High-resolution STEM Imaging Research Articles

Scalable Solid-State Synthesis of Carbon-Supported Ir Electrocatalysts for Acidic Oxygen Evolution Reaction: Exploring the Structure-Activity Relationship.

Enhancing iridium (Ir)-based electrocatalysts to achieve high activity and robust durability for the oxygen evolution reaction (OER) in acidic environments has been an ongoing mission in the commercialization of proton exchange membrane (PEM) electrolyzers. In this study, we present the synthesis of carbon-supported Ir nanoparticles (NPs) using a modified impregnation method followed by solid-state reduction, with Ir loadings of 20 and 40 wt % on carbon. Among the catalysts, the sample with an Ir loading of 20 wt % synthesized at 1000 °C with a heating rate of 300 °C/h demonstrated the highest mass-normalized OER performance of 1209 A gIr-1 and an OER current retention of 80% after 1000 cycles of cyclic voltammetry (CV). High-resolution STEM images confirmed the uniform dispersion of NPs, with diameters of 1.6 ± 0.4 nm across the support. XPS analysis revealed that the C-O and C═O peaks shifted slightly toward higher binding energies for the best-performing catalyst. In comparison, the metallic Ir state shifted toward lower binding energies compared to other samples. This suggests electron transfer from the carbon support to the Ir NPs, indicating a potential interaction between the catalyst and the support. This work underscores the strong potential of the solid-state method for the scalable synthesis of supported Ir catalysts.

High Spatiotemporal Resolution STEM Imaging at High Temperature

High Spatiotemporal Resolution STEM Imaging at High Temperature

A new insight into largely defocused HAADF-STEM imaging and visualization of strain field

A crystalline bilayer specimen with a semi-coherent interface can generate moiré fringes in the high-angle annular-dark field scanning transmission electron microscopy (HAADF-STEM) imaging. Moreover, when the probe is significantly defocused, this specimen can produce largely defocused probe (LDP)-STEM patterns. Although the electron channeling effect serves as the fundamental principles for HAADF-STEM imaging, its connection to the emergence of LDP-STEM patterns remains unclear. The missing link lies in identifying the location of the imaged region. To address this issue, we examined the strain field in three-dimensional space and its interaction with the convergent electron beam, taking the PbZrO3/SrTiO3 (PZO/STO) heterostructure as an example. We discovered a new intensity relationship for LDP-STEM patterns in the PZO/STO heterostructure, which can be well explained by our theory. We also found that, generated by imaging the strain zone, these patterns revealed information that might be obscured in traditional high resolution STEM images, showing a unique advantage in characterizing the strain field. Furthermore, we provided discussions on visualizing the strain field, including the misfit dislocation network and array. Our research offers a novel perspective on the LDP-STEM imaging and clarifies the approach to characterizing the strain field.

Unveiling Enhanced PEC Water Oxidation: Morphology Tuning and Interfacial Phase Change in α-Fe2O3@K-OMS-2 Branched Core-Shell Nanoarrays.

A simple fabrication method that involves two steps of hydrothermal reaction has been demonstrated for the growth of α-Fe2O3@K-OMS-2 branched core-shell nanoarrays. Different reactant concentrations in the shell-forming step led to different morphologies in the resultant composites, denoted as 0.25 OC, 0.5 OC, and 1.0 OC. Both 0.25 OC and 0.5 OC formed perfect branched core-shell structures, with 0.5 OC possessing longer branches, which were observed by SEM and TEM. The core K-OMS-2 and shell α-Fe2O3 were confirmed by grazing incidence X-ray diffraction (GIXRD), EDS mapping, and atomic alignment from high-resolution STEM images. Further investigation with high-resolution HAADF-STEM, EELS, and XPS indicated the existence of an ultrathin layer of Mn3O4 sandwiched at the interface. All composite materials offered greatly enhanced photocurrent density at 1.23 VRHE, compared to the pristine Fe2O3 photoanode (0.33 mA/cm2), and sample 0.5 OC showed the highest photocurrent density of 2.81 mA/cm2. Photoelectrochemical (PEC) performance was evaluated for the samples by conducting linear sweep voltammetry (LSV), applied bias photo-to-current efficiency (ABPE), electrochemical impedance spectroscopy (EIS), incident-photo-to-current efficiency (IPCE), transient photocurrent responses, and stability tests. The charge separation and transfer efficiencies, together with the electrochemically active surface area, were also investigated. The significant enhancement in sample 0.5 OC is ascribed to the synergetic effect brought by the longer branches in the core-shell structure, the conductive K-OMS-2 core, and the formation of the Mn3O4 thin layer formed between the core and shell.

