Advanced Scanning Transmission Electron Microscopy Research Articles

Graphene nanowalls formation investigated by Electron Energy Loss Spectroscopy

The properties of layered materials are significantly dependent on their lattice orientations. Thus, the growth of graphene nanowalls (GNWs) on Cu through PECVD has been increasingly studied, yet the underlying mechanisms remain unclear. In this study, we examined the GNWs/Cu interface and investigated the evolution of their microstructure using advanced Scanning transmission electron microscopy and Electron Energy Loss Spectroscopy (STEM-EELS). GNWs interface and initial root layers of comprise graphitic carbon with horizontal basal graphene (BG) planes that conform well to the catalyst surface. In the vertical section, the walls show a mix of graphitic and turbostratic carbon, while the latter becomes more noticeable close to the top edges of the GMWs film. Importantly, we identified growth process began with catalysis at Cu interface forming BG, followed by defect induction and bending at ‘coalescence points’ of neighboring BG, which act as nucleation sites for vertical growth. We reported that although classical thermal CVD mechanism initially dominates, growth of graphene later deviates a few nanometers from the interface to form GNWs. Nascent walls are no longer subjected to the catalytic action of Cu, and their development is dominated by the stitching of charged carbon species originating in the plasma with basal plane edges.

Atomistic origin of high grain boundary resistance in solid electrolyte lanthanum lithium titanate

Lanthanum lithium titanate is one of the promising electrolytes for solid-state lithium-ion batteries due to its high bulk ionic conductivity up to ∼10−3 S/cm. However, the practical application of this material has been bottlenecked by high grain boundary (GB) resistance, while the underlying mechanism is still under debate. Here we report a comprehensive study with direct evidence to reveal the origin of high GB resistance in La2/3–xLi3xTiO3 (LLTO). Atomic-scale observations via advanced scanning transmission electron microscopy show that the GBs are uniformly subject to subsurface segregation of La atoms to compensate for the excess surface charges. The La segregation leads to an abrupt decrease of charge carrier concentration neighboring GBs and hence is supposed to have deleterious effect on GB conductivity. The findings suggest a novel mechanism of space-charge-induced cation segregation, which shed lights on the intrinsic origin of low GB ionic conductivity in LLTO.

Probing Oxidation-Driven Amorphized Surfaces in a Ta(110) Film for Superconducting Qubit.

Recent advances in superconducting qubit technology have led to significant progress in quantum computing, but the challenge of achieving a long coherence time remains. Despite the excellent lifetime performance that tantalum (Ta) based qubits have demonstrated to date, the majority of superconducting qubit systems, including Ta-based qubits, are generally believed to have uncontrolled surface oxidation as the primary source of the two-level system loss in two-dimensional transmon qubits. Therefore, atomic-scale insight into the surface oxidation process is needed to make progress toward a practical quantum processor. In this study, the surface oxidation mechanism of native Ta films and its potential impact on the lifetime of superconducting qubits were investigated using advanced scanning transmission electron microscopy (STEM) techniques combined with density functional theory calculations. The results suggest an atomistic model of the oxidized Ta(110) surface, showing that oxygen atoms tend to penetrate the Ta surface and accumulate between the two outermost Ta atomic planes; oxygen accumulation at the level exceeding a 1:1 O/Ta ratio drives disordering and, eventually, the formation of an amorphous Ta2O5 phase. In addition, we discuss how the formation of a noninsulating ordered TaO1-δ (δ < 0.1) suboxide layer could further contribute to the losses of superconducting qubits. Subsurface oxidation leads to charge redistribution and electric polarization, potentially causing quasiparticle loss and decreased current-carrying capacity, thus affecting superconducting qubit coherence. The findings enhance the comprehension of the realistic factors that might influence the performance of superconducting qubits, thus providing valuable guidance for the development of future quantum computing hardware.

