High-angle Annular Dark-field Imaging Research Articles

Atomic-scale mapper for superlattice photodetectors analysis.

In this work, a new Python-based tool for atomic-scale mapping of high-angle annular dark-field (HAADF) and annular bright-field (ABF) scanning transmission electron microscopy (STEM) images using the Z-contrast method is introduced, aimed to help in the analysis of superlattice layers' composition, and in the determination of material of interfaces. The operation principle of the program, as well as specific examples of use, are explained in many details. Good customization flexibility using the user-friendly graphical user interface (GUI), allows the processing of a wide range of images, demonstrating a decent accuracy of coordinates extraction and performance.

A study on the correlation between micro and magnetic domain structure of Cu52Ni34Fe14 spinodal alloys

Magnetic spinodal alloys are ideal materials for studying the relationship between the microstructure of an alloy and its magnetic properties. To unravel this relation, a profound knowledge of the chemical as well as the magnetic microstructure, i.e. the magnetic domain structure, is necessary. However, mapping the magnetic domain structure is rarely accomplished even though it is of major interest for both, fundamental research as well as applications using such alloys.In this study, the magnetic domain structure as well as the evolution of the microstructure of spinodally decomposed Cu52Ni34Fe14 alloys is investigated with various modern (scanning) transmission electron microscopy ((S)TEM) methods. The magnetic domain structure was mapped using differential phase contrast imaging (STEM DPC) and magnetic-force microscopy (MFM). The chemical microstructure was determined using high-angle annular dark field imaging (HAADF) and energy-dispersive X-ray spectroscopy (EDXS) elemental mapping.

Trainable segmentation for transmission electron microscope images of inorganic nanoparticles.

We present a trainable segmentation method implemented within the python package ParticleSpy. The method takes user labelled pixels, which are used to train a classifier and segment images of inorganic nanoparticles from transmission electron microscope images. This implementation is based on the trainable Waikato Environment for Knowledge Analysis (WEKA) segmentation, but is written in python, allowing a large degree of flexibility and meaning it can be easily expanded using other python packages. We find that trainable segmentation offers better accuracy than global or local thresholding methods and requires as few as 100 user-labelled pixels to produce an accurate segmentation. Trainable segmentation presents a balance of accuracy and training time between global/local thresholding and neural networks, when used on transmission electron microscope images of nanoparticles. We also quantitatively investigate the effectiveness of the components of trainable segmentation, its filter kernels and classifiers, in order to demonstrate the use cases for the different filter kernels in ParticleSpy and the most accurate classifiers for different data types. A set of filter kernels is identified that are effective in distinguishing particles from background but that retain dissimilar features. In terms of classifiers, we find that different classifiers perform optimally for different image contrast; specifically, a random forest classifier performs best for high-contrast ADF images, but that QDA and Gaussian Naïve Bayes classifiers perform better for low-contrast TEM images.

Atomistic observation of in situ fractured surfaces at a V-doped WC Co interface

• Crack propagation dynamic across a V-doped WC Co interface is studied in TEM. • Aberration-corrected STEM is used to examine the as-fractured surface. • The fracture propagates between the V-containing trilayers and the abutting cobalt. • A loss of interfacial coherency accounts for the selected propagation path. An in situ mechanical test was performed on a V-doped WC Co specimen in a transmission electron microscope (TEM) to understand the crack propagation dynamics. The fracture occurs along a WC Co interface. Aberration-corrected high-angle annular dark-field (HAADF) imaging and energy-dispersive X-ray spectroscopy (EDS) mapping are combined to investigate the as-fractured surface. The interfacial cleavage plane is atomically flat, taking place between the V-containing trilayers and the abutting cobalt grain. No noticeable structural or compositional change is detected for the trilayer superstructure coherent with the underneath WC grain. Density functional theory (DFT) calculations reveal that the interlayer bonding within the coherent interfacial trilayer superstructure is strong while that between the superstructure and cobalt is substantially weaker due to incoherency. This study provides insights into the interfacial fracture behavior in hard metals and suggests the importance of interfacial coherency to fracture resistance.

