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Increasing interest in three-dimensional nanostructures adds impetus to electron microscopy techniques capable of imaging at or below the nanoscale in three dimensions. We present a reconstruction algorithm that takes as input a focal series of four-dimensional scanning transmission electron microscopy (4D-STEM) data. We apply the approach to a lead iridate, PbIrO, and yttrium-stabilized zirconia, YZrO, heterostructure from data acquired with the specimen in a single plan-view orientation, with the epitaxial layers stacked along the beam direction. We demonstrate that Pb–Ir atomic columns are visible in the uppermost layers of the reconstructed volume. We compare this approach to the alternative techniques of depth sectioning using differential phase contrast scanning transmission electron microscopy (DPC-STEM) and multislice ptychographic reconstruction.

The critical size limit of voltage-switchable electric dipoles has extensive implications for energy-efficient electronics, underlying the importance of ferroelectric order stabilized at reduced dimensionality. We report on the thickness-dependent antiferroelectric-to-ferroelectric phase transition in zirconium dioxide (ZrO 2 ) thin films on silicon. The emergent ferroelectricity and hysteretic polarization switching in ultrathin ZrO 2 , conventionally a paraelectric material, notably persists down to a film thickness of 5 angstroms, the fluorite-structure unit-cell size. This approach to exploit three-dimensional centrosymmetric materials deposited down to the two-dimensional thickness limit, particularly within this model fluorite-structure system that possesses unconventional ferroelectric size effects, offers substantial promise for electronics, demonstrated by proof-of-principle atomic-scale nonvolatile ferroelectric memory on silicon. Additionally, it is also indicative of hidden electronic phenomena that are achievable across a wide class of simple binary materials.

With the scaling of lateral dimensions in advanced transistors, an increased gate capacitance is desirable both to retain the control of the gate electrode over the channel and to reduce the operating voltage1. This led to a fundamental changein the gate stack in 2008,the incorporation of high-dielectric-constant HfO2(ref.2), which remains the material of choiceto date. Here we report HfO2-ZrO2 superlattice heterostructures as a gate stack, stabilized with mixed ferroelectric-antiferroelectric order, directly integrated onto Si transistors, and scaled down to approximately 20 ångströms, the same gate oxide thickness required for high-performance transistors. The overall equivalent oxide thickness in metal-oxide-semiconductor capacitors is equivalent to an effective SiO2 thickness of approximately 6.5 ångströms. Such a low effective oxide thickness and the resulting large capacitance cannot be achieved in conventional HfO2-based high-dielectric-constant gate stacks without scavenging the interfacial SiO2, which has adverse effects on the electron transport and gate leakage current3. Accordingly, our gate stacks, which do not require such scavenging, provide substantially lower leakage current and no mobility degradation. This work demonstrates that ultrathin ferroic HfO2-ZrO2 multilayers, stabilized with competing ferroelectric-antiferroelectric order in the two-nanometre-thickness regime, provide a path towards advanced gate oxide stacks in electronic devices beyond conventional HfO2-based high-dielectric-constant materials.

Dielectric electrostatic capacitors, due to their ultrafast charge-discharge capability, are attractive for high power energy storage applications. Along with ultrafast operation, on-chip integration can enable miniaturized energy storage devices for emerging autonomous microelectronics and microsystems. Additionally, state-of-the-art electrochemical miniaturized energy storage systems – microsupercapacitors and microbatteries – currently face safety, packaging, materials, and microfabrication challenges preventing on-chip technological readiness, leaving an opportunity for electrostatic microcapacitors. Here we report record-high energy storage density (ESD) and power density (PD) across all electrostatic systems in HfO2-ZrO2 (HZO)-based thin film microcapacitors integrated directly on silicon, through a three-pronged approach. First, to increase intrinsic energy storage, atomic-layer-deposited antiferroelectric HZO films are engineered near a field-driven ferroelectric phase transition to exhibit amplified charge storage via the negative capacitance (NC) effect, which enhances volumetric-ESD beyond the best-known back-end-of-the-line (BEOL) compatible dielectrics (115 J-cm−3). Second, to increase overall stored energy, superlattice engineering of amorphous-templated HZO-Al2O3 heterostructures scales-up the high-storage antiferroelectric-NC behavior to the 100 nm regime, which overcomes the conventional thickness limitations of HZO-based (anti)ferroelectricity (10-nm regime). Third, to increase storage-per-footprint, the superlattices are conformally integrated into three-dimensional (3D) capacitors, which boosts areal-ESD (areal-PD) 9-times (170-times) the best known 3D electrostatic capacitors: 80 mJ-cm−2 (300 kW-cm−2). This simultaneous demonstration of ultrahigh ESD and PD overcomes the traditional capacity-speed trade-off across the electrostatic-electrochemical energy storage hierarchy. Furthermore, integration of ultrahigh-density and ultrafast charging thin films within a BEOL-compatible process enables monolithic integration of on-chip microsupercapacitors, which opens the door for substantial energy storage and power delivery for electronic microsystems.

