Tatiana Gorelik

Towards automated diffraction tomography. Part II—Cell parameter determination

Automated diffraction tomography (ADT) allows the collection of three-dimensional (3d) diffraction data sets from crystals down to a size of only few nanometres. Imaging is done in STEM mode, and diffraction data are collected with quasi-parallel beam nanoelectron diffraction (NED). Here, we present a set of developed processing steps necessary for automatic unit-cell parameter determination from the collected 3d diffraction data. Cell parameter determination is done via extraction of peak positions from a recorded data set (called the data reduction path) followed by subsequent cluster analysis of difference vectors. The procedure of lattice parameter determination is presented in detail for a beam-sensitive organic material. Independently, we demonstrate a potential (called the full integration path) based on 3d reconstruction of the reciprocal space visualising special structural features of materials such as partial disorder. Furthermore, we describe new features implemented into the acquisition part.

Free-Standing Monolayer Two-Dimensional Supramolecular Organic Framework with Good Internal Order

Utilizing dynamic self-assembly and self-sorting to obtain large-area, molecularly precise monolayered structures represents a promising approach toward two-dimensional supramolecular organic frameworks (2D SOF) or 2D supramolecular polymers. So far, related approaches suffer from small domain sizes, fragility and weak long-range internal order. Here we report on the self-assembly of a host–guest enhanced donor–acceptor interaction, consisting of a tris(methoxynaphthyl)-substituted truxene spacer, and a naphthalene diimide substituted with N-methyl viologenyl moieties as donor and acceptor monomers, respectively, in combination with cucurbit[8]uril as host monomer toward monolayers of an unprecedented 2D SOF. Featuring orthogonal solubility, the participating molecules self-assemble at a liquid–liquid interface, yielding exceptionally large-area, insoluble films, which were analyzed by transmission electron microscopy, atomic force microscopy and optical microscopy to be monolayers with a thickness of 1.8 nm, homogeneously covering areas up to 0.25 cm2, and featuring the ability to be free-standing over holes of 10 μm2. Characterization with ultraviolet–visible absorption spectroscopy, solid-state nuclear magnetic resonance spectroscopy, infrared spectroscopy, and grazing incidence wide-angle X-ray scattering allowed for confirmation of a successful complexation of all three monomers toward an internal long-range order and gave indications to an expected hexagonal superstructure. Our results extend the existing variety of two-dimensional soft nanomaterials by a versatile supramolecular approach, whereas the possibility of varying the functional monomers is supposed to open adaptability to different applications like membranes, sensors, molecular sieves, and optoelectronics.

Structural Characterization of Organics Using Manual and Automated Electron Diffraction

In the last decade the importance of transmission electron microscopic studies has become increasingly important with respect to the characterization of organic materials, ranging from small organic molecules to polymers and biological macromolecules. This review will focus on the use of transmission electron microscope to perform electron crystallography experiments, detailing the approaches in acquiring electron crystallographic data. The traditional selected area approach and the recently developed method of automated diffraction tomography (ADT) will be discussed with special attention paid to the handling of electron beam sensitive organic materials.

Carbon onions produced by laser irradiation of amorphous silicon carbide

Abstract Onion-like carbon clusters embedded in crystalline SiC were observed after laser-induced crystallization of amorphous SiC and a process of their formation has been suggested. The carbon onions have a size in the range of 5–30 nm. The shells are defective with interplanar distances about 0.37 nm.

Chromium–scandium multilayer mirrors for the nitrogen K α line in the water window region

Chromium-scandium (Cr-Sc) is a promising material combination for multilayer mirrors in the water window region. A possible x-ray source for laboratory use in this wavelength range is the nitrogen K(alpha) line at 3.16 nm. High reflectivities at this wavelength can be achieved with Cr-Sc multilayer mirrors if the interfaces between adjacent layers are smooth. The growth parameters of the magnetron sputtering process for these materials have been optimized. It is shown that the reflectivity of such mirrors can be considerably improved by the application of a proper bias voltage during film growth. The high quality of the multilayer films is demonstrated with copper K(alpha) x-ray reflection and transmission electron microscopy. The reflective properties of the multilayers close to the nitrogen K(alpha) line were measured with synchrotron radiation for different angles of incidence. Reflectivities between R = 5.9% for near-normal incidence (theta = 1.5 degrees) and R = 29.6% for theta = 59.9 degrees were measured.

