Transmission Electron Energy Loss Spectroscopy Research Articles

Embedded Hybrid-Dimensional Heterointerface for Filament Modulation in 2D Material-Based Artificial Nociceptor.

Nociceptors are key sensory receptors that transmit warning signals to the central nervous system in response to painful stimuli. This fundamental process is emulated in an electronic device by developing a novel artificial nociceptor with an ultrathin, nonstoichiometric gallium oxide (GaOx)-silicon oxide heterostructure. A large-area 2D-GaOx film is printed on a substrate through liquid metal printing to facilitate the production of conductive filaments. This nociceptive structure exhibits a unique short-term temporal response following stimulation, enabling a facile demonstration of threshold-switching physics. The developed heterointerface 2D-GaOx film enables the fabrication of fast-switching, low-energy, and compliance-free 2D-GaOx nociceptors, as confirmed through experiments. The accumulation and extrusion of Ag in the oxide matrix are significant for inducing plastic changes in artificial biological sensors. High-resolution transmission electron microscopy and electron energy loss spectroscopy demonstrate that Ag clusters in the material dispersed under electrical bias and regrouped spontaneously when the bias is removed owing to interfacial energy minimization. Moreover, 2D nociceptors are stable; thus, heterointerface engineering can enable effective control of charge transfer in 2D heterostructural devices. Furthermore, the diffusive 2D-GaOx device and its Ag dynamics enable the direct emulation of biological nociceptors, marking an advancement in the hardware implementation of artificial human sensory systems.

Structure and Formation Mechanisms in Tantalum and Niobium Oxides in Superconducting Quantum Circuits.

Improving the qubit's lifetime (T1) is crucial for fault-tolerant quantum computing. Recent advancements have shown that replacing niobium (Nb) with tantalum (Ta) as the base metal significantly increases T1, likely due to a less lossy native surface oxide. However, understanding the formation mechanism and nature of both surface oxides is still limited. Using aberration-corrected transmission electron microscopy and electron energy loss spectroscopy, we found that Ta surface oxide has fewer suboxides than Nb oxide. We observed an abrupt oxidation state transition from Ta2O5 to Ta, as opposed to the gradual shift from Nb2O5, NbO2, and NbO to Nb, consistent with thermodynamic modeling. Additionally, amorphous Ta2O5 exhibits a closer-to-crystalline bonding nature than Nb2O5, potentially hindering H atomic diffusion toward the oxide/metal interface. Finally, we propose a loss mechanism arising from the transition between two states within the distorted octahedron in an amorphous structure, potentially causing two-level system loss. Our findings offer a deeper understanding of the differences between native amorphous Ta and Nb oxides, providing valuable insights for advancing superconducting qubits through surface oxide engineering.

Single atoms and metal nanoclusters anchored to graphene vacancies

Fabricating dispersed single atoms and size-controlled metal nanoclusters remains a difficult challenge due to sintering. Here, we demonstrate that atoms and clusters can be immobilized using atomically clean defect-engineered graphene as the matrix. The graphene is first cleaned of surface contamination with laser heating, after which low-energy Ar irradiation is used to create spatially well-separated vacancies into it. Metal atoms are then evaporated either via thermal or ebeam evaporation onto graphene, where they diffuse until being trapped into a vacancy. The density of embedded structures can be controlled through irradiation dose, and the size of the structures through evaporation time. The resulting structures are confirmed through atomic-resolution scanning transmission electron microscopy and electron energy loss spectroscopy. We demonstrate here incorporation of Al, Ti, Fe, Ag and Au single atoms or nanoclusters, but the method should work equally well for other elements.

Condensed Layer Deposition of Nanoscopic TiO2 Overlayers on High-Surface-Area Electrocatalysts.

Encapsulating an electrocatalytic material with a semipermeable, nanoscopic oxide overlayer offers a promising approach to enhancing its stability, activity, and/or selectivity compared to an unencapsulated electrocatalyst. However, applying nanoscopic oxide encapsulation layers to high-surface-area electrodes such as nanoparticle-supported porous electrodes is a challenging task. This study demonstrates that the recently developed condensed layer deposition (CLD) method can be used for depositing nanoscopic (sub-10 nm thick) titanium dioxide (TiO2) overlayers onto high-surface-area platinized carbon foam electrodes. Characterization of the overlayers by transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) showed that the films are amorphous, while X-ray photoelectron spectroscopy confirmed that they exhibit TiO2 stoichiometry. Electrodes were also characterized by hydrogen underpotential deposition (Hupd) and carbon monoxide (CO) stripping, demonstrating that the Pt electrocatalysts remain electrochemically active after encapsulation. Additionally, copper underpotential deposition (Cuupd) measurements revealed that TiO2 overlayers are effective at blocking Cu2+ from reaching the TiO2/Pt buried interface and were used to estimate that between 43 and 98% of Pt surface sites were encapsulated. Overall, this study shows that CLD is a promising approach for depositing nanoscopic protective overlayers on high-surface-area electrodes.

