Four-dimensional Scanning Transmission Electron Microscopy Research Articles

Structural and Morphological Characterization of Novel Organic Electrochemical Transistors via Four-dimensional (4D) Scanning Transmission Electron Microscopy

Structural and Morphological Characterization of Novel Organic Electrochemical Transistors via Four-dimensional (4D) Scanning Transmission Electron Microscopy

Multidimensional Nano-Imaging of Structure, Coupling, and Disorder in Molecular Materials.

A hierarchy of intramolecular and intermolecular interactions controls the properties of biomedical, photophysical, and novel energy materials. However, multiscale heterogeneities often obfuscate the relationship between microscopic structure and emergent function, and they are generally difficult to access with conventional optical and electron microscopy techniques. Here, we combine vibrational exciton nanoimaging in variable-temperature near-field optical microscopy (IR s-SNOM) with four-dimensional scanning transmission electron microscopy (4D-STEM), and vibrational exciton modeling based on density functional theory (DFT), to link local microscopic molecular interactions to macroscopic three-dimensional order. In the application to poly(tetrafluoroethylene) (PTFE), large spatio-spectral heterogeneities with C-F vibrational energy shifts ranging from sub-cm-1 to ≳25 cm-1 serve as a molecular ruler of the degree of local crystallinity and disorder. Spatio-spectral-structural correlations reveal a previously invisible degree of highly variable local disorder in molecular coupling as the possible missing link between nanoscale morphology and associated electronic, photonic, and other functional properties of molecular materials.

4D‐STEM: Interferometric 4D‐STEM for Lattice Distortion and Interlayer Spacing Measurements of Bilayer and Trilayer 2D Materials (Small 28/2021)

The electronic properties of stacked few-layer 2D materials are highly dependent on their precise structural arrangement. In article number 2100388, featured on the front cover, Michael J. Zachman, Miaofang Chi, and co-workers describe a four-dimensional scanning transmission electron microscopy technique that utilizes interference between Bragg discs to enable high-resolution mapping of picometer-scale structural reconstructions and measurement of average interlayer spacings in these materials.

Magic under the microscope.

Four-dimensional scanning transmission electron microscopy is demonstrated to be a powerful technique for interrogating local strain of twisted graphene bilayers, revealing a two-regime lattice reconstruction process below the ‘magic’ angle.

Interferometric 4D-STEM for Lattice Distortion and Interlayer Spacing Measurements of Bilayer and Trilayer 2D Materials.

Van der Waals materials composed of stacks of individual atomic layershave attracted considerable attention due to their exotic electronic properties that can be altered by, e.g., manipulating the twist angle of bilayer materials or the stacking sequence of trilayer materials. To fully understand and control the unique properties of these few-layer materials, a technique that can provide information about their local in-plane structural deformations, twist direction, and out-of-plane structure is needed. In principle, interference in overlap regions of Bragg disks originating from separate layers of a material encodes 3D information about the relative positions of atoms in the corresponding layers. Here, an interferometric 4D scanning transmission electron microscopy technique is described that utilizes this phenomenon to extract precise structural information from few-layer materials with nm-scale resolution. It is demonstrated how this technique enables measurement of local pm-scale in-plane lattice distortions as well as twist direction and average interlayer spacings in bilayer and trilayer graphene, and therefore provides a means to better understand the interplay between electronic properties and precise structural arrangements of few-layer 2D materials.

High-Resolution Imaging of Unstained Polymer Materials

Author(s): Jiang, X; Balsara, NP | Abstract: Electron microscopy has played an important role in polymer characterization. Traditionally, electron diffraction is used to study crystalline polymers while transmission electron microscopy is used to study microphase separation in stained block copolymers and other multiphase systems. We describe developments that eliminate the barrier between these two approaches - it is now possible to image polymer crystals with atomic resolution. The focus of this Review is on high-resolution imaging (30 A and smaller) of unstained polymers. Recent advances in hardware allow for capturing numerous (as many as 105) low-dose images from an unperturbed specimen; beam damage is a significant barrier to high-resolution electron microscopy of polymers. Machine-learning-based software is then used to sort and average the images to retrieve pristine structural information from a collection of noisy images. Acknowledging the heterogeneity in polymer samples prior to averaging is essential. Molecular conformations in a wide range of amphiphilic block copolymers, polymerized ionic liquids, and conjugated polymers can be gleaned from two-dimensional projections (2D), three-dimensional (3D) tomograms, and four-dimensional (4D) scanning transmission electron microscopy (STEM) data sets where 2D diffraction patterns are taken as a function of position. Some methods such as phase contrast STEM have been used to image closely related materials such as metal-organic frameworks but not polymers. With improvements in hardware and software, such methods may soon be applied to polymers. Our goal is to provide a comprehensive understanding of the strategies toward the high-resolution imaging of radiation sensitive polymer materials at different length scales.

