Annular Dark-field Scanning Transmission Electron Microscopy Research Articles

Atomic-Scale Imaging of Polymers and Precision Molecular Weight Analysis.

Polymer design requires fine control over syntheses and a thorough understanding of their macromolecular structure. Herein, near-atomic level imaging of polymers is achieved, enabling the precise determination of one of the most important macromolecular characteristics: molecular weight. By judiciously designing and synthesizing different linear metal(loid)-rich homopolymers, subnanoscale polymer imaging is achieved through annular dark field-scanning transmission electron microscopy (ADF-STEM), owing to the incorporation of high Z atoms in the side chain of the monomeric units. The molecular weight of these polymers can be precisely determined by detecting and counting their metal(loid) atoms upon ADF-STEM imaging, at sample concentrations as low as 10 μg·mL-1. Notably, a commonly used C, H, and O-containing polymer (i.e., poly(methyl acrylate)) that was thus far inaccessible at the atomic scale is derivatized to allow for subnano-level imaging, thus expanding the scope of our approach toward the atomic-level visualization of commodity polymers.

Toward a Procedure for the Template Free Growth of Te Nanowires Across an Insulator by Electrodeposition.

In this work, we present a method for direct, site-selective growth of tellurium nanowires by electrochemical deposition. The Te nanowires were grown laterally between two specially designed nanoband electrodes across a gap, and over a dielectric material, forming a lateral device structure directly. The resulting wires are crystalline and phase pure, as evidenced by Raman spectroscopy, EDS (energy dispersive X-ray spectroscopy), and ADF-STEM (annular dark field scanning transmission electron microscopy). The precise conditions for lateral growth of the nanowires were investigated and the fabrication of an electronic device from the as-deposited material, without the need for any transfer process or further contact fabrication, is demonstrated.

Quantitative revealing the solute segregation behavior at melt pool boundary in additively manufactured stainless steel using a novel processing method for precise positioning by HAADF-STEM

Laser-powder bed fusion (LPBF) enables the fabrication of complex metallic components by manipulating various laser scan strategies to control microstructure and texture. Multiple thermal cycling and rapid solidification lead to non-equilibrium, non-uniform microstructure, and micro-segregation at the melt pool boundary (MPB), whose accurate location is still invisible by transmission electron microscopy (TEM), and quantitative concentration remains imprecise. In this study, we proposed a novel method to make it clear by controlling the crystallographic texture of 316 L stainless steel through unique LPBF processing parameters to obtain a single-crystal-like microstructure of the cellular structures along the laser scanning direction. The accurate location of the track-track MPB is distinguishable by means of the transverse and longitudinal cellular dislocation structures on both sides. The edge-on state of the track-track MPB makes the quantitative concentration analysis precisely using high-angle annular dark-field scanning TEM with energy-dispersive X-ray spectroscopy, which is in good agreement with the Scheil-Gulliver solidification simulations.

Grain rotation mechanisms in nanocrystalline materials: Multiscale observations in Pt thin films.

Near-rigid-body grain rotation is commonly observed during grain growth, recrystallization, and plastic deformation in nanocrystalline materials. Despite decades of research, the dominant mechanisms underlying grain rotation remain enigmatic. We present direct evidence that grain rotation occurs through the motion of disconnections (line defects with step and dislocation character) along grain boundaries in platinum thin films. State-of-the-art in situ four-dimensional scanning transmission electron microscopy (4D-STEM) observations reveal the statistical correlation between grain rotation and grain growth or shrinkage. This correlation arises from shear-coupled grain boundary migration, which occurs through the motion of disconnections, as demonstrated by in situ high-angle annular dark-field STEM observations and the atomistic simulation-aided analysis. These findings provide quantitative insights into the structural dynamics of nanocrystalline materials.

Oxygen reduction reaction on Ag nanocatalysts prepared by the microemulsion method

The microemulsion (water-in-oil) method is used to prepare novel silver catalysts onto three different carbon supports (multi-walled carbon nanotubes (MWCNT), mesoporous carbon (MC) and Vulcan carbon (C)). It allows to control the Ag particle growth and produces particles that range between 2 and 3 nm. The Ag-based catalysts are characterised by scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDS). The electrocatalytic activity towards the oxygen reduction reaction (ORR) in 0.1 M KOH is studied using the rotating disc electrode method. High-angle annular dark-field (HAADF) STEM images reveal the Ag particle size range between 1.8 and 2.4 nm, and the EDS mapping shows uniform Ag distribution on the substrates used. Ag1/MC (two-step synthesis) and Ag2/MC (one-step synthesis) catalysts prepared onto the MC support show the highest mass activity of 30–37 A g−1. The two-step synthesis method is preferred to prepare Ag/MWCNT and Ag/C catalysts. The mass activity of the Ag1/MWCNT catalyst is more than two times higher than that of Ag2/MWCNT. Ag1/MWCNT shows the highest electrochemical stability after the accelerated durability test, with only a 6 mV shift in half-wave potential. The microemulsion method is very promising for the production of highly stable Ag-based catalysts with Ag particles smaller than 3 nm in size.

