Annular Dark-field Scanning Transmission Electron Microscopy Research Articles

Optimization of imaging conditions for composition determination by annular dark field STEM

Quantitative scanning transmission electron microscopy (STEM) allows composition determination for nanomaterials at an atomic scale. To improve the accuracy of the results obtained, optimized imaging parameters should be chosen for annular dark field imaging. In a simulation study, we investigate the influence of imaging parameters on the accuracy of the composition determination with the example of ternary III-V semiconductors. It is shown that inner and outer detector angles and semi-convergence angle can be optimized, also in dependence on specimen thickness. Both, a minimum sampling of the image and a minimum electron dose are required. These findings are applied experimentally by using a fast pixelated detector to allow free choice of detector angles.

In Situ Resolving the Atomic Reconstruction of SnO2 (110) Surface.

Understanding surface reconstruction of nanocrystals is of great importance to their applications, however it is still challenging due to lack of atomic-level structural information under reconstruction conditions. Herein, through in situ spherical aberration corrected scanning transmission electron microscopy (STEM), the reconstruction of nanocrystalline SnO2 (110) surface was studied. By identifying the precise arrangements of surface/subsurface Sn and O columns through both in situ bright-field and high-angle annular dark-field STEM images, an unexpected added Sn2O model was determined for SnO2 (110)-(1 × 2) surface. The protruded Snδ+ of this surface could act as the active sites for activating O2 molecules according to our density functional theory (DFT) calculations. On the basis of in situ observation of atomic-level reconstruction behaviors and DFT calculations, an energy-driven reconstruction process was also revealed. We anticipate this work would help to clarify the long-standing debate regarding the reconstruction of SnO2 (110) surface and its intrinsic property.

Real-time imaging of atomic electrostatic potentials in 2D materials with 30 keV electrons

Scanning transmission electron microscopy (STEM) is the most widespread adopted tool for atomic scale characterization of two-dimensional (2D) materials. Many 2D materials remain susceptible to electron beam damage, despite the standardized practice to reduce the beam energy from 200 keV to 80 or 60 keV. Although, all elements present can be detected by atomic electrostatic potential imaging using integrated differential phase contrast (iDPC) STEM or electron ptychography, capturing dynamics with atomic resolution and enhanced sensitivity has remained a challenge. Here, by using iDPC-STEM, we capture defect dynamics in 2D WS$_2$ by atomic electrostatic potential imaging with a beam energy of only 30 keV. The direct imaging of atomic electrostatic potentials with high framerate reveals the presence and motion of single atoms near defects and edges in WS$_2$ that are otherwise invisible with conventional annular dark-field STEM or cannot be captured sufficiently fast by electron ptychography.

Operando leaching of pre-incorporated Al and mechanism in transition-metal hybrids on carbon substrates for enhanced charge storage

Operando leaching of pre-incorporated Al and mechanism in transition-metal hybrids on carbon substrates for enhanced charge storage

Atomically Dispersed Manganese Lewis Acid Sites Catalyze Electrohydrogenation of Nitrogen to Ammonia

Atomically Dispersed Manganese Lewis Acid Sites Catalyze Electrohydrogenation of Nitrogen to Ammonia

Boosting the Energy Migration Upconversion through Inter-Shell Energy Transfer in Tb 3+ -Doped Sandwich Structured Nanocrystals

Boosting the Energy Migration Upconversion through Inter-Shell Energy Transfer in Tb ³⁺ -Doped Sandwich Structured Nanocrystals

Microstructures and Interface Magnetic Moments in Mn2VAl/Fe Layered Films Showing Exchange Bias.

Heusler alloys are a material class exhibiting various magnetic properties, including antiferromagnetism. A typical application of antiferromagnets is exchange bias that is a shift of the magnetization curve observed in a layered structure consisting of antiferromagnetic and ferromagnetic films. In this study, a layered sample consisting of a Heusler alloy, MnVAl and a ferromagnet, Fe, is selected as a material system exhibiting exchange bias. Although the fully ordered MnVAl is known as a ferrimagnet, with an optimum fabrication condition for the MnVAl layer, the MnVAl/Fe layered structure exhibits exchange bias. The appearance of the antiferromagnetic property in the MnVAl is remarkable; however, the details have been unclear. To clarify the microscopic aspects on the crystal structures and magnetic moments around the MnVAl/Fe interface, cross-sectional scanning transmission electron microscope (STEM) observation, and synchrotron soft X-ray magnetic circular dichroism (XMCD) measurements were employed. The high-angle annular dark-field STEM images demonstrated clusters of MnVAl with the L2 phase distributed only around the interface to the Fe layer in the sample showing the exchange bias. Furthermore, antiferromagnetic coupling between the Mn- and Fe-moments were observed in element-specific hysteresis loops measured using the XMCD. The locally ordered L2 phase and antiferromagnetic Mn-moments in the MnVAl were suggested as important factors for the exchange bias.

