Scanning Transmission Electron Microscopy Instrument Research Articles

Advanced Analytical Electron Microscopy Techniques for Probing Individual PGM-Free Catalyst Sites

Hydrogen fuel cells currently utilize expensive platinum group metal nanoparticles as catalysts [1]. To reduce the cost of catalyst materials, large efforts to develop viable platinum group metal-free (PGM-free) catalyst materials, which often consist of single transition metal atoms embedded in nitrogen-doped graphitic carbon structures, are being undertaken [2]. Given the atomic-scale nature of the metal sites in these materials, their performance and stability are highly dependent on the local coordination environment and consequently electronic structure of the sites [3]. A detailed understanding of the local elemental composition and lattice structure of individual sites, and how these properties vary between sites, is therefore needed to further develop improved PGM-free catalyst materials. While many bulk techniques are available that can provide average properties of these sites, such as Mössbauer and X-ray absorption spectroscopies, techniques with high spatial resolution are needed to measure the properties of individual sites. As a result, scanning transmission electron microscopy (STEM) combined with electron energy-loss spectroscopy (EELS) and energy-dispersive X-ray spectroscopy (EDS) has proven an invaluable tool for characterization of these materials due to its ability to probe structural and electronic properties at the atomic scale [4]. However, combined with the instability of many metal sites under the electron probe, the quantity and type of information accessible by conventional STEM instrumentation and acquisition methods is limited. To better understand the local coordination environment and electronic structure of individual sites, as well as how these properties vary site to site, new techniques and hardware are therefore needed.Here, we demonstrate advancements in STEM-EELS and -EDS that allow the quality and quantity of spectroscopic information obtained from individual sites to be significantly improved over conventional method. First, we demonstrate direct real-space mapping of metal sites by using a direct electron detector in the EELS spectrometer. This increases the data acquisition rate and signal-to-noise ratio sufficiently to map metal atom positions at the atomic scale. In addition, we show how automated metal atom position identification and subsequent probe positioning allow the rate at which metal sites are probed to be increased by another order of magnitude while simultaneously increasing the quantity of data obtained from each site. Using EELS and EDS signals acquired in parallel, this automated acquisition method enables a wide range of metal site elements to be identified, as well as the local coordination environment around the sites to be determined. Combined with electronic structure measurements of the metal atoms themselves, this technique provides significantly more information about individual sites than conventional methods. The techniques presented here are therefore poised to significantly improve our understanding of the local coordination environment and electronic structure of individual PGM-free metal sites, as well how these properties vary site to site, accelerating development of these low-cost hydrogen fuel cell catalyst materials [5].

X-ray imaging of atomic nuclei

Optically imaging atomic nuclei is a long-sought goal for scientific and applied research, but it has never been realized so far. We integrate aberration-corrected scanning transmission electron microscopy (STEM), the bremsstrahlung generation of X-ray photons, and the energy-dispersive X-ray spectroscopic (EDS) receiving and mapping of the photons into a new microscopy method of optical imaging, by which atomic nuclei of different materials are successfully imaged with X-ray photons. Moreover, this imaging method is shown to be workable with different STEM instruments and be capable of distinguishing atomic nuclei of different elements and resolving imaged size differences of atomic nuclei with the order of magnitude as small as 1 pm. Therefore, it is a general method that can image atomic nuclei and their evolutions in materials science, chemistry and physics.

Chemically Selective Imaging of Individual Bonds through Scanning Electron Energy-Loss Spectroscopy: Disulfide Bridges Linking Gold Nanoclusters

As proof-of-principle of chemically selective, spatially resolved imaging of individual bonds, we carry out electron energy-loss spectroscopy in a scanning transmission electron microscopy instrument on atomically precise, thiolate-coated gold nanoclusters linked with 5,5'-bis(mercaptomethyl)-2,2'-bipyridine dithiol ligands. The images allow the identification of bridging disulfide bonds (R-S-S-R) between clusters, and X-ray photoelectron spectra support the finding.