Accelerating precipitation hardening by natural aging in a 6082 Al-Mg-Si alloy

It is well known that long time natural aging (NA) after quenching from solution treatment will significantly reduce the precipitation hardening kinetics and peak hardness of most 6xxx aluminum alloys during later artificial aging (AA). Here we demonstrate an effective strategy to accelerate precipitation hardening, taking advantage of NA. It is found that by a short time pre-aging (PA) at AA temperature, NA for up to 1 year can reduce the time to peak strength in a 6082 alloy during later AA. A simultaneous increase in yield strength and uniform elongation at peak-aged condition can be achieved as a result of finer and denser age-hardening precipitates than those formed by direct AA treatment. Quantitative characterization of the precipitate microstructure by annular dark field scanning transmission electron microscopy (ADF-STEM) and atom probe tomography (APT) reveals that PA generates a small fraction of fine β″ needle precipitates composed of 6–9 β″-eyes and a substantially high density of GP-zones composed of 3–5 β″-eyes, which are stable at room temperature and can grow easily into β″ upon AA. During NA after PA, more GP-zones with at least 2 β″-eyes form while the larger GP-zones inherited from PA grow further, both of which can act as the precursors of β″ precipitates during later AA.

TEM Investigation on High Dose Al Implanted 4H-SiC Epitaxial Layer

Within this work, the effect of high dose Al ion implantation on 4H-SiC epitaxial layer is displayed. Through TEM investigation it is demonstrated that the implanted surface is suitable as seed for subsequent epitaxial regrowth generating a crystal free of extended defects. In order to assess the defects within the projected range of the ion implanted area, High Angle Annular Dark Field STEM (HAADF-STEM) analyses were performed demonstrating the atomic arrangement of the lattice in correspondence of the dislocation loop and the deviation of the crystallographic planes of 4H-SiC, driven by stress relaxation, that determine the staircase configuration of the implant pattern. Further emphasis is given to the detailed analysis of the precipitates atomic structure, whose preferential localization is ascertained. Using Energy-Dispersive X-ray spectroscopy (EDS) analysis, the precipitate is finally established as Al crystal with an FCC structure.

Simultaneous 2D Projection and 3D Topographic Imaging of Gas-Dependent Dynamics of Catalytic Nanoparticles.

Catalyst deactivation through pathways such as sintering of nanoparticles and degradation of the support is a critical factor when designing high-performance catalysts. Here, structural changes of supported nanoparticle catalysts are investigated in controlled gas environments (O2, H2O, and H2) at different temperatures by imaging simultaneously the nanoparticle structures in 2D projection and the 3D surface-sensitive topography. Platinum nanoparticles on carbon support as a model system are imaged in an environmental transmission electron microscope (ETEM), with concurrent acquisition of high-angle annular dark field scanning TEM (HAADF-STEM) and secondary electron (SE) images. Particle migration and coalescence occurs and shows gas-dependent kinetics, with nanoparticles moving across and through the support during and after coalescence. The temperature required for motion is lower in O2 than in H2O and H2, explained through the nature of the gas/nanoparticle interactions. In O2 and H2, the carbon support degrades by trench formation along migration pathways, and the particles move continuously, indicating a chemical reaction between gas and support. In H2O gas, motion is more discontinuous and oriented particle attachment occurs, as expected from theoretical predictions. These results suggest that multimodal imaging in ETEM that combines HAADF-STEM and SE data provides comprehensive information regarding catalyst dynamics and degradation mechanisms.

