Gold and iodine diffusion in large area perovskite solar cells under illumination.

Operational stability is the main issue hindering the commercialisation of perovskite solar cells. Here, a long term light soaking test was performed on large area hybrid halide perovskite solar cells to investigate the morphological and chemical changes associated with the degradation of photovoltaic performance occurring within the devices. Using Scanning Transmission Electron Microscopy (STEM) in conjunction with EDX analysis on device cross sections, we observe the formation of gold clusters in the perovskite active layer as well as in the TiO2 mesoporous layer, and a severe degradation of the perovskite due to iodine migration into the hole transporter. All these phenomena are associated with a drastic drop of all the photovoltaic parameters. The use of advanced electron microscopy techniques and data processing provides new insights on the degradation pathways, directly correlating the nanoscale structure and chemistry to the macroscopic properties of hybrid perovskite devices.

Rapid open-air deposition of uniform, nanoscale, functional coatings on nanorod arrays.

Coating of high-aspect-ratio nanostructures has previously been achieved using batch processes poorly suited for high-throughput manufacturing. It is demonstrated that uniform, nanoscale coatings can be rapidly deposited on zinc oxide nanorod arrays in open-air using an atmospheric pressure spatial deposition system. The morphology of the metal oxide coatings is examined and good electrical contact with the underlying nanorods is observed. The functionality of the coatings is demonstrated in colloidal quantum dot and hybrid solar cells.

Signature of magnetic-dependent gapless odd frequency states at superconductor/ferromagnet interfaces.

The theory of superconductivity developed by Bardeen, Cooper and Schrieffer (BCS) explains the stabilization of electron pairs into a spin-singlet, even frequency, state by the formation of an energy gap within which the density of states is zero. At a superconductor interface with an inhomogeneous ferromagnet, a gapless odd frequency superconducting state is predicted, in which the Cooper pairs are in a spin-triplet state. Although indirect evidence for such a state has been obtained, the gap structure and pairing symmetry have not so far been determined. Here we report scanning tunnelling spectroscopy of Nb superconducting films proximity coupled to epitaxial Ho. These measurements reveal pronounced changes to the Nb subgap superconducting density of states on driving the Ho through a metamagnetic transition from a helical antiferromagnetic to a homogeneous ferromagnetic state for which a BCS-like gap is recovered. The results prove odd frequency spin-triplet superconductivity at superconductor/inhomogeneous magnet interfaces.

Gas Exchanges and Dehydration in Different Intensities of Conditioning in Tifton 85 Bermudagrass: Nutritional Value during Hay Storage.

The present study aimed at evaluating the intensity of Tifton 85 conditioning using a mower conditioner with free-swinging flail fingers and storage times on dehydration curve, fungi presence, nutritional value and in vitro digestibility of Tifton 85 bermudagrass hay dry matter (DM). The dehydration curve was determined in the whole plant for ten times until the baling. The zero time corresponded to the plant before cutting, which occurred at 11:00 and the other collections were carried out at 8:00, 10:00, 14:00, and 16:00. The experimental design was randomised blocks with two intensities of conditioning (high and low) and ten sampling times, with five replications. The high and low intensities related to adjusting the deflector plate of the free iron fingers (8 and 18 cm). In order to determine gas exchanges during Tifton 85 bermudagrass dehydration, there were evaluations of mature leaves, which were placed in the upper middle third of each branch before the cutting, at every hour for 4 hours. A portable gas analyser was used by an infrared IRGA (6400xt). The analysed variables were photosynthesis (A), stomatal conductance (gs), internal CO2 concentration (Ci), transpiration (T), water use efficiency (WUE), and intrinsic water use efficiency (WUEi). In the second part of this study, the nutritional value of Tifton 85 hay was evaluated, so randomised blocks were designed in a split plot through time, with two treatments placed in the following plots: high and low intensity of cutting and five different time points as subplots: cutting (additional treatment), baling and after 30, 60, and 90 days of storage. Subsequently, fungi that were in green plants as well as hay were determined and samples were collected from the grass at the cutting period, during baling, and after 30, 60, and 90 days of storage. It was observed that Tifton 85 bermudagrass dehydration occurred within 49 hours, so this was considered the best time for drying hay. Gas exchanges were more intense before cutting, although after cutting they decreased until ceasing within 4 hours. The lowest values of acid detergent insoluble nitrogen were obtained with low conditioning intensity after 30 days of storage, 64.8 g/kg DM. The in vitro dry matter of Tifton 85 bermudagrass did not differ among the storage times or the conditioning intensities. There was no fungi present in the samples collected during the storage period up to 90 days after dehydration, with less than 30 colony forming units found on plate counting. The use of mower conditioners in different intensities of injury did not speed up the dehydration time of Tifton 85.