Direct Observation of Infrared Plasmonic Fano Antiresonances by a Nanoscale Electron Probe.

In this Letter, we exploit recent breakthroughs in monochromated aberration-corrected scanning transmission electron microscopy (STEM) to resolve infrared plasmonic Fano antiresonances in individual nanofabricated disk-rod dimers. Using a combination of electron energy-loss spectroscopy and theoretical modeling, we investigate and characterize a subspace of the weak coupling regime between quasidiscrete and quasicontinuum localized surface plasmon resonances where infrared plasmonic Fano antiresonances appear. This work illustrates the capability of STEM instrumentation to experimentally observe nanoscale plasmonic responses that were previously the domain only of higher-resolution infrared spectroscopies.

High-Voltage Scanning Transmission Electron Microscopy: A Tool for Structural Characterization of Micrometer-Thick Specimens

Herein, the advantages of high-voltage scanning transmission electron microscopy (STEM) as a tool for structural characterization of micrometer-thick specimens are reported. Dislocations introduced in a wedge-shaped Si crystal were clearly observed by bright-field STEM operating at 1 MV. Many of the dislocations were straight and parallel to the 〈110〉, 〈112〉 or 〈113〉 directions. The widths of the dislocations in the STEM images were almost constant at 13–16 nm (i.e., 4–5 pixels) in the thickness range between 1 and 7.5 µm. The latest high-voltage STEM instrumentation is thus useful for imaging crystal defects in micrometer-thick materials, and enables multi-scale fields of view from a few nanometers squared to over 100 µm2.

Three-dimensional visualization of dislocations in a ferromagnetic material by magnetic-field-free electron tomography

In conventional transmission electron microscopy, specimens to be observed are placed in between the objective lens pole piece and therefore exposed to a strong magnetic field about 2 T. For a ferromagnetic specimen, magnetization of the specimen causes isotropic and anisotropic defocusing, deflection of the electron beam as well as deformation of the specimen, which all become more severe when the specimen tilted. Therefore electron tomography on a ferromagnetic crystalline specimen is highly challenging because tilt-series data sets must be acquired without changing the excitation condition of a specific diffraction spot. In this study, a scanning transmission electron microscopy (STEM) tomography method without magnetizing a ferromagnetic specimen has been developed for three-dimensional (3D) visualization of dislocations in α-Fe, which is a typical ferromagnetic material. Magnetic-field-free environment down to 0.38 ± 0.07 mT at the specimen position is realized by demagnetizing the objective lens pole piece of a commercial STEM instrument. By using a spherical aberration corrector with the magnetic-field-free environment, an “aberration corrected Low-Mag STEM mode” with no objective lens field reaches a convergence semi angle ∼1 mrad and a spatial resolution ∼5 nm, and shows an adequate performance of imaging dislocations under a two-beam excitation condition for a low-index diffracted beam. The illumination condition for the aberration corrected Low-Mag STEM mode gives no overlap between the direct beam disk (spot) and neighboring diffraction disks. An electron channeling contrast imaging technique, in which an annular detector was located at a doughnut area between the direct beam and the neighboring diffracted beams, was effectively employed with the aberration corrected Low-Mag STEM mode to keep image intensity high enough even at large specimen-tilt angles. The resultant tomographic observation visualized 3D dislocation arrangements and active slip planes in a deformed α-Fe specimen.