Helium reservoirs in iron nanoparticles on the lunar surface

The Moon’s surface is directly exposed to the space environment and subject to alteration by space weathering. One agent of space weathering, the solar wind, enriches the lunar surface with helium. Although we understand how helium is delivered to the Moon, certain aspects of helium concentration processes on the surface remain unknown, such as why impact-generated glass aggregates contain more helium than equally sized soil grains of other types. Here we have analyzed the contents of vesicular iron nanoparticles in lunar impact glasses using aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy and show that the nanoparticles contain high concentrations of helium (10-24 atoms/nm3). The widespread occurrence of vesicular iron nanoparticles among lunar samples suggests that they may be an important helium reservoir. These results also suggest that space weathering of iron-rich minerals plays a role in helium sequestration on the Moon and potentially on other airless bodies.

Methanogen‐Mediated Precipitation of Mn Carbonates at the Expense of Mn Oxides

AbstractWhether Mn carbonates can be used as a proxy for the oxygenation event is debated. Here we examined the Early Cretaceous lacustrine Mn carbonates from North China, which contain abundant microbial fossils. The extremely positive δ13C (up to +15‰ relative to Vienna Peedee belemnite) and micro‐area enrichment of Ni strongly indicate a methanogenic archaea origin of these microorganisms. Transmission electron microscope and electron energy loss spectroscopy show the nanoscale transformation of Mn‐oxides (Mg‐exchanged phyllomanganate) to Mn carbonates (kutnohorite), on extracellular polymeric substances. The reaction of the Mn oxides with organic matter resulted in increasing pH and alkalinity, together with the fluctuating pH, offering a suitable micro‐environment for the transformation processes. These Mn carbonates are therefore indicative of an oxidized, sulfate‐absent environment. The depicted scenario serves as a reference to ocean of the early Earth and provides a referable Mn oxide tracer for determining the emergence of the Great Oxidation Event.

4H-SiC/SiO2 Interface Degradation in 1.2 kV 4H-SiC MOSFETs due to Power Cycling Tests

Power cycling tests (PCTs) assess the reliability of power devices by closely simulating their operating conditions. A PCT was performed on commercially available 1.2 kV 4H-SiC power metal–oxide–semiconductor field-effect transistors to observe its impact on the 4H-SiC/SiO2 interface. High-resolution transmission electron microscopy and electron energy loss spectroscopy measurements showed variations in the length of the 4H-SiC/SiO2 transition layer, depending on whether the device was power cycled. Moreover, the total resistance at Vg >> Vt in Rtot − (Vg-Vt)−1 graph increased to 16.5%, while it changed more radically to 47.3% at Vg ≈ Vt. The threshold voltage shifted negatively. These variations cannot be expected solely through the wearout of the package.

Grain refinement of Mg-Ca alloys by native MgO particles

In Mg-Ca alloys the grain refining mechanism, in particular regarding the role of nucleant substrates, remains the object of debates. Although native MgO is being recognised as a nucleating substrate accounting for grain refinement of Mg alloys, the possible interactions of MgO with alloying elements that may alter the nucleation potency have not been elucidated yet. Herein, we design casting experiments of Mg-xCa alloys varied qualitatively in number density of native MgO, which are then comprehensively studied by advanced electron microscopy. The results show that grain refinement is enhanced as the particle number density of MgO increases. The native MgO particles are modified by interfacial layers due to the co-segregation of Ca and N solute atoms at the MgO/Mg interface. Using aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy, we reveal the nature of these Ca/N interfacial layers at the atomic scale. Irrespective of the crystallographic termination of MgO, Ca and N co-segregate at the MgO/Mg interface and occupy Mg and O sites, respectively, forming an interfacial structure of a few atomic layers. The interfacial structure is slightly expanded, less ordered and defective compared to the MgO matrix due to compositional deviations, whereby the MgO substrate is altered as a poorer template to nucleate Mg solid. Upon solidification in a TP-1 mould, the impotent MgO particles account for the grain refining mechanism, where they are suggested to participate into nucleation and grain initiation processes in an explosive manner. This work not only reveals the atomic engineering of a substrate through interfacial segregation but also demonstrates the effectiveness of a strategy whereby native MgO particles can be harnessed for grain refinement in Mg-Ca alloys.

