Although scanning transmission electron microscopy (STEM) images of individual heavy atoms were reported 50 years ago, the applications of atomic-resolution STEM imaging became wide spread only after the practical realization of aberration correctors on field-emission STEM/TEM instruments to form sub-Ångstrom electron probes. The innovative designs and advances of electron optical systems, the fundamental understanding of electron–specimen interaction processes, and the advances in detector technology all played a major role in achieving the goal of atomic-resolution STEM imaging of practical materials. It is clear that tremendous advances in computer technology and electronics, image acquisition and processing algorithms, image simulations, and precision machining synergistically made atomic-resolution STEM imaging routinely accessible. It is anticipated that further hardware/software development is needed to achieve three-dimensional atomic-resolution STEM imaging with single-atom chemical sensitivity, even for electron-beam-sensitive materials. Artificial intelligence, machine learning, and big-data science are expected to significantly enhance the impact of STEM and associated techniques on many research fields such as materials science and engineering, quantum and nanoscale science, physics and chemistry, and biology and medicine. This review focuses on advances of STEM imaging from the invention of the field-emission electron gun to the realization of aberration-corrected and monochromated atomic-resolution STEM and its broad applications.

The carbon (C) ratios, namely the atomic ratios of C/(C + M), in nano-sized coherent MC precipitates (M = Ti, Nb) with the NaCl-type (B1) structure in ferritic steels, which had been isothermally aged at 580 °C, were investigated using atom probe tomography (APT). Considering the influences of the trajectory aberration, detection loss, and peak overlap, we determined the C ratios to be ~0.40 and ~0.45 for an equivalent volume diameter of 1.5–5 nm and 1–5 nm for the TiC and NbC precipitates, respectively, suggesting that there is a considerable fraction of C vacancies in both nano-sized precipitates. The apparent C ratios show significant scatter with decreasing particle size, while the apparent mean C ratios of very fine TiC particles, smaller than 1.5 nm, decreased with decreasing particle size. With the use of one of the latest APT instruments with a high detection efficiency, the scattering in the apparent C ratios was reduced because the counting statistics were improved; however, the artificial enrichment of C atoms to particular crystallographic directions of ferrite hindered the determination of the C ratio for very fine TiC particles smaller than 1.5 nm.

A two-step framework to analyze local microstructure variations of paper sheets based on 3D image data is presented. First, a multi-stage workflow efficiently acquires a large set of highly resolved tomographic image data, which enables—in combination with statistical image analysis—the quantification of local variations and pairwise correlations of morphological microstructure characteristics on length scales ranging from micrometers to centimeters. Secondly, the microstructure is analyzed in terms of the local behavior of porosity, thickness, and further descriptors related to transportation paths. The power of the presented framework is demonstrated, showing that it allows one (i) to quantitatively reveal the difference in terms of local structural variations between a model paper before and after unidirectional compression via hard-nip calendering and that (ii) the field of view which is required to reliably compute the probability distributions of the considered local microstructure characteristics is at least 20 mm$^{2}$. The results elucidate structural differences related to local densification. In particular, it is shown how calendering transforms local variations in sheet thickness into marked local mass density variations. The obtained results are in line with experimental measurements of macroscopic properties (basis weight, Bekk smoothness parameters, thickness, and Gurley retention times).

Investigating the earliest stages of crystallization requires the transmission electron microscope (TEM) and is particularly challenging for materials which can be affected by the electron beam. Typically, when imaging at magnifications high enough to observe local crystallinity, the electron beam's current density must be high to produce adequate image contrast. Yet, minimizing the electron dose is necessary to reduce the changes caused by the beam. With the advent of a sensitive, high-speed, direct-detection camera for a TEM that is corrected for spherical aberration, it is possible to probe the early stages of crystallization at the atomic scale. High-quality images with low contrast can now be analyzed using new computing methods. In the present paper, this approach is illustrated for crystallization in a Ge2Sb2Te5 (GST-225) phase-change material which can undergo particularly rapid phase transformations and is sensitive to the electron beam. A thin (20 nm) film of GST-225 has been directly imaged in the TEM and the low-dose images processed using Python scripting to extract details of the nanoscale nuclei. Quantitative analysis of the processed images in a video sequence also allows the growth of such nuclei to be followed.