Grain boundary segregation in iron doped strontium titanate: From dilute to concentrated solid solutions

Strontium titanate, a perovskite oxide, is a frequently studied material for a large variety of applications. When acceptor-doped (with Fe, for example), the material is useful for its mixed oxygen and electronic conductivity, with potential use in oxygen transport membranes or as a cathode for solid oxide fuel cells. A barrier to conductivity in perovskites is the presence of space charge regions at the grain boundaries, which form due to the segregation of charged point defects. Typically, space charge theory assumes bulk dopant concentrations beneath the dilute limit, however concentrated solid-solutions are often utilized in applications. The current work aims to address this disparity: grain boundary segregation in strontium ferrite-strontium titanate solid-solutions is analyzed at three compositions, with Fe contents ranging from near the dilute limit to well above the dilute limit (Fe contents of 2 %, 5 %, and 25 % on the B-site of the perovskite). Electrochemical impedance spectroscopy shows an increase in material conductivity as Fe is added. High-resolution STEM imaging and spectral mapping is utilized, showing that Fe segregates to the grain boundary core, contrary to what is expected from space charge theory. As the Fe content is increased, the amount of Fe segregated to the boundary increases significantly, but the segregation width of Fe at the boundary remains consistent.

Occurrence state and enrichment mechanism of rhenium in molybdenite from Merlin Deposit, Australia

Rhenium (Re) is one of the critical metals, and molybdenite (MoS2) is the main host mineral for Re. Previous studies have shown that the distribution of Re in molybdenite is highly heterogeneous, and the occurrence state and enrichment mechanism of Re in molybdenite is not clear. The molybdenite of Merlin deposit has typical Re rich characteristics, which is an ideal object to study the occurrence state and enrichment mechanism of Re in molybdenite. Based on the geological research of the deposit, this study systematically investigated the Re-rich molybdenite of the Merlin deposit using LA-ICP-MS and STEM techniques. The LA-ICP-MS results showed that the content of Re in molybdenite ranged from 67 to 2726 ppm, and the distribution of Re content in molybdenite was extremely uneven and irregular. The STEM results showed that there was no independent Re mineral in molybdenite, and Re atoms were found to substitute molybdenum (Mo) atoms in situ in the Re-rich area of molybdenite. The substitution mechanism of Re was clarified at the atomic scale in a visual form, and a corresponding rigid sphere stacking model was established. Mo atoms are sandwiched between two layers of S atoms, while Re atoms enter the molybdenite lattice and substitute Mo atoms in situ, thus changing the lattice structure of the original molybdenite matrix. Rare lattice defects such as five-fold twinning were identified in the Re-rich area of molybdenite in high-resolution HAADF STEM images, which are related to plastic deformation caused by the low stacking fault energy and stress of hexagonal molybdenite. It is speculated that lattice defects such as five-fold twinning is an important mechanism for the enrichment of Re in molybdenite. The magmatic-hydrothermal fluids released from the intrusion of igneous rocks may have provided the main source of ore-forming materials for the Merlin deposit. The ore-forming fluids, which are rich in Mo4+ and Re4+, underwent redox reactions with carbonaceous shale, resulting in the decrease in temperature and oxygen fugacity, and the increase in S2- concentration. This ultimately led to the precipitation and enrichment of Re4+ and Mo4+ to form the Re-rich molybdenite in the Merlin deposit.

