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We report on the automatic alignment of a transmission electron microscope equipped with an orbital angular momentum sorter using a convolutional neural network. The neural network is able to control all relevant parameters of both the electron-optical setup of the microscope and the external voltage source of the sorter without input from the user. It can compensate for mechanical and optical misalignments of the sorter, in order to optimize its spectral resolution. The alignment is completed over a few frames and can be kept stable by making use of the fast fitting time of the neural network.

The key to optimizing spatial resolution in a state-of-the-art scanning transmission electron microscope is the ability to precisely measure and correct for electron optical aberrations of the probe-forming lenses. Several diagnostic methods for aberration measurement and correction with maximum precision and accuracy have been proposed, albeit often at the cost of relatively long acquisition times. Here, we illustrate how artificial intelligence can be used to provide near-real-time diagnosis of aberrations from individual Ronchigrams. The demonstrated speed of aberration measurement is important as microscope conditions can change rapidly, as well as for the operation of MEMS-based hardware correction elements that have less intrinsic stability than conventional electromagnetic lenses., Comment: 18 pages, 5 figures, 1 table

Beam shaping - the ability to engineer the phase and the amplitude of massive and massless particles - has long interested scientists working on communication, imaging and the foundations of quantum mechanics. In light optics, the shaping of electromagnetic waves (photons) can be achieved using techniques that include, but are not limited to, direct manipulation of the beam source (as in X-ray Free Electron Lasers (XFELs) and Synchrotrons), deformable mirrors, spatial light modulators, mode converters and holograms. The recent introduction of holographic masks for electrons provides new possibilities for electron beam shaping. Their fabrication has been made possible by advances in micrometric and nanometric device production using lithography and focused ion beam patterning. This article provides a tutorial on the generation, production and analysis of synthetic holograms for transmission electron microscopy. It begins with an introduction to synthetic holograms, outlining why they are useful for beam shaping to study material properties. It then focuses on the fabrication of the required devices from theoretical and experimental perspectives, with examples taken from both simulations and experimental results. Applications of synthetic electron holograms as aberration correctors, electron vortex generators and spatial mode sorters are then presented.

•A deep convolutional neural network is used to evaluate and correct the alignment of an orbital angular momentum sorter.•The convolutional neural network automatically analyses OAM spectra at a rate of 50 ms/spectrum, allowing for real time implementation.•The method is easily transferable to any programmable beam shaping technique. A convolutional neural network is used to align an orbital angular momentum sorter in a transmission electron microscope. The method is demonstrated using simulations and experiments. As a result of its accuracy and speed, it offers the possibility of real-time tuning of other electron optical devices and electron beam shaping configurations.

Loss mechanisms in fluid heating of cobalt ferrite (CFO) nanoparticles and CFO–Pd heterodimer colloidal suspensions are investigated as a function of particle size, fluid concentration and magnetic field amplitude. The specific absorption rate (SAR) is found to vary with increasing particle size due to a change in dominant heating mechanism from susceptibility to hysteresis and frictional loss. The maximum SAR is obtained for particle diameters of 11–15 nm as a result of synergistic contributions of susceptibility loss, including Néel and Brownian relaxation and especially hysteresis loss, thereby validating the applicability of linear response theory to superparamagnetic CFO nanoparticles. Our results show that the ferrofluid concentration and magnetic field amplitude alter interparticle interactions and associated heating efficiency. The SAR of the CFO nanoparticles could be maximized by adjusting the synthesis parameters. Despite the paramagnetic properties of individual palladium nanoparticles, CFO–Pd heterodimer suspensions were observed to have surprisingly improved magnetization as well as SAR values, when compared with CFO ferrofluids. This difference is attributed to interfacial interactions between the magnetic moments of paramagnetic Pd and superparamagnetic/ferrimagnetic CFO. SAR values measured from CFO–Pd heterodimer suspensions were found to be 47–52 W gFerrite−1, which is up to a factor of two higher than the SAR values of commercially available ferrofluids, demonstrating their potential as efficient heat mediators. Our results provide insight into the utilization of CFO–Pd heterodimer suspensions as potential nanoplatforms for diagnostic and therapeutic biomedical applications, e.g., in cancer hyperthermia, cryopreserved tissue warming, thermoablative therapy, drug delivery and bioimaging.