Lattice-Plane-Dependent Distribution of Ce3+ at Pt and CeO2 Interfaces for Pt/CeO2 Catalysts.

The interaction between a metal and a support, which is known as the metal-support interaction, often plays a determining role in the catalytic properties of supported metal catalysts. Herein, we have developed model Pt/CeO2 catalysts, which enabled us to investigate the interface atomic and electronic structures between Pt and the {001}, {011}, and {111} planes of CeO2 using scanning transmission electron microscopy and electron energy-loss spectroscopy. We found that the number of Ce3+ ions around the Pt nanoparticles followed the order {001} > {011} > {111}, which was the opposite order of the generally accepted stability of low index surfaces of CeO2. Systematic first-principles calculations revealed that the presence of Pt nanoparticles facilitated the formation of oxygen vacancies and that the appearance of the Ptδ+ state was preferred when Pt nanoparticles were in contact with CeO2 {001} planes due to direct charge transfer from Pt to CeO2. These results provide important insights into the nature of the metal-support interaction for a comprehensive understanding of the properties of supported metal catalysts.

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.

Probing Functional Structures, Defects, and Interfaces of 2D Transition Metal Dichalcogenides by Electron Microscopy

Abstract2D transition metal dichalcogenides (TMDs) exhibit remarkable properties that are strongly influenced by their atomic structures, as well as by various types of defects and interfaces that can be precisely engineered and controlled. These features make 2D TMDs and TMD‐based materials highly promising for a wide range of applications in electronics, optoelectronics, magnetism, spintronics, catalysis, energy, etc. By providing a comprehensive approach to understand the structure–property–functionality relationship in materials at the atomic scale, electron microscopy, and spectroscopy techniques have emerged as invaluable tools for studying both the static characteristics and dynamic evolutions of 2D TMDs. In this review, the primary focus lies in exploring intrinsic and artificial structures in TMDs and their heterostructures, along with their corresponding properties, through cutting‐edge aberration‐corrected scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS). Additionally, recent advancements in the field of in situ visualization and manipulation of 2D TMDs using electron beams are highlighted. It is anticipated that the up‐to‐date overview provided, along with a glimpse into the future development of STEM‐based techniques, will make a substantial contribution to advancing research on 2D materials.

Atomic Layer Deposition of the Geometry Separated Lewis and Brønsted Acid Sites for Cascade Glucose Conversion.

Solid acid catalysts with bi-acidity are promising as workhouse catalysts in biorefining to produce high-quality chemicals and fuels. Herein, we report a new strategy to develop bi-acidic cascade catalysts by separating both acid sites in geometry via the atomic layer deposition (ALD) of Lewis acidic alumina on Brønsted acidic supports. Visualized by transmission electron microscopy and electron energy loss spectroscopy mapping, the ALD-deposited alumina forms a conformal alumina domain with a thickness of around 3 nm on the outermost surface of mesoporous silica-alumina. Solid state nuclear magnetic resonance investigation shows that the dominant Lewis acid sites distribute on the outermost surface, whereas intrinsic Brønsted acid sites locate inside the nanopores within the silica-rich substrate. In comparison to other bi-acidic solid catalyst counterparts, the special geometric distance of Lewis and Brønsted acid sites minimized the synergetic effect, leading to a cascade reaction environment. For cascade glucose conversion, the designed ALD catalyst showed a highly enhanced catalytic performance.

Laser machining of free-standing silicon nitride membranes

Patterning free-standing Silicon Nitride membranes has enabled the development of various SiN-based devices such as quantum resonators, biosensors, temperature detectors, and plasmonic devices. Patterning SiN membranes usually involves expensive and time-consuming cleanroom techniques that limit flexibility in the development of new SiN membrane designs. While ultrafast laser machining has been proposed to create micron to submicron features in these membranes, laser machining of large area features has not been reported as it often results in membrane failure due to stress concentration during laser machining. We show that continuous laser machining can be used to create a crack and to extract the fracture toughness of the membrane (1.9 ± 0.3 MPa.m1/2). To successfully patterned SiN membranes without failure, a low stress laser machining method is developed, where stress concentration can be minimized by adjusting the laser drilling sequence, a result confirmed by finite element simulations. Complex shapes can thus be machined over a large area with a very high success rate. Laser parameters are optimized to improve the quality of the laser-cut edges without the formation of laser-induced periodic surface structure. Transmission Electron Microscopy and Electron Energy Loss Spectroscopy indicate a modification of the Si/N ratio over a small region next to the laser machined features. These results demonstrate that low stress ultrafast laser machining can be used to create patterns in SiN membranes quickly and economically, enabling the rapid development of new membrane designs.