Observations of very fast electron traps at SiC/high-κ dielectric interfaces

Very fast interface traps have recently been suggested to be the main cause behind poor channel-carrier mobility in SiC metal–oxide–semiconductor field effect transistors. It has been hypothesized that the NI traps are defects located inside the SiO2 dielectric with energy levels close to the SiC conduction band edge and the observed conductance spectroscopy signal is a result of electron tunneling to and from these defects. Using aluminum nitride and aluminum oxide as gate dielectrics instead of SiO2, we detect NI traps at these SiC/dielectric interfaces as well. A detailed investigation of the NI trap density and behavior as a function of temperature is presented and discussed. Advanced scanning transmission electron microscopy in combination with electron energy loss spectroscopy reveals no SiO2 at the interfaces. This strongly suggests that the NI traps are related to the surface region of the SiC rather than being a property of the gate dielectric.

Probing individual single atom electrocatalyst sites by advanced analytical scanning transmission electron microscopy

Single atom electrocatalysts (SAEs) are promising next-generation materials for promoting a variety of important reactions, such as the oxygen reduction, nitrogen reduction, and CO2 reduction reactions. While bulk characterization techniques such as X-ray absorption spectroscopy and Mössbauer spectroscopy have significantly enhanced our understanding of these catalysts, direct probing of individual single metal atom sites at the atomic scale is necessary to understand local variations in the properties of these sites and accelerate design and synthesis of improved SAEs. Aberration-corrected scanning transmission electron microscopy (STEM) has become a powerful tool for providing this type of atomic-scale information about SAE metal sites. These sites are typically unstable under the electron beam, however, which, in combination with conventional acquisition methods and detectors, has limited the type and quantity of information obtainable by spectroscopic STEM techniques. Here, we map multiple individual SAE metal sites in a nitrogen-doped carbon containing atomically dispersed Fe and Re (FeReNC) at the atomic scale by direct electron detection electron energy-loss spectroscopy (EELS). Direct electron detection provides an improved signal-to-noise ratio over conventional scintillator-based detectors and enables detection and real space localization of weak signals. In addition, we demonstrate an automated method for identification of metal atom positions, placement of the probe on these sites, and simultaneous EELS and energy dispersive X-ray spectroscopic (EDS) signal acquisition. This simultaneous acquisition of EELS and EDS provides access to the composition and bonding of a wide range of SAE metal sites. Focusing the probe directly on the metal sites also increases the relevant data acquisition rate by more than an order of magnitude over two-dimensional mapping, enabling improved statistical measurements of site properties. The versatility, sensitivity, and speed that these techniques provide enhances our ability to probe the local elemental and chemical environment of a large number of individual SAE metal site structures at the atomic scale, enabling an improved understanding of the variations in the local properties of these electrocatalysts to be gained. As a result, significantly increased information about individual metal sites will be available to future electrochemical studies through these techniques, accelerating the development of advanced SAEs.

Uncovering the origin of surface-redox pseudocapacitance of molybdenum phosphides enables high-performance flexible sodium-ion capacitors

The flexible electrode based on surface redox pseudocapacitance delivers high specific capacity and superior rate capability, which shows excellent advantages in achieving low-cost and high-performance flexible sodium ion capacitors (FSICs). However, a considerable challenge to be solved is to explore the origin and optimization of surface pseudocapacitance. Herein, we report freestanding MoP nanowires flexible films (MoP-NWs-FF) with high surface-redox pseudocapacitance, and its conductive frameworks facilitate electron/ion transport and achieve superior mechanical flexibility. According to X-ray photoelectron spectroscopy (XPS) and advanced scanning transmission electron microscopy (STEM) technology, the amorphous oxides on the surface of MoP nanograins are demonstrated, which is positively correlated with the sodium ion storage capacity. As a result, the optimized MoP-NWs-FF electrode delivers a high reversible specific capacity of 293 mAh g−1 at 0.1 A g−1, superior rate performance, and cycling stability. Besides, based on the MoP-NWs-FF anode and Na3V2(PO4)2/C flexible film cathode, the assembled fully FSIC exhibits a high power density of ∼ 4 kW kg−1 (with an energy density of 53 Wh kg−1), corresponding to a discharging time of 1 min. This work provides a fundamental insight into the origin of surface-redox pseudocapacitance and paves a new way to develop next-generation high-power flexible energy storage devices.

