Unconventional ferroelectricity exhibited by hafnia-based thin films-robust at nanoscale sizes-presents tremendous opportunities in nanoelectronics. However, the exact nature of polarization switching remains controversial. We investigated a La0.67Sr0.33MnO3/Hf0.5Zr0.5O2 capacitor interfaced with various top electrodes while performing in situ electrical biasing using atomic-resolution microscopy with direct oxygen imaging as well as with synchrotron nanobeam diffraction. When the top electrode is oxygen reactive, we observe reversible oxygen vacancy migration with electrodes as the source and sink of oxygen and the dielectric layer acting as a fast conduit at millisecond time scales. With nonreactive top electrodes and at longer time scales (seconds), the dielectric layer also acts as an oxygen source and sink. Our results show that ferroelectricity in hafnia-based thin films is unmistakably intertwined with oxygen voltammetry.

Cerium-based compounds have been studied for decades as non-toxic candidates for the protection of aerospace aluminium alloys (AAs) like AA2024-T3. However, the complex heterogeneous microstructure of these alloys has hindered a thorough understanding of the subsequent stages of corrosion protection provided by this class of inhibitors. Thus, this work is devoted to unravelling the interaction mechanisms of different intermetallic particles (IMPs) in AA2024-T3 with cerium nitrate at the nanoscopic scale. This has been fulfilled through detailed top-view and cross-sectional analytical TEM investigations along with electrochemical evaluations. In line with our recent findings, we here report dealloying of IMPs as the main factor governing the rate of local cerium precipitation in contrast to micro-galvanic corrosion between IMPs and the surrounding matrix. Furthermore, we discuss a connection between the electrochemical response of the AA2024-T3 system and the morphological and compositional evolutions of individual IMPs including Al2CuMg, Al2Cu, Al7Cu2Fe(Mn) and Al76Cu6Fe7Mn5Si6 at different stages of a 96-h exposure.

The crystal structure of LiNi0.5Mn1.5O4 (LNMO) can adopt either low-symmetry ordered (Fd3¯ m) or high-symmetry disordered (P4332) space group depending on the synthesis conditions. A majority of published studies agree on superior electrochemical performance of disordered LNMO, but the underlying reasons for improvement remain unclear due to the fact that different thermal history of the samples affects other material properties such as oxygen content and particle morphology. In this study, ordered and disordered samples were prepared with a new strategy that renders samples with identical properties apart from their cation ordering degree. This was achieved by heat treatment of powders under pure oxygen atmosphere at high temperature with a final annealing step at 710 °C for both samples, followed by slow or fast cooling. Electrochemical testing showed that cation disordering improves the stability of material in charged (delithiated) state and mitigates the impedance rise in LNMO-1LTO (Li4Ti5O12) and LNMO-1Li cells. Through X-ray photoelectron spectroscopy (XPS), thicker surface films were observed on the ordered material, indicating more electrolyte side reactions. The ordered samples also showed significant changes in the Ni 2p XPS spectra, while the generation of ligand (oxygen) holes was observed in the Ni-O environment for both samples using X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). Moreover, high-resolution transmission electron microscopy (HRTEM) images indicated that the ordered samples show a decrease in ordering near the particle surface after cycling and a tendency toward rock-salt-like phase transformations. These results show that the structural arrangement of Mn/Ni (alone) has an effect on the surface and "near-surface"properties of LNMO, particularly in delithiated state, which is likely connected to the bulk electronic properties of this electrode material.

In microstructural corrosion studies, knowledge on the initiation of corrosion on an nm-scale is lacking. In situ transmission electron microscope (TEM) studies can elucidate where/how the corrosion starts, provided that the proper corrosive conditions are present during the investigation. In wet corrosion studies with liquid cell nanoreactors (NRs), the liquid along the electron beam direction leads to strong scattering and therefore image blurring. Thus, a quick liquid removal or thickness control of the liquid layer is preferred. This can be done by the use of a Peltier element embedded in an NR. As a prelude to such in situ work, we demonstrate the local wetting of a TEM sample, by creating a temperature decrease of 10 ± 2°C on the membrane of an NR with planar Sb/BiSb thermoelectric materials for the Peltier element. TEM samples were prepared and loaded in an NR using a dual-beam focused ion beam scanning electron microscope. A mixture of water vapor and carrier gas was passed through a chamber, which holds the micro-electromechanical system Peltier device and resulted in quick formation of a water layer/droplets on the sample. The TEM analysis after repeated corrosion of the same sample (ex situ studies) shows the onset and progression of O2 and H2S corrosion of the AA2024-T3 alloy and cold-rolled HCT980X steel lamellae.

In this paper, the growth of optimized vertically aligned multi-walled carbon nanotube (VA-MWCNT) forests by LPCVD method for use in a large-area absorber in infrared detectors is presented. The effect of synthesis temperature (500−700 °C) and time (1−10 min) on the optical absorption coefficient in the infrared (2−20 μm) is investigated by FT-IR measurement at various incident angles (15-80°). The structural properties of VA-MWCNT are characterized by SEM, TEM and Raman spectroscopy. Spectral measurements show an increasing absorption with the height of the forest that results at increased synthesis time and temperature. However, the absorption coefficient decreases with increasing synthesize time and temperature, while it is also affected by other properties, such as diameter, density, alignment, and uniformity. Moreover, the reduction in absorption at oblique incident angles demonstrates the relevance of surface properties. Finally, a circular graphite waveguide system is used to model the absorption characteristics of an MWCNT forest.

A method to grow multi layers graphene (MLG) just by thermal annealing in an inert atmosphere is reported. A molybdenum (Mo) catalyst layer is used in combination with a solid amorphous carbon (a-C) source on top or below the Mo layer. The formation of MLG directly on top of the catalyst substrate surface is confirmed by Raman spectroscopy, atomic force microscopy, cross-section transmission electron microscopy, electron energy loss spectroscopy and x-ray photoelectron spectroscopy. Growth of MLG on top of the Mo catalyst is demonstrated both with a-C below and above the Mo layer. The growth mechanism is attributed to the diffusion of a-C through the Mo layer and precipitation into the graphene at the surface, similar to the growth by chemical vapour deposition (CVD) on a Ni catalyst. The role of the inert Ar/H ₂ atmosphere, carbon thickness, catalyst thickness, anneal time and anneal temperature are reported. Fast growth of MLG (5 min) at 915 °C is demonstrated. The quality of MLG prepared by thermal annealing is at least as good as that of MLG synthesized by CVD. The relevant achievements presented in this study make the proposed technique a promising alternative to CVD based MLG.