4D-STEM of Beam-Sensitive Materials

ConspectusScanning electron nanobeam diffraction, or 4D-STEM (four-dimensional scanning transmission electron microscopy), is a flexible and powerful approach to elucidate structure from "soft" materials that are challenging to image in the transmission electron microscope because their structure is easily damaged by the electron beam. In a 4D-STEM experiment, a converged electron beam is scanned across the sample, and a pixelated camera records a diffraction pattern at each scan position. This four-dimensional data set can be mined for various analyses, producing maps of local crystal orientation, structural distortions, crystallinity, or different structural classes. Holding the sample at cryogenic temperatures minimizes diffusion of radicals and the resulting damage and disorder caused by the electron beam. The total fluence of incident electrons can easily be controlled during 4D-STEM experiments by careful use of the beam blanker, steering of the localized electron dose, and by minimizing the fluence in the convergent beam thus minimizing beam damage. This technique can be applied to both organic and inorganic materials that are known to be beam-sensitive; they can be highly crystalline, semicrystalline, mixed phase, or amorphous.One common example is the case for many organic materials that have a π-π stacking of polymer chains or rings on the order of 3.4-4.2 Å separation. If these chains or rings are aligned in some regions, they will produce distinct diffraction spots (as would other crystalline spacings in this range), though they may be weak or diffuse for disordered or weakly scattering materials. We can reconstruct the orientation of the π-π stacking, the degree of π-π stacking in the sample, and the domain size of the aligned regions. This Account summarizes illumination conditions and experimental parameters for 4D-STEM experiments with the goal of producing images of structural features for materials that are beam-sensitive. We will discuss experimental parameters including sample cooling, probe size and shape, fluence, and cameras. 4D-STEM has been applied to a variety of materials, not only as an advanced technique for model systems, but as a technique for the beginning microscopist to answer materials science questions. It is noteworthy that the experimental data acquisition does not require an aberration-corrected TEM but can be produced on a variety of instruments with the right attention to experimental parameters.

Powder Nano-Beam Diffraction in Scanning Electron Microscope: Fast and Simple Method for Analysis of Nanoparticle Crystal Structure.

We introduce a novel scanning electron microscopy (SEM) method which yields powder electron diffraction patterns. The only requirement is that the SEM microscope must be equipped with a pixelated detector of transmitted electrons. The pixelated detectors for SEM have been commercialized recently. They can be used routinely to collect a high number of electron diffraction patterns from individual nanocrystals and/or locations (this is called four-dimensional scanning transmission electron microscopy (4D-STEM), as we obtain two-dimensional (2D) information for each pixel of the 2D scanning array). Nevertheless, the individual 4D-STEM diffractograms are difficult to analyze due to the random orientation of nanocrystalline material. In our method, all individual diffractograms (showing randomly oriented diffraction spots from a few nanocrystals) are combined into one composite diffraction pattern (showing diffraction rings typical of polycrystalline/powder materials). The final powder diffraction pattern can be analyzed by means of standard programs for TEM/SAED (Selected-Area Electron Diffraction). We called our new method 4D-STEM/PNBD (Powder NanoBeam Diffraction) and applied it to three different systems: Au nano-islands (well diffracting nanocrystals with size ~20 nm), small TbF3 nanocrystals (size < 5 nm), and large NaYF4 nanocrystals (size > 100 nm). In all three cases, the STEM/PNBD results were comparable to those obtained from TEM/SAED. Therefore, the 4D-STEM/PNBD method enables fast and simple analysis of nanocrystalline materials, which opens quite new possibilities in the field of SEM.

Cepstral scanning transmission electron microscopy imaging of severe lattice distortions

The development of four-dimensional (4D) scanning transmission electron microscopy (STEM) using fast detectors has opened-up new avenues for addressing some of longstanding challenges in electron imaging. One of these challenges is how to image severely distorted crystal lattices, such as at a dislocation core. Here we develop a new 4D-STEM technique, called Cepstral STEM, for imaging disordered crystals using electron diffuse scattering. In contrast to analysis based on Bragg diffraction, which measures the average and periodic scattering potential, electron diffuse scattering can detect fluctuations caused by crystal disorder. Local fluctuations of diffuse scattering are captured by scanning electron nanodiffraction (SEND) using a coherent probe. The harmonic signals in electron diffuse scattering are detected through Cepstral analysis and used for imaging. By integrating Cepstral analysis with 4D-STEM, we demonstrate that information about the distortive part of electron scattering potential can be separated and imaged at nm spatial resolution. We apply the technique to the analysis of a dislocation core in SiGe and lattice distortions in a high entropy alloy.