In situ liquid cell transmission electron microscopy (LC-TEM) is an innovative method for studying the processes involved in the formation of crystals in liquids. However, it is difficult to capture early stages of crystallization because of the small field of view and the unfavorable changes in sample composition resulting from electron-beam radiolysis. Nevertheless, if the radiolysis required to induce the crystallization of a sample could be controlled in LC-TEM, this would be advantageous for observing the crystallization process. Here, we examined this possibility by using a mixture of sodium chlorate (NaClO3) and acetone in the LC-TEM. The electron beam induced the formation of dendritic crystals in a saturated acetone solution of NaClO3; moreover, these crystals consisted of sodium chloride (NaCl), rather than NaClO3, suggesting that chloride ions (Cl−), which were not present in the initial solution, were generated by radiolysis of chlorate ions ${\rm ( ClO}_3^- )$. As a result, the solution then supersaturated with NaCl because its solubility in acetone is much lower than that of NaClO3. The combination of radiolysis and a solvent in which a solute is much less soluble is potentially useful for establishing crystallization conditions for materials that are difficult to crystallize directly in LC-TEM experiments.

Two advanced, automated crystal orientation mapping techniques suited for nanocrystalline materials—precession electron diffraction (PED) in transmission electron microscopy (TEM) and on-axis transmission Kikuchi diffraction (TKD) in scanning electron microscopy (SEM)—are evaluated by comparing the orientation maps obtained from the identical location on a 30 nm-thick nanocrystalline tungsten (W) thin film. A side-by-side comparison of the orientation maps directly showed that the large-scale orientation features are almost identical. However, there are differences in the fine details, which arise from the fundamentally different nature of the spot pattern and Kikuchi line pattern in terms of the excitation volume and the angular resolution. While TEM-PED is more reliable to characterize grains oriented along low-index zone axes, the high angular resolution of SEM-TKD allows the detection of small misorientation between grains and thus yields better quantification and statistical analysis of grain orientation. Given that both TEM-PED and SEM-TKD orientation mapping techniques are complementary tools for nanocrystalline materials, one can be favorably selected depending on the requirements of the analysis, as they have competitive performance in terms of angular resolution and texture quantification.

Core holes are an important contributing factor to the core-loss fine structure in electron energy-loss spectroscopy (EELS). While there has been much work on bulk materials, less is known about core hole screening in more complex dielectric environments, such as free surfaces or interfaces between two different materials, even though the latter is frequently encountered in high spatial resolution EELS analysis. In this work, experimental O K- and Mg L3,2-EELS edges from the free surfaces of a MgO cube are measured using scanning transmission electron microscopy (STEM). The free surface O K-spectrum shows extra intensity at the edge onset compared with the “bulk” spectrum. Core hole screening near a free surface is modeled using electrodynamic theory. It is shown that much of the extra intensity is due to reduced core hole screening, while genuine surface states make a smaller contribution to the fine structure. The low energy Mg L3,2-edge, however, does not show any significant change at a free surface. This is because the measurement is less surface sensitive due to strong delocalization.

This in situ transmission electron microscopy work presents a nanoscale characterization of the microstructural evolution in 3D-printed Inconel 718 (IN718) while exposed to elevated temperature and an associated change in the mechanical property under tensile loading. Here, we utilized a specially designed specimen shape that enables tensile testing of nano-sized thin films without off-plane deformations. Additionally, it allows a seamless transition from the in situ heating to tensile experiment using the same specimen, which enables a direct correlation of the microstructure and the mechanical property of the sample. The method was successfully used to observe the residual stress relaxation and the formation of incoherent γ′ precipitates when temperature was increased to 700°C. The subsequent in situ tensile test revealed that the exposure of the as-printed IN718 to a high temperature without full heat treatment (solutionizing and double aging) leads to loss of ductility.

Electron-probe microanalysis of uranium and uranium alloys poses several problems, such as rapid oxidation, large poorly constrained correction factors, and a large number of characteristic x-ray lines. We show that U-metal can grow 10 nm of oxide within ~20 s of air exposure, increasing to 15–20 nm within a few minutes, which can produce a 30% quantification error at 5 kV. A 15 nm carbon coating on the UO2 reference material also produces an ~30% quantification error of the uncoated but surface oxidized U sample at 5 kV. Correcting for both the coating and oxide improved the analysis accuracy to better than ±1% down to 7 kV and ~2% at 5 kV, but the error increases strongly below this. The measurement of C in U identified a previously unreported U N6–O4 line interference on the C Kα peak, which can produce over 1% error in the analysis total. Oxide stoichiometry was demonstrated to have only a small impact on quantification. The measurement of the O Kα and U Mα mass absorption coefficients in U as 9,528 and 798 cm2/g, respectively, shows good agreement with recently published values and also produces small differences in a quantification error.

Understanding the physical structure of greases can provide critical insight into improving the lubricating performance of a grease. Observation of the grease structure can be quite difficult depending on the type of grease and the length scale of the structure. Polyurea greases in previous reports have typically been examined by removal of the oil phase, which significantly changes the polyurea structure. This paper examines the effect of sample preparation conditions on the microstructure of polyurea greases. This study reveals new structures in the polyurea that have not been observed in the previous literature, including entangled fibers and nanotubes. Correlation is found between the observed polyurea microstructure coverage and grease stiffness.