The orbital angular momentum (OAM) sorter is a new electron optical device for measuring an electron s OAM. It is based on two phase elements, which are referred to as the unwrapper and corrector and are placed in Fourier conjugate planes in an electron microscope. The most convenient implementation of this concept is based on the use of electrostatic phase elements, such as a charged needle as the unwrapper and a set of electrodes with alternating charges as the corrector. Here, we use simulations to assess the role of imperfections in such a device, in comparison to an ideal sorter. We show that the finite length of the needle and the boundary conditions introduce astigmatism, which leads to detrimental cross-talk in the OAM spectrum. We demonstrate that an improved setup comprising three charged needles can be used to compensate for this aberration, allowing measurements with a level of cross-talk in the OAM spectrum that is comparable to the ideal case.

Loss mechanisms in fluid heating of cobalt ferrite (CFO) nanoparticles and CFO-Pd heterodimer colloidal suspensions are investigated as a function of particle size, fluid concentration and magnetic field amplitude. The specific absorption rate (SAR) is found to vary with increasing particle size due to a change in dominant heating mechanism from susceptibility to hysteresis and frictional loss. The maximum SAR is obtained for particle diameters of 11-15 nm as a result of synergistic contributions of susceptibility loss, including Neel and Brownian relaxation and especially hysteresis loss, thereby validating the applicability of linear response theory to superparamagnetic CFO nanoparticles. Our results show that the ferrofluid concentration and magnetic field amplitude alter interparticle interactions and associated heating efficiency. The SAR of the CFO nanoparticles could be maximized by adjusting the synthesis parameters. Despite the paramagnetic properties of individual palladium nanoparticles, CFO-Pd heterodimer suspensions were observed to have surprisingly improved magnetization as well as SAR values, when compared with CFO ferrofluids. This difference is attributed to interfacial interactions between the magnetic moments of paramagnetic Pd and superparamagnetic/ferrimagnetic CFO. SAR values measured from CFO-Pd heterodimer suspensions were found to be 47-52 W gFerrite-1, which is up to a factor of two higher than the SAR values of commercially available ferrofluids, demonstrating their potential as efficient heat mediators. Our results provide insight into the utilization of CFO-Pd heterodimer suspensions as potential nanoplatforms for diagnostic and therapeutic biomedical applications, e.g., in cancer hyperthermia, cryopreserved tissue warming, thermoablative therapy, drug delivery and bioimaging.

Electron energy-loss spectroscopy (EELS) is a powerful technique for measuring the energy state of electrons after scattering. It has had incredible success in measuring the atomic and chemical properties of materials, allowing chemical maps to be recorded with atomic spatial resolution. Energy information alone is often sufficient to obtain information about chemical species, plasmons or even phonon excitations, especially when using high-energy-resolution spectrometers and gun monochromators. However, it is sometimes desirable to add a second dispersion variable, either in the form of momentum and energy double-dispersion EELS, or by acquiring a spectrum for a given momentum transfer.

The structural and compositional properties of CdSe-ZnS core-shell quantum dots (QDs) with a sub-nm shell thickness are analyzed at the atomic scale using electron microscopy. QDs with both wurtzite and zinc blende crystal structures, as well as intermixing of the two structures and stacking faults, are observed. High-angle annular dark-field scanning transmission electron microscopy suggests the presence of a lower atomic number epitaxial shell of irregular thickness around a CdSe core. The presence of a shell is confirmed using energy dispersive X-ray spectroscopy. Despite the thickness irregularities, the optical properties of the particles, such as photoluminescence and quantum yield, show clear enhancement after growth of the ZnS shell.

A novel nanostructured cemented carbide formed from WC-5%Co-20%Ni-based brazing alloy is described. During sintering, the Ni-brazing alloy is infiltrated into a green compact of WC-5%Co at 1050–1100 °C for 2–60 min. Perfect wetting behavior and a zero contact angle are achieved after only 40 s. Relative densities of 98.5% and 100% and microhardness values of above 1500HV1 and 1800HV1 are obtained after 2 and 30 min, respectively. A change in mean particle size of 550–650 nm in the precursor to a bimodal distribution of 350–400 nm and 10–20 nm is explained by a solution/reprecipitation mechanism.