Unveiling microstructural damage for leakage current degradation in SiC Schottky diode after heavy ions irradiation under 200 V

Single-event burnout and single-event leakage current (SELC) in silicon carbide (SiC) power devices induced by heavy ions severely limit their space application, and the underlying mechanism is still unclear. One fundamental problem is lack of high-resolution characterization of radiation damage in the irradiated SiC power devices, which is a crucial indicator of the related mechanism. In this Letter, high-resolution transmission electron microscopy (TEM) was used to characterize the radiation damage in the 1437.6 MeV 181Ta-irradiated SiC junction barrier Schottky diode under 200 V. The amorphous radiation damage with about 52 nm in diameter and 121 nm in length at the Schottky metal (Ti)–semiconductor (SiC) interface was observed. More importantly, in the damage site the atomic mixing of Ti, Si, and C was identified by electron energy loss spectroscopy and high-angle annular dark-field scanning TEM. It indicates that the melting of the Ti–SiC interface induced by localized Joule's heating is responsible for the amorphization and the possible formation of titanium silicide, titanium carbide, or ternary phases. The mushroom-like hillock in the Ti layer can be attributed to Rayleigh–Taylor instability, as another evidence for ever-happened localized melting near the Schottky interface. These modifications at nanoscale in turn cause localized degradation of the Schottky contact, resulting in permanent increase in leakage current. This experimental study provides very valuable clues for a thorough understanding of the SELC mechanism in SiC diodes.

Constrained patterning of orientated metal chalcogenide nanowires and their growth mechanism

One-dimensional metallic transition-metal chalcogenide nanowires (TMC-NWs) hold promise for interconnecting devices built on two-dimensional (2D) transition-metal dichalcogenides, but only isotropic growth has so far been demonstrated. Here we show the direct patterning of highly oriented Mo6Te6 NWs in 2D molybdenum ditelluride (MoTe2) using graphite as confined encapsulation layers under external stimuli. The atomic structural transition is studied through in-situ electrical biasing the fabricated heterostructure in a scanning transmission electron microscope. Atomic resolution high-angle annular dark-field STEM images reveal that the conversion of Mo6Te6 NWs from MoTe2 occurs only along specific directions. Combined with first-principles calculations, we attribute the oriented growth to the local Joule-heating induced by electrical bias near the interface of the graphite-MoTe2 heterostructure and the confinement effect generated by graphite. Using the same strategy, we fabricate oriented NWs confined in graphite as lateral contact electrodes in the 2H-MoTe2 FET, achieving a low Schottky barrier of 11.5 meV, and low contact resistance of 43.7 Ω µm at the metal-NW interface. Our work introduces possible approaches to fabricate oriented NWs for interconnections in flexible 2D nanoelectronics through direct metal phase patterning.

Bridge-oxygen bonding modulates Ru single atoms for peroxymonosulfate activation: Importance of high-valent Ru species and 1O2

The application of single-atom catalysts (SACs) to advanced oxidation processes (AOPs) based on peroxymonosulfate (PMS) has attracted considerable attention. However, the catalytic pathways and mechanisms underlying these processes remain unclear. In this study, NiFe-LDH was synthesized and single Ru atoms were stably loaded onto it by forming Ru–O–M (M=Ni or Fe) bonds (Ru@NiFe-LDH). This was demonstrated using high-angle annular dark-field scanning TEM (HAADF-STEM) and X-ray absorption fine structure spectra (XANES). The Ru@NiFe-LDH/PMS system showed a high catalytic reactivity (100 % sulfamethoxazole degradation in only 30 min), high stability (97 % reactivity was maintained after continuous operation for 400 min), and wide pH suitability (working pH range 3–11) for AOPs. The crucial roles of the high-valent species (Ru(V) = O) and 1O2 in this reaction were verified. Density functional theory (DFT) calculations revealed that electron transfer produced a positively charged Ru. This enhances the adsorption of negatively charged PMS anions onto the Ru monoatomic sites, thereby, causing the formation of Ru-PMS* complexes. This study implies that the structure–function relationship between organic compounds and SACs plays a significant role in PMS-based AOPs, and provides a comprehensive mechanism for the role of high-valent species in heterogeneous Fenton-like systems.

Atomic-Scale Imaging of Clay Mineral Nanosheets and Their Supramolecular Complexes through Electron Microscopy: A Supramolecular Chemist's Perspective.

Recent advancements in electron microscopy techniques have revolutionized the ability to directly visualize and understand the intricate world of supramolecular chemistry. This paper provides a concise overview of a study delving into the atomic-scale imaging of monolayer clay mineral nanosheets and their associated supramolecular complexes. The imaging is conducted by harnessing the power of aberration-corrected scanning transmission electron microscopy (STEM). Clay mineral nanosheets, with their anionic charge and ultrathin thickness (of 1 nm), serve as a stable Coulombic host material for cationic guest molecules through electrostatic interactions, facilitating exceptional stability and control during observation. By incorporation of heavy-metal atom markers coordinated within the target molecules, high-angle annular dark field STEM enables a clear visualization of these supramolecular complexes. This approach helps to overcome the limitations of graphene-based systems and expands the possibilities of atomic-scale imaging of nonperiodic molecular assemblies formed by weak supramolecular interactions. The fusion of electron microscopy techniques with the principles of supramolecular and material chemistry offers exciting opportunities for studying the structure, behavior, and properties of complex supramolecular systems. It sheds light on the intricate molecular architectures and design principles governing these systems. This study showcases the immense potential of electron microscopy in supramolecular chemistry and invites researchers from various disciplines to explore the transformative possibilities of atomic-scale imaging in the field.

