Advanced processing of differential phase contrast data: Distinction between different causes of electron phase shifts.

Differential phase contrast, in its high resolution modification also known as first moment microscopy or momentum resolved STEM [1-7] , basically measures the lateral momentum transfer to the electron probe due to the beam interaction with either electrostatic and/or magnetic fields, when the probe transmits the specimen. In other words, the result of the measurement is a vector field p→(x,y) which describes the lateral momentum transfer to the probe electrons. In the case of electric fields, this momentum transfer is easily converted to the electric field E→(x,y) causing the deflection, and from ϱ=ɛ0∇⋅E→ the local charge density can be calculated from the divergence of the electric field. However, from experimental data it is known that also the calculation of the vector field's curl ∇→×p→ in general yields non-zero results. In this paper, we use the Helmholtz decomposition (Wikipedia contributors, 2022), also known as the fundamental theorem of vector calculus, to split the measured vector fields into their curl-free and divergence-free components and to interpret the physical meaning of these components in detail. It will be shown, that non-zero curl components may be used to measure geometric phases occurring from irregularities in crystal structure such as a screw dislocation.

The differential phase contrast uncertainty relation: Connection between electron dose and field resolution.

Differential phase contrast (DPC) microscopy is a STEM imaging technique, which is used to measure magnetic and electric fields of mesoscopic and nanoscopic dimensions, i.e. interatomic distances (Chapman et al. 1978; Chapman et al. 1981; Chapman, 1984; Chapman et al. 1985; Chapman et al. 1997; Lohr et al. 2012; Shibata et al. 2015; Bauer et al. 2014; Carvalho et al. 2016; Lohr et al. 2016; Mueller-Caspary et al. 2019a,2019b; Mueller-Caspary et al. 2018; Mueller-Caspary et al. 2017; Mueller-Caspary et al. 2014; Winkler et al. 2020; Toyama et al. 2020). In this paper we will demonstrate that the electron dose per pixel deposited on the specimen is decisive to the precision and resolution of measurements of a field's local strength. Relations are given which connect a given electron dose per pixel to the fundamentally achievable precision to which the specimen's interaction with the electrons may be determined, taking into account quantum mechanical considerations. Vice versa, given a certain required precision, the required dose per pixel can be easily predicted for reliable measurements of a desired property. First, these relations are given for the case of a continuous, i.e. non-pixelated, detector followed by simulations which show that the same relations hold for pixelated detectors. Then, the achievable precision for detectors with different pixel counts in combination with different camera lengths is discussed and the maximum measurable field amplitude per set-up is determined. Finally, the effect of inhomogeneities within the diffraction disk is discussed and possible deviations from the derived relations are considered. We also demonstrate that Heisenberg's uncertainty relation determines the possible field resolution in differential phase contrast microscopy, and that the achievable local field resolution is a function of the applied electron dose per pixel.

Heterogeneous Olefin Hydrogenation Enabled by a Highly-Reduced Nickel(-II) Catalyst Precursor.

Invited for the cover of this issue is the group of Robert Wolf at the University of Regensburg and colleagues at the University of Hamburg. The image depicts the hydrogenation of triphenylethylene. Read the full text of the article at 10.1002/chem.201905537.

Heterogeneous Olefin Hydrogenation Enabled by a Highly-Reduced Nickel(-II) Catalyst Precursor.

The hydrogenation of olefins, styrenes, enoates, imines, and sterically hindered tri-substituted olefins was accomplished using the pre-catalyst dilithiumbis(cycloocta-1,5-diene)nickelate(-II) (1). The mild conditions tolerate hydroxyl, halide, ester, and lactone functionalities. Mechanistic studies, including reaction progress analyses, poisoning experiments, and multinuclear NMR monitoring, indicate that a heterotopic (nickel nanoparticle) catalyst is in operation.

Influence of combinatory effects of STEM setups on the sensitivity of differential phase contrast imaging.