Nanocrystal formation in SiC by Ge ion implantation and subsequent thermal annealing

Ge nanocrystals were produced in 4H–SiC by implantation of 250 keV Ge+ ions with a dose of 1×1016 cm−2 and subsequent rapid thermal annealing at 1400–1600 °C. Radiation damage and Ge distribution after implantation and annealing were analyzed by Rutherford backscattering spectrometry, cross-sectional transmission electron microscopy methods, and x-ray diffraction. After ion implantation a significant amount of Ge is incorporated into the SiC lattice and Ge nanocrystallites were not found. Thermal annealing leads to a local Ge redistribution and both Ge-rich and Ge nanocrystals are detected after annealing. The size of the nanocrystals varies between 2 and 10 nm.

Structure analysis of titanate nanorods by automated electron diffraction tomography.

A hitherto unknown phase of sodium titanate, NaTi(3)O(6)(OH)·2H(2)O, was identified as the intermediate species in the synthesis of TiO(2) nanorods. This new phase, prepared as nanorods, was investigated by electron diffraction, X-ray powder diffraction, thermogravimetric analysis and high-resolution transmission electron microscopy. The structure was determined ab initio using electron diffraction data collected by the recently developed automated diffraction tomography technique. NaTi(3)O(6)(OH)·2H(2)O crystallizes in the monoclinic space group C2/m. Corrugated layers of corner- and edge-sharing distorted TiO(6) octahedra are intercalated with Na(+) and water of crystallization. The nanorods are typically affected by pervasive defects, such as mutual layer shifts, that produce diffraction streaks along c*. In addition, edge dislocations were observed in HRTEM images.

Ab-initio crystal structure analysis and refinement approaches of oligo p-benzamides based on electron diffraction data

Ab-initio crystal structure analysis of organic materials from electron diffraction data is presented. The data were collected using the automated electron diffraction tomography (ADT) technique. The structure solution and refinement route is first validated on the basis of the known crystal structure of tri-p-benzamide. The same procedure is then applied to solve the previously unknown crystal structure of tetra-p-benzamide. In the crystal structure of tetra-p-benzamide, an unusual hydrogen-bonding scheme is realised; the hydrogen-bonding scheme is, however, in perfect agreement with solid-state NMR data.

Structure of the new mineral sarrabusite, Pb5CuCl4(SeO3)4, solved by manual electron-diffraction tomography

The new mineral sarrabusite Pb(5)CuCl(4)(SeO(3))(4) has been discovered in the Sardinian mine of Baccu Locci, near Villaputzu. It occurs as small lemon-yellow spherical aggregates of tabular crystals (< 10 µm) of less than 100 µm in diameter. The crystal structure has been solved from and refined against electron diffraction of a microcrystal. Data sets have been measured by both a manual and an automated version of the new electron-diffraction tomography technique combined with the precession of the electron beam. The sarrabusite structure is monoclinic and consists of (010) layers of straight chains formed by alternating edge-sharing CuO(4)Cl(2) and PbO(8) polyhedra parallel to the c axis, which share corners laterally with two zigzag corner-sharing chains of PbO(6)Cl(2) and PbO(4)Cl(4) bicapped trigonal prisms. These blocks are linked together by SeO(3)(2-) flat-pyramidal groups.

Structure solution with automated electron diffraction tomography data: different instrumental approaches

Over the past few years automated electron diffraction tomography has become an established technique for structure solution of nano‐crystalline material. The intentional choice of an arbitrary tilt axis and thus, the use of nonoriented diffraction patterns (off‐zone acquisition) together with fine equidistant sampling of the reciprocal space result in high quality intensity data sets. Coupling automated electron diffraction tomography with electron beam precession ( Vincent & Midgley, 1994 ) enables sampling of intensities between the static slices of reciprocal space and therefore enhances the quality of intensity data further; relatively complex structures have been solved using 3D electron diffraction intensities extracted from automated electron diffraction tomography data. Automated electron diffraction tomography data was collected initially using a dedicated automated module. In this manuscript we demonstrate that electron diffraction data of comparable quality can be collected using manual technique that mimics the automated process. A rather difficult material, i.e. a low symmetric (triclinic) sodium tetratungstate (Na2W4O13) including heavy and light scatterers, was selected for testing. In this paper we show, that all collected data sets – automatic and manual, with and without electron beam precession – were able to provide data slightly different but suitable for ab initio structure solution and refinement.