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1.
Nature ; 630(8017): 643-647, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38898295

RESUMO

Electrified solid-liquid interfaces (ESLIs) play a key role in various electrochemical processes relevant to energy1-5, biology6 and geochemistry7. The electron and mass transport at the electrified interfaces may result in structural modifications that markedly influence the reaction pathways. For example, electrocatalyst surface restructuring during reactions can substantially affect the catalysis mechanisms and reaction products1-3. Despite its importance, direct probing the atomic dynamics of solid-liquid interfaces under electric biasing is challenging owing to the nature of being buried in liquid electrolytes and the limited spatial resolution of current techniques for in situ imaging through liquids. Here, with our development of advanced polymer electrochemical liquid cells for transmission electron microscopy (TEM), we are able to directly monitor the atomic dynamics of ESLIs during copper (Cu)-catalysed CO2 electroreduction reactions (CO2ERs). Our observation reveals a fluctuating liquid-like amorphous interphase. It undergoes reversible crystalline-amorphous structural transformations and flows along the electrified Cu surface, thus mediating the crystalline Cu surface restructuring and mass loss through the interphase layer. The combination of real-time observation and theoretical calculations unveils an amorphization-mediated restructuring mechanism resulting from charge-activated surface reactions with the electrolyte. Our results open many opportunities to explore the atomic dynamics and its impact in broad systems involving ESLIs by taking advantage of the in situ imaging capability.

2.
Nature ; 577(7788): 64-68, 2020 01.
Artigo em Inglês | MEDLINE | ID: mdl-31739311

RESUMO

The size-dependent and shape-dependent characteristics that distinguish nanoscale materials from bulk solids arise from constraining the dimensionality of an inorganic structure1-3. As a consequence, many studies have focused on rationally shaping these materials to influence and enhance their optical, electronic, magnetic and catalytic properties4-6. Although a select number of stable clusters can typically be synthesized within the nanoscale regime for a specific composition, isolating clusters of a predetermined size and shape remains a challenge, especially for those derived from two-dimensional materials. Here we realize a multidentate coordination environment in a metal-organic framework to stabilize discrete inorganic clusters within a porous crystalline support. We show confined growth of atomically defined nickel(II) bromide, nickel(II) chloride, cobalt(II) chloride and iron(II) chloride sheets through the peripheral coordination of six chelating bipyridine linkers. Notably, confinement within the framework defines the structure and composition of these sheets and facilitates their precise characterization by crystallography. Each metal(II) halide sheet represents a fragment excised from a single layer of the bulk solid structure, and structures obtained at different precursor loadings enable observation of successive stages of sheet assembly. Finally, the isolated sheets exhibit magnetic behaviours distinct from those of the bulk metal halides, including the isolation of ferromagnetically coupled large-spin ground states through the elimination of long-range, interlayer magnetic ordering. Overall, these results demonstrate that the pore environment of a metal-organic framework can be designed to afford precise control over the size, structure and spatial arrangement of inorganic clusters.

3.
Proc Natl Acad Sci U S A ; 119(46): e2204346119, 2022 11 16.
Artigo em Inglês | MEDLINE | ID: mdl-36343237

RESUMO

A grand challenge in materials science is to identify the impact of molecular composition and structure across a range of length scales on macroscopic properties. We demonstrate a unified experimental-theoretical framework that coordinates experimental measurements of mesoscale structure with molecular-level physical modeling to bridge multiple scales of physical behavior. Here we apply this framework to understand charge transport in a semiconducting polymer. Spatially-resolved nanodiffraction in a transmission electron microscope is combined with a self-consistent framework of the polymer chain statistics to yield a detailed picture of the polymer microstructure ranging from the molecular to device relevant scale. Using these data as inputs for charge transport calculations, the combined multiscale approach highlights the underrepresented role of defects in existing transport models. Short-range transport is shown to be more chaotic than is often pictured, with the drift velocity accounting for a small portion of overall charge motion. Local transport is sensitive to the alignment and geometry of polymer chains. At longer length scales, large domains and gradual grain boundaries funnel charges preferentially to certain regions, creating inhomogeneous charge distributions. While alignment generally improves mobility, these funneling effects negatively impact mobility. The microstructure is modified in silico to explore possible design rules, showing chain stiffness and alignment to be beneficial while local homogeneity has no positive effect. This combined approach creates a flexible and extensible pipeline for analyzing multiscale functional properties and a general strategy for extending the accesible length scales of experimental and theoretical probes by harnessing their combined strengths.