Differential phase-contrast (DPC) imaging in the scanning transmission electron microscopy (STEM) mode has been suggested as a new method to visualize the nanoscale electromagnetic features of materials. However, the quality of the DPC image is very sensitive to the electron-beam alignment, microscope setup, and specimen conditions. Unlike normal STEM imaging, the microscope setup variables in the DPC mode are not independent; rather, they are correlated factors decisive for field sensitivity. Here, we systematically investigated the independent and combinatory effects of microscope setups on the sensitivity of the DPC image in a hard magnet, Nd2Fe14B alloy. To improve sensitivity, a smaller overlap of the electron beam with annular detectors and a greater camera length were required. However, these factors cannot be controlled independently in the two-condenser-lens system. In this linked system, the effect of the camera length on the DPC sensitivity was slightly more predominant than the overlap. Furthermore, the DPC signal was noisy and scattered at a small overlap of less than 11%. The electron-beam current does not evidently affect the sensitivity. In addition, the DPC sensitivity was examined with respect to the sample thickness, and the optimum thickness for high sensitivity was approximately 65 nm for the hard magnetic material Nd2Fe14B. This practical approach to the STEM setup and sample thickness may provide experimental guidelines for further application of the DPC analysis method.

Stereoselective Alkyne Hydrogenation by using a Simple Iron Catalyst.

The stereoselective hydrogenation of alkynes constitutes one of the key approaches for the construction of stereodefined alkenes. The majority of conventional methods utilize noble and toxic metal catalysts. This study concerns a simple catalyst comprised of the commercial chemicals iron(II) acetylacetonate and diisobutylaluminum hydride, which enables the Z-selective semihydrogenation of alkynes under near ambient conditions (1-3 bar H2 , 30 °C, 5 mol % [Fe]). Neither an elaborate catalyst preparation nor addition of ligands is required. Mechanistic studies (kinetic poisoning, X-ray absorption spectroscopy, TEM) strongly indicate the operation of small iron clusters and particle catalysts.

Introducing a non-pixelated and fast centre of mass detector for differential phase contrast microscopy.

With the advent of probe corrected STEM machines it became possible to probe specimens on a scale of less than 50 pm resolution. This opens completely new horizons for research, as it is e.g. possible to probe the electrostatic fields between individual rows of atoms, using differential phase contrast (DPC). However, in contrast to conventional DPC, where one deals with extended fields which can be assumed constant across the electron probe, this is not possible for sub-atomic probes in DPC. For the latter case it was shown [1,2], that the strongly inhomogeneous field distribution within the probe diameter, which usually is caused by the nuclear potentials of an atomic column, leads to a complicated intensity redistribution within the diffraction disk. The task is then to determine the intensity weighted centre of the diffraction disk pattern (frequently also called centre of mass, COM), which is proportional to the average lateral momentum gained by the average electron, transmitted through the probe diameter. In first reported measurements, the determination of this COM was achieved using a pixelated detector in combination with a software-based evaluation of the COM. This suffers from two disadvantages: first, the nowadays available pixelated detectors are still not very fast (approximately 1000 fps) and quite expensive, and second, the amount of data to be processed after acquisition is comparatively huge. In this paper we report on an alternative to a pixelated detector, which is able to directly deliver the COM of a diffraction disk's intensity distribution with frequencies up to 200 kHz. We present measurements on the sensitivity of this detector as well as first results from DPC imaging. From these results we expect the detector also to serve well in sub-atomic DPC field sensing, possibly replacing today's segmented or pixelated detectors.

Olefin-Stabilized Cobalt Nanoparticles for C=C, C=O, and C=N Hydrogenations.

The development of cobalt catalysts that combine easy accessibility and high selectivity constitutes a promising approach to the replacement of noble-metal catalysts in hydrogenation reactions. This report introduces a user-friendly protocol that avoids complex ligands, hazardous reductants, special reaction conditions, and the formation of highly unstable pre-catalysts. Reduction of CoBr2 with LiEt3 BH in the presence of alkenes led to the formation of hydrogenation catalysts that effected clean conversions of alkenes, carbonyls, imines, and heteroarenes at mild conditions (3 mol % cat., 2-10 bar H2 , 20-80 °C). Poisoning studies and nanoparticle characterization by TEM, EDX, and DLS supported the notion of a heterotopic catalysis mechanism.