A High-Entropy-Oxides-Based Memristor: Outstanding Resistive Switching Performance and Mechanisms in Atomic Structural Evolution.

The application of high-entropy oxide (HEO) has attracted significant attention in recent years owing to their unique structural characteristics, such as excellent electrochemical properties and long-term cycling stability. However, the application of resistive random-access memory (RRAM) has not been extensively studied, and the switching mechanism of HEO-based RRAM has yet to be thoroughly investigated. In this study, HEO (Cr, Mn, Fe, Co, Ni)3 O4 with a spinel structure is epitaxially grown on a Nb:STO conductive substrate, and Pt metal is deposited as the top electrode. After the resistive-switching operation, some regions of the spinel structure are transformed into a rock-salt structure and analyzed using advanced transmission electron microscopy and scanning transmission electron microscopy. From the results of X-ray photoelectron spectroscopy and electron energy loss spectroscopy, only specific elements would change their valence state, which results in excellent resistive-switching properties with a high on/off ratio on the order of 105 , outstanding endurance (>4550 cycles), long retention time (>104 s), and high stability, which suggests that HEO is a promising RRAM material.

Modulated Structure Formation in Dislocation Cells in 316L Stainless Steel Fabricated by Laser Powder Bed Fusion

Metal additive manufacturing enables producing complex geometric structures with high accuracy and breaks the design constraints of traditional manufacturing methods. Laser powder bed fusion, a typical additive manufacturing process, presents a challenge in experimentally understanding the nano-scaled microstructure-process relationship regarding the wide range of process parameters. In this study, we aim to reveal the novel nanoscale structural features by advanced scanning transmission electron microscopy to clarify the formation mechanisms in 316L stainless steel by laser powder bed fusion. Here we show that the slender columnar grains were confined to the centreline of the melt pool along the build direction, and the columnar cell structure at the side branching of the melt pool grew along orthogonal directions to follow drastic changes in thermal gradient across adjacent melt pools. Novel nano-scaled modulated structures have been observed in the dislocation cells parallel to the laser scan direction, which were mainly caused by the elastic strain involving the thermal gradient inside the melt pool and across adjacent melt pools as well as the effective strain field in the dislocation cell interiors. An in-depth understanding of microstructure developments is worthy of fabricating high-performance materials by controlling the additive manufacturing process.

Extended Oxygen Octahedral Tilt Proximity near Oxide Heterostructures.

The oxide interfaces between materials with different structural symmetries have been actively studied due to their novel physical properties. However, the investigation of intriguing interfacial phenomena caused by the oxygen octahedral tilt (OOT) proximity effect has not been fully exploited, as there is still no clear understanding of what determines the proximity length and what the underlying control mechanism is. Here, we achieved scalability of the OOT proximity effect in SrRuO3 (SRO) by epitaxial strain near the SRO/SrTiO3 heterointerface. We demonstrated that the OOT proximity length scale of SRO is extended from 4 unit cells to 14 unit cells by employing advanced scanning transmission electron microscopy. We also suggest that this variation may originate from changes in phonon dispersions due to electron-phonon coupling in SRO. This study will provide in-depth insights into the structural gradients of correlated systems and facilitate potential device applications.

High Power Factor Nb-Doped TiO2 Thermoelectric Thick Films: Toward Atomic Scale Defect Engineering of Crystallographic Shear Structures.