Developing convenient and reliable synthetic methodologies for solution processable 2D layered ultrathin nanostructures with lateral size control is one of the major challenges for practical applications. In this study, a rational understanding a long-chain amphiphilic surfactant assisted non-hydrolytic synthesis that is able to generate dimension-controllable 2D-WS

Lead halide (APbX3) perovskites, in polycrystalline thin films but also perovskite nanoparticles (NPs) has demonstrated excellent performance to implement a new generation of photovoltaic and photonic devices. The structural characterization of APbX3 thin films using (scanning) transmission electron microscopy ((S)TEM) techniques can provide valuable information that can be used to understand and model their optoelectronic performance and device properties. However, since APbX3 perovskites are soft materials, their characterization using (S)TEM is challenging. Here, we study and compare the structural properties of two different metal halide APbX3 perovskite thin films: bulk CH3NH3PbI3 prepared by spin-coating of the precursors in solution and CsPbBr3 colloidal NPs synthetized and deposited by doctor blading. Both specimen preparation methods and working conditions for analysis by (S)TEM are properly optimized. We show that CH3NH3PbI3 thin films grown by a one-step method are composed of independent grains with random orientations. The growth method results in the formation of tetragonal perovskite thin films with good adherence to an underlying TiO2 layer, which is characterized by a photoluminescence (PL) emission band centered at 775 nm. The perovskite thin films based on CsPbBr3 colloidal NPs, which are used as the building blocks of the film, are preserved by the deposition process, even if small gaps are observed between adjacent NPs. The crystal structure of CsPbBr3 NPs is cubic, which is beneficial for optical properties due to its optimal band gap. The absorption and PL spectra measured in both the thin film and the colloidal solution of CsPbBr3 NPs are very similar, indicating a good homogeneity of the thin films and the absence of aggregation of NPs. However, a particular care was required to avoid long electron irradiation times during our structural studies, even at a low voltage of 80 kV, as the material was observed to decompose through Pb segregation.

The key features of quantum mechanics are vividly illustrated by the Young-Feynman two-slit thought experiment, whose second part discusses the recording of an electron distribution with one of the two slits partially or totally closed by an aperture. Here, we realize the original Feynman proposal in a modern electron microscope equipped with a high brightness gun and two biprisms, with one of the biprisms used as a mask. By exciting the microscope lenses to conjugate the biprism plane with the slit plane, observations are carried out in the Fraunhofer plane with nearly ideal control of the covering of one of the slits. A second, new experiment is also presented, in which interference phenomena due to partial overlap of the slits are observed in the image plane. This condition is obtained by inserting the second biprism between the two slits and the first biprism and by biasing it in order to overlap their images. Published version

Two-dimensional transition-metal dichalcolgenides (2D-TMDs) are among the most intriguing materials for next-generation electronic and optoelectronic devices. Albeit still at the embryonic stage, building thin films by manipulating and stacking preformed 2D nanosheets is now emerging as a practical and cost-effective bottom-up paradigm to obtain excellent electrical properties over large areas. Herein, we exploit the ultrathin morphology and outstanding solution stability of 2D WS2 colloidal nanocrystals to make thin films of TMDs assembled on a millimetre scale by a layer-by-layer deposition approach. We found that a room-temperature surface treatment with a superacid, performed with the precise scope of removing the native insulating surfactants, promotes in-plane assembly of the colloidal WS2 nanoflakes into stacks parallel to the substrate, along with healing of sulphur vacancies in the lattice that are detrimental to electrical conductivity. The as-obtained 2D WS2 thin films, characterized by a smooth and compact morphology, feature a high planar conductivity of up to 1 μS, comparable to the values reported for epitaxially grown WS2 monolayers, and enable photocurrent generation upon light irradiation over a wide range of visible to near-infrared frequencies.

