Ultra-Small YPO4 -YAG:Ce Composite Nanophosphors with a Photoluminescence Quantum Yield Exceeding 50.

Synthesis of high quality colloidal Cerium(III) doped yttrium aluminum garnet (Y3 Al5 O12 :Ce3+ , "YAG:Ce") nanoparticles (NPs) meeting simultaneously both ultra-small size and high photoluminescence (PL) performance is challenging, as generally a particle size/PL trade-off has been observed for this type of nanomaterials. The glycothermal route is capable to yield ultra-fine crystalline colloidal YAG:Ce nanoparticles with a particle size as small as 10 nm but with quantum yield (QY) no more than 20%. In this paper, the first ultra-small YPO4 -YAG:Ce nanocomposite phosphor particles having an exceptional QY-to-size performance with an QY up to 53% while maintaining the particle size ≈10 nm is reported. The NPs are produced via a phosphoric acid- and extra yttrium acetate-assisted glycothermal synthesis route. Localization of phosphate and extra yttrium entities with respect to cerium centers in the YAG host has been determined by fine structural analysis techniques such as X-ray diffration (XRD), solid state nuclear magnetic resonance (NMR), and high resolution scanning transmission electron microscopy (HR-STEM), and shows distinct YPO4 and YAG phases. Finally, a correlation between the additive-induced physico-chemical environment change around cerium centers and the increasing PL performance has been suggested based on electron paramagnetic resonance (EPR), X-ray photoelectron spectrometry (XPS) data, and crystallographic simulation studies.

The delicate balance of phase speciation in bimetallic nickel cobalt nanoparticles.

Bimetallic nickel-cobalt nanoparticles are highly sought for their potential as catalytic and magnetic nanoparticles. These are typically prepared in organic solvents in the presence of strong stabilizing ligands such as tri-n-octylphosphine (TOP). Due to the variety of cobalt crystallographic phases and to the strong interaction of the ligands with the metallic surfaces, forming fcc nanoparticles rather than a phase mixture is a challenging endeavor. Here, using a two-step synthesis strategy that aims at a core-shell nickel-cobalt morphology, we demonstrated that many parameters have to be adjusted: concentration of the metal precursors, stoichiometry of TOP, and heating program from room temperature to 180 °C. We found optimized conditions to form size-controlled fcc NiCo nanoparticles from preformed Ni nanoparticles, and the phase attribution was confirmed with a combination of X-Ray diffraction on powder and X-Ray absorption spectroscopy at the Co K edge. We then investigated the early stages of Co nucleation on the nickel using a lower stoichiometry of Co, down to 0.05 equiv. vs. Ni. Using X-ray photoelectron spectroscopy and scanning transmission electron microscopy coupled to energy-dispersive X-Ray spectroscopy and electron energy loss spectroscopy, we showed that cobalt reacts first on the nickel nanoparticles but easily forms cobalt-rich larger aggregates in the further steps of the reaction.

Fast and efficient shear-force assisted production of covalently functionalized oxide nanosheets.

HYPOTHESIS: While controlled and efficient exfoliation of layered oxides often remains a time consuming challenge, the surface modification of inorganic nanosheets is of outmost importance for future applications. The functionalization of the bulk material prior to exfoliation should allow the application of tools developped for Van der Waals materials to directly produce functionalized oxide nanosheets. EXPERIMENTS: The Aurivillius phase Bi2SrTa2O9 is functionalized by a linear aliphatic phosphonic acid via microwave-assisted reactions. The structure of the hybrid material and the coordination of the phosphonate group is scrutinized, notably by Pair Distribution Function. This functionalized layered oxide is then exfoliated in one hour in organic solvent, using high shear force dispersion. The obtained nanosheets are characterized in suspension and as deposits to check their chemical integrity. FINDINGS: The covalent functionalization decreases the electrostatic cohesion between the inorganic layers leading to an efficient exfoliation in short time under shearing. The functionalization of the bulk material is preserved on the nanosheets upon exfoliation and plays a major role to enable liquid-phase exfoliation and in the stability of the resulting suspensions. This strategy is very promising for the straighforward preparation of functionalized nanosheets, paving the way for versatile design of new (multi)functional hybrid nanosheets for various potential applications.

Polarization-dependent optical band gap energy of aligned semiconducting titanium oxide nanowire deposits.

Thin deposits of aligned semiconducting titanium oxide and of zinc oxide nanowires are prepared by grazing incidence spraying on transparent substrates. By measuring the transmittance of linearly polarized light of these anisotropic assemblies as compared to that of randomly oriented nanowires and of spherical nanoparticles, we find that titanium oxide nanowires exhibit an orientation-dependent variation of the apparent optical band gap energy at room temperature (>100 meV), depending on the direction of the polarization of the light with respect to the direction of alignment of the nanowires.

In situ STEM study on the morphological evolution of copper-based nanoparticles during high-temperature redox reactions.