Assuntos
Polímeros , Semicondutores , Polímeros/química , Microscopia , Simulação por Computador , Modelos Moleculares
4.
Nano Lett ; 24(4): 1168-1175, 2024 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-38251890

RESUMO

Unveiling materials' corrosion pathways is significant for understanding the corrosion mechanisms and designing corrosion-resistant materials. Here, we investigate the corrosion behavior of Sn@Ni3Sn4 and Sn nanocrystals in an aqueous solution in real time by using high-resolution liquid cell transmission electron microscopy. Our direct observation reveals an unprecedented level of detail on the corrosion of Sn metal with/without a coating of Ni3Sn4 at the nanometric and atomic levels. The Sn@Ni3Sn4 nanocrystals exhibit "pitting corrosion", which is initiated at the defect sites in the Ni3Sn4 protective layer. The early stage isotropic etching transforms into facet-dependent etching, resulting in a cavity terminated with low-index facets. The Sn nanocrystals under fast etching kinetics show uniform corrosion, and smooth surfaces are obtained. Sn nanocrystals show "creeping-like" etching behavior and rough surfaces. This study provides critical insights into the impacts of coating, defects, and ion diffusion on corrosion kinetics and the resulting morphologies.

5.
J Am Chem Soc ; 146(5): 3160-3170, 2024 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-38276891

RESUMO

High or enriched-purity O2 is used in numerous industries and is predominantly produced from the cryogenic distillation of air, an extremely capital- and energy-intensive process. There is significant interest in the development of new approaches for O2-selective air separations, including the use of metal-organic frameworks featuring coordinatively unsaturated metal sites that can selectively bind O2 over N2 via electron transfer. However, most of these materials exhibit appreciable and/or reversible O2 uptake only at low temperatures, and their open metal sites are also potential strong binding sites for the water present in air. Here, we study the framework CuI-MFU-4l (CuxZn5-xCl4-x(btdd)3; H2btdd = bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), which binds O2 reversibly at ambient temperature. We develop an optimized synthesis for the material to access a high density of trigonal pyramidal CuI sites, and we show that this material reversibly captures O2 from air at 25 °C, even in the presence of water. When exposed to air up to 100% relative humidity, CuI-MFU-4l retains a constant O2 capacity over the course of repeated cycling under dynamic breakthrough conditions. While this material simultaneously adsorbs N2, differences in O2 and N2 desorption kinetics allow for the isolation of high-purity O2 (>99%) under relatively mild regeneration conditions. Spectroscopic, magnetic, and computational analyses reveal that O2 binds to the copper(I) sites to form copper(II)-superoxide moieties that exhibit temperature-dependent side-on and end-on binding modes. Overall, these results suggest that CuI-MFU-4l is a promising material for the separation of O2 from ambient air, even without dehumidification.

6.
Nano Lett ; 23(22): 10132-10139, 2023 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-37909501

RESUMO

Nanomotors in solution have many potential applications. However, it has been a significant challenge to realize the directional motion of nanomotors. Here, we report cadmium chloride tetrahydrate (CdCl2·4H2O) nanomotors with remarkable directional movement under electron beam irradiation. Using in situ liquid phase transmission electron microscopy, we show that the CdCl2·4H2O nanoparticle with asymmetric surface facets moves through the liquid with the flat end in the direction of motion. As the nanomotor morphology changes, the speed of movement also changes. Finite element simulation of the electric field and fluid velocity distribution around the nanomotor assists the understanding of ionic self-diffusiophoresis as a driving force for the nanomotor movement; the nanomotor generates its own local ion concentration gradient due to different chemical reactivities on different facets.

