Multi-modal and multi-scale non-local means method to analyze spectroscopic datasets

A multi-modal and multi-scale non-local means (M3S-NLM) method is proposed to extract atomically resolved spectroscopic maps from low signal-to-noise (SNR) datasets recorded with a transmission electron microscope. This method improves upon previously tested denoising techniques as it takes into account the correlation between the dark-field signal recorded simultaneously with the spectroscopic dataset without compromising on the spatial resolution. The M3S-NLM method was applied to electron energy dispersive X-ray and electron-energy-loss spectroscopy (EELS) datasets. We illustrate the retrieval of the atomic scale diffusion process in an Al1-xInxN alloy grown on GaN and the surface oxidation state of perovskite nanocatalysts. The improved SNR of the EELS dataset also allows the retrieval of atomically resolved oxidation maps considering the fine structure absorption edge of LaMnO3 nanoparticles.

Challenges and Applications to Operando and In Situ TEM Imaging and Spectroscopic Capabilities in a Cryogenic Temperature Range

Martial Duchamp, Reinis Ignatans, Vasiliki Tileli

In this Account, we describe the challenges and promising applications of transmission electron microscopy (TEM) imaging and spectroscopy at cryogenic temperatures. Our work focuses on two areas of application: the delay of electron-beam-induced degradation and following low-temperature phenomena in a continuous and variable temperature range. For the former, we present a study of LiMn1.5Ni0.5O4 lithium ion battery cathode material that undergoes electron beam-induced degradation when studied at room temperature by TEM. Cryogenic imaging reveals the true structure of LiMn1.5Ni0.5O4 nanoparticles in their discharged state. Improved stability under electron beam irradiation was confirmed by following the evolution of the O K-edge fine structure by electron energy-loss spectroscopy. Our results demonstrate that the effect of radiation damage on discharged LiMn1.5Ni0.5O4 was previously underestimated and that atomic-resolution imaging at cryogenic temperature has a potential to be generalized to most of the Li-based materials and beyond. For the latter, we present two studies in the imaging of low-temperature phenomena on the local scale, namely, the evolution of ferroelectric and ferromagnetic domains walls, in BaTiO3 and Y3Fe5O12 systems, respectively, in a continuous and variable temperature range. Continuous imaging of the phase transition in BaTiO3, a prototypical ferroelectric system, from the low-temperature orthorhombic phase continuously up to the centrosymmetric high-temperature phase is shown to be possible inside a TEM. Similarly, the propagation of domain walls in Y3Fe5O12, a magnetic insulator, is studied from similar to 120 to similar to 400 K and combined with the application of a magnetic field and electrical current pulses to mimic the operando conditions as in domain wall memory and logic devices for information technology. Such studies are promising for studying the pinning of the ferroelectric and magnetic domains versus temperature, spin-polarized current, and externally applied magnetic field to better manipulate the domain walls. The capability of combining operando TEM stimuli such as current, voltage, and/or magnetic field with in situ TEM imaging in a continuous cryogenic temperature range will allow the uncovering of fundamental phenomena on the nanometer scale These studies were made possible using a MEMS-based TEM holder that allowed an electron-transparent sample to be transferred and electrically contacted on a MEMS chip. The six-contact double-tilt holder allows the alignment of the specimen into its zone axis while simultaneously using four electrical contacts to regulate the temperature and two contacts to apply the electrical stimuli, i.e., operando TEM imaging. This Account leads to the demonstration of (i) the high-resolution imaging and spectroscopy of nanoparticles oriented in the desired [110] zone-axis direction at cryogenic temperatures to mitigate the electron beam degradation, (ii) imaging of low-temperature transitions with accurate and continuous control of the temperature that allowed single-frame observation of the presence of both the orthorhombic and tetragonal phases in the BaTiO3 system, and (iii) magnetic domain wall propagation as a function of temperature, magnetic field, and current pulses (100 ns with a 100 kHz repetition rate) in the Y3Fe5O12 system.

AMER CHEMICAL SOC2021

Angular Resolved low loss EELS for Materials Characterization

Simon Schneider

Electron Energy Loss Spectrometry (EELS) in Transmission Electron Microscopy (TEM) is a powerful tool for the investigation of the electronic structure of materials. In the low loss regime, one can access the optical properties which are governed by the dielectric function ε(ω), which may be retrieved thanks to the so-called "loss function". The energy range covered by EELS goes from the infrared (less than 1 eV) to the hard X-rays (about 3 keV), each region having its own interest. The low loss region (0–100 eV) serves to investigate the valence electron structure and the inter-band transition behavior. Using angular resolved EELS gives further information about the dispersion behavior of the investigated material. This work is a part of a large project aiming a closer agreement between theory and experiment in angular resolved EELS by improving the state of the art in both fields. The purpose of this work is to set up a reliable experimental technique to retrieve the momentum transfer resolved single scattering distribution at very low energy with good accuracy and resolutions. One of the main challenges was to use the newly installed JEOL 2200 FS transmission electron microscope that is equipped with an in-column Ω filter for retrieval of the loss function in diffraction energy filtered TEM. Issues such as the angular resolution, contamination, image-coupling in diffraction mode and plural scattering have been solved. Several optical alignments and operational modes of the JEOL 2200 FS have been tested, and finally nano-beam diffraction was found to be the optimal running mode. This work provides for the first time a full 3D energy loss data cube in diffraction mode with energy and angular resolutions of 1 eV and 0.5 nm−1 respectively. After processing, the energy and angular relevant data span an energy loss range from 2.75 eV to 40.25 eV and the angular momentum transfer up to 12.5 nm−1. Although theoretically, without CCD camera binning and the maximum available camera length of the JEOL (250 cm), a momentum transfer resolution of 0.04 nm−1 would have been possible, the effective angular resolution was limited by the smallest obtainable beam convergence as well as by the remaining aberrations of the microscope. The presented technique can be reproduced on any transmission electron microscope equipped with an in-column energy filter. Furthermore, it is demonstrated that the proposed method provides working ranges in energy, spatial and angular resolutions limited only by the perfor- mance of the microscope. Previous techniques did not provide experimental results showing an energy resolution independent of the spatial and angular resolutions.

EPFL2013

Magnetic circular dichroism in electron microscopy

Cécile Hébert

Although the analogies between the electron energy loss spectra and X-ray absorption spectra were recognized long ago, the possibility to observe the magnetic circular dichroism in the electron microscope was demonstrated only recently. This technique combines the atom specificity with the high spatial resolution of the transmission electron microscope. Being a very young technique, there are still many open questions concerning the optimization of the signal to noise ratio. In this paper we study the dichroic signal dependence on the sample thickness, acceleration voltage and incoming beam tilt angle of bcc-Fe and fcc-Ni.