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 AuAg3X2 phase 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.

Direct Measurement of Oxygen Mass Transport at the Nanoscale.

Tuning oxygen mass transport properties at the nanoscale offers a promising approach for developing high performing energy materials. A number of strategies for engineering interfaces with enhanced oxygen diffusivity and surface exchange have been proposed. However, the origin and the magnitude of such local effects remain largely undisclosed to date due to the lack of direct measurement tools with sufficient resolution. In this work, atom probe tomography with sub-nanometer resolution is used to study oxygen mass transport on oxygen-isotope exchanged thin films of lanthanum chromite. A direct 3D visualization of nanoscaled highly conducting oxygen incorporation pathways along grain boundaries, with reliable quantification of the oxygen kinetic parameters and correlative link to local chemistries, is presented. Combined with finite element simulations of the exact nanostructure, isotope exchange-atom probe tomography allowed quantifying an enhancement in the grain boundary oxygen diffusivity and in the surface exchange coefficient of lanthanum chromite of about 4 and 3 orders of magnitude, respectively, compared to the bulk. This remarkable increase of the oxygen kinetics in an interface-dominated material is unambiguously attributed to grain boundary conduction highways thanks to the use of a powerful technique that can be straightforwardly extended to the study of currently inaccessible multiple nanoscale mass transport phenomena.

Non-oxide precipitates in additively manufactured austenitic stainless steel.

Precipitates in an austenitic stainless steel fabricated via any Additive Manufacturing (AM), or 3D printing, technique have been widely reported to be only Mn-Si-rich oxides. However, via Transmission Electron Microscopy (TEM) studies on a 316L stainless steel, we show that non-oxide precipitates (intermetallics, sulfides, phosphides and carbides) can also form when the steel is fabricated via Laser Metal Deposition (LMD)-a directed energy deposition-type AM technique. An investigation into their origin is conducted with support from precipitation kinetics and finite element heat transfer simulations. It reveals that non-oxide precipitates form during solidification/cooling at temperatures ≥ 0.75Tm (melting point) and temperature rates ≤ 105 K/s, which is the upper end of the maximum rates encountered during LMD but lower than those encountered during Selective Laser Melting (SLM)-a powder-bed type AM technique. Consequently, non-oxide precipitates should form during LMD, as reported in this work, but not during SLM, in consistency with existing literature.

Direct Epitaxial Growth of Polar (1 - x)HfO2-(x)ZrO2 Ultrathin Films on Silicon.

Ultrathin Hf1-x Zr x O2 films have attracted tremendous interest since they show ferroelectric behavior at the nanoscale, where other ferroelectrics fail to stabilize the polar state. Their promise to revolutionize the electronics landscape comes from the well-known Si compatibility of HfO2 and ZrO2, which (in amorphous form) are already used as gate oxides in MOSFETs. However, the recently discovered crystalline ferroelectric phases of hafnia-based films have been grown on Si only in polycrystalline form. Better ferroelectric properties and improved quality of the interfaces have been achieved in epitaxially grown films, but these are only obtained on non-Si and buffered Si(100) substrates. Here, we report direct epitaxy of polar Hf1-x Zr x O2 phases on Si, enabled via in situ scavenging of the native a-SiO x layer by Zr (Hf), using pulsed laser deposition under ballistic deposition conditions. We investigate the effect of substrate orientation and film composition to provide fundamental insights into the conditions that lead to the preferential stabilization of polar phases, namely, the rhombohedral (r-) and the orthorhombic (o-) phases, against the nonpolar monoclinic (m-), on Si.

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

The physicochemical properties used in numerous advanced nanostructured devices are directly controlled by the oxidation states of their constituents. In this work we combine electron energy-loss spectroscopy, blind source separation, and computed tomography to reconstruct in three dimensions the distribution of Fe(2+) and Fe(3+) ions in a FeO/Fe3O4 core/shell cube-shaped nanoparticle with nanometric resolution. The results highlight the sharpness of the interface between both oxides and provide an average shell thickness, core volume, and average cube edge length measurements in agreement with the magnetic characterization of the sample.

