Disentangling Structural and Electronic Properties in V2O3 Thin Films: A Genuine Nonsymmetry Breaking Mott Transition.

Phase transitions are key in determining and controlling the quantum properties of correlated materials. Here, by using the combination of material synthesis and photoelectron spectroscopy, we demonstrate a genuine Mott transition undressed of any symmetry breaking side effects in the thin films of V2O3. In particular and in contrast with the bulk V2O3, we unveil the purely electronic dynamics approaching the metal-insulator transition, disentangled from the structural transformation that is prevented by the residual substrate-induced strain. On approaching the transition, the spectral signal evolves slowly over a wide temperature range, the Fermi wave-vector does not change, and the critical temperature is lower than the one reported for the bulk. Our findings are fundamental in demonstrating the universal benchmarks of a genuine nonsymmetry breaking Mott transition, extendable to a large array of correlated quantum systems, and hold promise of exploiting the metal-insulator transition by implementing V2O3 thin films in devices.

The Interaction of Amines with Gold Nanoparticles.

Understanding the interactions between amines and the surface of gold nanoparticles is important because of their role in the stabilization of the nanosystems, in the formation of the protein corona, and in the preparation of semisynthetic nanozymes. By using fluorescence spectroscopy, electrochemistry, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and molecular simulation, a detailed picture of these interactions is obtained. Herein, it is shown that amines interact with surface Au(0) atoms of the nanoparticles with their lone electron pair with a strength linearly correlating with their basicity corrected for steric hindrance. The kinetics of binding depends on the position of the gold atoms (flat surfaces or edges) while the mode of binding involves a single Au(0) with nitrogen sitting on top of it. A small fraction of surface Au(I) atoms, still present, is reduced by the amines yielding a much stronger Au(0)-RN.+ (RN. , after the loss of a proton) interaction. In this case, the mode of binding involves two Au(0) atoms with a bridging nitrogen placed between them. Stable Au nanoparticles, as those required for robust semisynthetic nanozymes preparation, are better obtained when the protein is involved (at least in part) in the reduction of the gold ions.

On the origin of the improved hydrogen evolution reaction in Mn- and Co-doped MoS2.

In the field of hydrogen production, MoS2 demonstrates good catalytic properties for the hydrogen evolution reaction (HER) which improve when doped with metal cations. However, while the role of sulfur atoms as active sites in the HER is largely reported, the role of metal atoms (i.e. molybdenum or the dopant cations) has yet to be studied in depth. To understand the role of the metal dopant, we study MoS2 thin films doped with Co and Mn ions. We identify the contribution of the electronic bands of the Mn and Co dopants to the integral valence band of the material using in situ resonant photoemission measurements. We demonstrate that Mn and Co dopants act differently: Mn doping favors the shift of the S-Mo hybridized band towards the Fermi level, while in the case of Co doping it is the less hybridized Co band that shifts closer to the Fermi level. Doping with Mn increases the effectiveness of S as the active site, thus improving the HER, while doping with Co introduces the metallic site of Co as the active site, which is less effective in improving HER properties. We therefore clarify the role of the dopant cation in the electronic structure determining the active site for hydrogen adsorption/desorption. Our results pave the way for the design of efficient materials for hydrogen production via the doping route, which can be extended to different catalytic reactions in the field of energy applications.

Nd:YAG infrared laser as a viable alternative to excimer laser: YBCO case study.

We report on the growth and characterization of epitaxial YBa[Formula: see text]Cu[Formula: see text]O[Formula: see text] (YBCO) complex oxide thin films and related heterostructures exclusively by Pulsed Laser Deposition (PLD) and using first harmonic Nd:Y[Formula: see text]Al[Formula: see text]O[Formula: see text] (Nd:YAG) pulsed laser source ([Formula: see text] = 1064  nm). High-quality epitaxial YBCO thin film heterostructures display superconducting properties with transition temperature [Formula: see text] 80 K. Compared with the excimer lasers, when using Nd:YAG lasers, the optimal growth conditions are achieved at a large target-to-substrate distance d. These results clearly demonstrate the potential use of the first harmonic Nd:YAG laser source as an alternative to the excimer lasers for the PLD thin film community. Its compactness as well as the absence of any safety issues related to poisonous gas represent a major breakthrough in the deposition of complex multi-element compounds in form of thin films.

How the Environment Encourages the Natural Formation of Hydrated V2O5.

Herein, we report the microscopic and spectroscopic signatures of the hydrated V2O5 phase, prepared from the α-V2O5 powder, which was kept in deionized water inside an airtight glass container for approximately 2.5 years. The experimental results show an evolution of the V4+ component in V 2p3/2 core energy level spectra, and a peak corresponding to σ-OH- bond appeared in the valence band spectra in the hydrated V2O5 powder sample due to the water intercalation. Vanadium metal oxide particles were found to be self-nucleated into micro/nanorods after a long period of exposure to an extremely humid environment. The distinct features in the spectra obtained with high-resolution transmission electron microscopy, micro-Raman scattering, and X-ray photoelectron spectroscopy confirmed the presence of structural water molecules for the first time in the long-aged naturally hydrated V2O5 phase.

Evidence of Mn-Ion Structural Displacements Correlated with Oxygen Vacancies in La0.7Sr0.3MnO3 Interfacial Dead Layers.

