Characterization of local chemical ordering and deformation behavior in high entropy alloys by transmission electron microscopy

Short-range ordering(SRO)is one of the most important structural features of high entropy alloys(HEAs).However,the chemical and structural analyses of SROs are very difficult due to their small size,complexed compositions,and varied locations.Transmission electron microscopy(TEM)as well as its aberration correction techniques are powerful for characterizing SROs in these compositionally complex alloys.In this short communication,we summarized recent progresses regarding characterization of SROs using TEM in the field of HEAs.By using advanced TEM techniques,not only the existence of SROs was confirmed,but also the effect of SROs on the deformation mechanism was clarified.Moreover,the perspective related to application of TEM techniques in HEAs are also discussed.

Probing the Nucleation and Growth Kinetics of Bismuth Nanoparticles via In-situ Transmission Electron Microscopy

The nucleation and growth mechanism of nanoparticles is an important theory,which can guide the preparation of nanomaterials.However,it is still lacking in direct observation on the details of the evolution of intermediate state structure during nucleation and growth.In this work,the evolution process of bismuth nanoparticles induced by electron beam was revealed by in-situ transmission electron microscopy(TEM)at atomic scale.The experimental results demonstrate that the size,stable surface and crystallographic defect have important influences on the growth of Bi nanoparticles.Two non-classical growth paths including single crystal growth and polycrystalline combined growth,as well as,corresponding layer-by-layer growth mechanism along{012}stable crystal plane of Bi nanoparticles with dodecahedron structure were revealed by in-situ TEM directly.These results provide important guidance and a new approach for in-depth understanding of the nucleation and growth kinetics of nanoparticles.

Capturing the non-equilibrium state in light–matter–free-electron interactions through ultrafast transmission electron microscopy

Ultrafast transmission electron microscope(UTEM) with the multimodality of time-resolved diffraction, imaging,and spectroscopy provides a unique platform to reveal the fundamental features associated with the interaction between free electrons and matter. In this review, we summarize the principles, instrumentation, and recent developments of the UTEM and its applications in capturing dynamic processes and non-equilibrium transient states. The combination of the transmission electron microscope with a femtosecond laser via the pump–probe method guarantees the high spatiotemporal resolution, allowing the investigation of the transient process in real, reciprocal and energy spaces. Ultrafast structural dynamics can be studied by diffraction and imaging methods, revealing the coherent acoustic phonon generation and photoinduced phase transition process. In the energy dimension, time-resolved electron energy-loss spectroscopy enables the examination of the intrinsic electronic dynamics of materials, while the photon-induced near-field electron microscopy extends the application of the UTEM to the imaging of optical near fields with high real-space resolution. It is noted that light–free-electron interactions have the ability to shape electron wave packets in both longitudinal and transverse directions, showing the potential application in the generation of attosecond electron pulses and vortex electron beams.

In situ observation of the electrochemical behavior of Li–CO_(2)/O_(2)batteries in an environmental transmission electron microscope

Li–CO_(2)/O_(2)batteries,a promising energy storage technology,not only provide ultrahigh discharge capacity but also capture CO_(2)and turn it into renewable energy.Their electrochemical reaction pathways'ambiguity,however,creates a hurdle for their practical application.This study used copper selenide(CuSe)nanosheets as the air cathode medium in an environmental transmission electron microscope to in situ study Li–CO_(2)/O_(2)(mix CO_(2)as well as O_(2)at a volume ratio of 1:1)and Li–O_(2)batteries as well as Li–CO_(2)batteries.Primary discharge reactions take place successively in the Li–CO_(2)/O_(2)–CuSe nanobattery:(I)4Li^(+)+O_(2)+4e^(−)→2Li_(2)O;(II)Li_(2)O+CO_(2)→Li_(2)CO_(3).The charge reaction proceeded via(III)2Li_(2)CO_(3)→4Li^(+)+2CO_(2)+O_(2)+4e^(−).However,Li–O_(2)and Li–CO_(2)nanobatteries showed poor cycling stability,suggesting the difficulty in the direct decomposition of the discharge product.The fluctuations of the Li–CO_(2)/O_(2)battery's electrochemistry were also shown to depend heavily on O_(2).The CuSe‐based Li–CO_(2)/O_(2)battery showed exceptional electrochemical performance.The Li^–CO_(2)/O_(2)battery offered a discharge capacity apex of 15,492 mAh g^(−1) and stable cycling 60 times at 100 mA g^(−1).Our research offers crucial insight into the electrochemical behavior of Li–CO_(2)/O_(2),Li–O_(2),and Li–CO_(2)nanobatteries,which may help the creation of high‐performance Li–CO_(2)/O_(2)batteries for energy storage applications.

