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The atomic structure of Ni-Pd nanoparticles has been studied using atomic pair distribution function (PDF) analysis of X-ray total scattering data and with transmission electron microscopy (TEM). Larger nanoparticles have PDFs corresponding to the bulk face-centered cubic packing. However, the smallest nanoparticles have PDFs that strongly resemble those obtained from bulk metallic glasses (BMGs). In fact, by simply scaling the distance axis by the mean metallic radius, the curves may be collapsed onto each other and onto the PDF from a metallic glass sample. In common with a wide range of BMG materials, the intermediate range order may be fit with a damped single-frequency sine wave. When viewed in high-resolution TEM, these nanoparticles exhibit atomic fringes typical of those seen in small metallic clusters with icosahedral or decahedral order. These two seemingly contradictory results are reconciled by calculating the PDFs of models of icosahedra that would be consistent with the fringes seen in TEM. These model PDFs resemble the measured ones when significant atom-position disorder is introduced, drawing together the two diverse fields of metallic nanoparticles and BMGs and supporting the view that BMGs may contain significant icosahedral or decahedral order.
Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. We use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. Our observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.
Chemical design of multicomponent nanocrystals requires atomic-level understanding of reaction kinetics. Here, we apply single-particle imaging coupled with atomistic simulation to study reaction pathways and rates of Pd@Au and Cu@Au core-shell nanocubes undergoing oxidative dissolution. Quantitative analysis of etching kinetics using in situ transmission electron microscopy (TEM) imaging reveals that the dissolution mechanism changes from predominantly edge-selective to layer-by-layer removal of Au atoms as the reaction progresses. Dissolution of the Au shell slows down when both metals are exposed, which we attribute to galvanic corrosion protection. Morphological transformations are determined by intrinsic anisotropy due to coordination-number-dependent atom removal rates and extrinsic anisotropy induced by the graphene window. Our work demonstrates that bimetallic coreshell nanocrystals are excellent probes for the local physicochemical conditions inside TEM liquid cells. Furthermore, single-particle TEM imaging and atomistic simulation of reaction trajectories can inform future design strategies for compositionally and architecturally sophisticated nanocrystals.
Observation of dynamic processes by transmission electron microscopy (TEM) is an attractive technique to experimentally analyze materials’ nanoscale phenomena and understand the microstructure-properties relationships in nanoscale. Even if spatial and temporal resolutions of real-time TEM increase significantly, it is still difficult to say that the researchers quantitatively evaluate the dynamic behavior of defects. Images in TEM video are a two-dimensional projection of three-dimensional space phenomena, thus missing information must be existed that makes image’s uniquely accurate interpretation challenging. Therefore, even though they are still a clustering high-dimensional data and can be compressed to two-dimensional, conventional statistical methods for analyzing images may not be powerful enough to track nanoscale behavior by removing various artifacts associated with experiment; and automated and unbiased processing tools for such big-data are becoming mission-critical to discover knowledge about unforeseen behavior. We have developed a method to quantitative image analysis framework to resolve these problems, in which machine learning and particle filter estimation are uniquely combined. The quantitative and automated measurement of the dislocation velocity in an Fe-31Mn-3Al-3Si autunitic steel subjected to the tensile deformation was performed to validate the framework, and an intermittent motion of the dislocations was quantitatively analyzed. The framework is successfully classifying, identifying and tracking nanoscale objects; these are not able to be accurately implemented by the conventional mean-path based analysis.
In situ Electron Energy Loss Spectroscopy (EELS) combined with Transmission Electron Microscopy (TEM) has traditionally been pivotal for understanding how material processing choices affect local structure and composition. However, the ability to monitor and respond to ultrafast transient changes, now achievable with EELS and TEM, necessitates innovative analytical frameworks. Here, we introduce a machine learning (ML) framework tailored for the real-time assessment and characterization of in operando EELS Spectrum Images (EELS-SI). We focus on 2D MXenes as the sample material system, specifically targeting the understanding and control of their atomic-scale structural transformations that critically influence their electronic and optical properties. This approach requires fewer labeled training data points than typical deep learning classification methods. By integrating computationally generated structures of MXenes and experimental datasets into a unified latent space using Variational Autoencoders (VAE) in a unique training method, our framework accurately predicts structural evolutions at latencies pertinent to closed-loop processing within the TEM. This study presents a critical advancement in enabling automated, on-the-fly synthesis and characterization, significantly enhancing capabilities for materials discovery and the precision engineering of functional materials at the atomic scale.