Atomic-scale characterization of the oxidation state of Ti in meteoritic hibonite: Implications for early solar system thermodynamics

Abstract Calcium-aluminum-rich inclusions (CAIs) in chondritic meteorites are composed of refractory minerals thought to be the first solids to have formed in the solar nebula. Among them, hibonite, nominally CaAl12O19, holds particular interest because it can incorporate significant amounts of Ti into its crystal structure in both Ti3+ and Ti4+ oxidation states. The relative amounts of these cations that are incorporated reflect the redox conditions under which the grain formed or last equilibrated and their measurement can provide insight into the thermodynamic landscape of the early solar nebula. Here we develop a new method for the quantification of Ti oxidation states using electron energy-loss spectroscopy (EELS) in an aberration-corrected scanning transmission electron microscope (STEM) to apply it to hibonite. Using a series of Ti-bearing oxides, we find that the onset intensity of the Ti L2,3 edge decreases with increasing Ti-oxidation state, which is corroborated by simulated Ti-oxide spectra using first-principles density-functional theory. We test the relationship on a set of synthetic hibonite grains with known Ti4+/ΣTi values and apply the developed method on a hibonite grain from a compact type A inclusion in the Northwest Africa (NWA) 5028 CR2 carbonaceous chondrite. The STEM-EELS data show that the chondritic hibonite grain is zoned with a Ti4+/ΣTi ratio ranging from 0.78 ± 0.04 to 0.93 ± 0.04 over a scale of 100 nm between the core and edge of the grain, respectively. The Ti substitution sites are characterized by experimental and calculated high-angle annular-dark-field (HAADF) images and atomic-level EEL spectrum imaging. Simulated HAADF images reveal that Ti is distributed between the M2 and M4 sites while Mg sits on the M3 site. Quantitative energy-dispersive X-ray spectroscopy shows that this grain is also zoned in Al and Ti. The Mg distribution is not well correlated with that of Ti and Ti4+/ΣTi at the nanoscale. The spatial decoupling of the element composition and Ti-oxidation states suggests a multistage evolution for this hibonite grain. We hypothesize that Ti and Mg were incorporated into the structure during condensation at high temperature through multiple reactions. Transient heating, presumably in the solar nebula, adds complexity to the crystal chemistry and potentially redistributed Ti and Mg. Concurrently, the formation of oxygen vacancies as a result of a reducing gas, led to the reduction of Ti4+ to Ti3+. The multiple defect reactions occurring in this single hibonite crystal preclude a simple relationship between the Ti4+/ΣTi and the fO2 of formation. However, moving forward, these measurements are fundamental inputs for modeling of the thermodynamic conditions under which hibonite formed in the early solar nebula.

A Polyimide-Based Photocatalyst for Continuous Hydrogen Peroxide Production Using Air and Water under Solar Light

A Polyimide-Based Photocatalyst for Continuous Hydrogen Peroxide Production Using Air and Water under Solar Light

Effects of Electron Microscope Parameters and Sample Thickness on High Angle Annular Dark Field Imaging.

Scanning transmission electron microscopy (STEM) developed into a very important characterization tool for atomic analysis of crystalline specimens. High-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) has become one of the most powerful tools to visualize material structures at atomic resolution. However, the parameter of electron microscope and sample thickness is the important influence factors on HAADF-STEM imaging. The effect of convergence angle, spherical aberration, and defocus to HAADF imaging process has been analyzed through simulation. The applicability of two HAADF simulation software has been compared, and suggestions for their usage have been given.

Atomically Dispersed Pt on Three-Dimensional Ordered Macroporous SnO2 for Highly Sensitive and Highly Selective Detection of Triethylamine at a Low Working Temperature.

