How Fast is Your Detector? The Effect of Temporal Response on Image Quality.

With increasing interest in high-speed imaging, there should be an increased interest in the response times of our scanning transmission electron microscope detectors. Previous works have highlighted and contrasted the performance of various detectors for quantitative compositional or structural studies, but here, we shift the focus to detector temporal response, and the effect this has on captured images. The rise and decay times of eight detectors' single-electron response are reported, as well as measurements of their flatness, roundness, smoothness, and ellipticity. We develop and apply a methodology for incorporating the temporal detector response into simulations, showing that a loss of resolution is apparent in both the images and their Fourier transforms. We conclude that the solid-state detector outperforms the photomultiplier tube-based detectors in all areas bar a slightly less elliptical central hole and is likely the best detector to use for the majority of applications. However, using the tools introduced here, we encourage users to effectively evaluate which detector is most suitable for their experimental needs.

Cryogenic electron ptychographic single particle analysis with wide bandwidth information transfer.

Advances in cryogenic transmission electron microscopy have revolutionised the determination of many macromolecular structures at atomic or near-atomic resolution. This method is based on conventional defocused phase contrast imaging. However, it has limitations of weaker contrast for small biological molecules embedded in vitreous ice, in comparison with cryo-ptychography, which shows increased contrast. Here we report a single-particle analysis based on the use of ptychographic reconstruction data, demonstrating that three dimensional reconstructions with a wide information transfer bandwidth can be recovered by Fourier domain synthesis. Our work suggests future applications in otherwise challenging single particle analyses, including small macromolecules and heterogeneous or flexible particles. In addition structure determination in situ within cells without the requirement for protein purification and expression may be possible.

Templated 2D Polymer Heterojunctions for Improved Photocatalytic Hydrogen Production.

2D polymers have emerged as one of the most promising classes of organic photocatalysts for solar fuel production due to their tunability, charge-transport properties, and robustness. They are however difficult to process and so there are limited studies into the formation of heterojunction materials incorporating these components. In this work, a novel templating approach is used to combine an imine-based donor polymer and an acceptor polymer formed through Knoevenagel condensation. Heterojunction formation is shown to be highly dependent on the topological match of the donor and acceptor polymers with the most active templated material found to be between three and nine times more active for photocatalysis than its constituent components. Transient absorption spectroscopy reveals that this improvement is due to faster charge separation and more efficient charge extraction in the templated heterojunction. The templated material shows a very high hydrogen evolution rate of >20 mmol h-1 m-2 with an ascorbic acid hole scavenger but also produces hydrogen in the presence of only water and a cobalt-based redox mediator. This suggests the improved charge-separation interface and reduced trapping accessed through this approach could be suitable for Z-scheme formation.

Synthesis of mono- and few-layered n-type WSe2 from solid state inorganic precursors.

Tuning the charge transport properties of two-dimensional transition metal dichalcogenides (TMDs) is pivotal to their future device integration in post-silicon technologies. To date, co-doping of TMDs during growth still proves to be challenging, and the synthesis of doped WSe2, an otherwise ambipolar material, has been mainly limited to p-doping. Here, we demonstrate the synthesis of high-quality n-type monolayered WSe2 flakes using a solid-state precursor for Se, zinc selenide. n-Type transport has been reported with prime electron mobilities of up to 10 cm2 V-1 s-1. We also demonstrate the tuneability of doping to p-type transport with hole mobilities of 50 cm2 V-1 s-1 after annealing in air. n-Doping has been attributed to the presence of Zn adatoms on the WSe2 flakes as revealed by X-ray photoelectron spectroscopy (XPS), spatially resolved time of flight secondary ion mass spectroscopy (SIMS) and angular dark-field scanning transmission electron microscopy (AD-STEM) characterization of WSe2 flakes. Monolayer WSe2 flakes exhibit a sharp photoluminescence (PL) peak at room temperature and highly uniform emission across the entire flake area, indicating a high degree of crystallinity of the material. This work provides new insight into the synthesis of TMDs with charge carrier control, to pave the way towards post-silicon electronics.

Element Specific Atom Counting at the Atomic Scale by Combining High Angle Annular Dark Field Scanning Transmission Electron Microscopy and Energy Dispersive X-ray Spectroscopy.

A new methodology is presented to count the number of atoms in multimetallic nanocrystals by combining energy dispersive X-ray spectroscopy (EDX) and high angle annular dark field scanning transmission electron microscopy (HAADF STEM). For this purpose, the existence of a linear relationship between the incoherent HAADF STEM and EDX images is exploited. Next to the number of atoms for each element in the atomic columns, the method also allows quantification of the error in the obtained number of atoms, which is of importance given the noisy nature of the acquired EDX signals. Using experimental images of an Au@Ag core-shell nanorod, it is demonstrated that 3D structural information can be extracted at the atomic scale. Furthermore, simulated data of an Au@Pt core-shell nanorod show the prospect to characterize heterogeneous nanostructures with adjacent atomic numbers.

