Phase retrieval from 4-dimensional electron diffraction datasets

We present a computational imaging mode for large scale electron microscopy data, which retrieves a complex wave from noisy/sparse intensity recordings using a deep learning approach and subsequently reconstructs an image of the specimen from the Convolutional Neural Network (CNN) predicted exit waves. We demonstrate that an appropriate forward model in combination with open data frameworks can be used to generate large synthetic datasets for training. In combination with augmenting the data with Poisson noise corresponding to varying dose-values, we effectively eliminate overfitting issues. The U-NET based architecture of the CNN is adapted to the task at hand and performs well while maintaining a relatively small size and fast performance. The validity of the approach is confirmed by comparing the reconstruction to well-established methods using simulated, as well as real electron microscopy data. The proposed method is shown to be effective particularly in the low dose range, evident by strong suppression of noise, good spatial resolution, and sensitivity to different atom types, enabling the simultaneous visualisation of light and heavy elements and making different atomic species distinguishable. Since the method acts on a very local scale and is comparatively fast it bears the potential to be used for near-real-time reconstruction during data acquisition.Comment: Accepted conference paper of IEEE ICIP 202

Fast generation of calculated ADF-EDX scattering cross-sections under channelling conditions

Advanced materials often consist of multiple elements which are arranged in a complicated structure. Quantitative scanning transmission electron microscopy is useful to determine the composition and thickness of nanostructures at the atomic scale. However, significant difficulties remain to quantify mixed columns by comparing the resulting atomic resolution images and spectroscopy data with multislice simulations where dynamic scattering needs to be taken into account. The combination of the computationally intensive nature of these simulations and the enormous amount of possible mixed column configurations for a given composition indeed severely hamper the quantification process. To overcome these challenges, we here report the development of an incoherent non-linear method for the fast prediction of ADF-EDX scattering cross-sections of mixed columns under channelling conditions. We first explain the origin of the ADF and EDX incoherence from scattering physics suggesting a linear dependence between those two signals in the case of a high-angle ADF detector. Taking EDX as a perfect incoherent reference mode, we quantitatively examine the ADF longitudinal incoherence under different microscope conditions using multislice simulations. Based on incoherent imaging, the atomic lensing model previously developed for ADF is now expanded to EDX, which yields ADF-EDX scattering cross-section predictions in good agreement with multislice simulations for mixed columns in a core-shell nanoparticle and a high entropy alloy. The fast and accurate prediction of ADF-EDX scattering cross-sections opens up new opportunities to explore the wide range of ordering possibilities of heterogeneous materials with multiple elements

Mapping electronic reconstruction at the metal/insulator interfaces in \ce{LaVO_3/SrVO_3} heterostructures

A \ce{(LaVO_3)_6/(SrVO_3)_3} superlattice is studied with a combination of sub-{\AA} resolved scanning transmission electron microscopy and monochromated electron energy-loss spectroscopy. The V oxidation state is mapped with atomic spatial resolution enabling to investigate electronic reconstruction at the \ce{LaVO_3}/\ce{SrVO_3} interfaces. Surprisingly, asymmetric charge distribution is found at adjacent chemically symmetric interfaces. The local structure is proposed and simulated with double channeling calculation which agrees qualitatively with our experiment. We demonstrate that local strain asymmetry is the likely cause of the electronic asymmetry of the interfaces. The electronic reconstruction at the interfaces extends much further than the chemical composition, varying from 0.5 to 1.2 nm. This distance corresponds to the length of charge transfer previously found in the \ce{(LaVO_3)_m}/\ce{(SrVO_3)_n} metal/insulating and the \ce{(LaAlO_3)_m}/\ce{(SrTiO_3)_n} insulating/insulating interfaces.Comment: 6 pages, 5 figures. Physical Review B, 201

In-situ Plasma Studies using a Direct Current Microplasma in a Scanning Electron Microscope

Microplasmas can be used for a wide range of technological applications and to improve our understanding of fundamental physics. Scanning electron microscopy, on the other hand, provides insights into the sample morphology and chemistry of materials from the mm-down to the nm-scale. Combining both would provide direct insight into plasma-sample interactions in real-time and at high spatial resolution. Up till now, very few attempts in this direction have been made, and significant challenges remain. This work presents a stable direct current glow discharge microplasma setup built inside a scanning electron microscope. The experimental setup is capable of real-time in-situ imaging of the sample evolution during plasma operation and it demonstrates localized sputtering and sample oxidation. Further, the experimental parameters such as varying gas mixtures, electrode polarity, and field strength are explored and experimental $V$-$I$ curves under various conditions are provided. These results demonstrate the capabilities of this setup in potential investigations of plasma physics, plasma-surface interactions, and materials science and its practical applications. The presented setup shows the potential to have several technological applications, e.g., to locally modify the sample surface (e.g., local oxidation and ion implantation for nanotechnology applications) on the $\mu$m-scale.Comment: LG, DC, and RDM contributed equally to this work. The videos mentioned in the manuscript can be found in the Zenodo repository linked in the pape