Towards the low-dose characterization of beam sensitive nanostructures via implementation of sparse image acquisition in scanning transmission electron microscopy

Scanning transmission electron microscopy (STEM) has been successfully utilized to investigate atomic structure and chemistry of materials with atomic resolution. However, STEM’s focused electron probe with a high current density causes the electron beam damages including radiolysis and knock-on damage when the focused probe is exposed onto the electron-beam sensitive materials. Therefore, it is highly desirable to decrease the electron dose used in STEM for the investigation of biological/organic molecules, soft materials and nanomaterials in general. With the recent emergence of novel sparse signal processing theories, such as compressive sensing and model-based iterative reconstruction, possibilities of operating STEM under a sparse acquisition scheme to reduce the electron dose have been opened up. In this paper, we report our recent approach to implement a sparse acquisition in STEM mode executed by a random sparse-scan and a signal processing algorithm called model-based iterative reconstruction (MBIR). In this method, a small portion, such as 5% of randomly chosen unit sampling areas (i.e. electron probe positions), which corresponds to pixels of a STEM image, within the region of interest (ROI) of the specimen are scanned with an electron probe to obtain a sparse image. Sparse images are then reconstructed using the MBIR inpainting algorithm to produce an image of the specimen at the original resolution that is consistent with an image obtained using conventional scanning methods. Experimental results for down to 5% sampling show consistency with the full STEM image acquired by the conventional scanning method. Although, practical limitations of the conventional STEM instruments, such as internal delays of the STEM control electronics and the continuous electron gun emission, currently hinder to achieve the full potential of the sparse acquisition STEM in realizing the low dose imaging condition required for the investigation of beam-sensitive materials, the results obtained in our experiments demonstrate the sparse acquisition STEM imaging is potentially capable of reducing the electron dose by at least 20 times expanding the frontiers of our characterization capabilities for investigation of biological/organic molecules, polymers, soft materials and nanostructures in general.

Cycling and Aging Studies of Li-Based Cathode Materials Via Aberration-Corrected STEM

The role of aberration-corrected scanning transmission electron microscopy (STEM) in materials characterization is examined with respect to layered-oxide cathode materials for battery applications. STEM-based methods are quickly becoming the most promising characterization tools for these materials, owed largely to the wide-range of techniques available on advanced STEM instruments, including the direct imaging of both heavy and light elements, and both energy-dispersive X-ray (EDX) and electron energy loss (EEL) spectroscopies. The current talk will focus on multiple Li-based, Mn-containing oxide cathode materials, for example, Li2MnO3 and Li(Ni0.5Co0.2Mn0.3)O2), characterized via STEM methods, in pristine, cycled, and in-situ irradiated states. The latter allows for single particle tracking of the dynamic processes occuring upon Li and O loss from the material, and is a form of accelerated ageing compared to the structural and electronic changes which occur upon electrochemical cycling. Various imaging modes, including high/low angle annular dark field (H/LAADF) and annular bright field (ABF), in conjunction with EELS/EDX, will be used extensively for this analysis, while parameters such as Mn valence, O presence, and light element occupation and intercalation will be discussed.

Advanced Characterization of Li- and Beyond Li-Ion Battery Cathode Materials Via Electron Microscopy

The role of aberration-corrected scanning transmission electron microscopy (STEM) in materials characterization is examined with respect to layered-oxide cathode materials for battery applications. STEM-based methods are quickly becoming the most promising characterization tools for these materials, owed largely to the wide-range of techniques available on advanced STEM instruments, including the direct imaging of both heavy and light elements, and both energy-dispersive X-ray (EDX) and electron energy loss (EEL) spectroscopies. The current talk will focus on multiple materials, including Li- and beyond Li-ion oxides, characterized via STEM methods, in pristine, cycled, and in-situ irradiated states. The latter allows for single particle tracking of the dynamic processes occuring upon Li and O loss from the material. Various imaging modes, including high/low angle annular dark field (H/LAADF) and annular bright field (ABF), in conjunction with EELS/EDX, will be used extensively for this analysis, while parameters such as Mn valence, O presence, and light element occupation and intercalation will be discussed.