Quantitative Characterization of Nanometer-Scale Electric Fields via Momentum-Resolved STEM.

Most of today's electronic devices, like solar cells and batteries, are based on nanometer-scale built-in electric fields. Accordingly, characterization of fields at such small scales has become an important task in the optimization of these devices. In this study, with GaAs-based p-n junctions as the example, key characteristics such as doping concentrations, polarity, and the depletion width are derived quantitatively using four-dimensional scanning transmission electron microscopy (4DSTEM). The built-in electric fields are determined by the shift they introduce to the center-of-mass of electron diffraction patterns at subnanometer spatial resolution. The method is applied successfully to characterize two p-n junctions with different doping concentrations. This highlights the potential of this method to directly visualize intentional or unintentional nanoscale electric fields in real-life devices, e.g., batteries, transistors, and solar cells.

X-ray linear dichroic ptychography

Biominerals such as seashells, coral skeletons, bone, and tooth enamel are optically anisotropic crystalline materials with unique nanoscale and microscale organization that translates into exceptional macroscopic mechanical properties, providing inspiration for engineering new and superior biomimetic structures. Using Seriatopora aculeata coral skeleton as a model, here, we experimentally demonstrate X-ray linear dichroic ptychography and map the c-axis orientations of the aragonite (CaCO3) crystals. Linear dichroic phase imaging at the oxygen K-edge energy shows strong polarization-dependent contrast and reveals the presence of both narrow (<35°) and wide (>35°) c-axis angular spread in the coral samples. These X-ray ptychography results are corroborated by four-dimensional (4D) scanning transmission electron microscopy (STEM) on the same samples. Evidence of co-oriented, but disconnected, corallite subdomains indicates jagged crystal boundaries consistent with formation by amorphous nanoparticle attachment. We expect that the combination of X-ray linear dichroic ptychography and 4D STEM could be an important multimodal tool to study nano-crystallites, interfaces, nucleation, and mineral growth of optically anisotropic materials at multiple length scales.

Non-negative matrix factorization for mining big data obtained using four-dimensional scanning transmission electron microscopy

Scientific instruments for material characterization have recently been improved to yield big data. For instance, scanning transmission electron microscopy (STEM) allows us to acquire many diffraction patterns from a scanning area, which is referred to as four-dimensional (4D) STEM. Here we study a combination of 4D-STEM and a statistical technique called non-negative matrix factorization (NMF) to deduce sparse diffraction patterns from a 4D-STEM data consisting of 10,000 diffraction patterns. Titanium oxide nanosheets are analyzed using this combined technique, and we discriminate the two diffraction patterns from pristine TiO2 and reduced Ti2O3 areas, where the latter is due to topotactic reduction induced by electron irradiation. The combination of NMF and 4D-STEM is expected to become a standard characterization technique for a wide range materials.

Orientation mapping of graphene using 4D STEM-in-SEM

A scanning diffraction technique is implemented in the scanning electron microscope. The technique, referred to as 4D STEM-in-SEM (four-dimensional scanning transmission electron microscopy in the scanning electron microscope), collects a diffraction pattern from each point on a sample which is saved to disk for further analysis. The diffraction patterns are collected using an on-axis lens-coupled phosphor/CCD arrangement. Synchronization between the electron beam and the camera exposure is accomplished with off-the-shelf data acquisition hardware. Graphene is used as a model system to test the sensitivity of the instrumentation and develop some basic analysis techniques. The data show interpretable diffraction patterns from monolayer graphene with integration times as short as 0.5 ms with a beam current of 245 pA (7.65×105 incident electrons per pixel). Diffraction patterns are collected at a rate of ca. 100/s from the mm to nm length scales. Using a grain boundary as a ‘knife-edge’, the spatial resolution of the technique is demonstrated to be ≤5.6nm (edge-width 25 % to 75 %). Analysis of the orientation of the diffraction patterns yields an angular (orientation) precision of ≤0.19∘ (full width at half maximum) for unsupported monolayer graphene. In addition, it is demonstrated that the 4D datasets have the information content necessary to analyze complex and heterogeneous multilayer graphene films.