Vortices in electron beams can manifest several types of topological phenomena, such as the formation of exotic structures or interactions with topologically structured electromagnetic fields. For instance, the wavefunction of an electron beam can acquire a phase vortex upon propagating through a magnetic monopole, which, in practice, provides a convenient method for generating electron vortex beams. Here, we show how an electric field must be structured in order to achieve a similar effect. We find that, much as in the case of magnetic fields, closed but not exact electric fields can produce electron vortex beams. We proceed by fabricating a versatile near-obstruction-free device that is designed to approximately produce such fields and we systematically study their influence on incoming electron beams. With such a single device, electron vortex beams that are defined by a wide range of topological charges can be produced by means of a slight variation of an applied voltage. For this reason, this device is expected to be important in applications that rely on the sequential generation and manipulation of different types of electron vortices., Comment: 5 pages, 3 figures!

An absolute scale match between experiment and simulation in atomic-resolution off-axis electron holography is demonstrated, with unknown experimental parameters determined directly from the recorded electron wave function using an automated numerical algorithm. We show that the local thickness and tilt of a pristine thin WSe_{2} flake can be measured uniquely, whereas some electron optical aberrations cannot be determined unambiguously for a periodic object. The ability to determine local specimen and imaging parameters directly from electron wave functions is of great importance for quantitative studies of electrostatic potentials in nanoscale materials, in particular when performing in situ experiments and considering that aberrations change over time.

The magnetic properties of nanowires (NWs) and square nanorings, which were deposited by focused electron beam induced deposition (FEBID) of a Co carbonyl precursor, are studied using off-axis electron holography (EH), Lorentz transmission electron microscopy (L-TEM) and magnetic force microscopy (MFM). EH shows that NWs deposited using beam energies of 5 and 15 keV have the characteristics of magnetic dipoles, with larger magnetic moments observed for NWs deposited at lower energy. L-TEM is used to image magnetic domain walls in NWs and nanorings and their motion as a function of applied magnetic field. The NWs are found to have almost square hysteresis loops, with coercivities of ca. 10 mT. The nanorings show two different magnetization states: for low values of the applied in-plane field (0.02 T) a horseshoe state is observed using L-TEM, while for higher values of the applied in-plane field (0.3 T) an onion state is observed at remanence using L-TEM and MFM. Our results confirm the suitability of FEBID for nanofabrication of magnetic structures and demonstrate the versatility of TEM techniques for the study and manipulation of magnetic domain walls in nanostructures.

In order to obtain a fundamental understanding of the interplay between charge, spin, orbital and lattice degrees of freedom in magnetic materials and to predict and control their physical properties1–3, experimental techniques are required that are capable of accessing local magnetic information with atomic-scale spatial resolution. Here, we show that a combination of electron energy-loss magnetic chiral dichroism 4 and chromatic-aberration-corrected transmission electron microscopy, which reduces the focal spread of inelastically scattered electrons by orders of magnitude when compared with the use of spherical aberration correction alone, can achieve atomic-scale imaging of magnetic circular dichroism and provide element-selective orbital and spin magnetic moments atomic plane by atomic plane. This unique capability, which we demonstrate for Sr2FeMoO6, opens the door to local atomic-level studies of spin configurations in a multitude of materials that exhibit different types of magnetic coupling, thereby contributing to a detailed understanding of the physical origins of magnetic properties of materials at the highest spatial resolution. By combining electron energy-loss magnetic chiral dichroism and chromatic-aberration-corrected transmission electron microscopy, it becomes possible to achieve atomic-scale imaging of magnetic circular dichroism.

Nearly eighty years ago, Scherzer showed that rotationally symmetric, charge-free, static electron lenses are limited by an unavoidable, positive spherical aberration. Following a long struggle, a major breakthrough in the spatial resolution of electron microscopes was reached two decades ago by abandoning the first of these conditions, with the successful development of multipole aberration correctors. Here, we use a refractive silicon nitride thin film to tackle the second of Scherzer's constraints and demonstrate an alternative method for correcting spherical aberration in a scanning transmission electron microscope. We reveal features in Si and Cu samples that cannot be resolved in an uncorrected microscope. Our thin film corrector can be implemented as an immediate low cost upgrade to existing electron microscopes without re-engineering of the electron column or complicated operation protocols and can be extended to the correction of additional aberrations.