High-precision atomic-scale strain mapping of nanoparticles from STEM images.

Strain is a crucial factor that influences the physicochemical properties of nanoparticles. Being able to precisely measure strain is important in understanding the intrinsic mechanism of the enhanced performance of nanoparticles. Techniques that have been developed for strain analysis using scanning transmission electron microscopy (STEM) images can be categorized into diffraction-based method and imaging-based method. Here, using image simulation techniques, it is found that the measured two-dimensional (2D) displacements from annular dark field (ADF) STEM images of a nanoparticle are a good approximation to a projection of the actual three-dimensional (3D) displacements. A methodology for deformation analysis is presented which is based on the detection of atomic columns from atomic-resolution STEM images in real space. Elastic deformation parameters such as strain are usually defined on the basis of a continuum of deformation. The appropriateness of various deformation parameters for atomic-scale investigation on STEM images is explored and a method for determining these is presented. We found that the local lattice parameter and principal strain components are the most physically meaningful parameters to express the materials distortion behaviour. Apart from the local lattice parameter, the other deformation parameters such as normal strains, shear strains and displacements, heavily rely on the choice of reference lattice. It is also found that different reference grids add a series of uniform offsets to these strain variations. Finally, this approach is applied to a PtCo3 bimetallic nanoparticle to quantify its deformation behaviour.

Significant Performance Improvement in n-Channel Organic Field-Effect Transistors with C60 :C70 Co-Crystals Induced by Poly(2-ethyl-2-oxazoline) Nanodots.

Solution-processed organic field-effect transistors (OFETs) have attracted great interest due to their potential as logic devices for bendable and flexible electronics. In relation to n-channel structures, soluble fullerene semiconductors have been widely studied. However, they have not yet met the essential requirements for commercialization, primarily because of low charge carrier mobility, immature large-scale fabrication processes, and insufficient long-term operational stability. Interfacial engineering of the carrier-injecting source/drain (S/D) electrodes has been proposed as an effective approach to improve charge injection, leading also to overall improved device characteristics. Here, it is demonstrated that a non-conjugated neutral dipolar polymer, poly(2-ethyl-2-oxazoline) (PEOz), formed as a nanodot structure on the S/D electrodes, enhances electron mobility in n-channel OFETs using a range of soluble fullerenes. Overall performance is especially notable for (C60 -Ih )[5,6]fullerene (C60 ) and (C70 -D5h(6) )[5,6]fullerene (C70 ) blend films, with an increase from 0.1 to 2.1 cm2 V-1 s-1 . The high relative mobility and eighteen-fold improvement are attributed not only to the anticipated reduction in S/D electrode work function but also to the beneficial effects of PEOz on the formation of a face-centered-cubic C60 :C70 co-crystal structure within the blend films.

Contrast transfer and noise considerations in focused-probe electron ptychography.

Electron ptychography is a 4-D STEM phase-contrast imaging technique with applications to light-element and beam-sensitive materials. Although the electron dose (electrons incident per unit area on the sample) is the primary figure of merit for imaging beam-sensitive materials, it is also necessary to consider the contrast transfer properties of the imaging technique. Here, we explore the contrast transfer properties of electron ptychography. The contrast transfer of focused-probe, non-iterative electron ptychography using the single-side-band (SSB) method is demonstrated experimentally. The band-pass nature of the phase-contrast transfer function (PCTF) for SSB ptychography places strict limitations on the probe convergence semi-angles required to resolve specific sample features with high contrast. The PCTF of the extended ptychographic iterative engine (ePIE) is broader than that for SSB ptychography, although when both high and low spatial frequencies are transferred, band-pass filtering is required to remove image artefacts. Normalisation of the transfer function with respect to the noise level shows that the transfer window is increased while avoiding noise amplification. Avoiding algorithms containing deconvolution steps may also increase the dose-efficiency of ptychographic phase reconstructions.

Atomic-scale microstructure of metal halide perovskite.

Hybrid organic-inorganic perovskites have high potential as materials for solar energy applications, but their microscopic properties are still not well understood. Atomic-resolution scanning transmission electron microscopy has provided invaluable insights for many crystalline solar cell materials, and we used this method to successfully image formamidinium lead triiodide [CH(NH2)2PbI3] thin films with a low dose of electron irradiation. Such images reveal a highly ordered atomic arrangement of sharp grain boundaries and coherent perovskite/PbI2 interfaces, with a striking absence of long-range disorder in the crystal. We found that beam-induced degradation of the perovskite leads to an initial loss of formamidinium [CH(NH2)2 +] ions, leaving behind a partially unoccupied perovskite lattice, which explains the unusual regenerative properties of these materials. We further observed aligned point defects and climb-dissociated dislocations. Our findings thus provide an atomic-level understanding of technologically important lead halide perovskites.

