Mapping Orthorhombic Domains with Geometrical Phase Analysis in Rare-Earth Nickelate Heterostructures

Most perovskite oxides belong to the Pbnm space group, composed by an anisotropic unit cell, A-site antipolar displacements and oxygen octahedral tilts. Mapping the orientation of the orthorhombic unit cell in epitaxial heterostructures that consist of at least one Pbnm compound is often required to understand and control the different degrees of coupling established at their coherent interfaces and, therefore, their resulting physical properties. However, retrieving this information from the strain maps generated with high-resolution scanning transmission electron microscopy can be challenging, because the three pseudocubic lattice parameters are very similar in these systems. Here, we present a novel methodology for mapping the crystallographic orientation in Pbnm systems. It makes use of the geometrical phase analysis algorithm, as applied to aberration-corrected scanning transition electron microscopy images, but in an unconventional way. The method is fast and robust, giving real-space maps of the lattice orientations in Pbnm systems, from both cross-sectional and plan-view geometries and across large fields of view. As an example, we apply our methodology to rare-earth nickelate heterostructures, in order to investigate how the crystallographic orientation of these films depends on various structural constraints that are imposed by the underlying single crystal substrates. We observe that the resulting domain distributions and associated defect landscapes mainly depend on a competition between the epitaxial compressive/tensile and shear strains, together with the matching of atomic displacements at the substrate/film interface. The results point towards strategies for controlling these characteristics by appropriate substrate choice.Comment: 32 pages, 5 figures, 2 table

Transpacific Transport of Asian Anthropogenic Aerosols and its Impact on Surface Air Quality in the United States

We use satellite (MODIS) observations of aerosol optical depths (AODs) over the North Pacific, together with surface aerosol measurements at a network of remote U.S. sites (IMPROVE), to improve understanding of the transpacific transport of Asian aerosol pollution and assess the ability of a global 3-D chemical transport model (GEOS-Chem CTM) to quantify Asian aerosol enhancements in U.S. surface air. The MODIS observations show the strongest transpacific transport occurring in spring at 40–55°N. This transport in the model takes place mainly in the lower free troposphere (900–700 hPa) because of scavenging during transport either in the boundary layer or during lifting to the upper troposphere. The preferential altitude of aerosol transpacific transport results in direct impact on the elevated terrain of the NW United States. Sulfate observations in the NW United States in spring 2001 show higher concentrations on the days of model-predicted maximum Asian influence (1.04 μg m−3) than seasonal mean values (0.69 μg m−3). No such Asian enhancements are observed for nitrate or for organic carbon (OC) aerosol. Distinct Asian sulfate episodes correlated with dust events are observed in the NW United States and simulated with the model. The mean Asian pollution enhancement in that region in spring is 0.16 μg m−3 with a 50% estimated uncertainty. This is higher than the estimated natural concentration of 0.09 μg m−3 presently used as objective for regulation of visibility in U.S. wilderness areas.Earth and Planetary SciencesEngineering and Applied Science

Competition between Carrier Injection and Structural Distortions in Electron-Doped Perovskite Nickelate Thin Films

The discovery of superconductivity in doped infinite-layer nickelate thin films has brought increased attention to the behavior of the doped perovskite phase. Despite this interest, the majority of existing studies pertain to hole-doped perovskite rare-earth nickelate thin films, while most electron-doping studies have been performed on bulk materials so far. To tackle this imbalance, a detailed study that addresses doping of NdNiO thin films using A-site substitution is presented, using Pb as a dopant and taking advantage of its valence-skipping nature. Through a combination of complementary techniques including X-ray diffraction, transport measurements, X-ray absorption spectroscopy, electron energy-loss spectroscopy and scanning transmission electron microscopy, the valence of Pb in the NdPbNiO structure is confirmed to be 4+, and the behavior of the doped thin films is found to be controlled by a competition between carrier injection and structural distortions, which respectively reduce and increase the metal-to-insulator transition temperature. This work provides a systematic study of electron doping in NdNiO, demonstrating that A-site substitution with Pb is an appropriate method for such doping in perovskite rare-earth nickelate systems