Three dimensional (3D) MoS 2 nanoflowers are successfully synthesized by hydrothermal method. Further, a composite of as prepared MoS 2 nanoflowers and rGO is constructed by simple ultrasonic exfoliation technique. The crystallography and morphological studies have been carried out by XRD, FE-SEM, TEM, HR-TEM and EDS etc. Here, XRD study revealed, a composite of exfoliated MoS 2 with expanded spacing of (002) crystal plane and rGO can be prepared by simple 40 minute of ultrasonic treatment. While, FE-SEM and TEM studies depict, individual MoS 2 nanoflowers with an average diameter of 200 nm are uniformly distributed throughout the rGO surface. When tested as sodium-ion batteries anode material by applying two different potential windows, the composite demonstrates a high reversible specific capacity of 575 mAhg -1 at 100 mAg -1 in between 0.01 V–2.6 V and 218 mAhg -1 at 50 mAg -1 when discharged in a potential range of 0.4 V–2.6 V. As per our concern, the results are one of the best obtained as compared to the earlier published one on MoS 2 based SIB anode material and more importantly this material shows such an excellent reversible Na-storage capacity and good cycling stability without addition of any expensive additive stabilizer, like fluoroethylene carbonate (FEC), in comparison to those in current literature.
A six-lobed membrane spanning cellulose synthesis complex (CSC) containing multiple cellulose synthase (CESA) glycosyltransferases mediates cellulose microfibril formation. The number of CESAs in the CSC has been debated for decades in light of changing estimates of the diameter of the smallest microfibril formed from the β-1,4 glucan chains synthesized by one CSC. We obtained more direct evidence through generating improved transmission electron microscopy (TEM) images and image averages of the rosette-type CSC, revealing the frequent triangularity and average cross-sectional area in the plasma membrane of its individual lobes. Trimeric oligomers of two alternative CESA computational models corresponded well with individual lobe geometry. A six-fold assembly of the trimeric computational oligomer had the lowest potential energy per monomer and was consistent with rosette CSC morphology. Negative stain TEM and image averaging showed the triangularity of a recombinant CESA cytosolic domain, consistent with previous modeling of its trimeric nature from small angle scattering (SAXS) data. Six trimeric SAXS models nearly filled the space below an average FF-TEM image of the rosette CSC. In conclusion, the multifaceted data support a rosette CSC with 18 CESAs that mediates the synthesis of a fundamental microfibril composed of 18 glucan chains.
TiO 2 (B) exhibits unique electrochemical lithiation behavior where two closely spaced reduction and oxidation peaks, referred to as “double peaks,” are observed for 3-D forms of bulk and nanostructured TiO 2 (B) while a single broad redox peak is observed for 2-D nanosheet architectures. Here, we have used a combination of transmission electron microscopy (TEM), powder X-ray diffraction (XRD), Raman spectroscopy and cyclic voltammetry on TiO 2 (B) nanosheets as well as a series of thermally annealed nanosheets to map the morphological and phase transformation pathways that help clarify the structure-dependent lithiation behavior. We found that the double peak redox behavior only arises once a three dimensional nanocrystalline structure of TiO 2 (B) exists by observing nanoparticle growth on the TiO 2 (B) nanosheet surface via TEM at temperatures above 150 °C. This morphological transformation was also verified by Raman spectroscopy. The appearance of low-energy torsional modes at temperatures above 150 °C which are not observed in 2-D morphologies of TiO 2 (B) agrees well with TEM evidence of 3-D nanoparticle formation. Using scan rate dependent cyclic voltammetry we also verified that all lithiation behavior associated with TiO 2 (B) (either nanosheet or nanoparticle) is due primarily to a surface redox (pseudocapacitive) mechanism. The thermal annealing study also shows the phase transformation of surface nucleated TiO 2 (B) nanoparticles to anatase nanoparticles at temperatures above 200 °C. These studies clearly show how nano-morphological control can influence electrochemical lithiation behavior and help identify a possible mechanism to explain the double peak phenomenon observed for TiO 2 (B).