The properties of half-metallic manganite thin films depend on the composition and structure in the atomic scale, and consequently, their potential functional behavior can only be based on fine structure characterization. By combining advanced transmission electron microscopy, electron energy loss spectroscopy, density functional theory calculations, and multislice image simulations, we obtained evidence of a 7 nm-thick interface layer in La0.7Sr0.3MnO3 (LSMO) thin films, compatible with the formation of well-known dead layers in manganites, with an elongated out-of-plane lattice parameter and structural and electronic properties well distinguished from the bulk of the film. We observed, for the first time, a structural shift of Mn ions coupled with oxygen vacancies and a reduced Mn valence state within such layer. Understanding the correlation between oxygen vacancies, the Mn oxidation state, and Mn-ion displacements is a prerequisite to engineer the magnetotransport properties of LSMO thin films.

Large Area Deposition by Radio Frequency Sputtering of Gd0.1Ce0.9O1.95 Buffer Layers in Solid Oxide Fuel Cells: Structural, Morphological and Electrochemical Investigation.

We investigate the influence of position, under large circular sputtering targets, on the final electrochemical performance of 35 mm diameter button solid oxide fuel cells with sputter-deposited Gadolinium doped Ceria barrier layers, positioned in order to almost cover the entirety of the area associated with a 120 × 80 mm2 industrial cell. We compare the results obtained via structural and morphological analysis to the Electrochemical Impedance Spectroscopy (EIS) measurements performed on the button cells, disentangling the role of different parameters. The Atomic Force Microscopy analysis makes it possible to observe a decrease in the roughness values from the peripheral to the central zones under the sputtering target, with peak-to-valley roughness values, respectively, decreasing from 380 nm to 300 nm, while Scanning Electron Microscopy and Energy Dispersive Spectroscopy show a dependence of the layer coverage from the position. The electrochemical performances of button cells with buffer layers of only 200 nm in thickness, and with negligible thickness gradients across them, show current density values of up to 478 mA/cm2 at 0.8 V and 650 °C, with an improvement of more than 67% with respect to button cells with standard (screen printed) buffer layers. These results point out the major influence exerted by parameters such as the thickness gradient and the coverage of the sputtered buffer layers in determining the final electrochemical performances.

Removal of supporting amorphous carbon film induced artefact from measured strain variation within a nanoparticle.

Strain variation within nanoparticles plays a crucial role in defining important properties related to their applications. Transmission electron microscopy (TEM) based imaging techniques are mostly used to determine strain variation within nanoparticle and supporting amorphous carbon film induced artefact in measured strain variation. In this present work, an algorithm is reported which is capable of removing supporting film induced artefacts from measured strain variations within nanoparticles. The effectivity of the algorithm was tested using simulated TEM results which proves that the algorithm works satisfactorily down to tp/tAC ratio of 0.25, where tp and tAC defines the thicknesses along the electron beam of nanoparticle and supporting amorphous film respectively. These simulations also reveal that changing the atomic number of atoms within the nanoparticle, or the density of the amorphous carbon does not affect the algorithm's effectiveness. When the algorithm was applied on experimental TEM results of a TiO2 nanoparticle, it even worked well for tp/tAC below 0.25, i.e. a relatively thick layer of amorphous carbon.

Unravelling the polarity of InN quantum dots using a modified approach of negative-spherical-aberration imaging.

InN quantum dots (QDs) are considered to be promising nanostructures for different device applications. For any hexagonal AB-stacking semiconductor system, polarity is an important feature which affects the electronic properties. Therefore, the determination of this characteristic on any wurtzite (semi)polar III-N compound or alloy is essential for defining its applicability. In this paper, the polarity of InN QDs grown on silicon by indium droplet epitaxy plus nitridation and annealing was determined by a modified approach combining exit wave reconstruction with negative-spherical-aberration high-resolution lattice imaging using TEM. Comparing the micrographs of two QDs from the same TEM specimen with the simulated images of InN slab structures generated under the same conditions as of the experiments, it was confirmed that the QDs of the present study are N polar. Given that the settlement of material's polarity has always been a tedious, indirect and controversial issue, the major value of our proposal is to provide a straightforward procedure to determine the polar direction from atomic-resolution focal series images.

Influence of supporting amorphous carbon film thickness on measured strain variation within a nanoparticle.

Strain variation within a nanoparticle plays a crucial role in tuning its properties. High Resolution Transmission Electron Microscopy (HRTEM) images of a nanoparticle supported on amorphous carbon film are used to determine the strain variation. Experimental measurements in this present study on a single crystalline silver nanoparticle exhibited an unexpected high strain variation. Generally, the influence of carbon film is not accounted for during interpretation of measured strain variation. However, experimental observations raise the question whether the supporting carbon film alters the measured strain variation. In order to address this, strain variation within a simulated Ag nanoparticle supported on an amorphous carbon is measured with varying film thicknesses. The results show that supporting carbon film thickness introduces an artefact leading to more strain variation than what is present within an unsupported nanoparticle. Moreover, the variation increases with increasing supporting carbon film thickness. This effect is more pronounced in a thinner nanoparticle. Without considering this influence, the interpretation of strain within a nanoparticle may introduce severe errors which in turn will affect the tunability of desirable properties for different applications. Since strain measurement depends on the accuracy of the atomic position, the interpretation of any result using the atomic position from HRTEM images of a nanoparticle should consider the influence of supporting film.