Competition between Carrier Injection and Structural Distortions in Electron‐Doped Perovskite Nickelate Thin Films

The discovery of superconductivity in doped infinite‐layer nickelate thin films has brought increased attention to the behavior of the doped perovskite phase. Despite this interest, the majority of existing studies pertain to hole‐doped perovskite rare‐earth nickelate thin films, while most electron‐doping studies have been performed on bulk materials so far. To tackle this imbalance, a detailed study that addresses doping of NdNiO$_{3}$ thin films using A‐site substitution is presented, using Pb as a dopant and taking advantage of its valence‐skipping nature. Through a combination of complementary techniques including X‐ray diffraction, transport measurements, X‐ray absorption spectroscopy, electron energy‐loss spectroscopy and scanning transmission electron microscopy, the valence of Pb in the Nd$_{1−x}$Pb$_{x}$NiO$_{3}$ structure is confirmed to be 4+, and the behavior of the doped thin films is found to be controlled by a competition between carrier injection and structural distortions, which respectively reduce and increase the metal‐to‐insulator transition temperature. This work provides a systematic study of electron doping in NdNiO$_{3}$, demonstrating that A‐site substitution with Pb is an appropriate method for such doping in perovskite rare‐earth nickelate systems

Mode Coupling in Plasmonic Heterodimers Probed with Electron Energy Loss Spectroscopy

While plasmonic antennas composed of building blocks made of the same material have been thoroughly studied, recent investigations have highlighted the unique opportunities enabled by making compositionally asymmetric plasmonic systems. So far, mainly heterostructures composed of nanospheres and nanodiscs have been investigated, revealing opportunities for the design of Fano resonant nanostructures, directional scattering, sensing and catalytic applications. In this article, an improved fabrication method is reported that enables precise tuning of the heterodimer geometry, with interparticle distances made down to a few nanometers between Au–Ag and Au–Al nanoparticles. A wide range of mode energy detuning and coupling conditions are observed by near field hyperspectral imaging performed with electron energy loss spectroscopy, supported by full wave analysis numerical simulations. These results provide direct insights into the mode hybridization of plasmonic heterodimers, pointing out the influence of each dimer constituent in the overall electromagnetic response. By relating the coupling of nondipolar modes and plasmon–interband interaction with the dimer geometry, this work facilitates the development of plasmonic heterostructures with tailored responses, beyond the possibilities offered by homodimers

Large-area MoS2 grown using H2S as the sulphur source

We report on the growth of molybdenum disulphide (MoS2) using H2S as a gas-phase sulfur precursor that allows controlling the domain growth direction of domains in both vertical (perpendicular to the substrate plane) and horizontal (within the substrate plane), depending on the H2S:H2 ratio in the reaction gas mixture and temperature at which they are introduced during growth. Optical and atomic force microscopy measurements on horizontal MoS2 demonstrate the formation of monolayer triangular-shape domains that merge into a continuous film. Scanning transmission electron microscopy of monolayer MoS2 shows a regular atomic structure with a hexagonal symmetry. Raman and photoluminescence spectra confirm the monolayer thickness of the material. Field-effect transistors fabricated on MoS2 domains that are transferred onto Si/Si2 substrates show a mobility similar to previously reported exfoliated and chemical vapor deposition-grown materials. © 2015 IOP Publishing Ltd

The local effects of ovarian diathermy in an ovine model of Polycystic Ovary Syndrome