Boosting Efficient Ammonia Synthesis over Atomically Dispersed Co-Based Catalyst via the Modulation of Geometric and Electronic Structures

Boosting Efficient Ammonia Synthesis over Atomically Dispersed Co-Based Catalyst via the Modulation of Geometric and Electronic Structures

Higher-voltage asymmetric-electrolyte metal-air batteries

Higher-voltage asymmetric-electrolyte metal-air batteries

Significant Improvement of Strength in Wrought 945A Ni-Based Superalloy by Aging Treatment

Ni-based superalloys have attracted much attention due to their good resistance to high-temperature and -pressure environments. Compared with the traditional 718 Ni-based superalloy, 945A Ni-based superalloy with a lower Ni content showed better performance in terms of precipitated hardening and corrosion resistance. In this study, the aging behavior and the evolution of mechanical properties of the wrought 945A Ni-based superalloy were investigated. Microstructures were analyzed by scanning electron microscopy (SEM), bright field transmission electron microscopy (TEM), high-resolution TEM and high-angle annular dark field scanning TEM. Mechanical properties were measured by tensile and compressive tests. The results illustrated that the compressive yield stress was significantly improved by increasing aging time from 229 to 809 MPa. The increase was greater than 220%. This improvement was mainly attributed to the precipitates of the γ′ phase and carbides during the aging treatment. The residual dislocations generated by the plastic processes stimulated the formation of these precipitates. The precipitation behavior and the strengthening mechanism are discussed in detail.

High-Performance Ru 2 P Anodic Catalyst for Alkaline Polymer Electrolyte Fuel Cells

High-Performance Ru ₂ P Anodic Catalyst for Alkaline Polymer Electrolyte Fuel Cells

Ash-Decorated and Ash-Painted Soot from Residual and Distillate-Fuel Combustion in Four Marine Engines and One Aviation Engine.

Soot is typically the dominant component of the nonvolatile particles emitted from internal combustion engines. Although soot is primarily composed of carbon, its chemistry, toxicity, and oxidation rates may be strongly influenced by internally mixed inorganic metal compounds (ash). Here, we describe the detailed microstructure of ash internally mixed with soot from four marine engines and one aviation engine. The engines were operated on different fuels and lubrication oils; the fuels included four residual fuels and five distillate fuels such as diesel, natural gas, and Jet A-1. Using annular-dark-field scanning transmission electron microscopy (ADF-STEM), we observed that ash may occur either as distinct nodules on the soot particle (decorated) or as continuous streaks (painted). Both structures may exist within a single particle. Decorated soot was observed for both distillate and residual fuels and contained elements associated with either the fuel (V, Ni, Fe, S) or with the lubrication oil (Zn, Ca, P). Painted soot was observed only for residual-fuel soot, and only contained elements associated with the fuel. Additional composition measurements by inductively coupled plasma mass spectrometry (ICP-MS) of filter samples indicated that the internal mixing trends of ash with soot were consistent with the overall ash-to-carbon ratio of the sampled combustion aerosols. Painted soot may form when molten ash coagulates with or condenses onto soot within engines.

An Inorganic–Organic Hybrid Polymer Cocatalyst for Photoelectrochemical Water Oxidation with Dual Functions of Accelerating Kinetics and Improving Charge Transfer

Oxygen evolution cocatalysts (OECs) play important roles in improving the efficiency of photocatalysts in solar water splitting. Inorganic–organic hybrid polymers (IOHPs), which have good electroly...

Resolving atomic-scale phase transformation and oxygen loss mechanism in ultrahigh-nickel layered cathodes for cobalt-free lithium-ion batteries

Summary Doped LiNiO2 has recently become one of the most promising cathode materials for its high specific energy, long cycle life, and reduced cobalt content. Despite this, the degradation mechanism of LiNiO2 and its derivatives still remains elusive. Here, by combining in situ electron microscopy and first-principles calculations, we elucidate the atomic-level chemomechanical degradation pathway of LiNiO2-derived cathodes. We uncover that the O1 phase formed at high voltages acts as a preferential site for rock-salt transformation via a two-step pathway involving cation mixing and shear along (003) planes. Moreover, electron tomography reveals that planar cracks nucleated simultaneously from particle interior and surface propagate along the [100] direction on (003) planes, accompanied by concurrent structural degradation in a discrete manner. Our results provide an in-depth understanding of the degradation mechanism of LiNiO2-derived cathodes, pointing out the concept that suppressing the O1 phase and oxygen loss is key to stabilizing LiNiO2 for developing next-generation high-energy cathode materials.