Advanced Electron Microscopy of Layered-Oxide Cathode Materials

The role of aberration-corrected scanning transmission electron microscopy (STEM) in materials characterization is examined with respect to layered-oxide cathode materials for battery applications. STEM-based methods are quickly becoming the most promising characterization tools for these materials, owed largely to the wide-range of techniques available on advanced STEM instruments, including the direct imaging of both heavy and light elements, and both energy-dispersive X-ray (EDX) and electron energy loss (EEL) spectroscopies. The current talk will focus on multiple materials, including Li- and beyond Li-ion oxides, characterized via STEM methods, in pristine, cycled, and in-situ irradiated states. The latter allows for single particle tracking of the dynamic processes occuring upon Li and O loss from the material. Various imaging modes, including high/low angle annular dark field (H/LAADF) and annular bright field (ABF), in conjunction with EELS/EDX, will be used extensively for this analysis, while parameters such as Mn valence, O presence, and light element occupation and intercalation will be discussed.

When will Low-Contrast Features be Visible in a STEM X-Ray Spectrum Image?

When will a small or low-contrast feature, such as an embedded second-phase particle, be visible in a scanning transmission electron microscopy (STEM) X-ray map? This work illustrates a computationally inexpensive method to simulate X-ray maps and spectrum images (SIs), based upon the equations of X-ray generation and detection. To particularize the general procedure, an example of nanostructured ferritic alloy (NFA) containing nm-sized Y2Ti2O7 embedded precipitates in ferritic stainless steel matrix is chosen. The proposed model produces physically appearing simulated SI data sets, which can either be reduced to X-ray dot maps or analyzed via multivariate statistical analysis. Comparison to NFA X-ray maps acquired using three different STEM instruments match the generated simulations quite well, despite the large number of simplifying assumptions used. A figure of merit of electron dose multiplied by X-ray collection solid angle is proposed to compare feature detectability from one data set (simulated or experimental) to another. The proposed method can scope experiments that are feasible under specific analysis conditions on a given microscope. Future applications, such as spallation proton-neutron irradiations, core-shell nanoparticles, or dopants in polycrystalline photovoltaic solar cells, are proposed.

A review of advantages of high-efficiency X-ray spectrum imaging for analysis of nanostructured ferritic alloys

Nanostructured ferritic alloys (NFAs) exhibit complex microstructures consisting of 100–500nm ferrite grains, grain boundary solute enrichment, and multiple populations of precipitates and nanoclusters (NCs). Understanding these materials’ excellent creep and radiation-tolerance properties requires a combination of multiple atomic-scale experimental techniques. Recent advances in scanning transmission electron microscopy (STEM) hardware and data analysis methods have the potential to revolutionize nanometer-to micrometer-scale materials analysis. Modern high-brightness, high-X-ray collection STEM instruments are capable of enabling advanced experiments, such as simultaneous energy dispersive X-ray spectroscopy and electron energy loss spectroscopy spectrum imaging at nm to sub-nm resolution, that are now well-established for the study of nuclear materials. In this paper, we review past results and present new results illustrating the effectiveness of latest-generation STEM instrumentation and data analysis.

Imaging and Spectroscopy of Pristine and Cycled Li2MnO3

Li-ion batteries have yet to reach their full application potential due to their inherent cycling performance issues, such as voltage instability and capacity fading, while fundamental questions remain unanswered regarding the mechanisms responsible. However, Mn-based layered oxides continue to be promising candidates for cathodes in high-energy-density Li batteries given their high voltage and high discharge capacities. A significant impediment to gaining insight into these layered oxides lies in their complexity and inhomogeneity. Thus, the focus of the present contribution will be on the parent material, Li2MnO3, which shows cycling characteristics similar to its more complex offspring. Scanning transmission electron microscopy (STEM) and spectroscopy are used to characterize structural and electronic properties of both pristine and cycled material. STEM-based methods are quickly becoming the most promising characterization tools for these and similar materials, owed largely to the wide-range of techniques available on advanced STEM instruments, including the direct imaging of both heavy and light elements, and both energy-dispersive X-ray (EDX) and electron energy loss (EEL) spectroscopies. Imaging modes such as high/low angle annular dark field (H/LAADF) and annular bright field (ABF) are exploited to image heavy atomic columns, strain contrast, and light atomic columns, respectively. Additionally, electron energy loss spectroscopy along with calculations based on density functional theory are used to probe the local electronic structure by monitoring the O K- and Mn L-edges, which can be used to track changes to both the O content and the Mn valence. Thus, the focus will remain on the structural and electronic evolution of the pristine layered oxide explored by combining spectroscopy and atomic-scale imaging with various in situ microscopy techniques and ex situ electrochemical cycling. Specifically, features such as the atomic ordering of Mn/Li atoms, O vacancy evolution, and Mn valence will be of particular interest.