7.
Nano Lett ; 23(24): 11395-11401, 2023 Dec 27.
Artigo em Inglês | MEDLINE | ID: mdl-38079217

RESUMO

Thermoelectric materials with high electrical conductivity and low thermal conductivity (e.g., Bi2Te3) can efficiently convert waste heat into electricity; however, in spite of favorable theoretical predictions, individual Bi2Te3 nanostructures tend to perform less efficiently than bulk Bi2Te3. We report a greater-than-order-of-magnitude enhancement in the thermoelectric properties of suspended Bi2Te3 nanoribbons, coated in situ to form a Bi2Te3/F4-TCNQ core-shell nanoribbon without oxidizing the core-shell interface. The shell serves as an oxidation barrier but also directly functions as a strong electron acceptor and p-type carrier donor, switching the majority carriers from a dominant n-type carrier concentration (∼1021 cm-3) to a dominant p-type carrier concentration (∼1020 cm-3). Compared to uncoated Bi2Te3 nanoribbons, our Bi2Te3/F4-TCNQ core-shell nanoribbon demonstrates an effective chemical potential dramatically shifted toward the valence band (by 300-640 meV), robustly increased Seebeck coefficient (∼6× at 250 K), and improved thermoelectric performance (10-20× at 250 K).

8.
J Am Chem Soc ; 145(12): 6648-6657, 2023 Mar 29.
Artigo em Inglês | MEDLINE | ID: mdl-36939571

RESUMO

Graphene liquid cell transmission electron microscopy is a powerful technique to visualize nanoscale dynamics and transformations at atomic resolution. However, the solution in liquid cells is known to be affected by radiolysis, and the stochastic formation of graphene liquid cells raises questions about the solution chemistry in individual pockets. In this study, electron energy loss spectroscopy (EELS) was used to evaluate a model encapsulated solution, aqueous CeCl3. First, the ratio between the O K-edge and Ce M-edge was used to approximate the concentration of cerium salt in the graphene liquid cell. It was determined that the ratio between oxygen and cerium was orders of magnitude lower than what is expected for a dilute solution, indicating that the encapsulated solution is highly concentrated. To probe how this affects the chemistry within graphene liquid cells, the oxidation of Ce3+ was measured using time-resolved parallel EELS. It was determined that Ce3+ oxidizes faster under high electron fluxes, but reaches the same steady-state Ce4+ concentration regardless of flux. The time-resolved concentration profiles enabled direct comparison to radiolysis models, which indicate rate constants and g-values of certain molecular species are substantially different in the highly concentrated environment. Finally, electron flux-dependent gold nanocrystal etching trajectories showed that gold nanocrystals etch faster at higher electron fluxes, correlating well with the Ce3+ oxidation kinetics. Understanding the effects of the highly concentrated solution in graphene liquid cells will provide new insight on previous studies and may open up opportunities to systematically study systems in highly concentrated solutions at high resolution.

9.
Nat Mater ; 21(11): 1290-1297, 2022 11.
Artigo em Inglês | MEDLINE | ID: mdl-36280703

RESUMO

Stable catalysts are essential to address energy and environmental challenges, especially for applications in harsh environments (for example, high temperature, oxidizing atmosphere and 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-but strategies to stabilize them can lead to decreased performance. Here we report stable catalysts prepared through the encapsulation of platinum nanoparticles inside an alumina framework, which was formed by depositing an alumina precursor within a separately prepared porous organic framework impregnated with platinum nanoparticles. These catalysts do not sinter at 800 °C in the presence of oxygen and steam, conditions in which conventional catalysts sinter to a large extent, while showing similar reaction rates. Extending this approach to Pd-Pt bimetallic catalysts led to the small particle size being maintained at temperatures as high as 1,100 °C in air and 10% steam. This strategy can be broadly applied to other metal and metal oxides for applications where sintering is a major cause of material deactivation.