The quantitative analysis of electron-optical phase images recorded using off-axis electron holography often relies on the use of computer simulations of electron propagation through a sample. However, simulations that make use of the independent atom approximation are known to overestimate experimental phase shifts by approximately 10%, as they neglect bonding effects. Here, we compare experimental and simulated phase images for few-layer WSe_{2}. We show that a combination of pseudopotentials and all-electron density functional theory calculations can be used to obtain accurate mean electron phases, as well as improved atomic-resolution spatial distribution of the electron phase. The comparison demonstrates a perfect contrast match between experimental and simulated atomic-resolution phase images for a sample of precisely known thickness. The low computational cost of this approach makes it suitable for the analysis of large electronic systems, including defects, substitutional atoms, and material interfaces.

Electron energy-loss magnetic chiral dichroism is a powerful technique that allows the local magnetic properties of materials to be measured quantitatively with close-to-atomic spatial resolution and element specificity in the transmission electron microscope. Until now, the technique has been restricted to measurements of the magnetic circular dichroism signal in the electron beam direction. However, the intrinsic magnetization directions of thin samples are often oriented in the specimen plane, especially when they are examined in magnetic-field-free conditions in the transmission electron microscope. Here, we introduce an approach that allows in-plane magnetic signals to be measured using electron magnetic chiral dichroism by selecting a specific diffraction geometry. We compare experimental results recorded from a cobalt nanoplate with simulations to demonstrate that an electron magnetic chiral dichroism signal originating from in-plane magnetization can be detected successfully., Electron energy-loss magnetic chiral dichroism enables the measurement of the local magnetic properties of a material using a transmission electron microscope, but is limited to signals in the electron-beam direction. Here, the authors demonstrate a method to extend this to in-plane magnetic signals too.

Electron waves that carry orbital angular momentum (OAM) are characterized by a quantized and unbounded magnetic dipole moment parallel to their propagation direction. When interacting with magnetic materials, the wavefunctions of such electrons are inherently modified. Such variations therefore motivate the need to analyse electron wavefunctions, especially their wavefronts, to obtain information regarding the material's structure. Here, we propose, design and demonstrate the performance of a device based on nanoscale holograms for measuring an electron's OAM components by spatially separating them. We sort pure and superposed OAM states of electrons with OAM values of between −10 and 10. We employ the device to analyse the OAM spectrum of electrons that have been affected by a micron-scale magnetic dipole, thus establishing that our sorter can be an instrument for nanoscale magnetic spectroscopy., Existing methods of characterizing electron beams carrying orbital angular momentum are inefficient as they allow measuring one OAM state at a time. Here the authors demonstrate an OAM spectrometer capable of analysing multiple OAM states and a potential tool for probing magnetic materials.

Free electron beams that carry high values of orbital angular momentum (OAM) possess large magnetic moments along the propagation direction. This makes them an ideal probe for measuring the electronic and magnetic properties of materials, as well as for fundamental experiments in magnetism. However, their generation requires the use of complex diffractive elements, which usually take the form of nano-fabricated holograms. Here, we show how the limitations of the current fabrication of such holograms can be overcome by using electron beam lithography. We demonstrate experimentally the realization of an electron vortex beam with the largest OAM value that has yet been reported to the first diffraction order (L = 1000 ℏ), paving the way for even more demanding demonstrations and applications of electron beam shaping.

The phase and amplitude of the electron wavefunction that has passed through ultra-thin flakes of WSe

Silicon oxide-based resistive switching devices show great potential for applications in nonvolatile random access memories. We expose a device to voltages above hard breakdown and show that hard oxide breakdown results in mixing of the SiOx layer and the TiN lower contact layers. We switch a similar device at sub-breakdown fields in situ in the transmission electron microscope (TEM) using a movable probe and study the diffusion mechanism that leads to resistance switching. By recording bright-field (BF) TEM movies while switching the device, we observe the creation of a filament that is correlated with a change in conductivity of the SiOx layer. We also examine a device prepared on a microfabricated chip and show that variations in electrostatic potential in the SiOx layer can be recorded using off-axis electron holography as the sample is switched in situ in the TEM. Taken together, the visualization of compositional changes in ex situ stressed samples and the simultaneous observation of BF TEM contrast variations, a conductivity increase, and a potential drop across the dielectric layer in in situ switched devices allow us to conclude that nucleation of the electroforming—switching process starts at the interface between the SiOx layer and the lower contact.