Atomic-Level EELS Mapping Using High-Energy Edges in Dualeels™ Mode

With advancements in aberration correction, the spatial resolution of scanning transmission electron microscopy (STEM) has been enormously improved. In addition to the reduction of the STEM probe size, a dramatic increase in the STEM probe current has been realized, leading to the routine acquisition of high-resolution elemental and chemical maps using electron energy loss spectrometry (EELS). Using EELS combined with these advanced STEM instruments, atomic-level resolution information can be obtained from various types of materials, revealing the nature of interfaces, elemental distribution, presence of defects, and much more. In addition to simple elemental composition distributions, EELS is capable of delivering information about the chemical bonding, local atomic coordination, oxidation states, band gaps, and chemical phases of a broad range of materials at the fundamental resolution limit of the property being probed. Atomic-level EELS maps of these fundamental material properties can now be obtained with the acquisition time, to a large extent, limited only by the speed of the EELS spectrometer and not by the signal being measured. The availability of fast EELS spectrometers with large angular collection efficiencies has closed the gap between the rate of signal generation in the specimen and the speed at which this signal can be detected. This significantly increases the amount of information that can be acquired using EELS. Using the most recent generation of spectrometers, EELS data can be acquired at well over 1,000 spectra per second with a high-duty cycle. Fifth-order spectral aberration correction in this generation of spectrometers allows the use of the large collection angles needed to match the increased convergence angle that Cs-probe-corrected systems present, improving collection efficiency while maintaining energy resolution. These advances, when taken together, result in a well matched source/detector system capable of recording high-energy EELS edges at atomic resolution at a rate fast enough to limit electron beam damage to the sample.

Spatially resolved diffractometry with atomic-column resolution

We demonstrate spatially resolved diffractometry in which diffraction patterns are acquired at two-dimensional positions on a specimen using scanning transmission electron microscopy (STEM), resulting in four-dimensional data acquisition. A high spatial resolution of about 0.1 nm is achieved using a stabilized STEM instrument, a spherical aberration corrector and various post-acquisition data processings. We have found a few novel results in the radial and the azimuthal scattering angle dependences of atomic-column contrast in STEM images. Atomic columns are clearly observed in dark field images obtained using the excess Kikuchi band intensity even in small solid-angle detection. We also find that atomic-column contrasts in dark field images are shifted in the order of a few tens of picometers on changing the azimuthal scattering angle. This experimental result is approximately interpretable on the basis of the impact parameter in Rutherford scattering. Spatially resolved diffractometry provides fundamental knowledge related to various STEM techniques, such as annular dark field (ADF) and annular bright field (ABF) imaging, and it is expected to become an analytical platform for advanced STEM imaging.

Local crystal structure analysis with 10-pm accuracy using scanning transmission electron microscopy

We demonstrate local crystal structure analysis based on annular dark-field (ADF) imaging in scanning transmission electron microscopy (STEM). Using a stabilized STEM instrument and customized software, we first realize high accuracy of elemental discrimination and atom-position determination with a 10-pm-order accuracy, which can reveal major cation displacements associated with a variety of material properties, e.g. ferroelectricity and colossal magnetoresistivity. A-site ordered/disordered perovskite manganites Tb(0.5)Ba(0.5)MnO(3) are analysed; A-site ordering and a Mn-site displacement of 12 pm are detected in each specific atomic column. This method can be applied to practical and advanced materials, e.g. strongly correlated electron materials.