Transforming in situ transmission electron microscopy (TEM) imaging into a tool for spatially-resolved operando characterization of solid-state reactions requires automated, high-precision semantic segmentation of dynamically evolving features. However, traditional deep learning methods for semantic segmentation often face limitations due to the scarcity of labeled data, visually ambiguous features of interest, and scenarios involving small objects. To tackle these challenges, we introduce MultiTaskDeltaNet (MTDN), a novel deep learning architecture that creatively reconceptualizes the segmentation task as a change detection problem. By implementing a unique Siamese network with a U-Net backbone and using paired images to capture feature changes, MTDN effectively leverages minimal data to produce high-quality segmentations. Furthermore, MTDN utilizes a multi-task learning strategy to exploit correlations between physical features of interest. In an evaluation using data from in situ environmental TEM (ETEM) videos of filamentous carbon gasification, MTDN demonstrated a significant advantage over conventional segmentation models, particularly in accurately delineating fine structural features. Notably, MTDN achieved a 10.22% performance improvement over conventional segmentation models in predicting small and visually ambiguous physical features. This work bridges key gaps between deep learning and practical TEM image analysis, advancing automated characterization of nanomaterials in complex experimental settings.
In this article, we explore the possibility of modifying the silicon nanocrystal areal density in SiO{sub x} single layers, while keeping constant their size. For this purpose, a set of SiO{sub x} monolayers with controlled thickness between two thick SiO{sub 2} layers has been fabricated, for four different compositions (x = 1, 1.25, 1.5, or 1.75). The structural properties of the SiO{sub x} single layers have been analyzed by transmission electron microscopy (TEM) in planar view geometry. Energy-filtered TEM images revealed an almost constant Si-cluster size and a slight increase in the cluster areal density as the silicon content increases in the layers, while high resolution TEM images show that the size of the Si crystalline precipitates largely decreases as the SiO{sub x} stoichiometry approaches that of SiO{sub 2}. The crystalline fraction was evaluated by combining the results from both techniques, finding a crystallinity reduction from 75% to 40%, for x = 1 and 1.75, respectively. Complementary photoluminescence measurements corroborate the precipitation of Si-nanocrystals with excellent emission properties for layers with the largest amount of excess silicon. The integrated emission from the nanoaggregates perfectly scales with their crystalline state, with no detectable emission for crystalline fractions below 40%. The combination of the structural and luminescence observations suggests that small Si precipitates are submitted to a higher compressive local stress applied by the SiO{sub 2} matrix that could inhibit the phase separation and, in turn, promotes the creation of nonradiative paths.
We report the growth of crystalline Al{sub 2}O{sub 3} thin films deposited by thermal Atomic Layer Deposition (ALD) at 200 °C, which up to now has always resulted in the amorphous phase. The 5 nm thick films were deposited on Ga{sub 2}O{sub 3}, ZnO, and Si nanowire substrates 100 nm or less in diameter. The crystalline nature of the Al{sub 2}O{sub 3} thin film coating was confirmed using Transmission Electron Microscopy (TEM), including high-resolution TEM lattice imaging, selected area diffraction, and energy filtered TEM. Al{sub 2}O{sub 3} coatings on nanowires with diameters of 10 nm or less formed a fully crystalline phase, while those with diameters in the 20–25 nm range resulted in a partially crystalline coating, and those with diameters in excess of 50 nm were fully amorphous. We suggest that the amorphous Al{sub 2}O{sub 3} phase becomes metastable with respect to a crystalline alumina polymorph, due to the nanometer size scale of the film/substrate combination. Since ALD Al{sub 2}O{sub 3} films are widely used as protective barriers, dielectric layers, as well as potential coatings in energy materials, these findings may have important implications.
Amorphous carbon films have been routinely used to enhance the preparation of frozen-hydrated samples for transmission electron microscopy (TEM), either in retaining protein concentration, providing mechanical stability or dissipating sample charge. However, strong background signal from the amorphous carbon support obstructs that of the sample, and the insulating properties of thin amorphous carbon films preclude any efficiency in dispersing charge. Graphene addresses the limitations of amorphous carbon. Graphene is a crystalline material with virtually no phase or amplitude contrast and unparalleled, high electrical carrier mobility. However, the hydrophobic properties of graphene have prevented its routine application in Cryo-TEM. This Letter reports a method for rendering graphene TEM supports hydrophilic—a convenient approach maintaining graphene's structural and electrical properties based on non-covalent, aromatic functionalization.