Assuntos
Nanopartículas Metálicas , Platina , Temperatura , Vapor , Óxido de Alumínio
10.
J Chem Phys ; 158(16)2023 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-37093142

RESUMO

Crystallization of amorphous materials by thermal annealing has been investigated for numerous applications in the fields of nanotechnology, such as thin-film transistors and thermoelectric devices. The phase transition and shape evolution of amorphous germanium (Ge) and Ag@Ge core-shell nanoparticles with average diameters of 10 and 12 nm, respectively, were investigated by high-energy electron beam irradiation and in situ heating within a transmission electron microscope. The transition of a single Ge amorphous nanoparticle to the crystalline diamond cubic structure at the atomic scale was clearly demonstrated. Depending on the heating temperature, a hollow Ge structure can be maintained or transformed into a solid Ge nanocrystal through a diffusive process during the amorphous to crystalline phase transition. Selected area diffraction patterns were obtained to confirm the crystallization process. In addition, the thermal stability of Ag@Ge core-shell nanoparticles with an average core of 7.4 and a 2.1 nm Ge shell was studied by applying the same beam conditions and temperatures. The results show that at a moderate temperature (e.g., 385 °C), the amorphous Ge shell can completely crystallize while maintaining the well-defined core-shell structure, while at a high temperature (e.g., 545 °C), the high thermal energy enables a freely diffusive process of both Ag and Ge atoms on the carbon support film and leads to transformation into a phase segregated Ag-Ge Janus nanoparticle with a clear interface between the Ag and Ge domains. This study provides a protocol as well as insight into the thermal stability and strain relief mechanism of complex nanostructures at the single nanoparticle level with atomic resolution.

11.
Microsc Microanal ; 29(6): 1950-1960, 2023 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-37851063

RESUMO

In a scanning transmission electron microscope (STEM), producing a high-resolution image generally requires an electron beam focused to the smallest point possible. However, the magnetic lenses used to focus the beam are unavoidably imperfect, introducing aberrations that limit resolution. Modern STEMs overcome this by using hardware aberration correctors comprised of many multipole elements, but these devices are complex, expensive, and can be difficult to tune. We demonstrate a design for an electrostatic phase plate that can act as an aberration corrector. The corrector is comprised of annular segments, each of which is an independent two-terminal device that can apply a constant or ramped phase shift to a portion of the electron beam. We show the improvement in image resolution using an electrostatic corrector. Engineering criteria impose that much of the beam within the probe-forming aperture be blocked by support bars, leading to large probe tails for the corrected probe that sample the specimen beyond the central lobe. We also show how this device can be used to create other STEM beam profiles such as vortex beams and probes with a high degree of phase diversity, which improve information transfer in ptychographic reconstructions.

12.
J Am Chem Soc ; 144(51): 23474-23482, 2022 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-36512727

RESUMO

Moiré superlattices are twisted bilayer materials in which the tunable interlayer quantum confinement offers access to new physics and novel device functionalities. Previously, moiré superlattices were built exclusively using materials with weak van der Waals interactions, and synthesizing moiré superlattices with strong interlayer chemical bonding was considered to be impractical. Here, using lead sulfide (PbS) as an example, we report a strategy for synthesizing moiré superlattices coupled by strong chemical bonding. We use water-soluble ligands as a removable template to obtain free-standing ultrathin PbS nanosheets and assemble them into direct-contact bilayers with various twist angles. Atomic-resolution imaging shows the moiré periodic structural reconstruction at the superlattice interface due to the strong metavalent coupling. Electron energy loss spectroscopy and theoretical calculations collectively reveal the twist-angle-dependent electronic structure, especially the emergent separation of flat bands at small twist angles. The localized states of flat bands are similar to well-arranged quantum dots, promising an application in devices. This study opens a new door to the exploration of deep energy modulations within moiré superlattices alternative to van der Waals twistronics.

