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The electric field control of functional properties is a crucial goal in oxide-based electronics. Nonvolatile switching between different resistivity or magnetic states in an oxide channel can be achieved through charge accumulation or depletion from an adjacent ferroelectric. However, the way in which charge distributes near the interface between the ferroelectric and the oxide remains poorly known, which limits our understanding of such switching effects. Here, we use a first-of-a-kind combination of scanning transmission electron microscopy with electron energy loss spectroscopy, near-total-reflection hard X-ray photoemission spectroscopy, and ab initio theory to address this issue. We achieve a direct, quantitative, atomic-scale characterization of the polarization-induced charge density changes at the interface between the ferroelectric BiFeO3 and the doped Mott insulator Ca(1-x)Ce(x)MnO3, thus providing insight on how interface-engineering can enhance these switching effects.
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Artificial multiferroic tunnel junctions combining a ferroelectric tunnel barrier of BaTiO(3) with magnetic electrodes display a tunnel magnetoresistance whose intensity can be controlled by the ferroelectric polarization of the barrier. This effect, called tunnel electromagnetoresistance (TEMR), and the corollary magnetoelectric coupling mechanisms at the BaTiO(3)/Fe interface were recently reported through macroscopic techniques. Here, we use advanced spectromicroscopy techniques by means of aberration-corrected scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) to probe locally the nanoscale structural and electronic modifications at the ferroelectric/ferromagnetic interface. Atomically resolved real-space spectroscopic techniques reveal the presence of a single FeO layer between BaTiO(3) and Fe. Based on this accurate description of the studied interface, we propose an atomistic model of the ferroelectric/ferromagnetic interface further validated by comparing experimental and simulated STEM images with atomic resolution. Density functional theory calculations allow us to interpret the electronic and magnetic properties of these interfaces and to understand better their key role in the physics of multiferroics nanostructures.
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Compuestos de Bario/química , Hierro/química , Nanoestructuras/química , Nanoestructuras/ultraestructura , Semiconductores , Titanio/química , Conductividad Eléctrica , Transporte de Electrón , Sustancias Macromoleculares/química , Ensayo de Materiales , Conformación Molecular , Tamaño de la Partícula , Propiedades de SuperficieRESUMEN
This review intends to illustrate how electron energy-loss spectroscopy (EELS) techniques in the electron microscope column have evolved over the past 60 years. Beginning as a physicist tool to measure basic excitations in solid thin foils, EELS techniques have gradually become essential for analytical purposes, nowadays pushed to the identification of individual atoms and their bonding states. The intimate combination of highly performing techniques with quite efficient computational tools for data processing and ab initio modeling has opened the way to a broad range of novel imaging modes with potential impact on many different fields. The combination of Angström-level spatial resolution with an energy resolution down to a few tenths of an electron volt in the core-loss spectral domain has paved the way to atomic-resolved elemental and bonding maps across interfaces and nanostructures. In the low-energy range, improved energy resolution has been quite efficient in recording surface plasmon maps and from them electromagnetic maps across the visible electron microscopy (EM) domain, thus bringing a new view to nanophotonics studies. Recently, spectrum imaging of the emitted photons under the primary electron beam and the spectacular introduction of time-resolved techniques down to the femtosecond time domain, have become innovative keys for the development and use of a brand new multi-dimensional and multi-signal electron microscopy.
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Microscopía Electrónica/métodos , Espectroscopía de Pérdida de Energía de Electrones/métodos , Análisis Espectral/métodos , Electrones , Historia del Siglo XX , Nanoestructuras/química , Propiedades de SuperficieRESUMEN
This contribution aims at reporting, from the subjective point of view of a witness based in Orsay, the fundamental role of Ondrej Krivanek in the spectacular emergence of EELS (Electron Energy-Loss Spectroscopy) as a key tool in analytical electron microscopy. In this regard, he has successively designed and built while he was at Gatan, serial EELS spectrometers, parallel EELS spectrometers and post-column energy filters which have been fitted to many different (S)TEM columns installed around the world. More recently the implementation of monochromators on the NION dedicated STEM together with the realization and performance of aberration correctors (which lie out of the scope of the present review), have placed the most advanced instrumental tool in the hands of continuously increasing populations of users in many domains of materials science and in life sciences. Furthermore, the impact of Ondrej Krivanek has spread widely beyond his technical achievements into that of a highly respected organizer of workshops, bringing together at regular intervals, all the experts from around the world and building up a real community of scientists.