Triethylamine (TEA) is a widely used volatile organic chemical, which is harmful and can cause headache, dizziness, and respiratory discomfort. Developing an efficient sensor to detect trace amounts of TEA is significant for industrial and healthcare monitoring. In this work, SnO2 with a three-dimensional ordered macroporous structure (3DOM) was prepared through a polymethylmethacrylate sphere template route. The TEA sensing performance of the 3DOM SnO2 was enhanced through Pt loading. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy images and X-ray absorption fine-structure analysis indicate that Pt on the 3DOM 0.20% Pt/SnO2 surface mainly exists in the state of atomic dispersion, which results in more active sites, higher Hall mobility and active oxygen contents, and lower response energy barriers. The 0.20% Pt/SnO2 sensor has a low operating temperature of 80 °C and a low limit of detection (0.32 ppb). Because of the uniform adsorption of TEA on the atomically dispersed Pt, the 3DOM Pt/SnO2 sensor exhibits high selectivity.

Single–atom Ir1 supported on rutile TiO2 for excellent selective catalytic oxidation of ammonia

Gaseous ammonia (NH3) in the atmosphere is potentially harmful to both human health and the environment. The selective catalytic oxidation of NH3 (termed as NH3–SCO) into N2 and H2O is a promising method for decreasing NH3 emissions. A highly efficient catalyst is required for controlling NH3 emissions by this method in practice. In this study, we prepared Ir/TiO2 catalysts using different crystal structures of TiO2 (rutile, P25 or anatase) as supports by a simple impregnation method and evaluated their performance in the NH3–SCO. We found that the Ir/TiO2–R (rutile) catalyst performed better than the Ir/TiO2–P25 (mixed–phase) and Ir/TiO2–A (anatase) catalyst. High–angle annular dark–field images of the aberration–corrected scanning transmission electron microscopy revealed that the Ir species were mainly atomically dispersed on the TiO2 support in Ir/TiO2–R with 1 wt% Ir loading, whereas the Ir species agglomerated to form clusters or nanoparticles in Ir/TiO2–P25 and Ir/TiO2–A. The combined results of X–ray absorption fine structure, H2–temperature–programmed reduction, and in situ diffuse reflectance for infrared Fourier Transform spectroscopy studies suggested that atomically dispersed Ir species had stronger electronic metal–support interaction with rutile TiO2, which resulted in easier to adsorb and activate O2 at the interface and thus, better low–temperature activity of the Ir/TiO2–R catalyst.

Ligand-Induced Ground- and Excited-State Chirality in Silicon Nanoparticles: Surface Interactions Matter.

Silicon-based light-emitting materials have emerged as a favorable substitute to various organic and inorganic systems due to silicon's high natural abundance, low toxicity, and excellent biocompatibility. However, efforts on the design of free-standing silicon nanoparticles with chiral non-racemic absorption and emission attributes are rather scare. Herein, we unravel the structural requirements for ligand-induced chirality in silicon-based nanomaterials by functionalizing with D- and L-isomers of a bifunctional ligand, namely, tryptophan. The structural aspects of these systems are established using high-resolution high-angle annular dark-field imaging in the scanning transmission electron microscopy mode, solid-state nuclear magnetic resonance, Fourier transform infrared, and X-ray photoelectron spectroscopy. Silicon nanoparticles capped with L- and D-isomers of tryptophan displayed positive and negative monosignated circular dichroic signals and circularly polarized luminescence indicating their ground- and excited-state chirality. Various studies supported by density functional theory calculations signify that the functionalization of indole ring nitrogen on the silicon surface plays a decisive role in modifying the chiroptical characteristics by generating emissive charge-transfer states. The chiroptical responses originate from the multipoint interactions of tryptophan with the nanoparticle surface through the indole nitrogen and -CO2- groups that can transmit an enantiomeric structural imprint on the silicon surface. However, chiroptical properties are not observed in phenylalanine- and alanine-capped silicon nanoparticles, which are devoid of Si-N bonds and chiral footprints. Thus, the ground- and excited-state chiroptics in tryptophan-capped silicon nanoparticles originates from the collective effect of ligand-bound emissive charge-transfer states and chiral footprints. Being the first report on the circularly polarized luminescence in silicon nanoparticles, this work will open newer possibilities in the field of chirality.

