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

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.

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

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

Duncan Alexander, Pascal Fua, Cécile Hébert, Quentin Thomas Jeangros, Antoine Letouzey, Guillaume Lucas, Emadeddin Oveisi, Robin Schäublin

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.

2017

From 2D to 3D Characterization of Materials Subjected to Extreme Pressure and Temperature Conditions

Farhang Nabiei

Planetesimal were the first planetary objects to form in the solar system, which later grew to make the proto-planets. Most of these bodies were differentiated as a result of internal heating. Several differentiated bodies have, then, been accreted following the giant impacts to create the terrestrial planets. As a result of these impacts, the newly formed Earth was molten and completely differentiated. Subsequent crystallization has given rise to Earth's current structure. In order to bring new constraints on the differentiation and melting relationship in the planets we have studied natural and synthetic samples corresponding to different stages of planetary evolution through state of the art electron microscopy techniques. We have, first, looked at carbonaceous materials in a ureilite meteorite (Almahata Sitta MS-170). Thin sections from ureilite diamonds were prepared with the focused ion beam (FIB) are observed by transmission electron microscopy and spectroscopy. The morphology of graphite bands in diamonds indicated that they result from the diamond to graphite transformation during a shock event. Moreover, the diamonds in this meteorite with crystallite sizes as large as ~20 ÎŒm can only form under static high-pressure condition of planetary interiors. We have, also, found three types of diamond inclusions in our samples. The majority of these inclusions are euhedral Fe-S inclusions. However, each of these inclusions has three phases, namely: kamacite (Fe, Ni), troilite (FeS), and schreibersite ((Fe, Ni)3 P). The chemical analysis of the intact inclusions shows them to be a stoichiometric phase, (Fe, Ni)3(S, P), that can only form above 21 GPa. The ureilite parent body (UPB) should have had the size about that of Mars to exert necessary pressure to grow the diamond inclusions in the core-mantle boundary. The other two types of inclusions are the Al- and Mg- free chromite, Cr2FeO4, and Ca-Fe phosphates that were previously observed only in iron meteorites. Our results suggest that the diamonds and their inclusions were formed from an S-rich metallic liquid. In the second part of the thesis, we have studied melting and fractional crystallization of the lower mantle using a laser-heated diamond anvil cell (LH-DAC). San Carlos olivine is used as a proxy to the mantle composition. The recovered samples are first analyzed with the 3D chemical tomography using a dual beam FIB instrument. The molten region in all the samples at pressure range from 30 to 71 GPa have at least three distinct zones: a ferropericlase shell (Fp), an intermediate bridgmanite (Brg) region and the Fe-rich melt core. Thin sections from the center of the same samples are analyzed with TEM and energy-dispersive x-ray (EDX) spectroscopy. The results from the samples heated at 45 GPa for 1, 3, and 6 minutes demonstrated that the temperature gradient in the heated zone shrinks through the time and, thus, the crystallization continues toward the center of the heating. Consequently, the melt becomes richer in iron. The melt core also gets more iron-rich with increasing pressure. In fact, in ~70 GPa we observe an Fe-O core with small Si and Mg concentration. This implies that the melt at the bottom of the mantle could become denser than the solid phases and sink down. The presence of the iron-rich melt or the oxides crystallizing from such a melt can explain the ultra-low velocity zones (ULVZs) found in the seismic surveys of the core-mantle boundary.

EPFL2017

Characterization at the Atomistic Level of Defective Structures in Complex Materials

Piyush Agrawal

EPFL2017

From 2D to 3D Characterization of Materials Subjected to Extreme Pressure and Temperature Conditions

Farhang Nabiei

EPFL2017