Donor-doped TiO2-based materials are promising thermoelectrics (TEs) due to their low cost and high stability at elevated temperatures. Herein, high-performance Nb-doped TiO2 thick films are fabricated by facile and scalable screen-printing techniques. Enhanced TE performance has been achieved by forming high-density crystallographic shear (CS) structures. All films exhibit the same matrix rutile structure but contain different nano-sized defect structures. Typically, in films with low Nb content, high concentrations of oxygen-deficient {121} CS planes are formed, while in films with high Nb content, a high density of twin boundaries are found. Through the use of strongly reducing atmospheres, a novel Al-segregated {210} CS structure is formed in films with higher Nb content. By advanced aberration-corrected scanning transmission electron microscopy techniques, we reveal the nature of the {210} CS structure at the nano-scale. These CS structures contain abundant oxygen vacancies and are believed to enable energy-filtering effects, leading to simultaneous enhancement of both the electrical conductivity and Seebeck coefficients. The optimized films exhibit a maximum power factor of 4.3 × 10-4 W m-1 K-2 at 673 K, the highest value for TiO2-based TE films at elevated temperatures. Our modulation strategy based on microstructure modification provides a novel route for atomic-level defect engineering which should guide the development of other TE materials.

Sub-Ångstrom-scale structural variations in high-entropy oxides.

High-entropy oxides (HEOs) are a special class of materials that utilize the concept of high-entropy alloys (HEAs) with five or more elements randomly distributing at a single sublattice in near-equiatomic proportions. HEOs have been attracting increasing attention owing to their many outstanding physical and chemical properties. However, unlike HEAs, for which local chemical compositions, order/disorder behaviors, and property-structure relationships have been comprehensively investigated, detailed information on the atomic-scale chemical and structural features and their correlations with functionalities in HEOs so far is still not sufficient. Herein, we select four typical HEOs with pyrochlore, spinel, perovskite and rock-salt type structures, and directly observe and quantify sub-Ångstrom-scale structure variations in different manners by means of advanced aberration-corrected scanning transmission electron microscopy techniques. Visualization and quantification of local structural variations and lattice distortions in the current work may show a valuable example for future investigations on local fluctuating structures and their relationships with properties in more systems of HEOs.

Study on corrosion resistance of artificially aged 7075 aluminium alloy by using Cs-corrected STEM

This research studied the mechanism of the corrosion resistance enhancement of artificially aged 7075 aluminium alloy using advanced Cs-corrected scanning transmission electron microscopy (STEM). The corrosion behaviors of artificially aged 7075 aluminium alloys in a 3.5 wt.% NaCl solution were investigated by impedance spectra, equivalent circuit analyses, polarization measurements and immersion tests. The results show that a longer aging treatment leads to better corrosion resistance, which can be attributed to the following microstructural features, as revealed by STEM. The Cu segregation at grain boundaries under over-aged conditions helps retard intergranular corrosion. The Mg(Zn, Cu)2 precipitates formed on the surfaces of Al18Mg3(Cr,Mn)2 dispersoids effectively insulate the dispersoids as cathodes in corrosion, from the Al matrix. This study demonstrates a potential strategy to design corrosion-resistant alloys achieved by proper alloying and subsequent aging.

Development of a High Electron Energy-loss Spectrometry System for Advanced Scanning Transmission Electron Microscopy

Development of a High Electron Energy-loss Spectrometry System for Advanced Scanning Transmission Electron Microscopy

Atomic origin of the coexistence of high critical current density and high Tc in CuBa2Ca3Cu4O10+δ superconductors

For cuprate superconductors, a high critical transition temperature (Tc) can be realized in compounds containing multiple CuO2 layers in the unit cell, while a high critical current density (Jc) is rarely sustained above liquid nitrogen temperature. The CuBa2Ca3Cu4O10+δ (Cu-1234) superconductors synthesized under high oxygen pressure incredibly exhibit high Tc (~117 K) and high Jc (>104 A/cm2, 100 K) values. Here, the “double high” traits of Cu-1234 were investigated with advanced scanning transmission electron microscopy. It was revealed that ordering vacancies and plate-like 90° microdomains induced efficient microstructure pinning centers that suppressed vortex flux flow and enhanced Jc. Furthermore, metallic charge-reservoir blocks [Ba2CuO3+δ] were composed of unique compressed [CuO6] octahedra, which induced many holes with 2pz symmetry that significantly decreased the superconducting anisotropy and dramatically enhanced the interlayer coupling that guaranteed a high Jc. On the other hand, optimally doped CuO2 planes inside the thick superconducting blocks [Ca3Cu4O8] maintained a high Tc. Our results are applicable to design and synthesis of new superconductors with “double high” traits.