Tribochemical insights into the carbon film formation induced by metallic species derived from layered double hydroxide nanoadditives

Layered double hydroxides (LDHs) have demonstrated excellent tribological performance in various studies. However, there remains a fundamental knowledge gap concerning the chemical composition of tribofilms across the cross-section. In this study, we seek to elucidate this question by tribologically testing various binary LDHs. It was found that five out of eight LDHs, denoted as CoAl-, CoFe-, MgAl-, NiFe-, and ZnAl-LDHs could induce hierarchical protective tribofilms due to the formation of rigid oxide layers and in situ carbon-based films. The five tribofilms helped to reduce wear loss and friction by approximately 90% and 20%, respectively. Remarkably, the Co-based tribofilms showed the best antiwear performance because of the thick carbon tribofilm formation and the strong bonding at the metallic/tribo-oxide interfaces. The formation mechanisms of the carbon tribofilm and its characteristic nature were evaluated and revealed by scanning transmission electron microscopy and electron energy loss spectroscopy. Meanwhile, the intriguing nano-scale mechanical properties, i.e., the hardness and reduced elastic modulus of different tribofilms, were well-demonstrated by nanoindentation and nanoscratch experiments. The correlation between chemical structures and mechanical properties of the tribofilms derived from LDH lubricant additives was first conducted and discussed, unveiling the tribochemical and lubrication mechanisms between the LDHs and sliding surfaces.

Hematite α‐Fe2O3(0001) in Top and Side View: Resolving Long‐Standing Controversies about Its Surface Structure

AbstractHematite is a common iron oxide found in nature, and the α‐Fe2O3(0001) plane is prevalent on the nanomaterial utilized in photo‐ and electrocatalytic applications. The atomic‐scale structure of the surface remains controversial despite decades of study, partly because it depends on sample history as well as the preparation conditions. Here, a comprehensive study is performed using an arsenal of surface techniques (non‐contact atomic force microscopy, scanning tunneling microscopy, low‐energy electron diffraction, and X‐ray photoemission spectroscopy) complemented by analyses of the near surface region by high‐resolution transmission electron microscopy and electron energy loss spectroscopy. The results show that the so‐called “bi‐phase” termination forms even under highly oxidizing conditions; a (1 × 1) surface is only observed in the presence of impurities. Furthermore, it is shown that the biphase is actually a continuous layer distorted due to a mismatch with the subsurface layers, and thus not the proposed mixture of FeO(111) and α‐Fe2O3(0001) phases. Overall, the results show how combining surface and cross‐sectional imaging provides a full view that can be essential for understanding the role of the near‐surface region on oxide surface properties.

Observing Carbon-(k) Near Edge Structure for Various Polymers at High Spatial Resolution with Modern Scanning Transmission Electron Microscopy and Electron Energy Loss Spectroscopy Instrumentation.

Observing Carbon-(k) Near Edge Structure for Various Polymers at High Spatial Resolution with Modern Scanning Transmission Electron Microscopy and Electron Energy Loss Spectroscopy Instrumentation.

Spalling induced van der Waals lift-off and transfer of 4-in. GaN epitaxial films