In order to develop a medical alternative to surgical ovarian diathermy (OD) in polycystic ovary syndrome (PCOS) more mechanistic information is required about OD. We therefore studied the cellular, molecular and vascular effects of diathermy on the ovary using an established ovine model of PCOS. Pregnant sheep were treated twice weekly with testosterone propionate (100 mg) from day 30–100 gestation. Their female offspring (n = 12) were studied during their second breeding season when the PCOS-like phenotype, with anovulation, is fully manifest. In one group (n = 4) one ovary underwent diathermy and it was collected and compared to the contralateral ovary after 24 hours. In another group a treatment PCOS cohort underwent diathermy (n = 4) and the ovaries were collected and compared to the control PCOS cohort (n = 4) after 5 weeks. Ovarian vascular indices were measured using contrast-enhanced ultrasound and colour Doppler before, immediately after, 24 hours and five weeks after diathermy. Antral follicles were assessed by immunohistochemistry and ovarian stromal gene expression by quantitative RT-PCR 24 hours and 5 weeks after diathermy. Diathermy increased follicular atresia (P<0.05) and reduced antral follicle numbers after 5 weeks (P<0.05). There was an increase in stromal CCL2 expression 24 hours after diathermy (P<0.01) but no alteration in inflammatory indices at 5 weeks. Immediately after diathermy there was increased microbubble transit time in the ovarian microvasculature (P = 0.05) but this was not seen at 24 hours. However 24 hours after diathermy there was a reduction in the stromal Doppler blood flow signal (P<0.05) and an increased ovarian resistance index (P<0.05) both of which persisted at 5 weeks (P<0.01; P<0.05). In the ovine model of PCOS, OD causes a sustained reduction in ovarian stromal blood flow with an increased ovarian artery resistance index associated with atresia of antral follicles

The Generation of Successive Unmarked Mutations and Chromosomal Insertion of Heterologous Genes in Actinobacillus pleuropneumoniae Using Natural Transformation

We have developed a simple method of generating scarless, unmarked mutations in Actinobacillus pleuropneumoniae by exploiting the ability of this bacterium to undergo natural transformation, and with no need to introduce plasmids encoding recombinases or resolvases. This method involves two successive rounds of natural transformation using linear DNA: the first introduces a cassette carrying cat (which allows selection by chloramphenicol) and sacB (which allows counter-selection using sucrose) flanked by sequences to either side of the target gene; the second transformation utilises the flanking sequences ligated directly to each other in order to remove the cat-sacB cassette. In order to ensure efficient uptake of the target DNA during transformation, A. pleuropneumoniae uptake sequences are added into the constructs used in both rounds of transformation. This method can be used to generate multiple successive deletions and can also be used to introduce targeted point mutations or insertions of heterologous genes into the A. pleuropneumoniae chromosome for development of live attenuated vaccine strains. So far, we have applied this method to highly transformable isolates of serovars 8 (MIDG2331), which is the most prevalent in the UK, and 15 (HS143). By screening clinical isolates of other serovars, it should be possible to identify other amenable strains

Efficient cleavage of aryl ether C–O linkages by Rh–Ni and Ru–Ni nanoscale catalysts operating in water

Bimetallic Ru–Ni and Rh–Ni nanocatalysts coated with a phase transfer agent efficiently cleave aryl ether C–O linkages in water in the presence of hydrogen. For dimeric substrates with weaker C–O linkages, i.e. α-O-4 and β-O-4 bonds, low loadings of the precious metal (Rh or Ru) in the nanocatalysts quantitatively afford monomers, whereas for the stronger 4-O-5 linkage higher amounts of the precious metal are required to achieve complete conversion. Under the optimized, relatively mild operating conditions, the C–O bonds in a range of substituted ether compounds are efficiently cleaved, and mechanistic insights into the reaction pathways are provided. This work paves the way to sustainable approaches for the hydrogenolysis of C–O bonds

The Semileptonic Decays B→πlνB\to\pi l\nu and D→πlνD\to\pi l\nu from Lattice QCD

We present a lattice QCD calculation of the form factors and differential decay rates for semileptonic decays of the heavy-light mesons $B$ and $D$ to the final state $\pi l\nu$. The results are obtained with three methodological improvements over previous lattice calculations: a matching procedure that reduces heavy-quark lattice artifacts, the first study of lattice-spacing dependence, and the introduction of kinematic cuts to reduce model dependence. We show that the main systematics are controllable (within the quenched approximation) and outline how the calculations could be improved to aid current experiments in the determination of~$|V_{ub}|$ and~$|V_{cd}|$.Comment: 35 pp, 12 fig