the large thermo-optic effect in silicon, we show reversible and wide thermal tuning of both the far- and near-fields of Mie resonances in isolated silicon nanospheres in the visible range. We perform in situ heating in a transmission electron microscope and electron energy-loss spectroscopy to show that the Mie resonances exhibit large spectral shifts upon heating. We leverage the spectral shifts to demonstrate near-field tuning between different Mie resonances. By combining electron energy-loss spectroscopy with energy-dispersive X-ray analysis, we show a reversible and stable operation of single silicon nanospheres up to a temperature of 1073 K. Our results demonstrate that thermal actuation offers dynamic near-field tuning of Mie resonances, which may open up applications in tunable nonlinear optics, Raman scattering, and light emission.

Unlocking the origin of compositional fluctuations in InGaN light emitting diodes

The accurate determination of the compositional fluctuations is pivotal in understanding their role in the reduction of efficiency in high indium content $In_{x}Ga_{1-x}N$ light-emitting diodes, the origin of which is still poorly understood. Here we have combined electron energy loss spectroscopy (EELS) imaging at sub-nanometer resolution with multiscale computational models to obtain a statistical distribution of the compositional fluctuations in $In_{x}Ga_{1-x}N$ quantum wells (QWs). Employing a multiscale computational model, we show the tendency of intrinsic compositional fluctuation in $In_{x}Ga_{1-x}N$ QWs at different Indium concentration and in the presence of strain. We have developed a systematic formalism based on the autonomous detection of compositional fluctuation in observed and simulated EELS maps. We have shown a direct comparison between the computationally predicted and experimentally observed compositional fluctuations. We have found that although a random alloy model captures the distribution of compositional fluctuations in relatively low In ($\sim$ 18%) content $In_{x}Ga_{1-x}N$ QWs, there exists a striking deviation from the model in higher In content ($\geq$ 24%) QWs. Our results highlight a distinct behavior in carrier localization driven by compositional fluctuations in the low and high In-content InGaN QWs, which would ultimately affect the performance of LEDs. Furthermore, our robust computational and atomic characterization method can be widely applied to study materials in which nanoscale compositional fluctuations play a significant role on the material performance.

In situ observation of hydride nucleation and selective growth in magnesium thin-films with environmental transmission electron microscopy

The comprehension of solute-induced phase transformations is crucial in a variety of research fields such as catalysis, memory switching or energy storage. We study solute-induced phase transformations on the model magnesium-hydrogen (Mg–H) system which provides high lattice expansion during the phase transformations. In situ precipitation and growth of MgH2 is analyzed in an environmental transmission electron microscope (ETEM), combining electron energy loss spectroscopy (EELS) and various imaging techniques. It is found that the Mg-hydride (MgH2) formation proceeds through the formation of nanocrystals that are separated by low-angle grain boundaries. This change in the microstructure is easily detectable in the ETEM and allows studying the growth of the hydride phase. The EELS results confirm the direct match between the nanocrystalline microstructure and the MgH2 phase. We attribute this microstructural change to large strains and stresses between the matrix and the MgH2 created during the transformation process. Half-spherical as well as finger-like regions of MgH2 is observed in the film. Combing the ETEM studies with finite element method simulations on the local stress distribution in the lamella suggests an influence of local stresses on the growth behavior. As the FEM simulations reveal, the local stress distribution depends on the shape of the hydrided region. This includes stresses that occur after the hydride nucleation and during the growth of the hydride. Hydrogen diffusion is suggested to be fast along the Pd/MgH2 interphase as well as along the high angle grain boundaries and less fast in low angle grain boundaries in MgH2, in contrast to the very slow diffusion in the MgH2 grains. This paper highlights the interdependency of the hydride growth and its self-created local stress fields in an in situ ETEM study. We consider these results not to be limited to the Mg–H system, but being of more general nature.