FCC phase transformation of Zr alloy during air cooling and aging

• Face-centered cubic (FCC) phase was firstly reported in air cooling and aging Zr alloy. • The orientation relationship between FCC-Zr and matrix was characterized at the atomic scale. • The mechanism of HCP→FCC phase transformation is thoroughly explained. Face-centered cubic (FCC) phase in air-cooled and aged Zr-1.0Sn-1.0Nb-0.3Fe alloy was characterized by transmission electron microscopy (TEM) and high angle annular dark field scanning TEM (HAADF-STEM). The gliding of Shockley partial dislocations on basal planes of hexagonal close-packed (HCP) matrix results in the observed < 1 2 ¯ 10 > HCP / / < 110 > FCC and { 0001 } HCP / / { 1 1 ¯ 1 } FCC orientation relationship. In addition, FCC-Zr phase can continue to grow during the aging process at 580°C instead of being replaced by HCP matrix.

Precipitation Behavior of Mg-7Gd-3Y-2Zn-0.5Zr Alloy during Isothermal Aging.

Precipitate phases in an Mg–7Gd–3Y–2Zn–0.5Zr alloy aged isothermally at 240 °C were examined using high-resolution transmission electron microscopy (TEM) and high-angle annular dark-field scanning TEM. The two types of precipitation sequence that involve Mg–Gd and long period stacking ordered (LPSO) type were found. The LPSO type sequence consisted of the precipitation of γ′′, γ′, 14H-LPSO/18R-LPSO. The Mg–Gd type precipitation sequence involved the formation of β′(b.c.o.) and β1(f.c.c.). The sequence, morphology, distribution, and crystal structure of these precipitates formed during isothermal aging were investigated. The results indicated that the priority precipitation of Mg–Gd and LPSO type sequences during aging can be affected by Nd, which has a higher diffusion coefficient than Gd and Y. The dislocation structures and strengthening mechanism were also discussed.

An efficient combination strategy for high-performance asymmetric-electrolyte metal–air batteries

Asymmetric-electrolyte metal–air batteries (AMABs) are the most promising technologies for realizing efficient energy conversion. However, the issues in cathode and separator parts seriously impede their practical applications. This article previews the latest finding on high-voltage AMABs with long cycle stability. Impressively, the generality of the developed approach is demonstrated by the AZnABs, ASiABs and ASnABs, exhibiting the enhanced operating voltage, power densities, and excellent rate performance.

Highly efficient Co single-atom catalyst for epoxidation of plant oils.

Epoxidation of bio-derived plant oils is a sustainable route to manufacturing plasticizers, additives in lubricants, and other chemicals. The traditional synthetic approaches suffer from the employment of corrosive mineral acid or expensive peroxides (e.g., H2O2). In this work, we report the epoxidation of plant oils using O2 as the terminal oxidant catalyzed by Co-N-C/SiO2 single-atom catalyst. The single-atom dispersion of cobalt is confirmed by high-angle annular dark field-STEM and x-ray absorption fine structure techniques. In the epoxidation of methyl oleate under mild reaction conditions (35 °C, 0.1 MPa O2), 99% selectivity to the desired product is achieved at full conversion. Even for crude oils, Co-N-C/SiO2 is also effective and good yields of the corresponding epoxides are obtained. In addition, the catalyst is easily recovered and can be reused five times without obvious decay in catalytic activity/selectivity. A superoxide radical involved reaction mechanism is proposed on the basis of kinetic study and EPR experiment.

Nanostructured Polymer Composite Electrolytes with Self-Assembled Polyoxometalate Networks for Proton Conduction

Nanostructured Polymer Composite Electrolytes with Self-Assembled Polyoxometalate Networks for Proton Conduction

Constructing FeN4/graphitic nitrogen atomic interface for high-efficiency electrochemical CO2 reduction over a broad potential window

Summary Atomically dispersed Fe–N–C catalyst has shown great performance in the CO2-to-CO conversion, yet the high CO selectivity is achieved only within a rather narrow potential range, which cannot well meet the requirements for the following CO dimerization or hydrogenation. Here, we developed a hydrogen-pyrolysis etching strategy to precisely manipulate the uncoordinated N dopants in the Fe–N–C catalyst. This strategy could preferentially eliminate pyridinic and pyrrolic N atoms while leaving graphitic N. The resulting catalyst gave a CO faradaic efficiency (FECO) above 90% over a broad window from −0.3 to −0.8 V (versus RHE) (in particular, FECO > 97% at −0.6 V). In situ ATR-SEIRAS and first-principle calculations further revealed that this strategy can not only suppress the parasitic H2 generation but also promote CO2 activation and protonation with the assistance of co-adsorbed H2O on the “atomic interface” of “FeN4/graphitic N.”