Effects of shear strain on HZO ferroelectric orthorhombic phases

The stabilities of hafnium and zirconium oxide ferroelectric orthorhombic phases, oIII-phase (Pca21) and oIV-phase (Pmn21), under shear strain are investigated theoretically by atomic modeling with density functional theory calculations. The results indicate that oIV-phase serves as a buffer state preventing oIII-phase from transforming into m-phase (P21/c) under structural distortion caused by shear strain and meanwhile preserves the remanent polarization to some certain degree. Shear strain will also induce the reduction in coercive field of the HZO film due to the distortion of oIII-phase or phase transition into oIV-phase. It is very possible to identify oIV-phase with careful analysis of high-resolution transmission electron microscopy and high-angle annular dark-field STEM images at the region having a crystal tilt angle smaller than 86°.

Denoising Autoencoder Trained on Simulation-Derived Structures for Noise Reduction in Chromatin Scanning Transmission Electron Microscopy.

Scanning transmission electron microscopy tomography with ChromEM staining (ChromSTEM), has allowed for the three-dimensional study of genome organization. By leveraging convolutional neural networks and molecular dynamics simulations, we have developed a denoising autoencoder (DAE) capable of postprocessing experimental ChromSTEM images to provide nucleosome-level resolution. Our DAE is trained on synthetic images generated from simulations of the chromatin fiber using the 1-cylinder per nucleosome (1CPN) model of chromatin. We find that our DAE is capable of removing noise commonly found in high-angle annular dark field (HAADF) STEM experiments and is able to learn structural features driven by the physics of chromatin folding. The DAE outperforms other well-known denoising algorithms without degradation of structural features and permits the resolution of α-tetrahedron tetranucleosome motifs that induce local chromatin compaction and mediate DNA accessibility. Notably, we find no evidence for the 30 nm fiber, which has been suggested to serve as the higher-order structure of the chromatin fiber. This approach provides high-resolution STEM images that allow for the resolution of single nucleosomes and organized domains within chromatin dense regions comprising of folding motifs that modulate the accessibility of DNA to external biological machinery.

Preparation of High-Quality Samples for MEMS-Based In-Situ (S)TEM Experiments.

A novel focused ion beam (FIB)-based methodology for the preparation of clean and artifact-free specimens on micro-electro-mechanical-system (MEMS)-based chips for in-situ electrical and electro-thermal experiments in a (scanning) transmission electron microscope ((S)TEM) is introduced. Owing to an alternative geometry, the lamellae are attached to a MEMS-based chip directly after the lift-out procedure and afterward further treated or thinned to electron transparency. The quality of produced lamellae on a chip resembles the quality of a classical FIB-prepared sample that is here demonstrated by high-resolution STEM imaging and analytical techniques. Various sample preparation parameters and the performance of in-situ prepared samples have been evaluated through electrical-biasing experiments.

(Invited) Electrode and Cell-Level Insights to Achieve High Performance and Long-Life AEM Fuel Cells and Electrolyzers

The past several years have seen an explosion in the level of interest in anion exchange membrane (AEM)-based energy conversion devices. However, most of the studies in the literature have reported very low achieved performance and durability in such systems. Despite this, or perhaps even because of it, there is a large body of literature emerging pushing for the design of new materials to concomitantly increase both performance and durability. Therefore, the first topic in this talk will be the effect of electrode design and cell operation on the performance and stability of AEM fuel cells and electrolyzers. It will be shown that in many cases significant improvements in both can be made without any new active materials – only new electrode design and cell optimization. In fact, it is only after the device operation is well-understood that new materials can be fairly evaluated and their impact on the performance and durability elucidated.The second topic in this talk will be the durability of AEM fuel cells. Here, an optimized AEM fuel cell was stably operated for a continuous 3600 hours (150 days). At the end of life, the cell was disassembled and subjected to a number of experiments probing the physical and chemical degradation that occurred during normal operation – including high resolution STEM imaging and chemical mapping. Based on the combination of data that well-described the physical and electrochemical evolution of the cell, degradation mechanisms will be discussed and those pathways leading to both reversible and irreversible performance loss will be identified.The final topic of this talk will be durability of AEM electrolyzers. Specifically, we will report a highly durable AEM electrolyzer that was operated continuously for 720 hours (30 days) at a constant current density of 1.0 A/cm2 with no significant degradation in performance. Akin to the fuel cell work, end-of-life characterization is done to explore the degradation mechanisms at work during “normal” operation.In total, the purpose of this presentation is to unveil important insights into the performance-limiting and lifetime-limiting aspects of these electrochemical devices and to help the field to take active steps towards their commercial viability.