Controlling transition metal atomic ordering in two-dimensional Mo1−x W x S2 alloys

The unique optical and electronic properties of two-dimensional transition metal dichalcogenides (2D TMDs) make them promising materials for applications in (opto-)electronics, catalysis and more. Specifically, alloys of 2D TMDs have broad potential applications owing to their composition-controlled properties. Several important challenges remain regarding controllable and scalable fabrication of these alloys, such as achieving control over their atomic ordering (i.e. clustering or random mixing of the transition metal atoms within the 2D layers). In this work, atomic layer deposition is used to synthesize the TMD alloy Mo1−x W x S2 with excellent composition control along the complete composition range 0 ⩽ x ⩽ 1. Importantly, this composition control allows us to control the atomic ordering of the alloy from well-mixed to clustered while keeping the alloy composition fixed, as is confirmed directly through atomic-resolution high-angle annular dark-field scanning transmission electron micrography imaging. The control over atomic ordering leads to tuning of the bandgap, as is demonstrated using optical transmission spectroscopy. The relation between this tuning of the electronic structure and the atomic ordering of the alloy was further confirmed through ab-initio calculations. Furthermore, as the atomic ordering modulates from clustered to well-mixed, the typical MoS2 and WS2 A1g vibrational modes converge. Our results demonstrate that atomic ordering is an important parameter that can be tuned experimentally to finely tune the fundamental properties of 2D TMD alloys for specific applications.

Studying GPI zones in Al-Zn-Mg alloys by 4D-STEM

A new methodology has been developed to study the fine details of GP zones in age-hardenable aluminium alloys. It is complementary to atomic resolution high-angle annular dark-field scanning transmission electron microscopy imaging, and combines scanning precession electron diffraction with diffraction simulations. To evaluate the method, data was collected from an Al-Zn-Mg alloy in a condition with a dense distribution of GPI zones. Diffraction patterns were recorded in the 〈001〉Al orientation, capturing GPI zones in three projections: along the unique [001]GPI axis, and along the two other mutually orthogonal orientations. The GPI zones viewed along [001]GPI revealed how the truncated octahedron units of the GPI zones were connected in multi-unit GP zones, while the two orientations normal to [001]GPI highlight the internal structure. The stability of the atomic models developed based on the experimental results was verified by density functional theory calculations.

Ruddlesden–Popper Faults in NdNiO3 Thin Films

The NdNiO3 (NNO) system has attracted a considerable amount of attention owing to the discovery of superconductivity in Nd0.8Sr0.2NiO2. In rare-earth nickelates, Ruddlesden–Popper (RP) faults play a significant role in functional properties, motivating our exploration of its microstructural characteristics and the electronic structure. Here, we employed aberration-corrected scanning transmission electron microscopy and spectroscopy to study a NdNiO3 film grown by layer-by-layer molecular beam epitaxy (MBE). We found RP faults with multiple configurations in high-angle annular dark-field images. Elemental intermixing occurs at the SrTiO3–NdNiO3 interface and in the RP fault regions. Quantitative analysis of the variation in lattice constants indicates that large strains exist around the substrate–film interface. We demonstrate that the Ni valence change around RP faults is related to a strain and structure variation. This work provides insights into the microstructure and electronic-structure modifications around RP faults in nickelates.