Polarization in Ferroelectric BiFeO3 Imaged in 3D Using Four-dimensional Scanning Transmission Electron Microscopy

Polarization in Ferroelectric BiFeO₃ Imaged in 3D Using Four-dimensional Scanning Transmission Electron Microscopy

Patterned probes for high precision 4D-STEM bragg measurements

Nanoscale strain mapping by four-dimensional scanning transmission electron microscopy (4D-STEM) relies on determining the precise locations of Bragg-scattered electrons in a sequence of diffraction patterns, a task which is complicated by dynamical scattering, inelastic scattering, and shot noise. These features hinder accurate automated computational detection and position measurement of the diffracted disks, limiting the precision of measurements of local deformation. Here, we investigate the use of patterned probes to improve the precision of strain mapping. We imprint a “bullseye” pattern onto the probe, by using a binary mask in the probe-forming aperture, to improve the robustness of the peak finding algorithm to intensity modulations inside the diffracted disks. We show that this imprinting leads to substantially improved strain-mapping precision at the expense of a slight decrease in spatial resolution. In experiments on an unstrained silicon reference sample, we observe an improvement in strain measurement precision from 2.7% of the reciprocal lattice vectors with standard probes to 0.3% using bullseye probes for a thin sample, and an improvement from 4.7% to 0.8% for a thick sample. We also use multislice simulations to explore how sample thickness and electron dose limit the attainable accuracy and precision for 4D-STEM strain measurements.

Structure retrieval from four-dimensional scanning transmission electron microscopy: Statistical analysis of potential pitfalls in high-dimensional data.

Four-dimensional (4D) scanning transmission electron microscopy is one of the most rapidly growing modes of electron microscopy imaging. The advent of fast pixelated cameras and the associated data infrastructure have greatly accelerated this process. Yet conversion of the 4D datasets into physically meaningful structure images in real space remains an open issue. In this work, we demonstrate that it is possible to systematically create filters that will affect the apparent resolution or even qualitative features of the real-space structure image, reconstructing artificially generated patterns. As initial efforts, we explore statistical model selection algorithms, aiming for robustness and reliability of estimated filters. This statistical model selection analysis demonstrates the need for regularization and cross validation of inversion methods to robustly recover structure from high-dimensional diffraction datasets.

Measuring Charge State at the Single-Atomic-Column-Base with Four-Dimensional Scanning Transmission Electron Microscopy

Measuring Charge State at the Single-Atomic-Column-Base with Four-Dimensional Scanning Transmission Electron Microscopy

Advanced Phase Reconstruction Methods Enabled by Four-Dimensional Scanning Transmission Electron Microscopy

Advanced Phase Reconstruction Methods Enabled by Four-Dimensional Scanning Transmission Electron Microscopy

Four-Dimensional Scanning Transmission Electron Microscopy (4D-STEM): From Scanning Nanodiffraction to Ptychography and Beyond.

Scanning transmission electron microscopy (STEM) is widely used for imaging, diffraction, and spectroscopy of materials down to atomic resolution. Recent advances in detector technology and computational methods have enabled many experiments that record a full image of the STEM probe for many probe positions, either in diffraction space or real space. In this paper, we review the use of these four-dimensional STEM experiments for virtual diffraction imaging, phase, orientation and strain mapping, measurements of medium-range order, thickness and tilt of samples, and phase contrast imaging methods, including differential phase contrast, ptychography, and others.

Manifold learning of four-dimensional scanning transmission electron microscopy

Four-dimensional scanning transmission electron microscopy (4D-STEM) of local atomic diffraction patterns is emerging as a powerful technique for probing intricate details of atomic structure and atomic electric fields. However, efficient processing and interpretation of large volumes of data remain challenging, especially for two-dimensional or light materials because the diffraction signal recorded on the pixelated arrays is weak. Here we employ data-driven manifold leaning approaches for straightforward visualization and exploration analysis of 4D-STEM datasets, distilling real-space neighboring effects on atomically resolved deflection patterns from single-layer graphene, with single dopant atoms, as recorded on a pixelated detector. These extracted patterns relate to both individual atom sites and sublattice structures, effectively discriminating single dopant anomalies via multi-mode views. We believe manifold learning analysis will accelerate physics discoveries coupled between data-rich imaging mechanisms and materials such as ferroelectric, topological spin, and van der Waals heterostructures.