In-situ isotopic analysis at nanoscale using parallel ion electron spectrometry: a powerful new paradigm for correlative microscopy

Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. 6Li and 7Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy

Oxide wizard : an EELS application to characterize the white lines of transition metal edges

Physicochemical properties of transition metal oxides are directly determined by the oxidation state of the metallic cations. To address the increasing need to accurately evaluate the oxidation states of transition metal oxide systems at the nanoscale, here we present Oxide Wizard. This script for Digital Micrograph characterizes the energy-loss near-edge structure and the position of the transition metal edges in the electron energy-loss spectrum. These characteristics of the edges can be linked to the oxidation states of transition metals with high spatial resolution. The power of the script is demonstrated by mapping manganese oxidation states in Fe3O4/Mn3O4 core/shell nanoparticles with sub-nanometer resolution in real space

Electron energy-loss spectroscopic tomography of FexCo(3-x)O4 impregnated Co3O4 mesoporous particles: unraveling the chemical information in three dimensions

Electron energy-loss spectroscopy-spectrum image (EELS-SI) tomography is a powerful tool to investigate the three dimensional chemical configuration in nanostructures. Here, we demonstrate, for the first time, the possibility to characterize the spatial distribution of Fe and Co cations in a complex FexCo(3-x)O4/Co3O4 ordered mesoporous system. This hybrid material is relevant because of the ferrimagnetic/antiferromagnetic coupling and high surface area. We unambiguously prove that the EELS-SI tomography shows a sufficiently high resolution to simultaneously unravel the pore structure and the chemical signal

Oxide wizard: an EELS application to characterize the white lines of transition metal edges

Physicochemical properties of transition metal oxides are directly determined by the oxidation state of the metallic cations. To address the increasing need to accurately evaluate the oxidation states of transition metal oxide systems at the nanoscale, here we present Oxide Wizard. This script for Digital Micrograph characterizes the energy-loss near-edge structure and the position of the transition metal edges in the electron energy-loss spectrum. These characteristics of the edges can be linked to the oxidation states of transition metals with high spatial resolution. The power of the script is demonstrated by mapping manganese oxidation states in Fe3O4/Mn3O4 core/shell nanoparticles with sub-nanometer resolution in real spac

EEL spectroscopic tomography: Towards a new dimension in nanomaterials analysis

Electron tomography is a widely spread technique for recovering the three dimensional (3D) shape of nanostructured materials. Using a spectroscopic signal to achieve a reconstruction adds a fourth chemical dimension to the 3D structure. Up to date, energy filtering of the images in the transmission electron microscope (EFTEM) is the usual spectroscopic method even if most of the information in the spectrum is lost. Unlike EFTEM tomography, the use of electron energy-loss spectroscopy (EELS) spectrum images (SI) for tomographic reconstruction retains all chemical information, and the possibilities of this new approach still remain to be fully exploited. In this article we prove the feasibility of EEL spectroscopic tomography at low voltages (80kV) and short acquisition times from data acquired using an aberration corrected instrument and data treatment by Multivariate Analysis (MVA), applied to FexCo(3-x)O4@Co3O4 mesoporous materials. This approach provides a new scope into materials; the recovery of full EELS signal in 3D

Patterning enhanced tetragonality in BiFeO3 thin films with effective negative pressure by helium implantation

Helium implantation in epitaxial thin films is a way to control the out-of-plane deformation independentlyfrom the in-plane strain controlled by epitaxy. In particular, implantation by means of a helium microscopeallows for local implantation and patterning down to the nanometer resolution, which is of interest for deviceapplications. We present here a study of bismuth ferrite (BiFeO3) films where strain was patterned locally byhelium implantation. Our combined Raman, x-ray diffraction, and transmission electron microscopy (TEM)study shows that the implantation causes an elongation of the BiFeO3unit cell and ultimately a transition towardsthe so-called supertetragonal polymorph via states with mixed phases. In addition, TEM reveals the onset ofamorphization at a threshold dose that does not seem to impede the overall increase in tetragonality. The phasetransition from the R-like to T-like BiFeO3appears as first-order in character, with regions of phase coexistenceand abrupt changes in lattice parameters