Entropy-limited topological protection of skyrmions.

Magnetic skyrmions are topologically protected whirls that decay through singular magnetic configurations known as Bloch points. We used Lorentz transmission electron microscopy to infer the energetics associated with the topological decay of magnetic skyrmions far from equilibrium in the chiral magnet Fe1-x Co x Si. We observed that the lifetime τ of the skyrmions depends exponentially on temperature, [Formula: see text]. The prefactor τ0 of this Arrhenius law changes by more than 30 orders of magnitude for small changes of the magnetic field, reflecting a substantial reduction of the lifetime of skyrmions by entropic effects and, thus, an extreme case of enthalpy-entropy compensation. Such compensation effects, being well known across many different scientific disciplines, affect topological transitions and, thus, topological protection on an unprecedented level.

A Complex Endomembrane System in the Archaeon Ignicoccus hospitalis Tapped by Nanoarchaeum equitans.

Based on serial sectioning, focused ion beam scanning electron microscopy (FIB/SEM), and electron tomography, we depict in detail the highly unusual anatomy of the marine hyperthermophilic crenarchaeon, Ignicoccus hospitalis. Our data support a complex and dynamic endomembrane system consisting of cytoplasmic protrusions, and with secretory function. Moreover, we reveal that the cytoplasm of the putative archaeal ectoparasite Nanoarchaeum equitans can get in direct contact with this endomembrane system, complementing and explaining recent proteomic, transcriptomic and metabolomic data on this inter-archaeal relationship. In addition, we identified a matrix of filamentous structures and/or tethers in the voluminous inter-membrane compartment (IMC) of I. hospitalis, which might be responsible for membrane dynamics. Overall, this unusual cellular compartmentalization, ultrastructure and dynamics in an archaeon that belongs to the recently proposed TACK superphylum prompts speculation that the eukaryotic endomembrane system might originate from Archaea.

On the achievable field sensitivity of a segmented annular detector for differential phase contrast measurements.

Differential phase contrast microscopy measures minute deflections of the electron probe due to electric and/or magnetic fields, using a position sensitive device. Although recently, pixelated detectors have become available which also serve as a position sensitive device, the most frequently used detector is a four-segmented annular semiconducting detector ring (or variations thereof), where the difference signals of opposing detector elements represent the components of the deflection vector. This deflection vector can be used directly to quantitatively determine the deflecting field, provided the specimen's thickness is known. While there exist many measurements of both electric and magnetic fields, even at an atomic level, until now the question of the smallest clearly resolvable field value for this detector has not yet been answered. This paper treats the problem theoretically first, leading to a calibration factor κ which depends solely on simple, experimentally accessible parameters and relates the deflecting field to the measured deflection vector. In a second step, the calibration factor for our combination of microscope and detector is determined experimentally for various combinations of camera length, condenser aperture and spot size to determine the optimum setup. From this optimized condition we determine the minimum change in field which leads to a clearly measurable signal change for both HMSTEM and LMSTEM operation. A strategy is described which allows the experimenter to choose the setup giving the highest field sensitivity. Quantification problems due to scattering processes in the specimen are addressed and ways are shown to choose a setup which is less sensitive to these artefacts.

Measurement of atomic electric fields and charge densities from average momentum transfers using scanning transmission electron microscopy.

This study sheds light on the prerequisites, possibilities, limitations and interpretation of high-resolution differential phase contrast (DPC) imaging in scanning transmission electron microscopy (STEM). We draw particular attention to the well-established DPC technique based on segmented annular detectors and its relation to recent developments based on pixelated detectors. These employ the expectation value of the momentum transfer as a reliable measure of the angular deflection of the STEM beam induced by an electric field in the specimen. The influence of scattering and propagation of electrons within the specimen is initially discussed separately and then treated in terms of a two-state channeling theory. A detailed simulation study of GaN is presented as a function of specimen thickness and bonding. It is found that bonding effects are rather detectable implicitly, e.g., by characteristics of the momentum flux in areas between the atoms than by directly mapping electric fields and charge densities. For strontium titanate, experimental charge densities are compared with simulations and discussed with respect to experimental artifacts such as scan noise. Finally, we consider practical issues such as figures of merit for spatial and momentum resolution, minimum electron dose, and the mapping of larger-scale, built-in electric fields by virtue of data averaged over a crystal unit cell. We find that the latter is possible for crystals with an inversion center. Concerning the optimal detector design, this study indicates that a sampling of 5mrad per pixel is sufficient in typical applications, corresponding to approximately 10×10 available pixels.