A review of in situ transmission electron microscopy study on the switching mechanism and packaging reliability in non-volatile memory

Non-volatile memory(NVM)devices with non-volatility and low power consumption properties are important in the data storage field.The switching mechanism and packaging reliability issues in NVMs are of great research interest.The switching process in NVM devices accompanied by the evolution of microstructure and composition is fast and subtle.Transmission electron microscopy(TEM)with high spatial resolution and versatile external fields is widely used in analyzing the evolution of morphology,structures and chemical compositions at atomic scale.The various external stimuli,such as thermal,electrical,mechanical,optical and magnetic fields,provide a platform to probe and engineer NVM devices inside TEM in real-time.Such advanced technologies make it possible for an in situ and interactive manipulation of NVM devices without sacrificing the resolution.This technology facilitates the exploration of the intrinsic structure-switching mechanism of NVMs and the reliability issues in the memory package.In this review,the evolution of the functional layers in NVM devices characterized by the advanced in situ TEM technology is introduced,with intermetallic compounds forming and degradation process investigated.The principles and challenges of TEM technology on NVM device study are also discussed.

Ultrastructural view of colon anastomosis under propolis effect by transmission electron microscopy

AIM： To evaluate the effect of propolis administration on the healing of colon anastomosis with light and transmission electron microscopes. METHODS： Forty-eight Wistar-AIbino female rats were divided into two groups and had colon resection and anastomosis. In group Ⅰ, rats were fed with standard rat chow pre- and postoperatively. The rats in group Ⅱ were fed with standard rat chow and began receiving oral supplementation of propolis 100 mg/kg per day beginning 7 d before the operation and continued until they were sacrificed. Rats were sacrificed 1, 3, 7 and 14 d after operation, and anastomotic bursting pressures measured. After the resection of anastomotic segments, histopathological examination was performed with light and transmission electron microscopes by two blinded histologists and photographed. RESULTS： The colonic bursting pressures of the propolis group were statistically significantly better than the control group. UItrastructural histopathological analysis of the colon anastomosis revealed that propotis accelerated the phases of the healing process and stimulated mature granulation tissue formation and collagen synthesis of fibroblasts. CONCLUSION： Bursting pressure measurements and ultra structural histopathological evaluation showed that administration of propolis accelerated the healing of colon anastomosis following surgical excision.

In situ investigation of the mechanical properties of nanomaterials by transmission electron microscopy

With the progress of modern transmission elec- tron microscopy （TEM） and development of dedicated func- tional TEM specimen holders, people can now manipulate a nano-object with nanometer-range precision and simulta- neously acquire mechanical data together with atomic-scale structural information. This advanced methodology is play- ing an increasingly important role in nanomechanics. The present review summarizes relevant studies on the in situ in- vestigation of mechanical properties of various nanomateri- als over the past decades. These works enrich our knowledge not only on nanomaterials （such as carbon nanotubes, car- bon onions, boron nitride nanotubes, silicon nanowires and graphene, etc.） but also on mechanics at the nanoscate.