Porous CN@MOF derived N, S-doped hierarchical framework carrying Co3Fe7/Fe0.8Co0.2S heterojunction: An efficient bifunctional cathode catalyst for Zn–air battery

The exploiting of bifunctional transition metal electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is of significance for the commercialization of rechargeable zinc-air batteries (ZABs). Herein, the N and S atoms-doped hierarchical carbon framework hosting the Co3Fe7/Fe0.8Co0.2S heterojunction is synthesized by employing porous g-C3N4 as framework and spacer, and FeCo-ZIF as metal source followed by sulfidation and pyrolysis. The detailed characterization confirms that the porous g-C3N4 plays a crucial role in improving the dispersion of metal nanoparticles. The obtained FeCo-Sx@NSC-900 catalysts exhibit layered accumulation configuration with uniformly distributed metal nanoparticles. Moreover, the typical carbon@metal nanoparticles and heterojunction structure can be observed from the HRTEM (High-Resolution Transmission Electron Microscopy) and HAADF-STEM (high-angle annular dark-field STEM) analysis results. The optimal FeCo-Sx@NSC-900 catalysts deliver exceptional ORR and OER performance with a potential difference between ORR and OER of merely 0.713 V, which is superior to the commercial Pt/C+RuO2 catalysts and other monometallic catalysts. Additionally, the ZAB assembled with the optimal FeCo-Sx@NSC-900 catalysts as cathode affords a good battery performance with high OCV (1.50 V), large power density (172 mW/cm2), good discharge stability, large specific capacity, and long-term charge/discharge stability (>300 cycles).

Growth mechanism of star-shaped Au–Ag nanoparticles synthesized by ascorbic acid reduction and underpotential deposition

The growth mechanism of star-shaped Au–Ag nanoparticles, which is important for improving the absorption efficiency of nanoparticles in the near-infrared region, remains to be clarified. In this study, the growth mechanism by stabilizing certain facets of Au in spines by underpotential deposition of Ag was investigated. The nanoparticles were analyzed primarily by scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy. Analysis of spines on nanoparticles synthesized with an Au/Ag ratio of 18/4 revealed that approximately 1 nm of Ag was deposited on the topmost surface of Au, and the growth direction of spines was <200>. Underpotential deposition of Ag nanolayers on specific facets of the spines on nanoparticles was observed for the first time by elemental mapping and high-angle annular dark-field STEM tomography. These findings are expected to contribute to the morphology control of plasmonic nanoparticles.

Electrocatalysis of ammonia on NiCu nanoclusters with higher activity and stability synthesized by a simplified polyol technique

This work focuses on a simplified polyol process by which to synthesize five different NiCu/C nanoclusters (NCs) electrocatalysts with the variation of mass and atomic ratio. NCs are characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy, transmission electron spectroscopy (TEM), and scanning electron microscopy with energy-dispersive spectroscopy (EDS) for their crystallite and electronic structures, morphological studies, and elemental composition. The high-angle annular dark-field scanning TEM coupled with EDS elemental mapping has confirmed that nanoparticles (NPs) are formed with Ni and Cu, and NPs are subsequently noted to conform into NCs in such a fashion that NiCu NPs are interconnected to each other rather than overlapping considered a unique distribution of NiCu NCs on the carbon support observed in STEM. NPs arrangement in the conformation of NCs has largely increased in the coverage of NiCu-oxyhydroxides working as active sites for ammonia electrocatalysis evidenced in cyclic voltammograms and XPS investigation. NCs were employed for the oxidation of NH4OH, NH4Cl, NH4NO3, and (NH4)2SO4 of which NiCu/C-2 has shown the highest performance over other NiCu/C samples and their individuals. NiCu/C-2 is also found to have higher stability than other mono/bi-metallic electrocatalysts on the stability test preformed in an electrochemical environment. In addition, the sharp drops of the current in the chronoamperometric curves have been investigated during the stability test.

A Comparative Study of Gallium-, Xenon-, and Helium-Focused Ion Beams for the Milling of GaN.