Amorphous silicates in meteoritic samples are significant as potential surviving interstellar dust from the formation of the Solar System. Amorphous silicate-rich grains called GEMS, glass with embedded metal and sulfides, are abundant in anhydrous interplanetary dust particles and some ultracarbonaceous Antarctic micrometeorites that have high presolar grain abundances. Some GEMS within these objects have been confirmed to be presolar. GEMS-like material, consisting of amorphous silicate with opaque inclusions, has been identified in the matrices of some primitive meteorites. We use specialized thin specimen preparation and transmission electron microscopy methods to compare the GEMS-like material in Paris (CM) and Acfer 094 (ungrouped) chondrites with GEMS in anhydrous, chondritic interplanetary dust particles. Specifically, we compared the amorphous silicate morphology, degree of partial ordering, elemental composition and dominant iron oxidation state. We find that the amorphous silicates in the GEMS-like materials in Paris and Acfer 094 show incipient ordering and are Fe-rich and highly oxidized, while those in GEMS are fully amorphous, Fe-poor, and anhydrous. From examination of various formation routes for the amorphous silicates, we conclude that the GEMS-like material in Paris and Acfer 094 is not GEMS and that it is unlikely that GEMS-like material accreted as primary amorphous material that retained its original amorphous structure since accretion. We also conclude that the presence of GEMS-like amorphous silicates in chondrite matrix is not a reliable indicator for high degrees of primitivity or pristinity since even mild, complex alteration processes may significantly alter silicate structure. Finally, we propose searches for presolar amorphous silicates in chondrite matrix samples that have been precharacterized by transmission electron microscopy methods to enable direct comparisons of presolar amorphous silicate abundances.

Recent work has revived interest in the scattering matrix formulation of electron scattering in transmission electron microscopy as a stepping stone toward atomic-resolution structure determination in the presence of multiple scattering. We discuss ways of visualizing the scattering matrix that make its properties clear. Through a simulation-based case study incorporating shot noise, we shown how regularizing on this continuity enables the scattering matrix to be reconstructed from 4D scanning transmission electron microscopy (STEM) measurements from a single defocus value. Intriguingly, for crystalline samples, this process also yields the sample thickness to nanometer accuracy with no a priori knowledge about the sample structure. The reconstruction quality is gauged by using the reconstructed scattering matrix to simulate STEM images at defocus values different from that of the data from which it was reconstructed.

Scanning transmission electron microscopy (STEM) allows for imaging, diffraction, and spectroscopy of materials on length scales ranging from microns to atoms. By using a high-speed, direct electron detector, it is now possible to record a full two-dimensional (2D) image of the diffracted electron beam at each probe position, typically a 2D grid of probe positions. These 4D-STEM datasets are rich in information, including signatures of the local structure, orientation, deformation, electromagnetic fields, and other sample-dependent properties. However, extracting this information requires complex analysis pipelines that include data wrangling, calibration, analysis, and visualization, all while maintaining robustness against imaging distortions and artifacts. In this paper, we present py4DSTEM, an analysis toolkit for measuring material properties from 4D-STEM datasets, written in the Python language and released with an open-source license. We describe the algorithmic steps for dataset calibration and various 4D-STEM property measurements in detail and present results from several experimental datasets. We also implement a simple and universal file format appropriate for electron microscopy data in py4DSTEM, which uses the open-source HDF5 standard. We hope this tool will benefit the research community and help improve the standards for data and computational methods in electron microscopy, and we invite the community to contribute to this ongoing project.

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.

Stable catalysts are essential to address energy and environmental challenges, especially in harsh environment applications (high temperature, oxidizing atmosphere, steam). In such conditions, supported metal catalysts deactivate due to sintering – a process where initially small nanoparticles grow into larger ones with reduced active surface area. Strategies to stabilize them lead to decreased performance. Here, we report stable catalysts prepared through the encapsulation of platinum particles inside an alumina framework. These catalysts do not sinter at 800 °C in the presence of oxygen and steam, conditions in which conventional catalysts sinter to large extents, while showing similar reaction rates. Extending this approach to Pd/Pt bimetallic catalysts leads to maintained small particle size at temperatures as high as 1,100 °C in air and steam. This strategy can be broadly applied to other metal and metal oxides for applications where sintering is a major cause of materials deactivation.