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Since their first realization, electron microscopes have demonstrated their unique ability to map with highest spatial resolution (sub-atomic in most recent instruments) the position of atoms as a consequence of the strong scattering of the incident high energy electrons by the nuclei of the material under investigation. When interacting with the electron clouds either on atomic orbitals or delocalized over the specimen, the associated energy transfer, measured and analyzed as an energy loss (Electron Energy Loss Spectroscopy) gives access to analytical properties (atom identification, electron states symmetry and localization). In the moderate energy-loss domain (corresponding to an optical spectral domain from the infrared (IR) to the rather far ultra violet (UV), EELS spectra exhibit characteristic collective excitations of the rather-free electron gas, known as plasmons. Boundary conditions, such as surfaces and/or interfaces between metallic and dielectric media, generate localized surface charge oscillations, surface plasmons (SP), which are associated with confined electric fields. This domain of research has been extraordinarily revived over the past few years as a consequence of the burst of interest for structures and devices guiding, enhancing and controlling light at the sub-wavelength scale. The present review focuses on the study of these surface plasmons with an electron microscopy-based approach which associates spectroscopy and mapping at the level of a single and well-defined nano-object, typically at the nanometer scale i.e. much improved with respect to standard, and even near-field, optical techniques. After calling to mind some early studies, we will briefly mention a few basic aspects of the required instrumentation and associated theoretical tools to interpret the very rich data sets recorded with the latest generation of (Scanning)TEM microscopes. The following paragraphs will review in more detail the results obtained on simple planar and spherical surfaces (or interfaces), extending then to more complex geometries isolated and in interaction, thus establishing basic rules from the classical to the quantum domain. A few hints towards application domains and prospective fields rich of interest will finally be indicated, confirming the demonstrated key role of electron-beam nanoplasmonics, the more as an yet-enhanced energy resolution down to the 10meV comes on the verge of current access.
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The need for understanding the structural and chemical properties of interfaces and grain boundaries in materials is being paralleled by new developments in transmission electron microscopy methods. The extraction of data on grain boundaries has to be carefully evaluated, freed from artefacts and allowing fairly direct interpretation. Besides improvements in data processing, a primary requirement is an improved knowledge of the ELNES fine structures of the relevant absorption edge. For the case of alumina, we first present a compilation of Al-L(23) edges with an energy resolution of 0.5-0.6eV. This allows identification of the ELNES features which are more likely to vary as a function of the aluminium atomic environment, i.e. the excitonic peaks between 77 and 79eV and the near-edge features between 83 and 86eV, which both clearly depend on the Al site environment. Our second investigation concerns the likely occurrence of electron radiation damage at interfaces which may adversely interfere with the identification of new bonding types. The Al-L(23) and O-K ELNES changes associated with several cases of damage are detailed.
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Here, we demonstrate that non-dipole allowed d-d excitations in NiO can be measured by electron energy loss spectroscopy (EELS) in transmission electron microscopes (TEM). Strong excitations from (3)A(2g) ground states to (3)T(1g) excited states are measured at 1.7 and 3 eV when transferred momentum are beyond 1.5 A(-1). We show that these d-d excitations can be collected with a nanometrical resolution in a dedicated scanning transmission electron microscope (STEM) by setting a good compromise between the convergence angle of the electron probe and the collected transferred momentum. This work opens new possibilities for the study of strongly correlated materials on a nanoscale.
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Electromagnetic response of individual boron nitride nanotubes (BNNTs) has been studied by spatially resolved electron energy loss spectroscopy (EELS). We demonstrate how dedicated EELS methods using subnanometer electron probes permit the analysis of local dielectric properties of a material on a nanometer scale. The continuum dielectric model has been used to analyze the low-loss EEL spectra recorded from these tubes. Using this model, we demonstrate the weak influence of the out-of-plane contribution to the dielectric response of BNNTs. The optical gap, which can be deduced from the measurements, is found to be equal to 5.8 +/- 0.2 eV, which is close to that of the hexagonal boron nitride. This value is found to be independent of the nanotubes configuration (diameter, helicity, number of walls, and interaction between the different walls).
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We report on the synthesis of C-BN single-walled nanotubes made of BN nanodomains embedded into a graphene layer. The synthesis process consists of vaporizing, by a continuous CO2 laser, a target made of carbon and boron mixed with a Co/Ni catalyst under N2 atmosphere. High-resolution transmission electron microscopy (HRTEM) and nanoelectron energy loss spectroscopy (nanoEELS) provide direct evidence that boron and nitrogen co-segregate with respect to carbon and form nanodomains within the hexagonal lattice of the graphene layer in a sequential manner. A growth model is proposed to account for the observed C-BN self-organization and to explain how kinetics and local energetics at intermediate states can tailor ultimate single layer BN-C heterojunctions.