The effect of interstitial carbon atoms on defect evolution in high entropy alloys under helium irradiation

In this work, a design strategy based on a typical multi-principal element alloy (Fe50Mn30Co10Cr10, at. %) was proposed to tune the irradiation behavior by adding interstitial carbon atoms (Fe49.5Mn30Co10Cr10C0.5, at. %). Advanced scanning transmission electron microscopy was employed to study the evolution of dislocation loops and helium bubbles in alloys after 400 keV He+ ion irradiation at three different temperatures ranging from 350 °C to 450 °C. The results showed that the interstitial carbon atoms inhibited the growth of He bubbles and irradiation hardening. The high-resolution energy dispersive spectroscopy mapping revealed that the segregation at the dislocation loops in Fe49.5Mn30Co10Cr10C0.5 was efficiently lessened compared to that in Fe50Mn30Co10Cr10, which shows an even superior performance than the equiatomic FeMnCoCrNi Cantor alloy. Radiation-induced “W-shaped” elemental oscillation patterns with a width of about 1 nm around dislocation loops, were observed for the first time in high-entropy alloys. Such nanoscale local elemental fluctuations are suggested to modify the lattice friction and thus have an impact on the mechanical properties of the material. First-principles calculations suggest that the interstitial carbon atoms can effectively enhance the site-to-site local lattice distortion and modify vacancy migration energy near carbon atoms. Our systematic experiments demonstrate that adding interstitial carbon atoms into multi-principal element or high-entropy alloy is beneficial for the reduction in irradiation hardening and volumetric swelling, as well as radiation-induced segregation.

Emergent interface vibrational structure of oxide superlattices

As the length scales of materials decrease, the heterogeneities associated with interfaces become almost as important as the surrounding materials. This has led to extensive studies of emergent electronic and magnetic interface properties in superlattices1–9. However, the interfacial vibrations that affect the phonon-mediated properties, such as thermal conductivity10,11, are measured using macroscopic techniques that lack spatial resolution. Although it is accepted that intrinsic phonons change near boundaries12,13, the physical mechanisms and length scales through which interfacial effects influence materials remain unclear. Here we demonstrate the localized vibrational response of interfaces in strontium titanate–calcium titanate superlattices by combining advanced scanning transmission electron microscopy imaging and spectroscopy, density functional theory calculations and ultrafast optical spectroscopy. Structurally diffuse interfaces that bridge the bounding materials are observed and this local structure creates phonon modes that determine the global response of the superlattice once the spacing of the interfaces approaches the phonon spatial extent. Our results provide direct visualization of the progression of the local atomic structure and interface vibrations as they come to determine the vibrational response of an entire superlattice. Direct observation of such local atomic and vibrational phenomena demonstrates that their spatial extent needs to be quantified to understand macroscopic behaviour. Tailoring interfaces, and knowing their local vibrational response, provides a means of pursuing designer solids with emergent infrared and thermal responses.

Insights into the performance and degradation of Ru@Pt core-shell catalysts for fuel cells by advanced (scanning) transmission electron microscopy.