Nitrogen-doped carbons (NC) are a class of sustainable materials for selective CO2 adsorption. We introduce a versatile concept to fabricate flexible NC-based sensor architectures for room-temperature sensing of CO2 in a one-step laser conversion of primary coatings cast from abundant precursors. By the unidirectional energy impact in conjunction with depth-dependent attenuation of the laser beam, a layered sensor heterostructure with porous transducer and active sensor layer is formed. Comprehensive microscopic and spectroscopic cross-sectional analyses confirm the preservation of a high content of imidazolic nitrogen in the sensor. The performance was optimized in terms of material morphology, chemical composition, and surface chemistry to achieve a linear relative resistive response of up to ∆R/R0 = -14.3% (10% of CO2). Thermodynamic analysis yields ΔadsH values of -35.6 kJ·mol-1 and 34.1 kJ·mol 1 for H2O and CO2, respectively. The sensor is operable even in humid environments (e.g., ∆R/R0,RH=80% = 0.53%) and shows good performance upon strong mechanical deformation.

Heterogeneous catalysts play a key role in the chemical and energy industries1. To date, most industrial-scale heterogeneous catalytic reactions have relied on nanocatalysts2,3. However, despite significant progress from theoretical, experimental and computational studies4-18, identifying the active sites of alloy nanocatalysts remains a major challenge. This limitation is mainly due to an incomplete understanding of the three-dimensional (3D) atomic and chemical arrangement of different constituents and structural reconstructions driven by catalytic reactions19-22. Here, we use atomic electron tomography23 to determine the 3D local atomic structure, surface morphology and chemical composition of 11 Pt alloy nanocatalysts for the electrochemical oxygen reduction reaction (ORR). We reveal the facet, surface concaveness, structural and chemical order/disorder, coordination number, and bond length with unprecedented 3D atomic detail. The experimental 3D atomic coordinates are used by first-principles trained machine learning to identify the active sites of the nanocatalysts, which are corroborated by electrochemical measurements. A striking feature is the difference of the ORR activity of the surface Pt sites on the nanocatalysts by several orders of magnitude. Furthermore, by analyzing the structure-activity relationship, we formulate an equation named the local environment descriptor to balance the strain and ligand effects and gain quantitative insights into the ORR active sites of the Pt alloy nanocatalysts. The ability to determine the 3D atomic structure and chemical composition of realistic nanoparticles coupled with machine learning could transform our fundamental understanding of the catalytic active sites and provide a guidance for the rational design of optimal nanocatalysts.

Structure and chemistry of metal/metal-oxide interfaces are critical for many catalytic processes and sensing. Pristine interfaces of Pt and γ-Al2O3 were fabricated using high-energy ion implantation and thermal processing. Amorphous regions of alumina develop in single crystal α-alumina during Pt+ implantation and an 800 °C thermal treatment crystalizes amorphized alumina to γ-Al2O3 and allows Pt ions to precipitate within the developing γ-alumina, yielding Pt nanoparticle tetrahedra terminated by {111} surfaces. The phase of alumina that developed and the distribution, morphology, and orientation of Pt nanoparticles was determined using x-ray diffraction, Rutherford backscattering spectrometry, transmission electron microscopy and scanning transmission electron microscopy.

Summary The reticular synthesis of covalent organic frameworks (COFs), extended porous two-dimensional (2D) or three-dimensional (3D) networks held together by strong, highly directional chemical bonds, has thus far been restricted to small, shape-persistent, molecular building blocks. Here, we demonstrate the growth of crystalline 2D COFs from a polydisperse macromolecule derived from single-layer graphene, bottom-up synthesized quasi-one-dimensional (1D) graphene nanoribbons (GNRs). X-ray scattering and transmission electron microscopy reveal that 2D sheets of GNR-COFs self-assembled at a liquid-liquid interface stack parallel to the layer boundary and exhibit an orthotropic crystal packing. Liquid-phase exfoliation of multilayer GNR-COF crystals gives access to large-area (>105 nm2) bilayer and trilayer cGNR-COF films. The functional integration of extended 1D materials into crystalline COFs greatly expands the structural complexity and the scope of mechanical and physical materials properties accessible through a deterministic reticular bottom-up approach.