The precise structural solution of crystals on a mesostructural scale is challenging due to the difficulties in obtaining electron diffraction and the complicated relationship between the crystal structure factors (CSFs) and the conventional underfocus phase-contrast transmission electron microscopy (TEM) images due to the large unit cell and the complex structures. Here, we present the structural investigation of mesostructured crystals via the combination of electron crystallographic Fourier synthesis and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) that only relies on the mass-thickness contrast. The three-dimensional electrostatic potential is reconstructed from the amplitudes and phases extracted from the Fourier transforms of the corresponding HAADF-STEM images and merged into a set of CSFs. This method is verified on silica scaffolds following a shifted double-diamond surface network with space group I41/amd. The results indicate that electron crystallography reconstruction by HAADF-STEM images is more suitable and accurate in determining the structure in comparison with conventional TEM electron crystallography reconstruction. This approach transfers the contrast of mesostructured crystals to images more accurately and the relationship between the Fourier transforms of HAADF-STEM images and the CSFs is more intuitive. It shows great advantages for the structural solution of crystals on the mesostructural scale.

Inorganic gunshot residue (GSR) analysis is carried out by scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS) in many forensic laboratories. Characteristic GSR often consists of lead–barium–antimony, commonly associated with sulfur. The strength of forensic GSR evidence increases when unusual elements are found in residues collected both from the suspect and from the discharged firearm. The presence of molybdenum in GSR, due to the use of MoS2 lubricants in firearms, is experimentally demonstrated here for the first time. The most intense molybdenum X-ray emissions are MoL peaks at 2.3 keV which overlap with PbM and SK families due to the poor resolution of EDS detectors. When Pb, S, and Mo are allegedly present in the same particle, the reliability of automatic EDS routines is at risk. Missing identifications or false detections and exclusions may then occur. Molybdenum should be considered as detected only if MoK emissions meet the peak-to-background ratio minimum requirements. A strategy to spot Mo-containing residues is described, based on the automated search of MoS2, using a new “Sulfur only” class added to the classification scheme, followed by careful manual review of all GSR particles at an acceleration voltage of 30 kV. Our proposal improves commonly adopted forensic procedures currently followed in casework.

We propose a method to measure the local porosity of porous samples from scanning electron microscopy images in the backscattered electron mode. The porous samples are impregnated with a polymer resin and observed in polished cross sections. Image intensities are calibrated with intensities from pure resin and the bulk phase. The calibration model is justified with Monte Carlo simulations on perfectly homogeneous virtual samples. Uncertainties in measured porosity are given as a function of uncertainties on physical properties of the resin and the bulk phase and on measured signals. The methodology is applied to a series of heterogeneous alumina catalyst supports with varying porosities. A good agreement is found between the averaged local porosity by scanning electron microscopy and global porosity determined by mercury intrusion porosimetry. The use of local porosity statistics allowed the quantitative characterization of the porosity fluctuations of these supports that appeared to be linked with their preparation parameters.

Algae like diatoms are widely studied as a means to remediate anthropogenically contaminated sites. In the present study, CL (cathodoluminescence) and EDX (energy-dispersive X-ray) spectroscopy in an SEM (scanning electron microscope) were optimized for the detection of Eu(III) sorbed on diatom biosilica. The required stability of biosilica under a focused electron beam was extensively investigated. Using experimentally determined data of thermal properties, the temperature increase within biosilica exposed to an electron beam was simulated by finite element calculations based on results from Monte Carlo simulations of electron scattering. Complementary thermogravimetric studies substantiated a chemical stability of biosilica in a wide temperature range, confirming its suitability for long-lasting SEM investigations. In subsequent EDX measurements, characteristic Eu lines were detected. Eu was found to preferentially accumulate and aggregate on silica fragments. CL spectra were obtained for the Eu(III) reference material, EuCl3. For Eu-loaded biosilica, even parts without detectable Eu signal in the EDX spectra show significant Eu(III) signals in the CL spectra. This highlights the sensitivity of CL in studying f-element sorption. CL data showed that Eu(III) was distributed on the entire surface. In conclusion, this work demonstrates the merit of CL and EDX methods for sorption studies on biogenic materials.

Quantitative structural characterization of nanomaterials is important to tailor their functional properties. Corrosion of AgAu-alloy nanoparticles (NPs) results in porous structures, making them interesting for applications especially in the fields of catalysis and surface-enhanced Raman spectroscopy. For the present report, structures of dealloyed NPs were reconstructed three-dimensionally using scanning transmission electron microscopy tomography. These reconstructions were evaluated quantitatively, revealing structural information such as pore size, porosity, specific surface area, and tortuosity. Results show significant differences compared to the structure of dealloyed bulk samples and can be used as input for simulations of diffusion or mass transport processes, for example, in catalytic applications.