Exploring the benefits of electron tomography to characterize the precise morphology of core-shell Au@Ag nanoparticles and its implications on their plasmonic properties.

In the design and engineering of functional core-shell nanostructures, material characterization at small length scales remains one of the major challenges. Here we show how electron tomography in high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) mode can be applied successfully to perform nano-metrological characterization of Au@Ag core-shell nanostructures. This work stresses the benefits of HAADF-STEM tomography and its use as a novel and rigorous tool for understanding the physical-chemical properties of complex 3D core-shell nanostructures. The reconstructed Au@Ag core-shell architecture was used as an input for discrete dipole approximation (DDA)-based electrodynamics simulations of the optical properties of the nanostructures. The implications of localized surface plasmon spectroscopy as well as Raman-enhanced spectroscopy are analysed.

Revealing lithium-silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy.

Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by (7)Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium-silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies.

Giant and reversible extrinsic magnetocaloric effects in La0.7Ca0.3MnO3 films due to strain.

Large thermal changes driven by a magnetic field have been proposed for environmentally friendly energy-efficient refrigeration, but only a few materials that suffer hysteresis show these giant magnetocaloric effects. Here we create giant and reversible extrinsic magnetocaloric effects in epitaxial films of the ferromagnetic manganite La(0.7)Ca(0.3)MnO(3) using strain-mediated feedback from BaTiO(3) substrates near a first-order structural phase transition. Our findings should inspire the discovery of giant magnetocaloric effects in a wide range of magnetic materials, and the parallel development of nanostructured bulk samples for practical applications.

Bottom-up engineering of the surface roughness of nanostructured cubic zirconia to control cell adhesion.

Nanostructured cubic zirconia is a strategic material for biomedical applications since it combines superior structural and optical properties with a nanoscale morphology able to control cell adhesion and proliferation. We produced nanostructured cubic zirconia thin films at room temperature by supersonic cluster beam deposition of nanoparticles produced in the gas phase. Precise control of film roughness at the nanoscale is obtained by operating in a ballistic deposition regime. This allows one to study the influence of nanoroughness on cell adhesion, while keeping the surface chemistry constant. We evaluated cell adhesion on nanostructured zirconia with an osteoblast-like cell line using confocal laser scanning microscopy for detailed morphological and cytoskeleton studies. We demonstrated that the organization of cytoskeleton and focal adhesion formation can be controlled by varying the evolution of surface nanoroughness.

Metastable crystalline AuGe catalysts formed during isothermal germanium nanowire growth.

We observe the formation of metastable AuGe phases without quenching, during strictly isothermal nucleation and growth of Ge nanowires, using video-rate lattice-resolved environmental transmission electron microscopy. We explain the unexpected formation of these phases through a novel pathway involving changes in composition rather than temperature. The metastable catalyst has important implications for nanowire growth, and more broadly, the isothermal process provides both a new approach to growing and studying metastable phases, and a new perspective on their formation.

High-rate production of functional nanostructured films and devices by coupling flame spray pyrolysis with supersonic expansion.

The fabrication of functional thin films and devices by direct deposition of nanoparticles from the gas phase is a promising approach enabling, for instance, the integration of complex analytical and sensing capabilities on microfabricated platforms. Aerosol-based techniques ensure large-scale nanoparticle production and they are potentially suited for this goal. However, they are not adequate in terms of fine control over the lateral resolution of the coatings, mild processing conditions (avoiding high temperature and aggressive chemicals), low contamination and compatibility with microfabrication processes. Here we report the high-rate and efficient production of functional nanostructured films by nanoparticle assembling obtained by the combination of flame spray pyrolysis and supersonic expansion. Our approach merges the advantages of flame spray pyrolysis for bulk nanopowders such as process stability and wide material library availability with those of supersonic cluster beam deposition in terms of lateral resolution and of direct integration of nanomaterials on devices. We efficiently produced nanostructured films and devices (such as gas sensors) using metal oxide, pure noble metal and oxide-supported noble metal nanoparticles.