Imaging of magnetic and electric fields by electron microscopy.

Nanostructured materials become more and more a part of our daily life, partly as self-assembled particles or artificially patterned. These nanostructures often possess intrinsic magnetic and/or electric fields which determine (at least partially) their physical properties. Therefore it is important to be able to measure these fields reliably on a nanometre scale. A rather common instrument for the investigation of these fields is the transmission electron microscope as it offers high spatial resolution. The use of an electron microscope to image electric and magnetic fields on a micron down to sub-nanometre scale is treated in detail for transmission electron microscopes (TEM) and scanning transmission electron microscopes (STEM). The formation of contrast is described for the most common imaging modes, the specific advantages and disadvantages of each technique are discussed and examples are given. In addition, the experimental requirements for the use of the techniques described are listed and explained.

On detector linearity and precision of beam shift detection for quantitative differential phase contrast applications.

Differential phase contrast is a STEM imaging mode where minute sideways deflections of the electron probe are monitored, usually by using a position sensitive device (Chapman, 1984 [1]; Lohr et al., 2012 [2]) or, alternatively in some cases, a fast camera (Müller et al., 2012 [3,4]; Yang et al., 2015 [5]; Pennycook et al., 2015 [6]) as a pixelated detector. While traditionally differential phase contrast electron microscopy was mainly focused on investigations of micro-magnetic domain structures and their specific features, such as domain wall widths, etc. (Chapman, 1984 [1]; Chapman et al., 1978, 1981, 1985 [7-9]; Sannomiya et al., 2004 [10]), its usage has recently been extended to mesoscopic (Lohr et al., 2012, 2016 [2,12]; Bauer et al., 2014 [11]; Shibata et al., 2015 [13]) and nano-scale electric fields (Shibata et al., 2012 [14]; Mueller et al., 2014 [15]). In this paper, the various interactions which can cause a beam deflection are reviewed and expanded by two so far undiscussed mechanisms which may be important for biological applications. As differential phase contrast microscopy strongly depends on the ability to detect minute beam deflections we first treat the linearity problem for an annular four quadrant detector and then determine the factors which limit the minimum measurable deflection angle, such as S/N ratio, current density, dwell time and detector geometry. Knowing these factors enables the experimenter to optimize the set-up for optimum performance of the microscope and to get a clear figure for the achievable field resolution error margins.

Epitaxial Growth of Room-Temperature Ferromagnetic MnAs Segments on GaAs Nanowires via Sequential Crystallization.

We investigate the incorporation of manganese into self-catalyzed GaAs nanowires grown in molecular beam epitaxy. Our study reveals that Mn accumulates in the liquid Ga droplet and that no significant incorporation into the nanowire is observed. Using a sequential crystallization of the droplet, we then demonstrate a deterministic and epitaxial growth of MnAs segments at the nanowire tip. This technique may allow the seamless integration of multiple room-temperature ferromagnetic segments into GaAs nanowires with high-crystalline quality.

Atomic electric fields revealed by a quantum mechanical approach to electron picodiffraction.

By focusing electrons on probes with a diameter of 50 pm, aberration-corrected scanning transmission electron microscopy (STEM) is currently crossing the border to probing subatomic details. A major challenge is the measurement of atomic electric fields using differential phase contrast (DPC) microscopy, traditionally exploiting the concept of a field-induced shift of diffraction patterns. Here we present a simplified quantum theoretical interpretation of DPC. This enables us to calculate the momentum transferred to the STEM probe from diffracted intensities recorded on a pixel array instead of conventional segmented bright-field detectors. The methodical development yielding atomic electric field, charge and electron density is performed using simulations for binary GaN as an ideal model system. We then present a detailed experimental study of SrTiO3 yielding atomic electric fields, validated by comprehensive simulations. With this interpretation and upgraded instrumentation, STEM is capable of quantifying atomic electric fields and high-contrast imaging of light atoms.