Epitaxial lift-off (ELO) of high-quality GaN layers allows for integration with a variety of materials enabling improved performance, reduced costs, and development of new electronics. Of the ELO technologies, two-dimensional (2D) material-based lift-off offers great promise but is still in the early stages of development and has yet to demonstrate the scale and yield of other ELO technologies. Here, we demonstrate the potential of this process's scalability, speed, and yield through epitaxial growth and lift-off of 4-in. GaN films using a 2D boron nitride (BN) van der Waals (vdW) buffer layer. Since the BN layer acts as the growth template and the mechanical release layer, both the quality and adhesion of the GaN layer are correlated with the BN morphology and uniformity. Detailed spectroscopic mapping demonstrates excellent BN uniformity, which translates into growth of high-quality GaN as shown in mapping of the x-ray rock curves (XRCs), atomic force microscopy, and photoluminescence. Scanning transmission electron microscopy and electron energy loss spectroscopy reveal abrupt chemically distinct interfaces between the sapphire, BN, and AlN/GaN layers essential for efficient lift-off. Combined with the BN/GaN vdW heterostructure, Ni spalling is used to efficiently lift-off and transfer a full 4-in. GaN layer. Post transfer characterization of a 1.9 μm thick GaN layer transferred to a SiO2/Si wafer shows a very minimal change in the XRC and photoluminescence. Strain measurements before and after transfer show that the process fully relaxes residual strain formed in the GaN during high-temperature growth. This work highlights the potential for industry scalability of an exciting 2D material-based lift-off technology, which can facilitate higher power and more efficient radio frequency devices.

In situ investigation of the ferroelectric phase transition in improper ferroelectric YMnO3 thin films by electron energy loss spectroscopy

The crystal and electronic structure of $\mathrm{YMn}{\mathrm{O}}_{3}$ thin films at the paraelectric-ferroelectric phase transition are monitored by scanning transmission electron microscopy and electron energy loss spectroscopy (EELS) during in situ heating experiments. At the phase transition of a 14-unit-cell-thick film at $\ensuremath{\sim}325\phantom{\rule{0.16em}{0ex}}{}^{\ensuremath{\circ}}\mathrm{C}$, we observe a clear transition from the polar $P{6}_{3}cm$ to the centrosymmetric $P{6}_{3}/mmc$ space group, manifested by the disappearance of the unit-cell tripling. Further, we reveal significant changes in the EELS data across the phase transition, and interpret them with the help of real-space multiple-scattering calculations. Upon crossing the Curie temperature, striking changes in the O-$K$ near-edge structure are identified, which are attributed to a modification in the Y $4d--\mathrm{O} 2p$ hybridization. In particular, a weakening of the Y $4d{}_{z}{}^{2}--\mathrm{O} 2{p}_{z}$ hybridization is detected for the paraelectric phase compared to the ferroelectric phase. Upon cooling below the Curie temperature, the ferroelectric phase is recovered and a stronger hybridization along the $c$-axis polarization direction is restored, stabilizing the zone-boundary ${\mathrm{K}}_{3}$ phonon mode. Our findings demonstrate the high sensitivity of the O-$K$ near-edge structure to structural distortions in $\mathrm{YMn}{\mathrm{O}}_{3}$ polymorphs and lay the groundwork for future studies on polymorphic phase transformations in improper ferroelectrics whose ferroelectricity emerges through coupling to a nonpolar lattice distortion.

Characterization of Cu-Cu direct bonding in ambient atmosphere enabled using (111)-oriented nanotwinned-copper

The copper-copper (Cu-Cu) direct bonding technology was proposed in recent years in order to realize precise preparation and reliable service under high current density for three-dimension (3D) packaging in the post-Moore-era. In this study, Cu-Cu direct bonding was achieved in the ambient atmosphere by utilizing highly (111) oriented copper with nanotwin structure (called (111) nt-Cu). The thermal compression with a pressure of 30 MPa was conducted on a couple of Cu films at 300 and 400 °C in air. The Cu-Cu joints after bonding were further investigated by scanning electron microscopy (SEM), electron back-scattered diffraction (EBSD) and transmission electron microscopy (TEM). Different from the polycrystalline copper, perfect bonding was achieved as confirmed by high-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS). The shear strength after air bonding was measured as 96.04 ± 5.67 MPa on average, which demonstrated relatively high performance in traditional Cu-Cu bonding. The excellent resistance to oxidation and fast Cu(111) surface diffusivity of (111) nt-Cu guaranteed the bonding process. Above all, the achievement of (111) nt-Cu high performance bonding in the ambient atmosphere should give an insight into developing new interconnected technology.

Tailoring Breathing Behavior of Solid Electrolyte Interphases Unraveled by Cryogenic Transmission Electron Microscopy (Adv. Energy Mater. 21/2023)

Solid Electrolyte Interphases In article number 2300240, Biao Zhang, Ye Zhu, and co-workers use identical-location cryogenic transmission electron microscopy and electron energy loss spectroscopy to reveal the origin of breathing behaviour of solid electrolyte interphases formed on Fe2O3 anode in Li-ion batteries.