Direct Observation of Ferrielectricity at Ferroelastic Domain Boundaries in CaTiO3 by Electron Microscopy

High-resolution aberration-corrected transmission electron microscopy aided by statistical parameter estimation theory is used to quantify localized displacements at a (110) twin boundary in orthorhombic CaTiO3. The displacements are 3–6 pm for the Ti atoms and confined to a thin layer. This is the first direct observation of the generation of ferroelectricity by interfaces inside this material which opens the door for domain boundary engineering.\ud \ud Graphical Abstract: http://onlinelibrary.wiley.com/store/10.1002/adma.201103717/asset/image_m/mcontent.jpg?v=1&s=833d8771f847e356acb7c65dffc61a359098e66

Synthesis of diarylamines in the benzo[b]thiophene series bearing electron donating or withdrawing groups by Buchwald–Hartwig C–N coupling

Diarylamines in the benzo[b]thiophene series bearing electron donating or withdrawing groups, were prepared by Buchwald– Hartwig C–N coupling in moderate to high yields. The conditions used were Pd(OAc)2 (3 mol%), BINAP as ligand (4 mol%) and Cs2CO3 as base (1.4 equiv.), in toluene at 1008C, being 6-bromo or amino benzo[b]thiophenes coupled, respectively, with substituted anilines or phenylbromides. The 6-aminobenzo[b]thiophene derivatives were also prepared by palladium catalyzed C–N coupling of the corresponding 6-bromo compounds with benzophenone imine, followed by acidic hydrolysis of the imino derivatives. When 4-nitrobromobenzene and 4-bromobenzonitrile were used as coupling components, triarylamines were also isolated in small amounts. The presence of a fluorine atom on the phenylbromide highly increases the diarylamine yield

Interface Pattern Engineering in Core-Shell Upconverting Nanocrystals: Shedding Light on Critical Parameters and Consequences for the Photoluminescence Properties

Advances in controlling energy migration pathways in core-shell lanthanide (Ln)-based hetero-nanocrystals (HNCs) have relied heavily on assumptions about how optically active centers are distributed within individual HNCs. In this article, it is demonstrated that different types of interface patterns can be formed depending on shell growth conditions. Such interface patterns are not only identified but also characterized with spatial resolution ranging from the nanometer- to the atomic-scale. In the most favorable cases, atomic-scale resolved maps of individual particles are obtained. It is also demonstrated that, for the same type of core-shell architecture, the interface pattern can be engineered with thicknesses of just 1 nm up to several tens of nanometers. Total alloying between the core and shell domains is also possible when using ultra-small particles as seeds. Finally, with different types of interface patterns (same architecture and chemical composition of the core and shell domains) it is possible to modify the output color (yellow, red, and green-yellow) or change (improvement or degradation) the absolute upconversion quantum yield. The results presented in this article introduce an important paradigm shift and pave the way toward the emergence of a new generation of core-shell Ln-based HNCs with better control over their atomic-scale organization

Preventing cation intermixing enables 50% quantum yield in sub-15 nm short-wave infrared-emitting rare-earth based core-shell nanocrystals

Short-wave infrared (SWIR) fluorescence could become the new gold standard in optical imaging for biomedical applications due to important advantages such as lack of autofluorescence, weak photon absorption by blood and tissues, and reduced photon scattering coefficient. Therefore, contrary to the visible and NIR regions, tissues become translucent in the SWIR region. Nevertheless, the lack of bright and biocompatible probes is a key challenge that must be overcome to unlock the full potential of SWIR fluorescence. Although rare-earth-based core-shell nanocrystals appeared as promising SWIR probes, they suffer from limited photoluminescence quantum yield (PLQY). The lack of control over the atomic scale organization of such complex materials is one of the main barriers limiting their optical performance. Here, the growth of either homogeneous (α-NaYF$_4$) or heterogeneous (CaF$_2$) shell domains on optically-active α-NaYF$_4$:Yb:Er (with and without Ce$^{3+}$ co-doping) core nanocrystals is reported. The atomic scale organization can be controlled by preventing cation intermixing only in heterogeneous core-shell nanocrystals with a dramatic impact on the PLQY. The latter reached 50% at 60 mW/cm$^2$; one of the highest reported PLQY values for sub-15 nm nanocrystals. The most efficient nanocrystals were utilized for in vivo imaging above 1450 nm