The impact of Mn nonstoichiometry on the oxygen mass transport properties of La0.8Sr0.2MnyO3±δ thin films

Oxygen mass transport in perovskite oxides is relevant for a variety of energy and information technologies. In oxide thin films, cation nonstoichiometry is often found but its impact on the oxygen transport properties is not well understood. Here, we used oxygen isotope exchange depth profile technique coupled with secondary ion mass spectrometry to study oxygen mass transport and the defect compensation mechanism of Mn-deficient La0.8Sr0.2Mn (y) O-3 +/-delta epitaxial thin films. Oxygen diffusivity and surface exchange coefficients were observed to be consistent with literature measurements and to be independent on the degree of Mn deficiency in the layers. Defect chemistry modeling, together with a collection of different experimental techniques, suggests that the Mn-deficiency is mainly compensated by the formation of La-x(Mn) antisite defects. The results highlight the importance of antisite defects in perovskite thin films for mitigating cationic nonstoichiometry effects on oxygen mass transport properties

Controlled 3D-coating of the pores of highly ordered mesoporous antiferromagnetic Co3O4 replicas with ferrimagnetic FexCo3-xO4 nanolayers

The controlled filling of the pores of highly ordered mesoporous antiferromagnetic Co3O4 replicas with ferrimagnetic FexCo3-xO4 nanolayers is presented as a proof-of-concept toward the integration of nanosized units in highly ordered, heterostructured 3D architectures. Antiferromagnetic (AFM) Co3O 4 mesostructures are obtained as negative replicas of KIT-6 silica templates, which are subsequently coated with ferrimagnetic (FiM) Fe xCo3-xO4 nanolayers. The tuneable magnetic properties, with a large exchange bias and coercivity, arising from the FiM/AFM interface coupling, confirm the microstructure of this novel two-phase core-shell mesoporous material. The present work demonstrates that ordered functional mesoporous 3D-materials can be successfully infiltrated with other compounds exhibiting additional functionalities yielding highly tuneable, versatile, non-siliceous based nanocomposites

3D Visualization of the Iron Oxidation State in FeO/Fe3O4 Core-Shell Nanocubes from Electron Energy Loss Tomography.

Left panel shows the explained variance ratio of the principal component analysis (PCA) decomposition. The six first components, which are enough to explain the whole data set, are plotted in the right panel. Components 0, 3 and 5 show no remarkable features in the Fe L2,3 ionization energy and seem rather related to the background of the spectra due to their power-law behaviour, while component 1 is almost constant and therefore could be related to the dark noise in the detector

Spontaneous Hetero-attachment of Single-Component Colloidal Precursors for the Synthesis of Asymmetric Au-Ag2X (X = S, Se) Heterodimers

Finding simple, easily controlled, and flexible synthetic routes for the preparation of ternary and hybrid nanostructured semiconductors is always highly desirable, especially to fulfill the requirements for mass production to enable application to many fields such as optoelectronics, thermoelectricity, and catalysis. Moreover, understanding the underlying reaction mechanisms is equally important, offering a starting point for its extrapolation from one system to another. In this work, we developed a new and more straightforward colloidal synthetic way to form hybrid Au-Ag2X (X = S, Se) nanoparticles under mild conditions through the reaction of Au and Ag2X nanostructured precursors in solution. At the solid-solid interface between metallic domains and the binary chalcogenide domains, a small fraction of a ternary AuAg3X2phase was observed to have grown as a consequence of a solid-state electrochemical reaction, as confirmed by computational studies. Thus, the formation of stable ternary phases drives the selective hetero-attachment of Au and Ag2X nanoparticles in solution, consolidates the interface between their domains, and stabilizes the whole hybrid Au-Ag2X systems