Elemental quantification using electron energy-loss spectroscopy with a low voltage scanning transmission electron microscope (STEM-EELS).

Electron beam damage in electron microscopes is becoming more and more problematic in material research with the increasing demand of characterization of new beam sensitive material such as Li based compounds used in lithium-ion batteries. To avoid radiolysis damage, it has become common practice to use Cryo-EM, however, knock-on damage can still occur in conventional TEM/STEM with a high-accelerating voltage (200-300 keV). In this work, electron energy loss spectroscopy with an accelerating voltage of 30,20 and 10 keV was explored with h-BN, TiB2 and TiN compounds. All Ti L2,3, N K and B K edges were successfully observed with an accelerating voltage as low as 10 keV. An accurate elemental quantification for all three samples was obtained using a multi-linear least square (MLLS) procedure which gives at most a 5 % of standard deviation which is well within the error of the computation of the inelastic partial-cross section used for the quantification. These results show the great potential of using low-voltage EELS which is another step towards a knock-on damage free analysis.

Synergetic interfacial conductivity modulation dictating hysteresis evolution in perovskite solar cells under operation.

In this work, the configuration of compact TiO2 coating (c-TiO2) interface as electron transport layer (ETL) in giving rise to loss and gain of fill factor (FF) and therefore modulation of hysteresis behavior in perovskite solar cells (PSCs) is investigated. For this purpose, PSCs based on planar compact TiO2 (c-TiO2) as well as a scaffold-based architecture are studied. In the latter case c-TiO2 coats a hydrothermally grown titania nanorod scaffold. The results demonstrate that when c-TiO2 is used in planar configuration, FF considerably improves with prolonged light soaking which is in sharp contrast to what is observed for scaffold-based PSCs. Moreover, higher thickness of planar c-TiO2 is shown to be beneficial for sustaining FF in forward scan. Finally, through studying the intricate interfacial dynamics utilizing electrochemical impedance spectroscopy (EIS), it was concluded that for a PSC under operation, the cumulative effect of conductivity modulation at the perovskite with transport layer interfaces, for their respective charge carriers, determines the loss and gain in performance depending on scan rate, applied bias and prolonged light soaking. This work points towards multiple factors affecting PSC output, which could work either in confluence or against one another depending on the interfacial configuration of transport layers.

Prediction of primary knock-on damage during electron microscopy characterization of lithium-containing materials.

To fulfill power and energy demands, lithium-ion battery (LIB) is being considered as a promising energy storage device. For the development of LIBs, high-resolution electron microscopy characterization of battery materials is crucial. During this characterization, the interaction of beam-electrons with Li-containing materials causes damage through several processes, especially knock-on damage. In this study, we investigated this damage by determining the probability of knock-on damage and performing Monte Carlo simulation. For this objective, the threshold displacement energies (TDEs) were computed using sudden approximation technique for three sets of materials, including pure elements, LiX (X = F, Cl, Br), and Li2MSiO4 (M = Fe, Co, Mn). By including the Climbing-Image Nudge Elastic Band (CI-NEB) method into the sudden approximation approach, it was found that the accuracy of the predicted TDEs could be improved. Results also indicated that at moderate electron energies, the knock-on damage for Li in both its elemental and compound forms maximized. In addition, it was shown that the TDE should be the principal parameter for assessing the Li sensitivity to knock-on damage across similar structures. Nonetheless, other parameters, including cross-section, density, weight fraction, atomic weight, and atomic number, were found to impact the knock-on damage.

ZAFG Method for Quantitative Characterization of Spherical Particles: Deriving a Universal Equation for Geometrical Correction.

This study introduces a universal equation to calculate the geometrical correction factor (G) as the fourth factor in the conventional ZAF method for quantifying spherical particles (specifically, NIST-K411 glass microspheres mounted on bulk carbon substrate). Note that the fluorescence correction factor (F) is not considered in this study. Our findings demonstrate that the G factor, as a function of the particle diameter (D) and the range of emitted X-rays in a bulk sample (Xe), provides the best model. Xe depends on the chemical composition and accelerating voltage. We observed excellent agreement between the G factor predicted by our model and experimental data obtained from NIST-K411 standard particles. Our results show that when Xe is greater than D, the G factor decays exponentially, independent of the incident electron energy, X-ray lines, and chemical composition of the particles. We also found that when DXe > 1, the particle behaves as a bulk sample, and G = 1. Notably, our data indicate that the G factor depends only on DXe, not on the chemical composition or beam energy.

Correlation between hysteresis dynamics and inductance in hybrid perovskite solar cells: studying the dependency on ETL/perovskite interfaces.