Transport behavior of gold nanostructures on Si(100) substrate during annealing under high vacuum has been investigated using in-situ real time transmission electron microscopy (TEM). A comparative study has been done on the morphological changes due to annealing under different vacuum environments. Au thin films of thickness ∼2.0 nm were deposited on native oxide covered silicon substrate by using thermal evaporation system. In-situ real time TEM measurements at 850 °C showed the isotropic growth of rectangular/square shaped gold-silicon alloy structures. During the growth, it is observed that the alloying occurs in liquid phase followed by transformation into the rectangular shapes. For similar system, ex-situ annealing in low vacuum (10{sup −2} millibars) at 850 °C showed the spherical gold nanostructures with no Au-Si alloy formation. Under low vacuum annealing conditions, the rate of formation of the oxide layer dominates the oxide desorption rate, resulting in the creation of a barrier layer between Au and Si, which restricts the inter diffusion of Au in to Si. This work demonstrates the important role of interfacial oxide layer on the growth of nanoscale Au-Si alloy structures during the initial growth. The time dependent TEM images are presented to offer a direct insight into the fundamental dynamics of the sintering process at the nanoscale.
In magnetic recording media, the grains or clusters reverse their magnetization over a range of reversal field, resulting in a switching field distribution. In order to achieve high areal densities, it is desirable to understand and minimize such a distribution. Clusters of grains which contain stacking faults (SF) or fcc phase have lower anisotropy, an order lower than those without them. It is believed that such low anisotropy regions reverse their magnetization at a much lower reversal field than the rest of the material with a larger anisotropy. Such clusters/grains cause recording performance deterioration, such as adjacent track erasure and dc noise. Therefore, the observation of clusters that reverse at very low reversal fields (nucleation sites, NS) could give information on the noise and the adjacent track erasure. Potentially, the observed clusters could also provide information on the SF. In this paper, we study the reversal of nucleation sites in granular perpendicular media based on a magnetic force microscope (MFM) methodology and validate the observations with high resolution cross-section transmission electron microscopy (HRTEM) measurements. Samples, wherein a high anisotropy CoPt layer was introduced to control the NS or SF in a systematic way, were evaluated by MFM, TEM, and magnetometry. The magnetic properties indicated that the thickness of the CoPt layer results in an increase of nucleation sites. TEM measurements indicated a correlation between the thickness of CoPt layer and the stacking fault density. A clear correlation was also observed between the MFM results, TEM observations, and the coercivity and nucleation field of the samples, validating the effectiveness of the proposed method in evaluating the nucleation sites which potentially arise from stacking faults.
Suppression of the transverse-electromagnetic (TEM) mode leakage is crucial in the design of a triaxial klystron amplifier with high gain, because a small microwave leakage from the buncher or the output cavity could overwhelm the input signal with low power. In this paper, a specially designed reflector is proposed to suppress the TEM mode leakage, whose axial electric field is approximately zero at the beam radial position. Theoretical analysis indicates that the reflector introduces little influence on the normal modulation of the beam while keeping a high reflection coefficient. By using two such reflectors with different eigen frequencies located in front of the buncher cavity and the output cavity, respectively, an improved triaxial klystron amplifier is presented. The simulation results show that the reflectors substantially decrease the TEM mode leakage power and achieve very good isolation among the cavities. The improved triaxial klystron amplifier can operate normally with 10's kW microwave injection without self-oscillations.
In situ transmission electron microscopy (TEM) was performed to observe the hydrogenation of Mg-Ni films in a hydrogen atmosphere of 80–100 Pa. An aberration-corrected environmental TEM with a differential pumping system allows us to reveal the Angstrom-scale structure of the films in the initial stage of hydrogenation: first, nucleation and growth of Mg{sub 2}NiH{sub 4} crystals with a lattice spacing of 0.22 nm in an Mg-rich amorphous matrix of the film occurs within 20 s after the start of the high-resolution observation, then crystallization of MgH{sub 2} with a smaller spacing of 0.15 nm happens after approximately 1 min. Our in situ TEM method is also applicable to the analysis of other hydrogen-related materials.
The Lembang fault is located around eight kilometers from Bandung City, West Java, Indonesia. The existence of this fault runs through densely populated settlement and tourism area. It is an active fault structure with increasing seismic activity where the 28 August 2011 earthquake occurred. The seismic response at the site is strongly influenced by local geological conditions. The ambient noise measurements from the western part of this fault give strong implication for a complex 3-D tectonic setting. Hence, near surface Electromagnetic (EM) measurements are carried out to understand the location of the local active fault of the research area. Hence, near surface EM measurements are carried out to understand the location of the local active fault and the top of the basement structure of the research area. The Transientelectromagnetic (TEM) measurements are carried out along three profiles, which include 35 TEM soundings. The results indicate that TEM data give detailed conductivity distribution of fault structure in the study area.