Scanning transmission electron microscopy and its application to the study of nanoparticles and nanoparticle systems

Scanning transmission electron microscopy (STEM) techniques can provide imaging, diffraction and spectroscopic information, either simultaneously or in a serial manner, of the specimen with an atomic or a sub-nanometer spatial resolution. High-resolution STEM imaging, when combined with nanodiffraction, atomic resolution electron energy-loss spectroscopy and nanometer resolution X-ray energy dispersive spectroscopy techniques, is critical to the fundamental studies of importance to nanoscience and nanotechnology. The availability of sub-nanometer or sub-angstrom electron probes in a STEM instrument, due to the use of a field emission gun and aberration correctors, ensures the greatest capabilities for studies of sizes, shapes, defects, crystal and surface structures, and compositions and electronic states of nanometer-size regions of thin films, nanoparticles and nanoparticle systems. The various imaging, diffraction and spectroscopy modes available in a dedicated STEM or a field emission TEM/STEM instrument are reviewed and the application of these techniques to the study of nanoparticles and nanostructured catalysts is used as an example to illustrate the critical role of the various STEM techniques in nanotechnology and nanoscience research.

Ultra-high resolution with off-axis STEM holography

It has previously been demonstrated that the scheme of Rodenburg and colleagues for deriving ultra-high resolution images from arrays of nanodiffraction patterns recorded in a scanning transmission electron microscopy instrument is capable of producing reconstructed images with an improvement in resolution by a factor greater than two, but the method is limited to weak-phase objects and the desired image is accompanied by an unwanted background. It is now shown that these limitations of the method can be avoided if the technique is combined with an off-axis electron holography scheme.

APPLICATIONS OF STEM INSTRUMENTS FOR SURFACE STUDIES

Scanning transmission electron microscopy (STEM) instruments have some particular advantages as compared with the more common transmission electron microscopes for some applications to surface research. Imaging of surfaces and mapping of the elemental distributions on surfaces with spatial resolutions approaching 1 nm are possible in an ultrahigh-vacuum STEM instrument when the low-energy secondary electrons or the Auger-emitted electrons are collected with high efficiency. In the imaging of surface layers on thin-film substrates, viewed in transmission, the use of a thin annular detector in STEM may greatly enhance the contrast, as illustrated by the case of the imaging of very thin nanocrystalline carbon layers on much thicker amorphous SiO2 films. The scanning reflection mode in a STEM instrument can provide some useful forms of contrast in images of surface structure. Standing wave fields can be formed on the surfaces of crystals with electrons, as with X-rays, one advantage of the electron case being that the standing wave fields may be imaged. Two new forms of electron holography, involving a STEM instrument and suitable for the study of surface structure, are proposed.

The enhancement of electron microscope resolution by use of atomic focusers

It is confirmed by computer simulation that, when an electron beam of energy 100–400 keV passes through a single heavy atom, or a row of atoms parallel to the beam (an “atomic focuser”), a very fine beam of diameter less than 0.05 nm, is formed in the region within 1 or 2 nm of the atomic focuser. This very fine beam may be used in scanning transmission electron microscopy (STEM) or in conventional transmission electron microscopy (TEM) to give image resolutions of the order of 0.05 nm if the specimen is held within 1 or 2 nm of the atomic focuser and translated with respect to it by means of, for example, a piezoelectric manipulator system such as that used for atomic probe microscopies. If a thin crystal is made to act as a multiple atomic focuser and the specimen is placed at a Fourier image distance from the crystal, the relative translations of the specimen and the atomic focuser may be more simply achieved by varying the angle of incidence for TEM or the angle of detection for STEM. The achievement of the enhanced resolution with several schemes involving relatively minor modifications of existing TEM or STEM instruments appears to be feasible.