Formation of metastable liquid catalyst during subeutectic growth of germanium nanowires.

Lattice-resolved, video-rate environmental transmission electron microscopy shows the formation of a liquid Au-Ge layer on sub-30-nm Au catalyst crystals and the transition of this two-phase Au-Ge/Au coexistence to a completely liquid Au-Ge droplet during isothermal digermane exposure at temperatures far below the bulk Au-Ge eutectic temperature. Upon Ge crystal nucleation and subsequent Ge nanowire growth, the catalyst either recrystallizes or remains liquid, apparently stabilized by the Ge supersaturation. We argue that there is a large energy barrier to nucleate diamond-cubic Ge, but not to nucleate the Au-Ge liquid. As a result, the system follows the more kinetically accessible path, forming a liquid even at 240 degrees C, although there is no liquid along the most thermodynamically favorable path below 360 degrees C.

Hierarchical TiO2 photoanode for dye-sensitized solar cells.

Hierarchical or one-dimensional architectures are among the most exciting developments in material science these recent years. We present a nanostructured TiO(2) assembly combining these two concepts and resembling a forest composed of individual, high aspect-ratio, treelike nanostructures. We propose to use these structures for the photoanode in dye-sensitized solar cells, and we achieved 4.9% conversion efficiency in combination with C101 dye. We demonstrate this morphology beneficial to hamper the electron recombination and also mass transport control in the mesopores when solvent-free ionic liquid electrolyte is used.

Template nanowires for spintronics applications: nanomagnet microwave resonators functioning in zero applied magnetic field.

Low-cost spintronic devices functioning in zero applied magnetic field are required for bringing the idea of spin-based electronics into the real-world industrial applications. Here we present first microwave measurements performed on nanomagnet devices fabricated by electrodeposition inside porous membranes. In the paper, we discuss in details a microwave resonator consisting of three nanomagnets, which functions in zero external magnetic field. By applying a microwave signal at a particular frequency, the magnetization of the middle nanomagnet experiences the ferromagnetic resonance (FMR), and the device outputs a measurable direct current (spin-torque diode effect). Alternatively, the nanodevice can be used as a microwave oscillator functioning in zero field. To test the resonators at microwave frequencies, we developed a simple measurement setup.

Controlling the catalyst during carbon nanotube growth.

We have recently been able to grow single-walled carbon nanotubes by purely thermal chemical vapour deposition (CVD) at temperatures as low as 400 degrees C. This has been achieved by separating the catalyst pre-treatment step from the growth step. In the pre-treatment step, a thin film catalyst is re-arranged into a series of nano-droplets, which are then the active catalysts. Both steps have been studied by in-situ environmental transmission electron microscopy and X-ray photoemission spectroscopy. We have also studied the catalyst yield, the weight of nanotubes grown per weight of transition metal catalyst. Using very thin layers of Fe on Al2O3 support in a remote plasma-assisted CVD, we have achieved yields of order 100,000. This may be due to control of catalyst poisoning by ensuring an etching path.

A simple low temperature synthesis route for ZnO-MgO core-shell nanowires.

We report a hydrothermal synthesis method for MgO shell coatings directly onto the surface of ZnO nanowire arrays. The entire process can be carried out below 100 °C. The MgO shells are produced by the addition of 10 mM magnesium nitrate with 0.2 M sodium hydroxide in water, resulting in a shell thickness of up to 8 nm, verified by high resolution transmission electron microscopy. The viability of the MgO layer as a functional element of optoelectronic devices was tested on solid-state organic hole-transporter based dye-sensitized solar cells. Incorporation of the MgO shell into the solar cell resulted in substantive efficiency improvements of over 400% in comparison to the pristine ZnO nanowire based photovoltaics, indicating that electrons can efficiently tunnel through the 'insulating' MgO shell.

