Tilt-less 3-D electron imaging and reconstruction of complex curvilinear structures

The ability to obtain three-dimensional (3-D) information about morphologies of nanostructures elucidates many interesting properties of materials in both physical and biological sciences. Here we demonstrate a novel method in scanning transmission electron microscopy (STEM) that gives a fast and reliable assessment of the 3-D configuration of curvilinear nanostructures, all without needing to tilt the sample through an arc. Using one-dimensional crystalline defects known as dislocations as a prototypical example of a complex curvilinear object, we demonstrate their 3-D reconstruction two orders of magnitude faster than by standard tilt-arc TEM tomographic techniques, from data recorded by selecting different ray paths of the convergent STEM probe. Due to its speed and immunity to problems associated with a tilt arc, the tilt-less 3-D imaging offers important advantages for investigations of radiation-sensitive, polycrystalline, or magnetic materials. Further, by using a segmented detector, the total electron dose is reduced to a single STEM raster scan acquisition; our tilt-less approach will therefore open new avenues for real-time 3-D electron imaging of dynamic processes.

Characterization at the Atomistic Level of Defective Structures in Complex Materials

Piyush Agrawal

Defects are key to enhance or deploy particular materials properties. In this thesis I present analyses of the impact of defects on the electronic structure of materials using combined experimental and theoretical Electron energy loss spectroscopy (EELS) in (Scanning) Transmission Electron Microscopy. The energy loss near-edge structure (ELNES) in EELS reflects the element-specific electronic structure providing insights into bonding characteristics of individual atomic species. New electron optical devices have boosted the analytical capabilities by which materials can be investigated with atomic resolution and single atom sensitivity using (scanning) transmission electron spectroscopy (STEM/TEM).With the help of aberration correctors for forming small electron probes, high intensity electron beams can nowadays be focused to clearly less than 100 pm which has enhanced the resolution and sensitivity in analytical scanning transmission electron microscopy (STEM). Various kinds of defects in different complex oxides were studied: point defects like oxygen vacancies in BiVO4 and SrMnO3, edge-dislocations in BiFeO3, and planar defects in GaAs. By comparison with experimental data, structures for these systems were proposed based on all-electron density functional theory (DFT) code Wien2k. By comparing theoretical calculations and experimental data, a pronounced surface reduction in the oxidation state of vanadium in BiVO4 from +5 to +4 was unveiled, which is due to a high density of oxygen vacancies, and its importance in potential application of BiVO4 in photoelectrochemical energy conversion. A similar study was performed on a series of SrMnO3 thin films with different epitaxial strain where theoretical investigations revealed the impact of oxygen non-stoichiometry and strain on the O-K ELNES. In the next study, molecular dynamics simulations were combined with FEFF-based EELS calculations and its comparison with experiments was helpful for the correct prediction of the edge dislocation core structure in BiFeO3. This study also confirmed the presence of Fe atoms in the core of the edge dislocation which possibly makes these defects ferromagnetic whereas the bulk structure is known to be antiferromagnetic. This thesis has established methodologies for utilizing different codes, illustrating how links between experimental and theoretical ELNES can be used in revealing structural information around defects and how defects affect materials properties. This tandem methodology of theory and experiments is applicable to various future materials where the reliable interpretation of EELS data is pivotal in unfolding mysteries of such technologically important materials.

EPFL2017

Advanced analytical electron microscopy applied to Solid Oxide Cell materials and their degradation

Stéphane François Jean Poitel

Electron microscopy offers a wide range of techniques to study materials. Environmental Scanning Electron Microscopy (ESEM), in particular, allows the characterisation of samples at high-temperature using a laser heating stage, and under various gaseous atmospheres leading to direct observation of the sample surface morphology dynamics in conditions that are close to those in real operating devices (i.e. at high temperature in various gases). Solid Oxide Fuel Cells (SOFC) operating around 800°C in both oxidising and reducing gases, with proven co-generation efficiencies of 90%, offer very promising solutions in the ongoing energy transition. However, production costs and materials degradation in those demanding operating conditions remain significant barriers to their large-scale deployment. Studying SOFC materials' degradation through a combination of ESEM with other advanced microscopy techniques fulfilled the double aim of demonstrating the power of an ESEM and improving the understanding of SOFC materials' degradation during operation. Two materials from the SOFC stack were selected for degradation case studies at around 800°C in oxidising/reducing gases: coated ferritic steel interconnect and Ni-YSZ anode. The objectives were to explore the parameters' influence (temperature, heating ramp, pressure, gas exposure...), set the boundaries and define the guidelines of the ESEM technique while demonstrating its capabilities. The two different materials sets were selected for their relevance both for the SOFC field and for their different specific characteristics allowing a wide range of experiments to be explored. A specific method for the study of the oxidation of coated steel was developed combining ESEM, Focused Ion Beam (FIB) and Scanning Transmission Electron Microscopy (STEM). Post-test segmentation of the in-situ observed images demonstrated the possibility to obtain quantitative data. FIB sample preparation from the exact site of ESEM observation allowed to correlate the underlying microstructure with the in-situ surface observation. Applying this method, oxidation mechanisms of several coatings were characterised and specific behaviours observed and explained such as the appearance of oxide ridges and the behaviour of a cerium barrier layer in case of cobalt-cerium coated steel. The heating ramp speed and the oxidation temperature were demonstrated to be crucial parameters to obtain the desired microstructure. The nitriding pretreatment of interconnect was investigated too and shows promising results for improving the steel oxidation resistance. Another combination of techniques was developed for the study of the Ni-YSZ anode by complementing the ESEM observation with continuous Mass Spectrometer (MS) acquisition. The first reduction of the NiO-YsZ anode was analysed under gas flows of hydrogen and hydrocarbons. Redox cycling effect on the anode microstructure was investigated and the resulting observations were in line with models from the literature for the reduction and re-oxidation kinetics. Finally, the demonstration of an active solid oxide cell in the microscope operating at more than 700°C under mixed gas paves the way to further possible studies approaching the device's observation in real operating conditions. Limitation of the ESEM techniques are discussed and recommendations for further improvements and perspectives given.

EPFL2020

Three-dimensional electron imaging of dislocations from a single sample tilt

Pascal Fua, Cécile Hébert, Antoine Letouzey, Emadeddin Oveisi

Linear crystal defects called dislocations are one of the most fascinating concepts in materials science that govern mechanical and optoelectronic properties of many materials across a broad range of application. Three-dimensional (3-D) study of dislocation network is in principle accessible by conventional tomographic and stereoscopic techniques in Transmission Electron Microscopy (TEM). In these techniques in general the need to tilt the specimen for acquiring image series over large tilt ranges remain however an intricate problem, in particular when diffraction contrast or sensitivity to electron beam are involved. Here, a novel method in scanning TEM (STEM) is presented that provides a reliable and fast assessment of the 3-D configuration of dislocations using data acquired from just one sample tilt. This technique acquires a stereoscopic pair of images by selecting different ray paths of a convergent illumination in STEM mode. The resulting images are then treated with a dedicated stereovision reconstruction algorithm, yielding a full 3-D reconstruction of dislocations arrangement. The success of this method is demonstrated by measurement of dislocation arrangements in two experimental cases.