Strain effects in core-shell PtCo nanoparticles: a comparison of experimental observations and computational modelling.

Strain in Pt nanoalloys induced by the secondary metal has long been suggested as a major contributor to the modification of catalytic properties. Here, we investigate strain in PtCo nanoparticles using a combination of computational modelling and microscopy experiments. We have used a combination of molecular dynamics (MD) and large-scale density functional theory (DFT) for our models, alongside experimental work using annular dark field scanning transmission electron microscopy (ADF-STEM). We have performed extensive validation of the interatomic potential against DFT using a Pt568Co18 nanoparticle. Modelling gives access to 3 dimensional structures that can be compared to the 2D ADF-STEM images, which we use to build an understanding of nanoparticle structure and composition. Strain has been measured for PtCo and pure Pt nanoparticles, with MD annealed models compared to ADF-STEM images. Our analysis was performed on a layer by layer basis, where distinct trends between the Pt and PtCo alloy nanoparticles are observed. To our knowledge, we show for the first time a way in which detailed atomistic simulations can be used to augment and help interpret the results of ADF-STEM strain mapping experiments, which will enhance their use in characterisation towards the development of improved catalysts.

Low-dose phase retrieval of biological specimens using cryo-electron ptychography.

Cryo-electron microscopy is an essential tool for high-resolution structural studies of biological systems. This method relies on the use of phase contrast imaging at high defocus to improve information transfer at low spatial frequencies at the expense of higher spatial frequencies. Here we demonstrate that electron ptychography can recover the phase of the specimen with continuous information transfer across a wide range of the spatial frequency spectrum, with improved transfer at lower spatial frequencies, and as such is more efficient for phase recovery than conventional phase contrast imaging. We further show that the method can be used to study frozen-hydrated specimens of rotavirus double-layered particles and HIV-1 virus-like particles under low-dose conditions (5.7 e/Å2) and heterogeneous objects in an Adenovirus-infected cell over large fields of view (1.14 × 1.14 µm), thus making it suitable for studies of many biologically important structures.

Measuring Dynamic Structural Changes of Nanoparticles at the Atomic Scale Using Scanning Transmission Electron Microscopy.

We propose a new method to measure atomic scale dynamics of nanoparticles from experimental high-resolution annular dark field scanning transmission electron microscopy images. By using the so-called hidden Markov model, which explicitly models the possibility of structural changes, the number of atoms in each atomic column can be quantified over time. This newly proposed method outperforms the current atom-counting procedure and enables the determination of the probabilities and cross sections for surface diffusion. This method is therefore of great importance for revealing and quantifying the atomic structure when it evolves over time via adatom dynamics, surface diffusion, beam effects, or during in situ experiments.

Control of Knock-On Damage for 3D Atomic Scale Quantification of Nanostructures: Making Every Electron Count in Scanning Transmission Electron Microscopy.

Understanding nanostructures down to the atomic level is the key to optimizing the design of advanced materials with revolutionary novel properties. This requires characterization methods capable of quantifying the three-dimensional (3D) atomic structure with the highest possible precision. A successful approach to reach this goal is to count the number of atoms in each atomic column from 2D annular dark field scanning transmission electron microscopy images. To count atoms with single atom sensitivity, a minimum electron dose has been shown to be necessary, while on the other hand beam damage, induced by the high energy electrons, puts a limit on the tolerable dose. An important challenge is therefore to develop experimental strategies to optimize the electron dose by balancing atom-counting fidelity vs the risk of knock-on damage. To achieve this goal, a statistical framework combined with physics-based modeling of the dose-dependent processes is here proposed and experimentally verified. This model enables an investigator to theoretically predict, in advance of an experimental measurement, the optimal electron dose resulting in an unambiguous quantification of nanostructures in their native state with the highest attainable precision.

Targeted T1 Magnetic Resonance Imaging Contrast Enhancement with Extraordinarily Small CoFe2O4 Nanoparticles.

Extraordinarily small (2.4 nm) cobalt ferrite nanoparticles (ESCIoNs) were synthesized by a one-pot thermal decomposition approach to study their potential as magnetic resonance imaging (MRI) contrast agents. Fine size control was achieved using oleylamine alone, and annular dark-field scanning transmission electron microscopy revealed highly crystalline cubic spinel particles with atomic resolution. Ligand exchange with dimercaptosuccinic acid rendered the particles stable in physiological conditions with a hydrodynamic diameter of 12 nm. The particles displayed superparamagnetic properties and a low r2/ r1 ratio suitable for a T1 contrast agent. The particles were functionalized with bile acid, which improved biocompatibility by significant reduction of reactive oxygen species generation and is a first step toward liver-targeted T1 MRI. Our study demonstrates the potential of ESCIoNs as T1 MRI contrast agents.