Strain measurement in semiconductor heterostructures by scanning transmission electron microscopy.

This article deals with the measurement of strain in semiconductor heterostructures from convergent beam electron diffraction patterns. In particular, three different algorithms in the field of (circular) pattern recognition are presented that are able to detect diffracted disc positions accurately, from which the strain in growth direction is calculated. Although the three approaches are very different as one is based on edge detection, one on rotational averages, and one on cross correlation with masks, it is found that identical strain profiles result for an In x Ga1-x N y As1-y /GaAs heterostructure consisting of five compressively and tensile strained layers. We achieve a precision of strain measurements of 7-9·10-4 and a spatial resolution of 0.5-0.7 nm over the whole width of the layer stack which was 350 nm. Being already very applicable to strain measurements in contemporary nanostructures, we additionally suggest future hardware and software designs optimized for fast and direct acquisition of strain distributions, motivated by the present studies.

Differential phase contrast 2.0--opening new "fields" for an established technique.

Differential phase contrast microscopy has become known as a high resolution imaging technique for magnetic micro-structures in the past. The method senses the local induction by measuring the deflection of the probe beam after it passes through a specimen area carrying a magnetic field. Little attention has been paid, however, to the fact that this technique is also capable of measuring electric fields. An application of the technique to measure piezoelectric polarization fields inside multi-layered structures such as quantum wells is demonstrated. For this purpose, piezoelectric fields within non-centrosymmetric crystal structures, based on GaN/InGaN/GaN quantum wells, are investigated. It can be shown that the technique is sensitive to these fields and yields detailed information about the field distribution. The specific information and experimental limitations as well as artefacts of the technique will be discussed in detail and first measurements are shown. The main advantages turn out to be high sensitivity for electric fields, combined with a very high resolution, which is limited only by the STEM probe size. Another advantage is the large achievable field of view.

Analysis of the surface proteins of Acidithiobacillus ferrooxidans strain SP5/1 and the new, pyrite-oxidizing Acidithiobacillus isolate HV2/2, and their possible involvement in pyrite oxidation.

Two strains of rod-shaped, pyrite-oxidizing acidithiobacilli, their cell envelope structure and their interaction with pyrite were investigated in this study. Cells of both strains, Acidithiobacillus ferrooxidans strain SP5/1 and the moderately thermophilic Acidithiobacillus sp. strain HV2/2, were similar in size, with slight variations in length and diameter. Two kinds of cell appendages were observed: flagella and pili. Besides a typical Gram-negative cell architecture with inner and outer membrane, enclosing a periplasm, both strains were covered by a hitherto undescribed, regularly arranged 2-D protein crystal with p2-symmetry. In A. ferrooxidans, this protein forms a stripe-like structure on the surface. A similar surface pattern with almost identical lattice vectors was also seen on the cells of strain HV2/2. For the surface layer of both bacteria, a direct contact to pyrite crystals was observed in ultrathin sections, indicating that the S-layer is involved in maintaining this contact site. Observations on an S-layer-deficient strain show, however, that cell adhesion does not strictly depend on the presence of the S-layer and that this surface protein has an influence on cell shape. Furthermore, the presented data suggest the ability of the S-layer protein to complex Fe3+ ions, suggesting a role in the physiology of the microorganisms.

Position controlled self-catalyzed growth of GaAs nanowires by molecular beam epitaxy.

GaAs nanowires are grown by molecular beam epitaxy using a self-catalyzed, Ga-assisted growth technique. Position control is achieved by nano-patterning a SiO(2) layer with arrays of holes with a hole diameter of 85 nm and a hole pitch varying between 200 nm and 2 µm. Gallium droplets form preferentially at the etched holes acting as catalyst for the nanowire growth. The nanowires have hexagonal cross-sections with {110} side facets and crystallize predominantly in zincblende. The interdistance dependence of the nanowire growth rate indicates a change of the III/V ratio towards As-rich conditions for large hole distances inhibiting NW growth.