In this study, to elucidate the origin of inductance and its relationship with the phenomenon of hysteresis in hybrid perovskite solar cells (PSCs), two electron transport layer (ETL) structures have been utilized: (a) rutile titania nanorods grown over anatase titania (AR) and (b) anatase titania covering the rutile titania nanorods (RA). The rutile and anatase phases are prepared via hydrothermal synthesis and spray pyrolysis, respectively. PSCs based on an ETL with an RA structure attain higher short-circuit current density (JSC) and open-circuit voltage (VOC) while showing a slightly lower fill factor (FF) compared with their AR counterparts. Using electrochemical impedance spectroscopy (EIS) measurements, we show that the ETL plays a major role in setting the tone for ionic migration speed and consequent accumulation. Moreover, we consider the conductivity of transport layers as a determining factor in not only giving rise to inductive features but also dictating the bias region under which recombination takes place, ultimately influencing hysteresis locus.

Line-rotated remapping for high-resolution electron backscatter diffraction.

A novel approach, termed line-rotated remapping (LRR), for high resolution electron backscatter diffraction is proposed to remap patterns with large rotation. In LRR, the displacements during the first-pass cross-correlation is modified to a function of the corresponding Kikuchi lines and the points on the reference pattern. Then, the finite rotation matrix to remap the test pattern to a similar orientation of the reference pattern is determined using the parameters of the Kikuchi lines. We apply LRR to simulated Si patterns with random orientations, and obtain measurement errors below ∼1.0 × 10-3 for lattice rotations up to ∼26°. The maximum angle that may be remapped by LRR decreases with the distance between the specimen and the screen, which in turn reduces the number of matched Kikuchi lines. We also employ LRR in experiments to quantitatively characterize rotations and elastic strains of a Ni single crystal subject to nanoindentation and tension measurements. Although more experimental data on pattern center and image contrast are required to properly assess the performance of LRR, our method is a promising technique to improve strain measurements in the presence of large rotations.

Structural Study of Sulfur-Added Carbon Nanohorns.

In the past few decades, nanostructured carbons (NCs) have been investigated for their interesting properties, which are attractive for a wide range of applications in electronic devices, energy systems, sensors, and support materials. One approach to improving the properties of NCs is to dope them with various heteroatoms. This work describes the synthesis and study of sulfur-added carbon nanohorns (S-CNH). Synthesis of S-CNH was carried out by modified chemical vapor deposition (m-CVD) using toluene and thiophene as carbon and sulfur sources, respectively. Some parameters such as the temperature of synthesis and carrier gas flow rates were modified to determine their effect on the properties of S-CNH. High-resolution scanning and transmission electron microscopy analysis showed the presence of hollow horn-type carbon nanostructures with lengths between 1 to 3 µm and, diameters that are in the range of 50 to 200 nm. Two types of carbon layers were observed, with rough outer layers and smooth inner layers. The surface textural properties are attributed to the defects induced by the sulfur intercalated into the lattice or bonded with the carbon. The XRD patterns and X-ray microanalysis studies show that iron serves as the seed for carbon nanohorn growth and iron sulfide is formed during synthesis.

Phase differentiation based on x-ray energy spectrum correlation with an energy dispersive spectrometer (EDS).

Generating quantitative phase maps is unvaluable to access the phase distribution in a material. X-ray hyperspectral mapping using an energy dispersive spectrometer (EDS) attached to a scanning electron microscope (SEM) is the most practical way to collect these data, mainly due to its relatively ease of operation and availability around the world. In this work, we demonstrate an innovative technique to produce high-quality phase maps based on the correlation between each hyperspectral image pixel spectrum and a set of standards spectra. The standards spectra can be obtained experimentally from bulk specimens of known materials but also via analytical computations. The method is not only robust against electron beam current and spectrometer instabilities but also to statistical noise in the standards as well as in the hyperspectral image spectra. Equally, the method is reliable to produce phase distribution maps at low operating voltage where SEM-EDS quantitative x-ray microscopy is limited by many factors like peak overlapping, continuous background approximations and produces inaccurate phase maps. The results presented in this study will certainly open a new path to produce useful x-ray quantitative data and potentially break the locks of conventional x-ray microanalysis using EDS.

Study of the Peak to Background (P/B) Method Behavior as a Function of Take-Off Angle, Tilt Angle, Particle Size, and Beam Energy.

Monte Carlo simulations were performed to investigate the behavior of the peak to background ratio (P/B) of particles on a substrate as a function of different variables such as take-off angle, tilt angle, particle size, and beam energy. The results showed that the P/B highly depends on the beam energy, the size of particles, and the composition of the substrates. Results showed that the rate of intensity reduction of the peak is less than the background for a high tilt angle (60 degrees), and thereby, the P/B increases at a high tilt angle. It was shown that by increasing the take-off angle, the P/B initially reduces and then reaches a plateau. Results showed that the P/B highly depends on the size of particles. Analyses showed that by moving the electron beam from the center to the side of the particle, the P/B increases. Finally, the spherical particles have higher sensitivity of the P/B to the beam position than the cubical particles.