Mapping of the energetically lowest exciton in bulk1T−HfS2

By combining electron energy-loss spectroscopy and state-of-the-art computational methods, we were able to provide an extensive picture of the excitonic processes in $1T$-HfS$_2$. The results differ significantly from the properties of the more scrutinized group VI semiconducting transition metal dichalcogenides such as MoS$_2$ and WSe$_2$. The measurements revealed a parabolic exciton dispersion for finite momentum $\textbf{q}$ parallel to the $\Gamma$K direction which allowed the determination of the effective exciton mass. The dispersion decreases monotonically for momentum exchanges parallel to the $\Gamma$M high symmetry line. To gain further insight into the excitation mechanisms, we solved the ab-initio Bethe-Salpeter equation for the system. The results matched the experimental loss spectra closely, thereby confirming the excitonic nature of the observed transitions, and produced the momentumdependent binding energies. The simulations also demonstrated that the excitonic transitions for $\textbf{q}$ || $\Gamma$M occur exactly along that particular high symmetry line. For $\textbf{q}$ || $\Gamma$K on the other hand, the excitations traverse the Brillouin zone crossing various high symmetry lines. A particular interesting aspect of our findings was that the calculation of the electron probability density revealed that the exciton assumes a six-pointed star-like shape along the real space crystal planes indicating a mixed Frenkel-Wannier character.

Carrier Transport and Recombination in Efficient “All‐Small‐Molecule” Solar Cells with the Nonfullerene Acceptor IDTBR

AbstractReaching device efficiencies that can rival those of polymer‐fullerene Bulk Heterojunction (BHJ) solar cells (>10%) remains challenging with the “All‐Small‐Molecule” (All‐SM) approach, in part because of (i) the morphological limitations that prevail in the absence of polymer and (ii) the difficulty to raise and balance out carrier mobilities across the active layer. In this report, the authors show that blends of the SM donor DR3TBDTT (DR3) and the nonfullerene SM acceptor O‐IDTBR are conducive to “All‐SM” BHJ solar cells with high open‐circuit voltages (VOC) >1.1 V and PCEs as high as 6.4% (avg. 6.1%) when the active layers are subjected to a post‐processing solvent vapor‐annealing (SVA) step with dimethyl disulfide (DMDS). Combining electron energy loss spectroscopy (EELS) analyses and systematic carrier recombination examinations, the authors show that SVA treatments with DMDS play a determining role in improving charge transport and reducing non‐geminate recombination for the DR3:O‐IDTBR system. Correlating the experimental results and device simulations, it is found that substantially higher BHJ solar cell efficiencies of >12% can be achieved if the IQE and carrier mobilities of the active layer are increased to >85% and >10−4 cm2 V−1 s−1, respectively, while suppressing the recombination rate constant k to <10−12 cm3 s−1.

In situ tracking the reversible spinel-rocksalt structural transformation between Mn3O4 and MnO

Electron beam irradiation is well known to induce damage in materials. The structural transformation involved in the damage is usually believed to be an irreversible solid state chemical reaction. Here we use in situ transmission electron microscopy (TEM) combined electron-energy loss spectroscopy (EELS) technique in an aberration-corrected TEM to track the structural transformation in spinel Mn3O4 induced by electron beam irradiation. It is clarified that spinel Mn3O4 is transformed to rocksalt structured MnO by irradiation and the reversed recovering transition from rocksalt MnO to spinel Mn3O4 can occur by aging in the gentle electron beam circumstance. The mechanisms including the role of O desorption/adsorption and the displacement of Mn and O involved in the reversible transformation processes are discussed. The work presents an implication that electron beam can modify the structure at atomic dimension yielding diverse assemblies of surfaces, interfaces and colorful properties.

Unveiling nanometer scale extinction and scattering phenomena through combined electron energy loss spectroscopy and cathodoluminescence measurements.

Plasmon modes of the exact same individual gold nanoprisms are investigated through combined nanometer-resolved electron energy-loss spectroscopy (EELS) and cathodoluminescence (CL) measurements. We show that CL only probes the radiative modes, in contrast to EELS, which additionally reveals dark modes. The combination of both techniques on the same particles thus provides complementary information and also demonstrates that although the radiative modes give rise to very similar spatial distributions when probed by EELS or CL, their resonant energies appear to be different. We trace this phenomenon back to plasmon dissipation, which affects in different ways the plasmon signatures probed by these techniques. Our experiments are in agreement with electromagnetic numerical simulations and can be further interpreted within the framework of a quasistatic analytical model. We therefore demonstrate that CL and EELS are closely related to optical scattering and extinction, respectively, with the addition of nanometer spatial resolution.

