Near-Atomic-Scale Mapping of Electronic Phases in Rare Earth Nickelate Superlattices

Nanoscale mapping of the distinct electronic phases characterizing the metal-insulator transition displayed by most of the rare-earth nickelate compounds is fundamental for discovering the true nature of this transition and the possible couplings that are established at the interfaces of nickelate-based heterostructures. Here, we demonstrate that this can be accomplished by using scanning transmission electron microscopy in combination with electron energy-loss spectroscopy. By tracking how the O K and Ni L edge fine structures evolve across two different NdNiO3/SmNiO3 superlattices, displaying either one or two metal- insulator transitions depending on the individual layer thickness, we are able to determine the electronic state of each of the individual constituent materials. We further map the spatial configuration associated with their metallic/insulating regions, reaching unit cell spatial resolution. With this, we estimate the width of the metallic/insulating boundaries at the NdNiO3/SmNiO3 interfaces, which is measured to be on the order of four unit cells.

Optimization of composition and structure of cemented carbide cutting tools

Samy Adjam

WC-Co cemented carbides are composites, which combine a hard phase consisting of WC grains and a metallic ductile phase as a binder. Their excellent mechanical properties, combining high hardness, toughness and refractory properties, make them excellent materials for cutting processes such as turning, drilling and milling. For such applications, cemented carbides are coated with thin ceramic films that increase their resistance to thermal stress as well as to the mechanical and chemical wear inherent in extreme machining conditions. Three main characteristics determine the performance and wear resistance of cutting tools: the cohesion of the hard phase above 1200 K, the ductility of the cobalt binder, and the mechanical and thermal resistance of the coatings. This work focuses on the impact of the microstructural behaviour of the cobalt binder on the tool-life of the cutting tools. The aim is to develop new binders for cemented carbides with improved impact resistance. The techniques of transmission electron microscopy at room temperature and in-situ at high temperature, as well as mechanical spectroscopy in a forced torsion pendulum have proved to be essential for the identification of the microstructure of cobalt and for the study of the relaxation phenomena occurring therein. Mechanical spectroscopy has evidenced the presence of two relaxation peaks, P1 and P2 in the cobalt phase and a peak (P3) related to WC-WC grain boundary sliding. The peak P1 appears to be correlated with the cutting tool life measured in interrupted cutting tests. In this work, the role of the binder is highlighted in particular by the identification of a glass-type transition observed for cobalt. The thermodynamics of the transition is evidenced by the behavior of P1 whose relaxation time diverges according to a Vogel-Fulcher-Tammann model, which is characteristic of glass transitions. The state of the material corresponding to temperatures below this transition shows a strong dependence on its thermomechanical history. This dependence is confirmed by a divergence in plastic deformations over two identical temperature cycles with different thermomechanical histories. Such a divergence on a standard protocol, called (ZFC/FC), seems to indicate a break in the thermodynamic hypothesis of ergodicity, even though it could not be attributed solely to the behaviour of cobalt. Transmission electron microscopy at room temperature has determined that the low temperature phase of the cobalt binder has a face-centred cubic structure and is composed of twinned nanodomains containing nanotwins. This state is therefore characterised by a short-range order without the long-range order, which is characteristic of glassy materials. In-situ observations have highlighted a detwinning process corresponding to the temperatures of the cobalt relaxation peak identified by mechanical spectroscopy. This detwinning process continues until the appearance of a long-range ordered face-centred cubic phase above 1050K, which is favourable to deformation. Mechanically, this transition is similar to a brittle-to-ductile transition, greatly influencing the properties of the material and its toughness. The cutting tool life could benefit from lowering the brittle to ductile transition temperature.

EPFL2021

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

Synthesis of carbon nanotubes and characterization of nanotubes as atomic force microscopy tips

Yanki Keles

This thesis describes the synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD) and the evaluation of them as tips of atomic force microscope (AFM) probes. Both arc-discharge and CVD grown nanotubes were investigated as AFM tips. Two methods were used to produce nanotube tipped AFM probes: (i) nanotubes were directly grown on the apex of AFM probes by CVD and (ii) pre-grown nanotubes were mechanically attached onto the apex of AFM probes. The first part of the thesis describes experiments that sought to control the growth of carbon nanotubes by chemical vapor deposition. The effects of various parameters e.g. catalyst, the carbon source, the addition of hydrogen and the growth temperature, on carbon nanotube growth were investigated. Ethylene was found to lead to better quality nanotubes than the acetylene. Grown nanotubes' quality was found to improve upon flow of hydrogen during the synthesis. Nanotubes synthesized on 3 nm iron film at 840°C using ethylene and hydrogen led to utilizable carbon nanotube tipped AFM probes. The second part of the thesis focuses on the mechanical production of nanotube tipped AFM probes in high resolution electron microscopes using nanomanipulators. Scanning electron microscopy (SEM) was found to be more convenient than transmission electron microscopy (TEM) to carry out the nanomanipulation process. Both arc-discharge and CVD grown nanotubes were successfully attached onto the AFM probes using a custom made nanomanipulator. Nanotubes were glued onto the probes by focused electron beam (FEB) induced amorphous carbon deposits. FEB irradiation deposited amorphous carbon performed more reliable attachment on CVD nanotubes than the arc-discharge nanotubes. The last part of the thesis describes tapping mode AFM measurements done using nanotube tipped AFM probes. Different nanotube tipped probes were investigated as AFM tips for scanning colloidal gold particles with different diameters and gratings from Digital Instruments™ AFMs. High resolution AFM images were obtained by arc-discharge nanotube tips. CVD grown nanotubes were shown to be more resilient to tip crashes than the arc-discharge grown nanotubes. However, all the AFM images acquired from the scans by CVD nanotubes had the same kind of ringing artifact, in good agreement with a previously reported data about the artifacts of the CVD nanotube tipped AFM probes. Open ends of the CVD nanotubes, lack of crystallinity and the defects in their structure are suggested to be the reason for these artifacts.

EPFL2006