Atomic-scale 3D imaging of individual dopant atoms in an oxide semiconductor.

The physical properties of semiconductors are controlled by chemical doping. In oxide semiconductors, small variations in the density of dopant atoms can completely change the local electric and magnetic responses caused by their strongly correlated electrons. In lightly doped systems, however, such variations are difficult to determine as quantitative 3D imaging of individual dopant atoms is a major challenge. We apply atom probe tomography to resolve the atomic sites that donors occupy in the small band gap semiconductor Er(Mn,Ti)O3 with a nominal Ti concentration of 0.04 at. %, map their 3D lattice positions, and quantify spatial variations. Our work enables atomic-level 3D studies of structure-property relations in lightly doped complex oxides, which is crucial to understand and control emergent dopant-driven quantum phenomena.

Improved electrochemical performance and solid electrolyte interphase properties of electrolytes based on lithium bis(fluorosulfonyl)imide for high content silicon anodes.

Electrodes containing 60 wt% micron-sized silicon were investigated with electrolytes containing carbonate solvents and either LiPF6 or lithium bis(fluorosulfonyl)imide (LiFSI) salt. The electrodes showed improved performance, with respect to capacity, cycling stability, rate performance, electrode resistance and cycle life with the LiFSI salt, attributed to differences in the solid electrolyte interphase (SEI). Through impedance spectroscopy, cross sectional analysis using transmission electron microscopy (TEM) and focused ion beam (FIB) in combination with scanning electron microscopy (SEM), and electrode surface characterization by X-ray photoelectron spectroscopy (XPS), differences in electrode morphological changes, SEI composition and local distribution of SEI components were investigated. The SEI formed with LiFSI has a thin, inner, primarily inorganic layer, and an outer layer dominated by organic components. This SEI appeared more homogeneous and stable, more flexible and with a lower resistivity than the SEI formed in LiPF6 electrolyte. The SEI formed in the LiPF6 electrolyte appears to be less passivating and less flexible, with a higher resistance, and with higher capacitance values, indicative of a higher interfacial surface area. Cycling in LiPF6 electrolyte also resulted in incomplete lithiation of silicon particles, attributed to the inhomogeneous SEI formed. In contrast to LiFSI, where LiF was present in small grains in-between the silicon particles, clusters of LiF were observed around the carbon black for the LiPF6 electrolyte.

Nanocrystal segmentation in scanning precession electron diffraction data.

Scanning precession electron diffraction (SPED) enables the local crystallography of materials to be probed on the nanoscale by recording a two-dimensional precession electron diffraction (PED) pattern at every probe position as a dynamically rocking electron beam is scanned across the specimen. SPED data from nanocrystalline materials commonly contain some PED patterns in which diffraction is measured from multiple crystals. To analyse such data, it is important to perform nanocrystal segmentation to isolate both the location of each crystal and a corresponding representative diffraction signal. This also reduces data dimensionality significantly. Here, two approaches to nanocrystal segmentation are presented, the first based on virtual dark-field imaging and the second on non-negative matrix factorization. Relative merits and limitations are compared in application to SPED data obtained from partly overlapping nanoparticles, and particular challenges are highlighted associated with crystals exciting the same diffraction conditions. It is demonstrated that both strategies can be used for nanocrystal segmentation without prior knowledge of the crystal structures present, but also that segmentation artefacts can arise and must be considered carefully. The analysis workflows associated with this work are provided open-source. LAY DESCRIPTION: Scanning precession electron diffraction is an electron microscopy technique that enables studies of the local crystallography of a broad selection of materials on the nanoscale. The technique involves the acquisition of a two-dimensional diffraction pattern for every probe position in an area of the sample. The four-dimensional dataset collected by this technique can typically comprise up to 500 000 diffraction patterns. For nanocrystalline materials, it is common that single diffraction patterns contain signals from overlapping crystals. To process such data, we use nanocrystal segmentation, where a representative diffraction pattern is constructed for each individual crystal, together with a real space image showing its morphology and location in the data. This reduces the dimensionality of the data and allows unmixing of signals from overlapping crystals. In this work, we demonstrate two methods for nanocrystal segmentation, one based on creating virtual dark-field images, and one based on unsupervised machine learning. A model system of partly overlapping nanoparticles is used to demonstrate the segmentation, and a demanding case for segmentation is highlighted, where some crystals are not discernible based on their diffraction patterns. To obtain a more complete nanocrystal segmentation, we add an image segmentation routine to both methods, and we discuss benefits and limitations of the two methods. The demonstration data and the used code are provided open-source, so that it can be used by everyone for analysis of nanocrystalline materials or as a starting point for further development of nanocrystal segmentation in scanning precession electron diffraction data.

Atomic resolution imaging of beryl: an investigation of the nano-channel occupation.

Beryl in different varieties (emerald, aquamarine, heliodor etc.) displays a wide range of colours that have fascinated humans throughout history. Beryl is a hexagonal cyclo-silicate (ring-silicate) with channels going through the crystal along the c-axis. The channels are about 0.5 nm in diameter and can be occupied by water and alkali ions. Pure beryl (Be3 Al2 Si6 O18 ) is colourless (variety goshenite). The characteristic colours are believed to be mainly generated through substitutions with metal atoms in the lattice. Which atoms that are substituted is still debated it has been proposed that metal ions may also be enclosed in the channels and that this can also contribute to the crystal colouring. So far spectroscopy studies have not been able to fully answer this. Here we present the first experiments using atomic resolution scanning transmission electron microscope imaging (STEM) to investigate the channel occupation in beryl. We present images of a natural beryl crystal (variety heliodor) from the Bin Thuan Province in Vietnam. The channel occupation can be visualized. Based on the image contrast in combination with ex situ element analysis we suggest that some or all of the atoms that are visible in the channels are Fe ions.