Off-axis electron holography has been extended to in situ observations in gas atmospheres. The Yttria-stabilized zirconia (YSZ)-Pt hetero-interface was characterized by electron holography at high temperature in a vacuum and in an oxygen atmosphere. Analysis of the phase shift profiles revealed high mobility of anions in the oxide in the vicinity of the interface in the oxygen atmosphere. This would compensate for any increase in the number of oxygen vacancies in YSZ through the metal interface.

In Fig. 1 of the version of this Letter originally published, the word 'Subtract' was missing from the green box to the left of panel f. This has now been corrected in all versions of the Letter.

Novel caustic phenomena, which contain fold, butterfly and elliptic umbilic catastrophes, are observed in defocused images of two approximately collinear oppositely biased metallic tips in a transmission electron microscope. The observed patterns depend sensitively on defocus, on the applied voltage between the tips and on their separation and lateral offset. Their main features are interpreted on the basis of a projected electrostatic potential model for the electron-optical phase shift.

Recent progress in phase modulation using nanofabricated electron holograms has demonstrated how the phase of an electron beam can be controlled. In this paper, we apply this concept to the correction of spherical aberration in a scanning transmission electron microscope and demonstrate an improvement in spatial resolution. Such a holographic approach to spherical aberration correction is advantageous for its simplicity and cost-effectiveness., 5 pages, 2 figures

Recent advances in transmission electron microscopy and specimen preparation now permit the revival of an old idea, originally pioneered by Marton, of using single crystals as amplitude division beam splitters. As a first step in the direction of realizing a three crystal electron interferometer, we present results obtained from a double crystal interferometer, in which the gap between the two crystals is under experimental control and perfect registry is obtained by using focused ion beam milling to fabricate the interferometer from a single Si crystal. Published version

Solid oxide fuel cells (SOFCs) are promising candidates for use in alternative energy technologies. A full understanding of the reaction mechanisms in these dynamic material systems is required to optimize device performance and overcome present limitations. Here, we show that in situ transmission electron microscopy (TEM) can be used to study redox reactions and ionic conductivity in SOFCs in a gas environment at elevated temperature. We examine model ultrathin half and complete cells in two environmental TEMs using off-axis electron holography and electron energy-loss spectroscopy. Our results from the model cells provide insight into the essential phenomena that are important for the operation of commercial devices. Changes in the activities of dopant cations in the solid electrolyte are detected during oxygen anion conduction, demonstrating the key role of dopants in electrolyte architecture in SOFCs.

Figure 1 shows representative results acquired at 80 kV using off-axis electron holography from an MoS2 flake. The holographic interference fringe spacing was 30 pm and a mask corresponding to a spatial resolution of 90 pm was applied to the sideband (Fig. 1c) before reconstructing the phase image. Figure 1d shows part of a phase image reconstructed from the hologram, showing a two and three monolayer region of the flake and the presence of some contamination at the specimen edge.

Redox reactions were studied at a single yttria-stabilized zirconia (YSZ)/Pt electrode interface, in parallel with pure YSZ with no catalyst electrode, by in situ analytical electron microscopy at elevated temperatures and in an oxygen atmosphere. In situ electron holography showed that the oxide underwent reduction at elevated temperatures in a vacuum and was consequently reoxidized upon exposure to an oxygen flux at the same temperature. In situ energy loss spectroscopy measurements were in agreement with in situ electron holography observations and indicated that the oxidation state of the host cation zirconium was altered in the reduced state of the YSZ to the metastable state Zr3+.

Extended abstract of a paper presented at Microscopy and Microanalysis 2013 in Indianapolis, Indiana, USA, August 4 – August 8, 2013.