13.
J Am Chem Soc ; 144(27): 12167-12176, 2022 07 13.
Artigo em Inglês | MEDLINE | ID: mdl-35732002

RESUMO

Two-dimensional (2D) magnetic crystals hold promise for miniaturized and ultralow power electronic devices that exploit spin manipulation. In these materials, large, controllable magnetocrystalline anisotropy (MCA) is a prerequisite for the stabilization and manipulation of long-range magnetic order. In known 2D magnetic crystals, relatively weak MCA typically results in soft ferromagnetism. Here, we demonstrate that ferromagnetic order persists down to the thinnest limit of FexTaS2 (Fe-intercalated bilayer 2H-TaS2) with giant coercivities up to 3 T. We prepare Fe-intercalated TaS2 by chemical intercalation of van der Waals-layered 2H-TaS2 crystals and perform variable-temperature transport, transmission electron microscopy, and confocal Raman spectroscopy measurements to shed new light on the coupled effects of dimensionality, degree of intercalation, and intercalant order/disorder on the hard ferromagnetic behavior of FexTaS2. More generally, we show that chemical intercalation gives access to a rich synthetic parameter space for low-dimensional magnets, in which magnetic properties can be tailored by the choice of the host material and intercalant identity/amount, in addition to the manifold distinctive degrees of freedom available in atomically thin, van der Waals crystals.


Assuntos
Imãs , Tantálio , Dissulfetos , Eletrônica , Ferro
14.
Nat Mater ; 20(7): 956-963, 2021 07.
Artigo em Inglês | MEDLINE | ID: mdl-33859383

RESUMO

Van der Waals heteroepitaxy allows deterministic control over lattice mismatch or azimuthal orientation between atomic layers to produce long-wavelength superlattices. The resulting electronic phases depend critically on the superlattice periodicity and localized structural deformations that introduce disorder and strain. In this study we used Bragg interferometry to capture atomic displacement fields in twisted bilayer graphene with twist angles <2°. Nanoscale spatial fluctuations in twist angle and uniaxial heterostrain were statistically evaluated, revealing the prevalence of short-range disorder in moiré heterostructures. By quantitatively mapping strain tensor fields, we uncovered two regimes of structural relaxation and disentangled the electronic contributions of constituent rotation modes. Further, we found that applied heterostrain accumulates anisotropically in saddle-point regions, generating distinctive striped strain phases. Our results establish the reconstruction mechanics underpinning the twist-angle-dependent electronic behaviour of twisted bilayer graphene and provide a framework for directly visualizing structural relaxation, disorder and strain in moiré materials.

15.
Acc Chem Res ; 54(11): 2543-2551, 2021 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-33979131

RESUMO

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.

16.
Langmuir ; 38(23): 7168-7178, 2022 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-35621188

RESUMO

Nanocapsules are hollow nanoscale shells that have applications in drug delivery, batteries, self-healing materials, and as model systems for naturally occurring shell geometries. In many applications, nanocapsules are designed to release their cargo as they buckle and collapse, but the details of this transient buckling process have not been directly observed. Here, we use in situ liquid-phase transmission electron microscopy to record the electron-irradiation-induced buckling in spherical 60-187 nm polymer capsules with ∼3.5 nm walls. We observe in real time the release of aqueous cargo from these nanocapsules and their buckling into morphologies with single or multiple indentations. The in situ buckling of nanoscale capsules is compared to ex situ measurements of collapsed and micrometer-sized capsules and to Monte Carlo (MC) simulations. The shape and dynamics of the collapsing nanocapsules are consistent with MC simulations, which reveal that the excessive wrinkling of nanocapsules with ultrathin walls results from their large Föppl-von Kármán numbers around 105. Our experiments suggest design rules for nanocapsules with the desired buckling response based on parameters such as capsule radius, wall thickness, and collapse rate.