The Mixed-Layer Structures of Ikunolite, Laitakarite, Joséite-B and Joséite-A

We used high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) to image the crystal structures of four minerals in the Bi4X3 isoseries (X = Te, Se, S), a subgroup of the tetradymite homologous series: ikunolite (Bi4S3), laitakarite (Bi4Se2S), joséite-B (Bi4Te2S), and joséite-A (Bi4TeS2). The four minerals are isostructural and interpretable in terms of regular stacking of seven-atom packages: [Bi–S–Bi–S–Bi–S–Bi], [Bi–Se–Bi–S–Bi–Se–Bi], [Bi–Te–Bi–S–Bi–Te–Bi], and [Bi–S–Bi–Te–Bi–S–Bi], respectively. The four phases are mixed-layer structures representing the Bi2kTe3 (k = 2) module within the tetradymite series. Diffraction patterns confirm they are seven-fold superstructures of a rhombohedral subcell with c/3 = d~1.89–1.93 Å. Modulation along the d* interval matches calculations of reflection intensity using the fractional shift method for Bi4X3. Internal structures can be discerned by high-resolution HAADF STEM imaging and mapping. Paired bismuth atoms are positioned at the outside of each seven-atom layer, giving the minerals a modular structure that can also be considered as being composed of five-atom (X–Bi–X–Bi–X) and two-atom (Bi–Bi) sub-modules. The presence of mixed sites for substituting cations is shown, particularly for Pb. Moreover, Pb may be important in understanding the incorporation of Ag and Au in Bi–chalcogenides. Visualisation of crystal structures by HAADF STEM contributes to understanding relationships between phases in the tetradymite homologous series and will play an invaluable role in the characterization of potential additional members of the series.

Bubble formation in helium-implanted nanostructured ferritic alloys at elevated temperatures

Helium bubble formation was examined by scanning/transmission electron microscopy (S/TEM) in Fe-9/10Cr binary alloys and two dispersion strengthened nanostructured alloys (CNA3 and 14YWT containing 5–10 nm diameter carbide and oxide particles, respectively) after ex-situ and in-situ He implantation to ~10,000 appm at 500 to 900 °C. The combination of high-resolution STEM images and electron energy loss spectroscopy (EELS) revealed that the Y-Ti-O nanoparticles in 14YWT were uniformly distributed and exhibited a one-to-one relationship for bubble attachment to the nanoclusters. In the in-situ experiment at 900 °C, grain boundary cracking was severe in the Fe-10Cr model alloy, but not in the nanostructured alloys. From 500 to 900 °C, the bubble size generally increased with increasing irradiation temperature, while the bubble density decreased with increasing temperature. At the same temperatures, the bubble size in the implanted materials was in the order of Fe-9/10Cr > CNA3 > 14YWT, while the bubble density showed the opposite order. The observed bubble number densities for the nanostructured alloys are comparable to the nanoparticle density, suggesting that the nanoparticles in both alloys were effective in trapping He. Our results indicate that very high He concentrations can be managed in nanostructured alloys by sequestering the helium into smaller bubbles (which leads to a lower volume swelling value) and to shield He from the grain boundaries. This can be attributed to the much higher sink strength associated with the nanoclusters or the He trapping ability between different types of nanoclusters.

LPE growth of Tb3Al5O12:Ce single crystalline film converters for WLED application

Efficient phosphor converters for white LEDs based on TbAG:Ce single crystalline films, LPE grown onto YAG substrates, is developed. The film-substrate interface of TbAG:Ce SCF/YAG epitaxial structures was studied using high-resolution STEM images.