Summary Porous graphitic framework (PGF) is a two-dimensional (2D) material that has emerging energy applications. An archetype contains stacked 2D layers, the structure of which features a fully annulated aromatic skeleton with embedded heteroatoms and periodic pores. Due to the lack of a rational approach in establishing in-plane order under mild synthetic conditions, the structural integrity of PGF has remained elusive and ultimately limited its material performance. Here, we report the discovery of the unusual dynamic character of the C=N bonds in the aromatic pyrazine ring system under basic aqueous conditions, which enables the successful synthesis of a crystalline porous nitrogenous graphitic framework with remarkable in-plane order, as evidenced by powder X-ray diffraction studies and direct visualization using high-resolution transmission electron microscopy. The crystalline framework displays superior performance as a cathode material for lithium-ion batteries, outperforming the amorphous counterparts in terms of capacity and cycle stability.

Yu et al . suggested calculating precisely the size ranges of the three parts of our figure 3A, adjusting the free-energy levels in figure 3B, and considering the shape effect in the first-principles calculation. The first and second suggestions raise strong concerns for misinterpretation and overinterpretation of our experiments. The original calculation is sufficient to support our claim about crystalline-to-disordered transformations.

High-throughput grain mapping with sub-nanometer spatial resolution is demonstrated using scanning nanobeam electron diffraction (also known as 4D scanning transmission electron microscopy, or 4D-STEM) combined with high-speed direct-electron detection. An electron probe size down to 0.5 nm in diameter is used and the sample investigated is a gold–palladium nanoparticle catalyst. Computational analysis of the 4D-STEM data sets is performed using a disk registration algorithm to identify the diffraction peaks followed by feature learning to map the individual grains. Two unsupervised feature learning techniques are compared: principal component analysis (PCA) and non-negative matrix factorization (NNMF). The characteristics of the PCA versus NNMF output are compared and the potential of the 4D-STEM approach for statistical analysis of grain orientations at high spatial resolution is discussed.

Nanostructured ferritic alloys (NFAs) contain an ultra-high density of 2–4 nm fcc pyrochlore Y2Ti2O7 nano-oxides (NOs) embedded in a bcc Fe-14Cr ferritic matrix. Characterization of helium interactions with NOs and associated Fe-Y2Ti2O7 interfaces is important to the development of structural materials for nuclear fusion and fission applications. A benchmark 14YWT NFA was first annealed to coarsen the NOs, then insoluble helium was implanted at 700 °C to produce a high number density of bubbles. High-resolution scanning transmission electron microscopy characterization shows two dominant Fe-Y2Ti2O7 crystallographic orientation relationships (cube-on-edge and cube-on-cube). The smallest NOs (≈ 2 nm) are associated with the smaller bubbles (≈ 1.5 nm), while some of the largest NOs (> 6 nm) have larger, and sometimes multiple, bubbles. NO corner {111} facets are the preferred sites for He bubble nucleation. A refined sequence of events for He trapping and bubble formation is presented. These observations offer new insight on He management in NFAs, and provide a foundation for detailed modeling studies.

Large superelastic deformation in ferroelastic-ferroelectrics (FMs) is a complex phenomenon involving multiple mechanisms operating simultaneously. Understanding how these mechanisms contribute corporately is critical to apply this useful property to the intrinsically brittle FMs, which can therefore display both excellent functional and mechanical performance. Here, we have directly observed and quantitatively analyzed in situ in a transmission electron microscope the three main mechanisms of twinning domain, phase transformation and mobile point defect contributing to extremely large superelastic deformation in single-crystal BaTiO3 (5.0% strain) and Pb(Mg1/3Nb2/3)O3-PbTiO3 (10.1% strain). Our results reveal the hierarchical origin of large recoverable strain in “brittle” FMs.

The self-assembly of nanoparticles, a process whereby nanocrystal building blocks organize into even more ordered superstructures, is of great interest to nanoscience. Here we report the layer-by-layer assembly of 2D perovskite nanosheet building blocks. Structural analysis reveals that the assembled superlattice nanocrystals match with the layered Ruddlesden-Popper perovskite phase. This assembly proves reversible, as these superlattice nanocrystals can be reversibly exfoliated back into their building blocks via sonication. This study demonstrates the opportunity to further understand and exploit thermodynamics to increase order in a system of nanoparticles and to study emergent optical properties of a superlattice from 2D, weakly attracted, perovskite building blocks.