The f-ratio model for quantitative X-ray microanalysis.

The f-ratio method is a new quantitative X-ray microanalysis method developed based on a cold field emission scanning electron microscope/energy dispersive spectroscopy system. The f-ratio is calculated with the characteristic X-ray intensities, and the Monte Carlo simulation is employed to build the theoretical relation between the system composition and the f-ratio. In this study, the f-ratio model is formulated with the elemental concentrations and the f-ratio coefficients. The f-ratio models in the binary S-Fe system and the ternary O-Al-Si system were studied, and the beam energy effects were investigated. The quantitative analyses were performed on the standard pyrite (FeS2) and kyanite (Al2SiO5) specimens, and the results show that the f-ratio model is able to achieve a satisfying accuracy.

Enhancing Singlet Oxygen Photocatalysis with Plasmonic Nanoparticles.

Photocatalysts able to trigger the production of singlet oxygen species are the topic of intense research efforts in organic synthesis. Yet, challenges still exist in improving their activity and optimizing their use. Herein, we exploited the benefits of plasmonic nanoparticles to boost the activity of such photocatalysts via an antenna effect in the visible range. We synthesized silica-coated silver nanoparticles (Ag@SiO2 NPs), with silica shells which thicknesses ranged from 7 to 45 nm. We showed that they served as plasmonically active supports for tris(bipyridine)ruthenium(II), [Ru(bpy)3]2+, and demonstrated an enhanced catalytic activity under white light-emitting diode (LED) irradiation for citronellol oxidation, a key step in the commercial production of rose oxide fragrance. A maximum enhancement of the plasmon-mediated reactivity of approximately 3-fold was observed with a 28 nm silica layer along with a 4-fold enhancement in the emission intensity of the photocatalyst. Using electron energy loss spectroscopy (EELS) and boundary element method simulations, we mapped the decay of the plasmonic signal around the Ag core and provided a rationale for the observed catalytic enhancement. This work provides a systematic analysis of the promising properties of plasmonic NPs used as catalysis-enhancing supports for common homogeneous photocatalysts and a framework for the successful design of such systems in the context of organic transformations.

Scanning Electron Microscopy versus Transmission Electron Microscopy for Material Characterization: A Comparative Study on High-Strength Steels.

The microstructures of quenched and tempered steels have been traditionally explored by transmission electron microscopy (TEM) rather than scanning electron microscopy (SEM) since TEM offers the high resolution necessary to image the structural details that control the mechanical properties. However, scanning electron microscopes, apart from providing larger area coverage, are commonly available and cheaper to purchase and operate compared to TEM and have evolved considerably in terms of resolution. This work presents detailed comparison of the microstructure characterization of quenched and tempered high-strength steels with TEM and SEM electron channeling contrast techniques. For both techniques, similar conclusions were made in terms of large-scale distribution of martensite lath and plates and nanoscale observation of nanotwins and dislocation structures. These observations were completed with electron backscatter diffraction to assess the martensite size distribution and the retained austenite area fraction. Precipitation was characterized using secondary imaging in the SEM, and a deep learning method was used for image segmentation. In this way, carbide size, shape, and distribution were quantitatively measured down to a few nanometers and compared well with the TEM-based measurements. These encouraging results are intended to help the material science community develop characterization techniques at lower cost and higher statistical significance.

Extraction of 3D quantitative maps using EDS-STEM tomography and HAADF-EDS bimodal tomography.

Electron tomography has been widely applied to three-dimensional (3D) morphology characterization and chemical analysis at the nanoscale. A HAADF-EDS bimodal tomographic (HEBT) reconstruction technique has been developed to extract high resolution element-specific information. However, the reconstructed elemental maps cannot be directly converted to quantitative compositional information. In this work, we propose a quantification approach for obtaining elemental weight fraction maps from the HEBT reconstruction technique using the physical parameters extracted from a Monte Carlo code, MC X-ray. A similar quantification approach is proposed for the EDS-STEM tomographic reconstruction. The performance of the two quantitative reconstruction methods, using the simultaneous iterative reconstruction technique, are evaluated and compared for a simulated dataset of a two-dimensional phantom sample. The effects of the reconstruction parameters including the number of iterations and the weight of the HAADF signal are discussed. Finally, the two approaches are applied to an experimental dataset to show the 3D structure and quantitative elemental maps of a particle of flux melted metal-organic framework glass.