Transmission Electron Microscopy as a Powerful Tool for Investigating Lithium-ion Battery Materials

Transmission electron microscopy(TEM) stands out as one of the most powerful tools for characterizing materials at multiple scales and dimensions. This unique technique has nowadays been widely employed in investigating the lithium-ion battery(LIB) materials. The present perspective paper focuses on several LIB related aspects that are recently revealed by using TEM. Finally, we present outlook on the future directions of TEM for LIB research and development.

Lattice Distortion Analysis Directly from High Resolution Transmission Electron Microscopy Images —the LADIA Program Package

Direct strain mapping from high resolution transmission electron microscopy images is possible for coherent structures. At proper imaging conditions the intensity peaks in the image have a constant spatial relationship with the projected atom columns. This allows the determination of the geometry of the projected unit cell without comparison with image simulations. The fast procedure is particularly suited for the analysis of large areas. The software package LADIA is written in the PV-WAVE code and provides all necessary tools for image processing and analysis. Image intensity peaks are determined by a cross-correlation technique, which avoids problems from noise in the low spatial frequency range. The lower limit of strain that can be detected at a sampling rate of 44 pixels/nm is≈2%.

Scanning transmission electron microscopy: A review of high angle annular dark field and annular bright field imaging and applications in lithium-ion batteries

Scanning transmission electron microscopy（STEM） has been shown as powerful tools for material characterization,especially after the appearance of aberration-corrector which greatly enhances the resolution of STEM. High angle annular dark field（HAADF） and annular bright field（ABF） imaging of the aberration-corrected STEM are widely used due to their high-resolution capabilities and easily interpretable image contrasts. However, HAADF mode of the STEM is still limited in detecting light elements due to the weak electron-scattering power. ABF mode of the STEM could detect light and heavy elements simultaneously, providing unprecedented opportunities for probing unknown structures of materials. Atomiclevel structure investigation of materials has been achieved by means of these imaging modes, which is invaluable in many fields for either improving properties of materials or developing new materials. This paper aims to provide a introduction of HAADF and ABF imaging techniques and reviews their applications in characterization of cathode materials, study of electrochemical reaction mechanisms, and exploring the effective design of lithium-ion batteries（LIBs）. The future prospects of the STEM are also discussed.

Recent progress on advanced transmission electron microscopy characterization for halide perovskite semiconductors

Halide perovskites are strategically important in the field of energy materials. Along with the rapid development of the materials and related devices, there is an urgent need to understand the structure–property relationship from nanoscale to atomic scale. Much effort has been made in the past few years to overcome the difficulty of imaging limited by electron dose,and to further extend the investigation towards operando conditions. This review is dedicated to recent studies of advanced transmission electron microscopy(TEM) characterizations for halide perovskites. The irradiation damage caused by the interaction of electron beams and perovskites under conventional imaging conditions are first summarized and discussed. Low-dose TEM is then discussed, including electron diffraction and emerging techniques for high-resolution TEM(HRTEM) imaging. Atomic-resolution imaging, defects identification and chemical mapping on halide perovskites are reviewed. Cryo-TEM for halide perovskites is discussed, since it can readily suppress irradiation damage and has been rapidly developed in the past few years. Finally, the applications of in-situ TEM in the degradation study of perovskites under environmental conditions such as heating,biasing, light illumination and humidity are reviewed. More applications of emerging TEM characterizations are foreseen in the coming future, unveiling the structural origin of halide perovskite’s unique properties and degradation mechanism under operando conditions, so to assist the design of a more efficient and robust energy material.