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. (6)Li and (7)Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy.

Hantzsch dihydropyridines: Privileged structures for the formation of well-defined gold nanostars.

Anisotropic and branched gold nanoparticles have great potential in optical, chemical and biomedical applications. However their syntheses involve multi-step protocols and the use of cytotoxic agents. Here, we report a novel one-step method for the preparation of gold nanostructures using only Hantzsch 1,4-dihydropyridines as mild reducing agents. The substituent pattern of the dihydropyridine nucleus was closely related to the ease of formation, morphology and stability of the nanoparticles. We observed nanostructures such as spheres, rods, triangles, pentagons, hexagons, flowers, stars and amorphous. We focused mainly on the synthesis and characterization of well-defined gold nanostars, which were produced quickly at room temperature (25°C) in high yield and homogeneity. These nanostars presented an average size of 68 nm with mostly four or six tips. Based on our findings, we propose that the growth of the nanostars occurs in the (111) lattice plane due to a preferential deposition of the gold atoms in the early stages of particle formation. Furthermore, the nanostars were easily modified with peptides remaining stable for more than six months in their colloidal state and showing a better stability than unmodified nanostars in different conditions. We report a new approach using dihydropyridines for the straightforward synthesis of gold nanostructures with controlled shape, feasible for use in future applications.

EELS tomography in multiferroic nanocomposites: from spectrum images to the spectrum volume.

Electron Energy Loss Spectroscopy (EELS) in a transmission electron microscope offers the possibility of extracting high accuracy maps of composition and electronic properties through EELS spectrum images (EELS-SI). Acquiring EELS-SI for different tilt angles, a 3D tomographic reconstruction of EELS information can be achieved. In the present work we show that an EELS spectrum volume (EELS-SV), a 4D dataset where every voxel contains a full EELS spectrum, can be reconstructed from the EELS-SI tilt series by the application of multivariate analysis. We apply this novel approach to characterize a nanocomposite material consisting of CoFe2O4 nanocolumns embedded in a BiFeO3 matrix grown on a LaNiO3 buffered LaAlO3 (001) substrate.

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.

Controlled 3D-coating of the pores of highly ordered mesoporous antiferromagnetic Co3O4 replicas with ferrimagnetic Fe(x)Co(3-x)O4 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) Co3O4 mesostructures are obtained as negative replicas of KIT-6 silica templates, which are subsequently coated with ferrimagnetic (FiM) FexCo3-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.

Learning from nature to improve the heat generation of iron-oxide nanoparticles for magnetic hyperthermia applications.

The performance of magnetic nanoparticles is intimately entwined with their structure, mean size and magnetic anisotropy. Besides, ensembles offer a unique way of engineering the magnetic response by modifying the strength of the dipolar interactions between particles. Here we report on an experimental and theoretical analysis of magnetic hyperthermia, a rapidly developing technique in medical research and oncology. Experimentally, we demonstrate that single-domain cubic iron oxide particles resembling bacterial magnetosomes have superior magnetic heating efficiency compared to spherical particles of similar sizes. Monte Carlo simulations at the atomic level corroborate the larger anisotropy of the cubic particles in comparison with the spherical ones, thus evidencing the beneficial role of surface anisotropy in the improved heating power. Moreover we establish a quantitative link between the particle assembling, the interactions and the heating properties. This knowledge opens new perspectives for improved hyperthermia, an alternative to conventional cancer therapies.

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 (80 kV) and short acquisition times from data acquired using an aberration corrected instrument and data treatment by Multivariate Analysis (MVA), applied to Fe(x)Co((3-x))O(4)@Co(3)O(4) mesoporous materials. This approach provides a new scope into materials; the recovery of full EELS signal in 3D.