Effects of IrO2 nanoparticle sizes on Ir/Al2O3 catalysts for the selective catalytic oxidation of ammonia

Gaseous ammonia (NH3), especially that emitted from selective catalytic reduction with NH3 (NH3–SCR) units in the atmosphere is potentially harmful to both human health and the environment. The noble metal catalytic oxidation technology placed behind the SCR unit has been considered to be a promising method for decreasing NH3 slip. In this study, we prepared Ir/Al2O3 catalysts using two different crystal structures of Al2O3 (α–Al2O3 or γ–Al2O3) as supported by an impregnation method and evaluated the performance of the selective catalytic oxidation of NH3 (NH3–SCO). We found that the Ir/γ–Al2O3 catalyst performed better than the Ir/α–Al2O3 catalysts, with 99% of NH3 converted at 260 °C. The X–ray absorption fine structure revealed that the active species on the Ir/Al2O3 catalysts are mainly oxidized IrO2. High–angle annular dark–field images of aberration–corrected scanning transmission electron microscopy revealed that IrO2 species over 1 nm in diameter are beneficial for activity. In situ diffuse reflectance for infrared Fourier transform spectroscopy studies suggested that the differences in NH3–SCO activity were caused by the activity of reactive oxygen species, and the formation of –NH2 may be the decisive step of the NH3 oxidation reaction.

Precious metals can be green

In this chapter, a general view of metallic alloys nanoparticles from the atomic-scale view using advanced transmission electron microscopy techniques such as aberration-corrected electron microscopy (Cs-corrected) and high-resolution electron microscopy, is covered. It is well established that catalytic activity of metal nanoparticles is increased by roughness at the atomic scale. Indeed a flat smooth surface will be less active than its stepped counterpart. Metal nanoparticles have in most cases facets with different Miller indexes. However, the control of the shape and crystal structure is not easy to achieve. The possibility of passivizing the nanoparticle surface with organic molecules is a way to control the nanoparticle shape. Using separation techniques such as electrophoresis, it is possible to obtain a batch of particles with the same mass in average and hence the same number of atoms. Passivized particles still have enough free sites to allow catalytic activity. Then, it is possible by using aberration-corrected electron microscopy to obtain the structure and surface structure of nanoparticles. In this work, we will report those methods and demonstrate its application for mono- and multimetallic clusters. The surface of the metallic nanoparticles plays a crucial role in the catalytic activity and interaction between elements in the surface and in the core of the core-shell structures. In this way, the analysis of chemical composition and chemical bonding needs to be obtained using analytic techniques such as X-ray energy-dispersive spectroscopy and electron energy-loss spectroscopy. Herein, we also present quantitative analysis of particles with few atoms by atomic counting using a statistical method applied in Cs-corrected high-angle annular dark-field scanning transmission electron microscopy images.

Two-Dimensional Metal–Organic Frameworks with Unique Oriented Layers for Oxygen Reduction Reaction: Tailoring the Activity through Exposed Crystal Facets

Two-Dimensional Metal–Organic Frameworks with Unique Oriented Layers for Oxygen Reduction Reaction: Tailoring the Activity through Exposed Crystal Facets

A new type of compositionally complex M5Si3 silicides: Cation ordering and unexpected phase stability

A new type of compositionally complex (medium- or high-entropy) M5Si3 silicides is synthesized. Both (V1/5Cr1/5Nb1/5Ta1/5W1/5)5Si3 and (Ti1/5Zr1/5Nb1/5Mo1/5Hf1/5)5Si3 form single-phase homogenous solid solutions. Notably, (V1/5Cr1/5Nb1/5Ta1/5W1/5)5Si3 forms the hexagonal γ (D88) phase, while all its five constituent binary silicides, V5Si3, Cr5Si3, Nb5Si3, Ta5Si3, and W5Si3, are stable in the tetragonal α (D8l) or β (D8m) phases. Annealing at 1600 °C demonstrates that this hexagonal γ phase is stable. Comparison of the experimental and calculated X-ray diffraction patterns, Rietveld refinements, and analysis of aberration-corrected scanning transmission electron microscopy high-angle annular dark-field images suggest cation ordering, which reduces the configurational entropy. This work expands the field of high-entropy and compositional complex ceramics by not only discovering a new compositionally complex silicide phase but also demonstrating cation ordering and unusual phase stability. These compositionally complex silicides can be combined with refractory high-entropy alloys to make the high-entropy counterparts to the Nb-silicide and Mo-Si-B composites.