Solid solution effects in the Ti2Al(CxNy) MAX phases: Synthesis, microstructure, electronic structure and transport properties

Ti2AlCxNy solid solutions are synthesized using hot isostatic pressing. The X site solid solution effects are investigated, focusing on the microstructure, electronic structure and transport properties of the Ti2AlCxNy MAX phases. Combining X-ray diffraction with scanning electron microscopy and wavelength dispersive X-ray spectroscopy measurements, it is shown that solid solutions can be synthesized with well-controlled chemical compositions in the entire composition range (x=0–1). The measured a and c lattice-parameter values are shown to be in good agreement with those calculated using the cluster-expansion formalism. Combining electron energy-loss spectroscopy (EELS) and band structure calculations, it is demonstrated by Arroyave et al. that solid solution effects induce weak perturbations on the electronic structure. The solid solution effect thus results mainly in a rigid shift of the Fermi energy in a flat part of the electron density of states of Ti2AlC (or Ti2AlN). From these observations, the variations in two key parameters of the conductivity are rationalized. The relative variations in the residual resistivity in the whole composition range are shown to be small, which agrees well with the weak disorder evidenced by EELS. However, the values of the slope of the variation in resistivity vs. temperature are shown to vary quite significantly, evidencing a deviation from Matthiessen’s rule in these systems. By comparing the experimental data with calculations based on the semi-classical Boltzmann equation, it is demonstrated that the observed variations are due to a combination of band structure effects and changes in the scattering mechanisms. Finally, vacancies are also shown to have a prominent effect on the transport properties of Ti2AlCxNy solid solutions. In particular, both residual resistivity and dρ(T)/dT values are shown to be significantly higher than those of the corresponding stoichiometric compounds.

TEM study of impurity segregations in beryllium pebbles

Beryllium is planned to be used as a neutron multiplier in the Helium-cooled Pebble Bed European concept of a breeding blanket of demonstration power reactor DEMO. In order to evaluate the irradiation performance, individual pebbles and constrained pebble beds were neutron-irradiated at temperatures typical of fusion blankets. Beryllium pebbles 1mm in diameter produced by the rotating electrode method were subjected to a TEM study before and after irradiation at High Flux Reactor, Petten, Netherlands at 861K. The grain size varied in a wide range from sub-micron size up to several tens of micrometers, which indicated formation bimodal grain size distribution. Based on the application of combined electron energy loss spectroscopy and energy dispersive X-ray spectroscopy methods, we suggest that impurity precipitates play an important role in controlling the mechanical properties of beryllium. The impurity elements were present in beryllium at a sub-percent concentration form beryllide particles of a complex (Fe/Al/Mn/Cr)B composition. These particles are often ordered along dislocations lines, forming several micron-long chains. It can be suggested that fracture surfaces often extended along these chains in irradiated material.

Loss spectroscopy of molecular solids: combining experiment and theory

The nature of the lowest-energy electronic excitations in prototypical molecular solids is studied here in detail by combining electron energy loss spectroscopy (EELS) experiments and state-of-the-art many-body calculations based on the Bethe–Salpeter equation. From a detailed comparison of the spectra in picene, coronene and tetracene we generally find a good agreement between theory and experiment, with an upshift of the main features of the calculated spectrum of 0.1–0.2 eV, which can be considered the error bar of the calculation. We focus on the anisotropy of the spectra, which illustrates the complexity of this class of materials, showing a high sensitivity with respect to the three-dimensional packing of the molecular units in the crystal. The differences between the measured and the calculated spectra are explained in terms of the small differences between the crystal structures of the measured samples and the structural model used in the calculations. Finally, we discuss the role played by the different electron–hole interactions in the spectra. We thus demonstrate that the combination of highly accurate experimental EELS and theoretical analysis is a powerful tool to elucidate and understand the electronic properties of molecular solids.

Structural phase transformation and Fe valence evolution in FeOxF2−x/C nanocomposite electrodes during lithiation and de-lithiation processes

In this study, the structural changes of FeOxF2−x/C during the first discharge and recharge cycles were studied by ex situ electron microscopy techniques including annular dark field scanning transmission electron microscopy (DF-STEM) imaging, selected area electron diffraction (SAED) and electron energy loss spectroscopy (EELS) as well as by in situ X-ray absorption spectroscopy (XAS). The evolution of the valence state of Fe was determined by combined EELS using the Fe-L edge and XAS using the Fe-K edge. The results of this investigation show that the conversion reaction path during 1st lithiation is very different from the re-conversion path during 1st delithiation. During lithiation, intercalation is first observed followed by conversion into a lithiated rocksalt (Li–Fe–O–F) structure, and metallic Fe and LiF phases. During delithiation, the rocksalt phase does not disappear, but co-exists with an amorphous (rutile type) phase formed initially by the reaction of LiF and Fe. However, a de-intercalation stage is still observed at the end of reconversion similar to a single phase process despite the coexistence of these two (rocksalt and amorphous) phases.