Nanostructured Ag(4)O(4) films with enhanced antibacterial activity.

Ag(4)O(4) (i.e. silver(I)-silver(III) oxide) thin films with tailored structure and morphology at the nanoscale have been grown by reactive pulsed laser deposition (PLD) in an oxygen-containing atmosphere and they are shown to exhibit a very strong antibacterial activity towards Gram-negative bacteria (E. coli) and to completely inhibit the growth of Gram-positive bacteria (S. aureus). The formation of this particular high-valence silver oxide is explained in terms of the reactions occurring during the expansion of the ablated species in the reactive atmosphere, leading to the formation of low-stability Ag-O dimers and atomic oxygen, providing reactive species at the substrate where the film grows. PLD is shown to allow control of the structure (i.e. crystallinity and grain size) and of the morphology of the films, from compact and columnar to foam-like, thus allowing the deposition of nanocrystalline films with increased porosity and surface area. The antibacterial action towards E. coli is demonstrated and is shown to be superior to that of nanostructured Ag-based medical products. This can be related to the release of Ag ions with high oxidation number, which are known to be very reactive towards bacteria, and to the peculiar morphology at the nanoscale resulting in a large effective surface area.

Deterministic shape-selective synthesis of nanowires, nanoribbons and nanosaws by steady-state vapour-transport.

We demonstrate the deterministic shape-selective synthesis and growth of CdSe nanowires, nanosaws and nanoribbons by a simple vapour-transport process in a tube furnace. The key step, in order to achieve reproducible shape selectivity for a given set of deposition parameters, is to exclude any effects of the temperature ramping. We prove that an efficient precursor-flow shutter is achieved just by varying the total furnace pressure. We then present a shape-diagram linking the different nanocrystals morphologies to only two parameters: powder and substrate temperature. These are varied in the 550-700 °C and 400-600 °C range, respectively. A model explaining the shape control is discussed.

Nanocrystalline metal/carbon composites produced by supersonic cluster beam deposition.

In this work we show that supersonic cluster beam deposition is a viable method for the synthesis of nanocrystalline metal/carbon composites. By assembling carbon and metallic clusters seeded in a supersonic beam, we have grown films consisting of metal nanoparticles embedded in a nano-structured carbon matrix. Samples containing 3d transition metals (Ti, Ni) and noble metals (Au, Pd, Pt) with different metal abundances, particle size and dilution have been characterized by transmission electron microscopy. The influence of different metals on the structure of the carbon matrix has been investigated. Spatially resolved ultraviolet photoemission electron spectroscopy showed substantial surface oxidation of 3d transition metal clusters. On a micrometric scale, the spatial distribution of the metallic nanoparticles appeared to be homogeneous.

A simple method for the synthesis of silicon carbide nanorods.

SiC nanorods were synthesized by a reaction at a temperature of 1200 degrees C, under an argon gas atmosphere, from silicon and amorphous carbon powders mixed by ball milling. The reaction product, which contain SiC nanorods and nanoparticles, has been characterized by high-resolution transmission electron microscopy, X-ray diffraction, and micro-Raman spectroscopy. The synthesized nanorods are more than 1 micron long with a mean diameter of about 10-30 nm. The nanorods possess a well-defined crystalline structure with a thin layer of amorphous SiO2 on the surface. Raman shifts of SiC nanorods and the role of structural defects are discussed.

[Nursing ethics committees at health institutions in Ribeirao Preto]. / Comissões de ética de enfermagem em instituições de saúde de Ribeirão Preto.

The aim of this study was to identify hospitals in Ribeirão Preto, Brazil which have a Nursing Ethics Committee established according to the Decision of the Nursing Regional Council, to examine their activities and attributions, the reasons why they were created and the enforcement of legislation. The results have shown that from the eleven hospitals visited, eight ought to have instituted their Committees; however, only three had done it and only one of them was effectively active. The study made it possible to identify the most frequent infractions to ethics as well as the penalties occasionally inflicted and evidenced the unpreparedness of Nursing professionals as to their attitudes concerning Committees.