Stavros Nicolopoulos

Automated nanocrystal orientation and phase mapping in the transmission electron microscope on the basis of precession electron diffraction

Abstract An automated technique for the mapping of nanocrystal phases and orientations in a transmission electron microscope is described. It is primarily based on the projected reciprocal lattice geometry that is extracted from electron diffraction spot patterns. Precession electron diffraction patterns are especially useful for this purpose. The required hardware allows for a scanning-precession movement of the primary electron beam on the crystalline sample and can be interfaced to any older or newer mid-voltage transmission electron microscope (TEM). Experimentally obtained crystal phase and orientation maps are shown for a variety of samples. Comprehensive commercial and open-access crystallographic databases may be used in support of the nanocrystal phase identification process and are briefly mentioned.

Precession Electron Diffraction Assisted Orientation Mapping in the Transmission Electron Microscope

Precession electron diffraction (PED) is a new promising technique for electron diffraction pattern collection under quasi-kinematical conditions (as in X-ray Diffraction), which enables “ab-initio” solving of crystalline structures of nanocrystals. The PED technique may be used in TEM instruments of voltages 100 to 400 kV and is an effective upgrade of the TEM instrument to a true electron diffractometer. The PED technique, when combined with fast electron diffraction acquisition and pattern matching software techniques, may also be used for the high magnification ultra-fast mapping of variable crystal orientations and phases, similarly to what is achieved with the Electron Backscattered Diffraction (EBSD) technique in Scanning Electron Microscopes (SEM) at lower magnifications and longer acquisition times.

Fast electron diffraction tomography

A fast and fully automatic procedure for collecting electron diffraction tomography data is presented. In the case of a very stable goniometer it is demonstrated how, by variation of the tilting speed and the CCD detector parameters, it is possible to obtain fully automatic precession-assisted electron diffraction tomography data collections, rotation electron diffraction tomography data collections or new integrated electron diffraction tomography data collections, in which the missing wedge of the reciprocal space between the patterns is recorded by longer exposures during the crystal tilt. It is shown how automatic data collection of limited tilt range can be used to determine the unit-cell parameters, while data of larger tilt range are suitable to solve the crystal structure ab initio with direct methods. The crystal structure of monoclinic MgMoO4 has been solved in this way as a test structure. In the case where the goniometer is not stable enough to guarantee a steady position of the crystal over large tilt ranges, an automatic method for tracking the crystal during continuous rotation of the sample is proposed.

Orientation and Phase Mapping in TEM Microscopy (EBSD-TEM Like): Applications to Materials Science

EBSD is a well known technique that allows orientation and phase mapping using an SEM. Although the technique is very powerful, has serious limitations related with a) special resolution limited to 50 nm (SEM-FEG) and b) specimen preparation issues as is not possible to obtain EBSD signal from rough surfaces or strained materials , nanoparticles etc.. To address those difficulties , a novel technique has been developed recently (EBSD-TEM like) allowing automatic orientation and phase mapping using template matching analysis of acquired diffraction patterns in TEM. Electron beam is scanned through the sample area of interest ; the acquired electron diffraction patterns from several sample locations are compared via cross-correlation matching techniques with pre-calculted simulated templates to reveal local crystal orientation and phases. The dedicated device (ASTAR) allows orientation and phase identification of crystallographic orientation in a region of interest up to 10µm2, with a step size ranging from 1nm to 20nm depending on the transmission electron microscope setting (FEG or LaB6).

Precession electron diffraction & automated crystallite orientation/phase mapping in a transmission electron microscope

The basics of precession electron diffraction (PED) in a transmission electron microscope (TEM) are briefly discussed. An automated system for the mapping of nanocrystal phases and orientations in a TEM is briefly described. This system is primarily based on the projected reciprocal lattice geometry as extracted from experimental precession electron diffraction spot patterns. Comprehensive open-access crystallographic databases may be used in support of the automated crystallite phase identification process and are, therefore, also briefly mentioned.

Hafnium-silicon precipitate structure determination in a new heat-resistant ferritic alloy by precession electron diffraction techniques.

The structure determination of an HfSi4 precipitate has been carried out by a combination of two precession electron diffraction techniques: high precession angle, 2.2°, single pattern collection at eight different zone axes and low precession angle, 0.5°, serial collection of patterns obtained by increasing tilts of 1°. A three-dimensional reconstruction of the associated reciprocal space shows an orthorhombic unit cell with parameters a = 11.4 Å, b = 11.8 Å, c = 14.6 Å, and an extinction condition of (hkl) h + k odd. The merged intensities from the high angle precession patterns have been symmetry tested for possible space groups (SG) fulfilling this condition and a best symmetrization residual found at 18% for SG 65 Cmmm. Use of the SIR2011 direct methods program allowed solving the structure with a structure residual of 18%. The precipitate objects of this study were reproducibly found in a newly implemented alloy, designed according to molecular orbital theory.