Association of iron oligomeric species with natural organic matter: a combined EELS and Mössbauer investigation

The nature of the interaction between iron oxyhydroxide compounds and natural organic matter (NOM) may take various forms and is still a matter of debate. It is an important field to understand, especially for water treatment applications and for the knowledge of iron transport in the environment. The nature of association reached between iron oligomeric species and NOM is here investigated using Mossbauer spectroscopy and electron energy-loss spectroscopy (EELS) at the Fe-L3 edge. Raw water NOM taken from Moselle River (France), natural humic substances extracted from the riverine suspended matter, and a synthesized humic-like substance, are coagulated with iron nitrate according to a jar-test procedure. The results from Mossbauer spectroscopy indicate that Fe is present in an octahedral coordination environment, which is consistent with prior X-ray absorption spectroscopy reported in the literature. The areas beneath the peaks (Fe L3 edge) and the peak shapes of EELS spectra differ according to the origin of the organic matter, suggesting that various types of Fe populations can be distinguished using the EELS technique. Combining the selectivity of both Mossbauer spectroscopy for identifying trace, poorly crystalline Fe solids, oxidation state and of EELS for being able to characterize the population of Fe based on L-edge spectra, appears promising for characterizing Fe in systems containing NOM.

Characterization of Ti 1−xAl xN coatings with selective IR reflectivity

Ti 1− x Al x N thin films were deposited by reactive magnetron sputtering. The obtained different stoichiometries give rise to different optical properties as the films change from metallic to dielectric. In this work the IR reflectivity of these coatings is investigated taking into account different application fields for IR selective Ti 1− x Al x N thin films. Low Al content coatings present high reflectivity, high absorptance and low thermal emittance. High Al compositions give raise to coatings with high absorptance and high thermal emittance. The composition of the coatings was evaluated combining electron energy loss spectroscopy (EELS) and energy dispersive spectroscopy. Scanning electron microscopy (SEM) revealed a columnar structure. Reflectance spectra for the visible and infrared spectral ranges were used to obtain the solar absorptance and thermal emittance values, used to calculate the equilibrium temperature of the coatings. The thermal stability in air from 300 to 600 °C was also evaluated.

Valence electron energy-loss spectroscopy of nanoporous MgO

This work reports experimental evidence for a redshift in the main peak in the valence electron energy loss spectrum of nanoporous MgO. An interpretation is given based on effective-medium response theory. We find that the main peak energy depends on the density of nanopores within the illuminated area. As a result, by combining electron energy loss spectroscopy with transmission electron microscopy imaging, the loss peak position may be used to measure the porosity of nanoporous materials.

Electron energy loss spectroscopy andab initioinvestigation of iron oxide nanomaterials grown by a hydrothermal process

We first describe with the help of reference experiments (at the $\text{Fe}\text{ }2p$ and $\text{O}\text{ }1s$ edges) and ab initio calculations how electron energy loss spectroscopy (EELS) can be used in order to characterize phases of iron oxide and/or hydroxide nanomaterials. In particular we show that dehydration of iron hydroxides such as goethite can easily appear under the electron beam but might be followed by monitoring the $\text{O}\text{ }K$ peak. Indeed both local spin-density approximation (LSDA) and $\text{LSDA}+U$ calculations confirm that intensity of the prepeak of $\text{O}\text{ }K$ should increase while H atoms are removed. We also demonstrate that different magnetic orders do not change significantly the $\text{O}\text{ }K$ EELS fine structure of goethite. Thus, nanomaterials (particles and wires) synthesized by a hydrothermal treatment of nanoscale (10--40 nm) magnetite particles have been conducted. Among them, crystalline iron oxide nanowires with average diameter of 20 nm and length of up to $10\text{ }\ensuremath{\mu}\text{m}$ are reported. The $\text{O}\text{ }K$ edge and $\text{Fe}\text{ }{L}_{2,3}$ edges were studied by EELS for these nanostructures. The results indicated that the valence of iron is $3+$ in the wires while it is the mixture of $2+$ and $3+$ in the particles. From these combined EELS, scanning transmission electron microscopy, diffraction, and high-resolution electron microscopy, the complexity of the produced phases from these hydrothermal treatments can be revealed. This work shows how EELS with high-energy resolution is a unique tool to differentiate iron oxide compounds such as the tricky magnetite-maghemite solid solution or the case of partially dehydrated phases, even on a nanometer scale.