Effect of nitrogen vacancies on the growth, dislocation structure, and decomposition of single crystal epitaxial (Ti1-xAlx)Ny thin films

The effect of varying nitrogen vacancies on the growth, microstructure, spinodal decomposition and hardness values of predominantly single crystal cubic phase c-(Ti1-xAlx)Ny films was investigated. Epitaxial c-(Ti1−xAlx)Ny films with y = 0.67, 0.79, and 0.92 were grown on MgO(001) and MgO(111) substrates by magnetron sputter deposition. High N vacancy c-(Ti1−xAlx)N0.67 films deposited on MgO(111) contained coherently oriented w-(0001) structures while segregated conical structures were observed on the films grown on MgO(001). High resolution STEM images revealed that the N-deficient growth conditions induced segregation with small compositional fluctuations that increase with the number of N vacancies. Similarly, strain map analysis of the epitaxial c-(Ti1−xAlx)Ny (001) and (111) films show fluctuations in strain concentration that scales with the number of N vacancies and increases during annealing. The spinodal decomposition coarsening rate of the epitaxial c-(Ti1−xAlx)Ny films was observed to increase with decreasing N vacancies. Nanoindentation showed decreasing trends in hardness of the as-deposited films as the N vacancies increase. Isothermal post-anneal at 1100 °C in vacuum for 120 min revealed a continuation in the increase in hardness for the film with the largest number of N vacancies (y = 0.67) while the hardness decreased for the films with y = 0.79 and 0.92. These results suggest that nitrogen-deficient depositions of c-(Ti1-xAlx)Ny films help to promote a self-organized phase segregation, while higher N vacancies generally increase the coherency strain which delays the coarsening process and can influence the hardness at high temperatures.

Nanostructuring Pt Electrocatalysts Supported on Nanocrystalline SnO2 for Polymer Electrolyte Fuel Cells

For nanostructuring PEFC electrocatalysts using oxides stable under strongly acidic conditions, freeze drying is applied as an effective fabrication procedure for highly dispersing SnO2 nanoparticles of a few nanometers in diameter, on relatively-stable conductive framework in the electrocatalyst layers. Platinum catalysts are deposited on SnO2 nanocrystals on an atomic level by applying a chemical procedure for preparing oxide-core Pt-shell electrocatalysts. Their high-resolution STEM images and preliminary electrochemical results are reported, and remaining issues are discussed.

High Performance UV-LED Activated Sensor Development By Modulating the Morphology and Composition

Metal Oxide Semiconductor (MOS) gas sensors have been studied for monitoring indoor/outdoor air pollutants. A drawback of conventional chemical-resistive gas sensing is the high operating temperature (up to 500°C) that is required for surface reactions. The high temperature operation, however, causes drift problems and makes sensors unsafe for environments containing flammable gases.Ultraviolet light-emitting diode (UV-LED) is a new technological field that has recently seen rapid improvements and novel possible applications. These include the development of UV-LED based gas sensors. UV photons emitted from UV-LED could activate sensors to allow detection of chemicals at ambient temperature. UV irradiation can also improve the sensor performance in harsh environments, where SO2 or NOx gases are present, through desorbing surface contaminants. The state-of-the-art ultraviolet light emitting diode (UV-LED) that emit radiation at a power of a few milli-watts is a promising UV source for this application.UV-activated sensors have a variety of advantages, compared to the traditional chemi-resistive metal oxide semiconductor (MOS) sensors, such as higher stability, lower preparation time, and the ability to safely detect flammable gases. The advances in ultra-violet light emitting diode (UV-LED) technology and its utilization in the gas sensing industry may offer a breakthrough in UV-based sensors, providing several important progresses such as broader application, smaller size, and higher efficiency of the developed sensors.Among the various metal oxides that have been studied for gas sensing applications, ZnO nano-materials have shown promisebecause of high electron conductivity features. ZnO has strong luminescent properties, broad UV absorption, and high stability. Thephoto-activity of ZnO can be improved by synthesizing one-dimensional (1D) nanostructuresand by functionalizing with catalytic metal nanoparticles. This combination lowers the requiredactivationenergy and reduces the recombination rate of photo-generated charge carriers.We will present the fabrication of a sensitive 1D nanostructure ZnO gas sensor decorated with Pt nanoparticles to detect low concentrations of toxic gases at room temperature under UV-LED irradiation (Figure 1). ZnO nanoparticles and nanowires decorated with platinum nanoparticles in different loading concentrations were prepared to detect low concentrations of NO2 under UV-LED irradiation. Solution precipitation, self-assembly crystallization, and photo-deposition techniques were used to synthesize the sensing material. The synthesized sensors at different stages of development were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) analyses.To obtain a certain visual evidence of Pt nanoparticleson the surface of ZnO nanowires, High-resolution transmission electron microscopy (HRTEM) and STEM imaging were employed. The presence of Pt nanoparticles was further confirmed through high-angle annular dark-field (HAADF) STEM analysis.Although the sensing response of the pristine ZnO nanoparticles was relatively high (0.4) for NO2 detection, the sensing response improved significantly using ZnO nanowires in the identical photo-activation settings. The decoration ofthe surface of the ZnO nanowires with Pt nanoparticles further enhanced the sensing performance, whereas the 0.1wt% Pt-decorated ZnO nanowire sensor exhibited a response of more than one order of magnitude higher (1.5) than the response generated by the ZnO nanoparticles. This improved performance is attributed to the role of Pt active sites in promoting NO2 adsorption on the ZnO nanowires’ surface as well as enhancing the layer electron utilization.We will present the results and discuss how UV-LED has the potential to significantly impact sensor development and portable gas monitoring systems by enabling novel sensor design concepts. Figure 1