The milling profiles of single-crystal gallium nitride (GaN) when subjected to focused ion beams (FIBs) using gallium (Ga), xenon (Xe), and helium (He) ion sources were investigated. An experimental analysis via annular dark-field scanning transmission electron microscopy (ADF-STEM) and high-resolution transmission electron microscopy (HRTEM) revealed that Ga-FIB milling yields trenches with higher aspect ratios compared to Xe-FIB milling for the selected ion beam parameters (30 kV, 42 pA), while He-FIB induces local lattice disorder. Molecular dynamics (MD) simulations were employed to investigate the milling process, confirming that probe size critically influences trench aspect ratios. Interestingly, the MD simulations also showed that Xe-FIB generates higher aspect ratios than Ga-FIB with the same probe size, indicating that Xe-FIB could also be an effective option for nanoscale patterning. Atomic defects such as vacancies and interstitials in GaN from He-FIB milling were suggested by the MD simulations, supporting the lattice disorder observed via HRTEM. This combined experimental and simulation approach has enhanced our understanding of FIB milling dynamics and will benefit the fabrication of nanostructures via the FIB technique.

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°.

Transmission Electron Microscopy Peeled Surface Defect of Perovskite Quantum Dots to Improve Crystal Structure.

Transmission electron microscopy (TEM) is an excellent characterization method to analyze the size, morphology, crystalline state, and microstructure of perovskite quantum dots (PeQDs). Nevertheless, the electron beam of TEM as an illumination source provides high energy, which causes morphological variation (fusion and melting) and recession of the crystalline structure in low radiolysis tolerance specimens. Hence, a novel and facile strategy is proposed: electron beam peel [PbBr6]4- octahedron defects from the surface of QDs to optimize the crystal structure. TEM and high-angle annular dark-field scanning TEM (HAADF) tests indicate that the [PbBr6]4- octahedron would be peeled from the surface of QDs when QDs samples were irradiated under high-power irradiation, and then a clear image would be obtained. To avoid interference from a protective film of "carbon deposits" on the surface of the sample when using high resolution TEM, amorphous carbon film (15-20 nm) was deposited on the surface of QDs film and then characterized by TEM and HAADF. The detection consequences showed that the defection of PbBr2 on the surface of QDs will gradually disappear with the extension of radiation time, which further verifies the conjecture.

The formation of (Al, Si)3(Ti, Sc) through microalloying and solidification control synergy in Al-7Si-0.7Mg refines α-Al greatly

The grain refinement mechanism of Al-7Si-0.7Mg alloy by Sc and Ti have been systematically investigated at different cooling rate. The Si-poisoning effect have been avoided by synergistic inoculation of Sc and Ti at special where slow cooling rate before solidification is required. The inoculation of Sc and Ti avoid the Si-poisoning effect by forming a new phase of (Al, Si)3(Ti, Sc). The gradient solidification is adopted to make the (Al, Si)3(Ti, Sc) phase reappear at fast cooling rate to avoid Si-poisoning. The average grain size of Al-7Si-0.7Mg-0.15Ti-0.5Sc alloy solidified through gradient solidification is refined to 131 µm decreased 45 % compared with traditional cast. The mechanism for anti Si-poisoning is also investigated using first-principles calculation and High-Angle Annular Dark-Field STEM. Data availabilityData will be made available on request.

A combined simulation and experimental study of the equilibrium shapes of η′ and α precipitates in Mn-containing 7xxx Al-alloys

The addition of Mn to 7xxx series Al-alloys helps improve tensile properties owed to the presence of α precipitates (Al(Mn,Fe)Si, simple cubic, 50–200 nm, non-shearable) in addition to the η′ precipitates (Mg2Zn5−xAl2+x, hexagonal, 4–6 nm, shearable) commonly observed in the 7xxx series Al-alloys. The coexistence of multiple α and η′ variants, 24 for α and 4 for η′, coupled with their small size-scale, makes the experimental determination by x-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) challenging. This work formulates a phase-field model to predict precipitate shapes in three-dimension (3D) using experimental characterization as inputs to create virtual precipitate cross-sections for use in morphological comparison with experimental 2D (S)TEM images. Based on the atomic structures and orientation relationships observed in the experiments, the lattice site correspondences between the matrix and the two precipitate phases are derived, which are required for the prediction of shapes of coherent precipitates. Systematic phase-field simulations are then carried out to document the 3D shapes for all possible variants, as well as the corresponding 2D cross-sectional shapes when observed parallel to low-index matrix planes. These 2D cross-sectional shapes are compared with high-angle annular dark-field STEM (HAADF-STEM) images, which demonstrates that the identification of Mn precipitate type is possible by such comparisons. This helps unravel some of the complications encountered when characterizing precipitate microstructures in Mn containing Al-alloys by STEM. Finally, the equilibrium shapes as a function of precipitate size and the effect of interfacial energy anisotropy are investigated.