Light elements quantitative x-ray microanalysis of thin samples in STEM. Absorption correction using EELS data

Quantification of low Z elements like oxygen by energy-dispersive x-ray spectrometry requires x-rays absorption correction even the in the case of thin films analysis in scanning transmission electron microscope. Absorption correction needs the knowledge of the sample local mass thickness. The purpose of this paper is to propose a method which allows the obtainment of the sample local mass thickness and then permits the quantification of all the elements of the sample using the quantification ratio method. Combining electron energy loss spectroscopy measured relative specimen thickness, and x-rays characteristic peaks intensities, we determine with an iterative process the local mass thickness and the absorption corrected elemental weight concentrations. We validate our method with four standard samples (SiO, SiO2, CaSiO3 and Li4SiO4) by the determination of the O/Si atomic ratio. We also ensure the method by analysing a native bioactive glass sample of known composition and of inhomogeneous mass thickness.

Measuring the Thickness of Aluminium Alloy Thin Foils Using Electron Energy Loss Spectroscopy

Combining electron energy loss spectroscopy and convergent beam electron diffraction measurements, we have determined the mean-free-path for inelastic electron scattering for four different aluminium alloys. Electron energy loss spectroscopy spectra were acquired with the transmission electron microscope in image mode, without any objective aperture inserted. The value for pure aluminium was determined as 119 ± 5nm at an incident electron energy of 150keV. For the most common alloys with moderate amounts of alloying elements, no significant changes in the mean-free-path values are measured within the 5% accuracy of the method. The-mean-free path values are required for accurate determination of the thickness of thin foils for transmission electron microscopy using electron energy loss spectroscopy. On the basis of our experimental results, we estimate a single measurement of foil thickness to have an accuracy of better than 8% if the mean-free-path is known within 5%. The outlined procedure for thickness measurements is very robust, with thickness results being insensitive to experimental details such as inclination of the specimen or diffracting conditions.

Atomic Structure and Properties of the (310) Symmetrical Tilt Grain Boundary (STGB) in SrTiO3 Part II: Comparison with Experimental Studies

The atomistic simulation results presented in Part I for SrTiO3 (310) symmetrical tilt grain boundary (STGB, the so-called Σ = 5 GB with 36.8° symmetrical misorientation about [001]) are analyzed in the context of available experimental studies. In particular, atomic imaging studies of SrTiO3 GBs via high resolution TEM and incoherent Z-contrast STEM imaging; and determination of oxygen positions by combining electron energy loss spectroscopy (EELS) and bond-valence-sum rules, are compared with simulation results. The atomistic simulation data on the GB energies are compared with relative experimental estimates obtained via a novel approach of faceting of focused ion beam (FIB) induced microvoids. While there are considerable differences in details of simulation and experimental results, some basic trends seem to emerge about the core structural framework of GBs in SrTiO3. The paper highlights the limitations of both, experimental and simulation techniques, and argues in favor of synergistic use of diverse experimental and simulation approach to determine the atomic structure and properties of GBs.

Chemical-bond analysis of nanostructured materials using near-edge fine structures (ELNES)

The paper is concerned with the application of combined electron energy loss spectroscopy (EELS) and transmission electron microscopy (TEM) to the characterization of the chemical-bond state of elements at nanometer resolution. Respective information is contained in the energy loss near-edge fine structure (ELNES) usually appearing in the energy range up to about 30 eV above the edge onset. The practical way of chemical-bond analysis was chosen, viz. to compare the ELNES of the feature under investigation with those of known stoichiometry. The efficiency of this special technique is demonstrated for different material systems, particularly fiber-reinforced composites and functional ceramics, having structural details of some ten nanometres, or smaller.