Twin thickness and dislocation interactions affect the incoherent-twin boundary phase in face-centered cubic metals

Incoherent-twin boundaries (ITBs) can significantly affect the mechanical properties exhibited by metals. Although numerous studies have been conducted to date, the atomic structures of such ITBs remain unclear, owing to difficulties in imaging their structure. In this study, high-angle annular dark-field imaging was used to reveal the atomic structure of the ITBs present in Pt. We discovered that both the twin thickness and the dislocation-ITB interaction can affect the ITB phase structure. In thin twins, the {111} planes between the ITB remain flat without any obvious displacement along the <111> direction, whereas in thicker twins, the {111} planes between the ITB exhibit clear displacement along the <111> direction, with this displacement increasing as the twin thickness increases. The ITBs frequently absorb full dislocations, which leads to the formation of dislocation-misaligned ITBs. This twin-thickness effect and dislocation-ITB interaction, which resulted ITB-phase variation, has rarely been reported.

Copper and platinum dual-single-atoms supported on crystalline graphitic carbon nitride for enhanced photocatalytic CO2 reduction

Single-atom Pt catalysts are designed to promote efficient atom utilization, whereas effective decrease of Pt loading and improvement of photocatalytic activity in monoatomic Pt-deposited systems is still ongoing. Atomically dispersed metal species in crystalline carbon nitride are still challenging owing to their high crystallization and structural stability. In this study, we developed a novel single-atomic Pt-Cu catalyst for reducing noble metal loading by combining Pt with earth-abundant Cu atoms and enhancing photocatalytic CO 2 reduction. N-vacancy-rich crystalline carbon nitride was used as a fine-tuning ligand for isolated Pt-Cu atom dispersion based on its accessible functional N vacancies as the seeded centers. The synthesized dimetal Pt-Cu atoms on crystalline carbon nitride (PtCu-crCN) exhibited high selectivity and activity for CO 2 conversion without the addition of any cocatalyst or sacrificial agent. In particular, we demonstrated that the diatomic Pt-Cu exhibited high mass activity with only 0.32 wt% Pt loading and showed excellent photocatalytic selectivity toward CH 4 generation. The mechanism of CO 2 photoreduction for PtCu-crCN was proposed based on the observations and analysis of aberration-corrected high-angle annular dark-field scanning transmission electron microscopy images, in situ irradiated X-ray photoelectron spectroscopy, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The findings of this work provide insights for abrogating specific bifunctional atomic metal sites in noble metal-based photocatalysts by reducing noble metal loading and maximizing their effective mass activity. Atomically dispersed Pt-Cu sites inside crystalline carbon nitride were designed to maximize Pt mass activity and integrate their respective merits, leading to enhanced CO 2 photoreduction.

Epitaxial Growth of GaAs Nanowires on Synthetic Mica by Metal-Organic Chemical Vapor Deposition.

The epitaxial growth of III-V nanowires with excellent optoelectronic properties on low-cost, light-weight, and flexible substrates is a key step for the design and engineering of future optoelectronic devices. In our study, GaAs nanowires were grown on synthetic mica, a two-dimensional layered material, via vapor-liquid-solid growth using metal-organic chemical vapor deposition. The effect of basic epitaxial growth parameters such as temperature and V/III ratio on the vertical yield of the nanowires is investigated. A vertical yield of over 60% is achieved at an optimum growth temperature of 400 °C and a V/III ratio 18. The structural properties of the nanowires are investigated using various techniques including scanning electron microscopy, high-resolution transmission electron microscopy, and high-angle annular dark-field imaging. The vertical nanowires grown at a low temperature and a high V/III ratio are found to have a zincblende phase with a [111] B polarity. The optical properties are investigated by photoluminescence (PL) and time-resolved PL measurements. First-principles electronic structure calculations within the framework of density functional theory elucidate the van der Waals nature of the nanowire/mica interface. Our results also show that these nanowires can be easily lifted off the bulk 2D mica template, providing a pathway for flexible nanowire devices.