Ru@Pt core-shell nanoparticles are currently being explored as carbon monoxide tolerant anode catalysts for proton exchange membrane fuel cells. However, little is known about their degradation under fuel cell conditions. In the present work, two types of Ru@Pt nanoparticles with nominal shell thicknesses of 1 (Ru@1Pt) and 2 (Ru@2Pt) Pt monolayers are studied as synthesized and after accelerated stress tests. These stress tests were designed to imitate the degradation occurring under fuel cell operating conditions. Our advanced (scanning) transmission electron microscopy characterization explains the superior initial electrochemical performance of Ru@1Pt. Moreover, the 3D reconstruction of the Pt shell by electron tomography reveals an incomplete shell for both samples, which results in a less stable Ru metal being exposed to an electrolyte. The degree of coverage of the Ru cores provides insights into the higher stability of Ru@2Pt during the accelerated stress tests. Our results explain how to maximize the initial performance of Ru@Pt-type catalysts, without compromising their stability under fuel cell conditions.

Anisotropic defect distribution in He+-irradiated 4H-SiC: Effect of stress on defect distribution

Irradiation-induced anisotropic swelling in hexagonal α-SiC is known to degrade the mechanical properties of SiC; however, the associated physical mechanism and microstructural process remain insufficiently understood. In this study, an anisotropic swelling condition where the surface normal direction was allowed to freely expand with constraint in the lateral direction was introduced in 4H-SiC using selected-area He+ irradiation, and the internal defect distribution was investigated using transmission electron microscopy (TEM) and advanced scanning TEM. The defect distribution was compared to that in non-selected-area He+-irradiated 4H-SiC and electron-irradiated TEM-foil 4H-SiC. An anisotropic defect distribution was observed in the selected-area He+-ion-irradiated 4H-SiC, with interstitial defects preferentially redistributed in the surface normal direction ([0004]) and negative volume defects (such as vacancies and/or carbon antisite defects) dominantly located in the lateral directions ([112¯0] and [101¯0]). This anisotropy of the defect distribution was substantially lower in the non-selected-area He+-irradiated and electron-irradiated samples. The stress condition in the three samples was also measured and analyzed. In the selected-area He+-irradiated 4H-SiC, compressive stress was introduced in the lateral directions (([101¯0] and [112¯0])), with little stress introduced in the surface normal direction ([0004]); this stress condition was introduced at the beginning of ion irradiation. The compressive stress likely inhibits the formation of interstitial defects in the lateral directions, enhancing the anisotropy of the defect distribution in SiC.

Direct imaging and electronic structure modulation of moir\xe9 superlattices at the 2D/3D interface

The atomic structure at the interface between two-dimensional (2D) and three-dimensional (3D) materials influences properties such as contact resistance, photo-response, and high-frequency electrical performance. Moiré engineering is yet to be utilized for tailoring this 2D/3D interface, despite its success in enabling correlated physics at 2D/2D interfaces. Using epitaxially aligned MoS2/Au{111} as a model system, we demonstrate the use of advanced scanning transmission electron microscopy (STEM) combined with a geometric convolution technique in imaging the crystallographic 32 Å moiré pattern at the 2D/3D interface. This moiré period is often hidden in conventional electron microscopy, where the Au structure is seen in projection. We show, via ab initio electronic structure calculations, that charge density is modulated according to the moiré period, illustrating the potential for (opto-)electronic moiré engineering at the 2D/3D interface. Our work presents a general pathway to directly image periodic modulation at interfaces using this combination of emerging microscopy techniques.

The micro-mechanism of rhenium promoting the formation of stacking faults in the Ni-based model single crystal superalloys

It is important and necessary to understand the micro-mechanism of rhenium (Re) effect in the deformation process. The in-situ tensile experiments of Ni–Al and Ni–Al-Re model single crystal superalloys have been carried out in scanning electron microscope at 750 °C. It is found that Re can promote the complex stacking fault (CSF) formation, which is similar to the previous results after tensile experiments at room temperature. The micro-mechanism of Re promoting the CSF formation has been investigated by means of advanced probe-corrected scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. The local high concentration of Re is observed at CSF regions after tensile experiments both at room temperature and 750 °C. The first principles calculation results further indicate that low concentration of Re increases CSF energy, while high concentration of Re decreases CSF energy, which is consistent with the experimental results.