High dose efficiency atomic resolution imaging via electron ptychography.

Radiation damage places a fundamental limitation on the ability of microscopy to resolve many types of materials at high resolution. Here we evaluate the dose efficiency of phase contrast imaging with electron ptychography. The method is found to be far more resilient to temporal incoherence than conventional and spherical aberration optimized phase contrast imaging, resulting in significantly greater clarity at a given dose. This robustness is explained by the presence of achromatic lines in the four dimensional ptychographic dataset.

Low-Dose Aberration-Free Imaging of Li-Rich Cathode Materials at Various States of Charge Using Electron Ptychography.

Imaging the complete atomic structure of materials, including light elements, with minimal beam-induced damage of the sample is a long-standing challenge in electron microscopy. Annular bright-field scanning transmission electron microscopy is often used to image elements with low atomic numbers, but due to its low efficiency and high sensitivity to precise imaging parameters it comes at the price of potentially significant beam damage. In this paper, we show that electron ptychography is a powerful technique to retrieve reconstructed phase images that provide the full structure of beam-sensitive materials containing light and heavy elements. Due to its much higher efficiency, we can reduce the beam currents used down to the subpicoampere range. Electron ptychography also allows residual lens aberrations to be corrected at the postprocessing stage, which avoids the need for fine-tuning of the probe that would result in further beam damage and provides aberration-free reconstructed phase images. We have used electron ptychography to obtain structural information from aberration-free reconstructed phase images in the technologically relevant lithium-rich transition metal oxides at different states of charge. We can unambiguously determine the position of the lithium and oxygen atomic columns while amorphization of the surface, formation of beam-induced surface reconstruction layers, or migration of transition metals to the alkali layers are drastically reduced.

Determining EDS and EELS partial cross-sections from multiple calibration standards to accurately quantify bi-metallic nanoparticles using STEM.

Spectroscopic signals such as EDS and EELS provide an effective way of characterising multi-element samples such as Pt-Co nanoparticles in STEM. The advantage of spectroscopy over imaging is the ability to decouple composition and mass-thickness effects for thin samples, into the number of various types of atoms in a sample. This is currently not possible for multi element samples using conventional ADF quantification techniques alone. With recent developments in microscope hardware and software, it is now possible to acquire the ADF, EDS and EELS signals simultaneously and at high speed. However, the methods of quantifying the signals emitted from the sample vary greatly. Most approaches use pure-element standards in the form of needles, nanoparticles and wedges to quantify the spectroscopic signal into either partial scattering cross-sections, zeta-factors or k-factors. But self-consistency between the different methods has not been verified and the units of the quantification are not standardised. We present a robust approach for measuring and combining ADF, EDS and EELS signals using needle and nanoparticle standards in units of the partial scattering cross-section. The partial scattering cross-section allows an easy interpretation of the signals emitted from the sample and enables accurate atom-counting of the sample.

Managing dose-, damage- and data-rates in multi-frame spectrum-imaging.

As an instrument, the scanning transmission electron microscope is unique in being able to simultaneously explore both local structural and chemical variations in materials at the atomic scale. This is made possible as both types of data are acquired serially, originating simultaneously from sample interactions with a sharply focused electron probe. Unfortunately, such scanned data can be distorted by environmental factors, though recently fast-scanned multi-frame imaging approaches have been shown to mitigate these effects. Here, we demonstrate the same approach but optimized for spectroscopic data; we offer some perspectives on the new potential of multi-frame spectrum-imaging (MFSI) and show how dose-sharing approaches can reduce sample damage, improve crystallographic fidelity, increase data signal-to-noise, or maximize usable field of view. Further, we discuss the potential issue of excessive data-rates in MFSI, and demonstrate a file-compression approach to significantly reduce data storage and transmission burdens.

Electron ptychographic microscopy for three-dimensional imaging.

Knowing the three-dimensional structural information of materials at the nanometer scale is essential to understanding complex material properties. Electron tomography retrieves three-dimensional structural information using a tilt series of two-dimensional images. In this paper, we report an alternative combination of electron ptychography with the inverse multislice method. We demonstrate depth sectioning of a nanostructured material into slices with 0.34 nm lateral resolution and with a corresponding depth resolution of about 24-30 nm. This three-dimensional imaging method has potential applications for the three-dimensional structure determination of a range of objects, ranging from inorganic nanostructures to biological macromolecules.Three-dimensional ptychographic imaging with electrons has remained a challenge because, unlike X-rays, electrons are easily scattered by atoms. Here, Gao et al. extend multi-slice methods to electrons in the multiple scattering regime, paving the way to nanometer-scale 3D structure determination with electrons.