Precession electron diffraction and its utility for structural fingerprinting in the transmission electron microscope

Precession electron diffraction (PED) in a transmission electron microscope (TEM) is discussed in order to illustrate its utility for structural fingerprinting of nanocrystals. While individual nanocrystals may be fingerprinted structurally from PED spot patterns, ensembles of nanocrystals may be fingerprinted from powder PED ring patterns.

Electron Microscopy and Electron Energy-Loss Spectroscopy Study of Nd 1− x Sr x CoO 3− δ (0≤ x ≤1) System

A solid solution of Nd 1-x Sr x CoO 3-δ (with x=0, 1/3, 2/3, and 1) has been prepared and characterized by a combination of X-ray diffraction, electron microscopy, and electron energy-loss spectroscopy (EELS). The structural characterization indicates that Nd-doped materials present an orthorhombic symmetry with a=√2xa p, b=√2xa p, and c=2xa p (a p refers to lattice parameter of simple cubic perovskite), while SrCoO2.5 has an orthorhombic symmetry with a=√2xa p, b=4xa p, and c=√2xa p. EELS analysis revealed that Co are in 3+ oxidation states but in different spin configurations.

TEM Random & Ultra-fast Precession ED Tomography for analysis of nm crystals

Since the invention of Precession Electron Diffraction (PED) in Transmission Electron Microscopy (TEM) by Vincent & Midgley [1] in 1994 and mainly after the introduction of dedicated PED devices to different TEM, the structure of various nano-sized crystals have been solved by Electron Crystalography. The most popular technique that was recently developed based on beam precession is the 3D Precession Diffraction Tomography (PEDT) [2]. A series of ED patterns are collected every 1° while the sample is tilted around the goniometer axis. By the automatic measurement of ED intensities (ADT 3D software), the unit cell, crystal symmetry and the detailed crystal structure can be determined. A large number of crystal structures, such as complex metals, alloys, organic pigments, MOF, catalysts etc., have been solved by the 3D PEDT technique. A drawback of 3D PEDT (especially for beam sensitive materials) is the long acquisition times (45–120 min), due to the time consuming step of tracking the crystal under the beam during tilting. To deal with this problem, we have developed two novel approaches: the Random Electron Diffraction Tomography (rPEDT) technique and the UltraFast 3D diffraction tomography (UF PEDT) [3]. By rPEDT technique, a sample area (few microns), where several crystals in different (random) orientations are present, is scanned rapidly using an ASTAR precession device (NanoMEGAS SPRL). PED patterns of all scanned crystals are collected by a fast speed CCD camera (up to 120 frames/sec; 8/12 bit). Concerning UF PEDT, the data acquisition time can be 10-20 times faster compared to hitherto 3D PEDT procedure. UF PEDT can be applied when the crystal shift is stable and reproducible during tilting the sample for a specific tilt range. Thus, such crystals can be tracked by shifting the beam following the crystal displacement during tilting (using ASTAR beam scanning). Obtained PED patterns can be recorded with a fast CCD camera, while crystal is tilted. As a conclusion, rPEDT and UF-PEDT can be considered as breakthrough techniques in electron crystallography as they can be performed in any commercial TEM. Both techniques reduce considerable 3D intensity data acquisition time, and allow the analysis of unknown compounds, including beam sensitive organic crystals, as fast techniques prevents crystal beam damage. The authors acknowledge financial support from EU ESTEEM-2 project (European Network for Electron Microscopy www.esteem2.eu).

Automated crystal phase and orientation mapping of nanocrystals in a transmission electron microscope

An automated technique for the mapping of nanocrystal phases and orientations in a transmission electron microscope (TEM) is described. It is based on the projected reciprocal lattice geometry that is extracted from electron diffraction spot patterns. The required hardware allows for a scanning‐precession movement of the primary electron beam on the crystalline sample and can be interfaced to any newer or older TEM. The software that goes with this hardware is flexible in its intake of raw data so that it can also create orientation and phase maps of nanocrystal from high resolution TEM (HRTEM) images. When the nanocrystals possess a structure with a small to medium sized unit cell, e.g. noble metals or minerals that possess the halite structural prototype, an objective‐lens aberration corrected microscope needs to be utilize for the recording of the HRTEM images that are to be processed by this software. Experimentally obtained crystal phase and orientation maps are shown for iron oxide and clausthalite ...