17.
Nano Lett ; 21(15): 6640-6647, 2021 08 11.
Artigo em Inglês | MEDLINE | ID: mdl-34324356

RESUMO

Selective adsorption of ligands on nanocrystal surfaces can affect oxidative etching. Here, we report the etching of palladium nanocrystals imaged using liquid cell transmission electron microscopy. The adsorption of surface ligands (i.e., iron acetylacetonate and its derivatives) and their role as inhibitor molecules on the etching process were investigated. Our observations revealed that the etching was dominated by the interplay between palladium facets and ligands and that the etching exhibited different pathways at different concentrations of ligands. At a low concentration of iron acetylacetonate (0.1 mM), rapid etching primarily at {100} facets led to a concave structure. At a high concentration (1.0 mM), the etch rate was decreased owing to a protective film of iron acetylacetonate on the {100} facets and a round nanoparticle was achieved. Ab initio calculations showed that the differences in adsorption energy of inhibitor molecules on palladium facets were responsible for the etching behavior.


Assuntos
Nanopartículas , Paládio , Adsorção , Ligantes , Microscopia Eletrônica de Transmissão
18.
Proc Natl Acad Sci U S A ; 115(26): 6608-6613, 2018 06 26.
Artigo em Inglês | MEDLINE | ID: mdl-29891720

RESUMO

The solar system formed from interstellar dust and gas in a molecular cloud. Astronomical observations show that typical interstellar dust consists of amorphous (a-) silicate and organic carbon. Bona fide physical samples for laboratory studies would yield unprecedented insight about solar system formation, but they were largely destroyed. The most likely repositories of surviving presolar dust are the least altered extraterrestrial materials, interplanetary dust particles (IDPs) with probable cometary origins. Cometary IDPs contain abundant submicron a-silicate grains called GEMS (glass with embedded metal and sulfides), believed to be carbon-free. Some have detectable isotopically anomalous a-silicate components from other stars, proving they are preserved dust inherited from the interstellar medium. However, it is debated whether the majority of GEMS predate the solar system or formed in the solar nebula by condensation of high-temperature (>1,300 K) gas. Here, we map IDP compositions with single nanometer-scale resolution and find that GEMS contain organic carbon. Mapping reveals two generations of grain aggregation, the key process in growth from dust grains to planetesimals, mediated by carbon. GEMS grains, some with a-silicate subgrains mantled by organic carbon, comprise the earliest generation of aggregates. These aggregates (and other grains) are encapsulated in lower-density organic carbon matrix, indicating a second generation of aggregation. Since this organic carbon thermally decomposes above ∼450 K, GEMS cannot have accreted in the hot solar nebula, and formed, instead, in the cold presolar molecular cloud and/or outer protoplanetary disk. We suggest that GEMS are consistent with surviving interstellar dust, condensed in situ, and cycled through multiple molecular clouds.

19.
Microsc Microanal ; 27(1): 129-139, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33303043

RESUMO

One of the primary uses for transmission electron microscopy (TEM) is to measure diffraction pattern images in order to determine a crystal structure and orientation. In nanobeam electron diffraction (NBED), we scan a moderately converged electron probe over the sample to acquire thousands or even millions of sequential diffraction images, a technique that is especially appropriate for polycrystalline samples. However, due to the large Ewald sphere of TEM, excitation of Bragg peaks can be extremely sensitive to sample tilt, varying strongly for even a few degrees of sample tilt for crystalline samples. In this paper, we present multibeam electron diffraction (MBED), where multiple probe-forming apertures are used to create multiple scanning transmission electron microscopy (STEM) probes, all of which interact with the sample simultaneously. We detail designs for MBED experiments, and a method for using a focused ion beam to produce MBED apertures. We show the efficacy of the MBED technique for crystalline orientation mapping using both simulations and proof-of-principle experiments. We also show how the angular information in MBED can be used to perform 3D tomographic reconstruction of samples without needing to tilt or scan the sample multiple times. Finally, we also discuss future opportunities for the MBED method.

20.
Microsc Microanal ; 27(4): 712-743, 2021 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-34018475

RESUMO

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.

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