KA-2 Structural Analysis Based on Measurements of Slight Cation Displacements from High Resolution STEM Images

KA-2 Structural Analysis Based on Measurements of Slight Cation Displacements from High Resolution STEM Images

In-situ Low Energy Argon Ion Source for Artifact Free High Resolution STEM Imaging

Journal Article In-situ Low Energy Argon Ion Source for Artifact Free High Resolution STEM Imaging Get access Mikhail Dutka, Mikhail Dutka Thermo Fisher Scientific, Achtseweg Noord 5, 5651 GG Eindhoven, Netherlands Search for other works by this author on: Oxford Academic Google Scholar Romaine Isaacs, Romaine Isaacs Thermo Fisher Scientific, Vlastimila Pecha 12, 627 00 Brno, Czech Republic Search for other works by this author on: Oxford Academic Google Scholar Anna Prokhodtseva, Anna Prokhodtseva Thermo Fisher Scientific, Achtseweg Noord 5, 5651 GG Eindhoven, Netherlands Search for other works by this author on: Oxford Academic Google Scholar Tomáš Vystavěl Tomáš Vystavěl Thermo Fisher Scientific, Vlastimila Pecha 12, 627 00 Brno, Czech Republic Search for other works by this author on: Oxford Academic Google Scholar Microscopy and Microanalysis, Volume 25, Issue S2, 1 August 2019, Pages 548–549, https://doi.org/10.1017/S1431927619003477 Published: 01 August 2019

Evaluation of High-Resolution STEM Imaging Advancement Under Gas-Environment with Open Window MEMS Holder and Gas Injection System

Evaluation of High-Resolution STEM Imaging Advancement Under Gas-Environment with Open Window MEMS Holder and Gas Injection System

Improving the imaging capability of an on-axis transmission Kikuchi detector

Transmission Kikuchi Diffraction (TKD) in the scanning electron microscope has been developing at a fast pace since its introduction less than a decade ago. The recently presented on-axis detector configuration, with its optimized geometry, has significantly increased the signal yield and facilitated the acquisition of STEM images in bright field (BF) and dark field (DF) mode, in addition to the automated orientation mapping of nanocrystalline electron transparent samples. However, the physical position of the integrated imaging system, located outside the detector screen, requires its movement in order to combine high resolution STEM images with high resolution orientation measurements. The difference between the two positions makes it impossible to acquire optimal signals simultaneously, leading to challenges when investigating site-specific nanocrystalline microstructures. To eliminate this drawback, a new imaging capability was added at the centre of the on-axis TKD detector, thus enabling acquisition of optimal quality BF images and orientation maps without detector movement. The advantages brought about by this new configuration are presented and the associated limitations are discussed.