THE INFLUENCE OF ISLAND-INDUCED STRAIN ON THE Si SURFACE MORPHOLOGY IN Ge-Si MULTILAYERS: A TRANSMISSION ELECTRON MICROSCOPY STUDY

Growth and ordering of coherently strained Ge-rich islands in Ge/Si single layer and multilayer systems and the influence of island arrangements on the evolutio n of the surface morphology of Si cap layers during deposition by low-pressure c hemical vapour deposition(LPCVD) on Si(001) substrates at 700℃ have been invest igated by TEM of cross-section and plan-view specimens. At distances between the Ge layers of 35-50nm, vertical order of GeSi islands is observed for Ge-Si bila yer systems and for Ge-Si multilayer systems consisting of 5 layer pairs whereas lateral ordering parallel to <100> substrate directions is observed for the lat ter case only. In agreement with earlier results the vertical ordering in the mu ltilayer system can be understood as result of the elastic interaction between i sland nuclei forming in the layers with close islands in a buried layer below. T he lateral ordering along <100> may be attributed to the anisotropy of the elast ic interaction. Characteristic for all Si surfaces are the spatial correlation b etween the presence of island-induced lattice strain and the appearance of array s of larger square-shaped pyramids with distinct faceting and facet edges along <110>. The results reflect the importance of the control of growth parameters an d of the island-induced strain state for the evolution of the Si top layer surfa ce morphology during LPCVD growth.

Visualization of atomic scale reaction dynamics of supported nanocatalysts during oxidation and ammonia synthesis using in-situ environmental(scanning) transmission electron microscopy

Reaction dynamics in gases at operating temperatures at the atomic level are the basis of heterogeneous gas-solid catalyst reactions and are crucial to the catalyst function.Supported noble metal nanocatalysts such as platinum are of interest in fuel cells and as diesel oxidation catalysts for pollution control,and practical ruthenium nanocatalysts are explored for ammonia synthesis.Graphite and graphitic carbons are of interest as supports for the nanocatalysts.Despite considerable literature on the catalytic processes on graphite and graphitic supports,reaction dynamics of the nanocatalysts on the supports in different reactive gas environments and operating temperatures at the single atom level are not well understood.Here we present real time in-situ observations and analyses of reaction dynamics of Pt in oxidation,and practical Ru nanocatalysts in ammonia synthesis,on graphite and related supports under controlled reaction environments using a novel in-situ environmental(scanning) transmission electron microscope with single atom resolution.By recording snapshots of the reaction dynamics,the behaviour of the catalysts is imaged.The images reveal single metal atoms,clusters of a few atoms on the graphitic supports and the support function.These all play key roles in the mobility,sintering and growth of the catalysts.The experimental findings provide new structural insights into atomic scale reaction dynamics,morphology and stability of the nanocatalysts.

TRANSMISSION ELECTRON MICROSCOPY INVESTIGATIONS OF LOW-PRESSURE CVD GROWTH AND STRAIN RELAXATION OF Ge ISLANDS ON Si(110)

Shapes, dimensions, arrangements and the microstructure of self-assembled island s fabricated by low-pressure chemical vapour deposition (LPCVD) of Ge at 700℃ o nto Si(110) substrates have been investigated for different nominal Ge coverage by transmission electron microscopy (TEM) of plan-view and cross-section specime ns and have been compared with photoluminescence (PL) measurements of Si-capped layer samples. The transition from the 2-dimensional layer to the 3-dimensional island growth mode takes place for a Ge deposition of nominally less than 2 mono layers. Upon this transition, many coherent islands and few larger islands with extended defects are observed. The coherent islands possess a dome-like shape an d lateral sizes up to 130nm. Photoluminescence spectra show island-related peaks whose energy positions are shifted towards lower energy with higher Ge coverage .

Characterization of swift heavy ion tracks in MoS2 by transmission electron microscopy

The various morphologies of tracks in MoS2 irradiated by swift heavy ions at normal and 30° incidence with 9.5–25.0 MeV/u 86Kr, 129Xe, 181Ta, and 209Bi ions were investigated by transmission electron microscopy. The diameter of ion tracks increases from 1.9 nm to 4.5 nm with increasing electronic energy loss. The energy loss threshold of the track formation in MoS2 is predicted as about 9.7 keV/nm based on the thermal spike model and it seems consistent with the experimental results. It is shown that the morphology of ion tracks is related to the penetration length of ions in MoS2. The formation process of ion tracks is discussed based on the cooperative process of outflow and recrystallization of the molten phase during rapid quenching.

Misfit-layered compound PbTiS_3 with incommensurate modulation:Transmission electron microscopy analysis and transport properties

The microstructural characteristic of the misfit-layered compound PbTiS3 has been studied with transmission electron microscopy. All the incommensurate modulation-induced satellite spots and main diffraction spots of basic sublattices can be indexed systematically with a superspace group method. Finally, the relationship between the electronic transport properties and the crystal structure is discussed.

Transmission electron microscopic study of the fine-grained vein matrix in the Suizhou L6 meteorite

The mineralogy of shock vein matrix in the Suizhou meteorite has been investigated by optical and transmission electron microscopy. It was revealed that the vein matrix is composed of majorite-pyrope garnet, mag- aesiowtistite, and ringwoodite, with FeNi-FeS inter- growths. The observation and character of ring-like selected electron diffraction （SAED） patterns indicate that Lhe idiomorphic garnet crystals in the vein matrix have different orientations. The polycrystalline nature of magnesiowtistite is also confirmed by a ring-like SAED pattern. Both garnet and magnesiowtistite crystals showed sharp Jiffraction spots, signifying the good crystallinity of these ：wo minerals. The SAED pattern of cryptocrystalline 5ngwoodite shows only diffuse concentric diffraction tings. FeNi metal and troilite （FeS）, which were molten during the shock event, occur in the matrix as fine eutectic FeNi-FeS intergrowths filling the interstices between garaet and magnesiowiistite grains. Based on the phase dia- gram of the Allende chondrite and the results of this TEM study, it is inferred that majorite-pyrope garnet first crystallized from the Suizhou chondritic melt at 22-26 GPa, Followed by crystallization of magnesiowtistite at 20-24 GPa, and then ringwoodite at 18-20 GPa. The eutectic intergrowths of FeNi-metal and troilite are proposed to have crystallized during meteorite cooling and solidified at the last stage of vein formation.

Transmission Electron Microscopy Investigation of the Ar^+ Ion Irradiation Effect in Semiconductor GaAs

Room temperature irradiation effect of GaAs compound semiconductor by 100 keV Ar+ ions has been systematically studied by means of transmission electron microscopy. The dose dependenceoof the Ar+ ion irradiation and room temperature annealing effects have been investigated. The experimental results show that the structure of GaAs transforms from perfect crystalline through weakly and severely damaged crystalline to amorphous states with the increase of the irradiation dose and the damaged states are changed during room temperature annealing.

Characterization of Li-rich layered oxides by using transmission electron microscope

Lithium-rich layered oxides(LrLOs) deliver extremely high specific capacities and are considered to be promising candidates for electric vehicle and smart grid applications. However, the application of LrLOs needs further understanding of the structural complexity and dynamic evolution of monoclinic and rhombohedral phases, in order to overcome the issues including voltage decay, poor rate capability, initial irreversible capacity loss and etc. The development of aberration correction for the transmission electron microscope and concurrent progress in electron spectroscopy, have fueled rapid progress in the understanding of the mechanism of such issues. New techniques based on the transmission electron microscope are first surveyed, and the applications of these techniques for the study of the structure, migration of transition metal, and the activation of oxygen of LrLOs are then explored in detail, with a particular focus on the mechanism of voltage decay.

High-resolution transmission electron microscopy and bulk magnetometry study of LaFe_(11.5)Si_(1.5) compound

This paper studies the microstructural and magnetic properties of LaFe11.5Si1.5 compound by means of highresolution transmission electron microscope and bulk magnetometry measurements. The crystalline structure is accompanied with the noncrystalline and nanocrystalline structures. This characteristic is the reflection of the crystalline process held by quenching. The inverse susceptibilities diverge and deviate from Curie-Weiss law under low applied magnetic fields. This paper proposes the possible mechanism between the anomalous susceptibilities and microstructure, and offers a perspective on the magnetic properties of metastable intermetallic compounds.