Despite the broad relevance of copper nanoparticles in industrial applications, the fundamental understanding of oxidation and reduction of copper at the nanoscale is still a matter of debate and remains within the realm of bulk or thin film-based systems. Moreover, the reported studies on nanoparticles vary widely in terms of experimental parameters and are predominantly carried out using either ex situ observation or environmental transmission electron microscopy in a gaseous atmosphere at low pressure. Hence, dedicated studies in regards to the morphological transformations and structural transitions of copper-based nanoparticles at a wider range of temperatures and under industrially relevant pressure would provide valuable insights to improve the application-specific material design. In this paper, copper nanoparticles are studied using in situ Scanning Transmission Electron Microscopy to discern the transformation of the nanoparticles induced by oxidative and reductive environments at high temperatures. The nanoparticles were subjected to a temperature of 150 °C to 900 °C at 0.5 atm partial pressure of the reactive gas, which resulted in different modes of copper mobility both within the individual nanoparticles and on the surface of the support. Oxidation at an incremental temperature revealed the dependency of the nanoparticles' morphological evolution on their initial size as well as reaction temperature. After the formation of an initial thin layer of oxide, the nanoparticles evolved to form hollow oxide shells. The kinetics of formation of hollow particles were simulated using a reaction-diffusion model to determine the activation energy of diffusion and temperature-dependent diffusion coefficient of copper in copper oxide. Upon further temperature increase, the hollow shell collapsed to form compact and facetted nanoparticles. Reduction of copper oxide was carried out at different temperatures starting from various oxide phase morphologies. A reduction mechanism is proposed based on the dynamic of the reduction-induced fragmentation of the oxide phase. In a broader perspective, this study offers insights into the mobility of the copper phase during its oxidation-reduction process in terms of microstructural evolution as a function of nanoparticle size, reaction gas, and temperature.

Nanometer scale insight on the analysis of limpets mineralized teeth: Special focus on the silica-containing regions.

We report the electron microscopy-based analysis of the major lateral tooth of the limpet Colisella subrugosa during early and intermediate stages of development. We aimed to analyze the structural relationship among the needle-like crystals of the iron oxide goethite, the amorphous silica phase that forms the tooth base and occupy inter-crystalline spaces in the cusp, and the chitin fibers of the matrix. Goethite crystals followed the three dimensional organization pattern of the chitin fibers in the cusp. In the tooth base, spherical individual silica granules were found in regions where the chitin fibers cross. The spherical granules near the interface between the tooth base and the cusp (junction zone) formed an almost continuous medium that could easily be ultrathin-sectioned for further analysis. By contrast, the nearby silica-rich region localized on the other side of the junction zone contained needle-like goethite crystals immersed in the matrix and presented a conchoidal fracture. The chitin fibers from the silica granules of the tooth base were dotted or undulating in projection with a periodicity of about 6 nm when observed by high magnification transmission electron microscopy. Very thin goethite crystals were present in the base of the cusp near the junction zone surrounded by silica. On several occasions, crystals presented internal thin straight white lines parallel to the major axis, indicating a possible growth around fibers. We propose that silica and iron oxide phases mineralization may occur simultaneously at least for some period and that silica moderates the dimensions of the iron oxide crystals.

Strong interfacial coupling through exchange interactions in soft/hard core-shell nanoparticles as a function of cationic distribution.

Exchange coupled core-shell nanoparticles present high potential to tune adequately the magnetic properties for specific applications such as nanomedicine or spintronics. Here, we report on the design of core-shell nanoparticles by performing the successive thermal decomposition of Fe and Co complexes. Depending on the thermal stability and the concentration of the Co precursor, we were able to control the formation of a hard ferrimagnetic (FiM) Co-ferrite shell or an antiferromagnetic (AFM) CoO shell at the surface of a soft FiM Fe3-δO4 core. The formation of the Co-ferrite shell was also found to occur through two different mechanisms: the diffusion of Co or the growth at the iron oxide surface. The structural properties of core-shell nanoparticles were investigated by a wide panel of techniques such as HAADF, STEM and XRD. The distribution of Fe and Co elements in the crystal structure was described accurately by XAS and XMCD. The operating conditions influenced significantly the oxidation rate of Fe2+ in the core as well as the occupancy of Oh sites by Fe2+ and Co2+ cations. The structural properties of nanoparticles were correlated with their magnetic properties which were investigated by SQUID magnetometry. Each core-shell nanoparticle displayed enhanced effective magnetic anisotropy energy (Eeff) in comparison with pristine Fe3-δO4 nanoparticles because of magnetic coupling at the core-shell interface. The Co-ferrite FiM shells resulted in better enhancement of Eeff than a CoO AFM shell. In addition, the magnetic properties were also influenced by the core size. The coercive field (HC) was increased by core reduction while the blocking temperature (TB) was increased by a larger core. Element-specific XMCD measurements showed the fine coupling of Fe and Co cations which agree with Co-ferrite in each sample, e.g. the formation of a Co-doped interfacial layer in the Fe3-δO4@CoO nanoparticles.

Nanoscale design of polarization in ultrathin ferroelectric heterostructures.

The success of oxide electronics depends on the ability to design functional properties such as ferroelectricity with atomic accuracy. However, despite tremendous advances in ferroelectric heterostructures, the development towards multilevel architectures with precise layer-by-layer command over the polarization is impeded by the lack of continuous control over the balance of electrostatics, strain, chemistry and film thickness during growth. Moreover, the polarization in the deeper layers becomes inaccessible when these are buried by the ongoing deposition. Taking ferroelectric BaTiO3 and multiferroic BiFeO3 as model systems, we observe and engineer the emergence, orientation and interaction of ferroelectric polarization in ultrathin heterostructures with monolayer accuracy. We achieve this by optical second harmonic generation which tracks the evolution of spontaneous polarization in real time throughout the deposition process. Such direct and in situ access to the polarization during growth leads us to heterostructures with user-defined polarization sequences-towards a new class of functional ferroic materials.

Uncovering the Stabilization Mechanism in Bimetallic Ruthenium-Iridium Anodes for Proton Exchange Membrane Electrolyzers.

Proton exchange membrane (PEM) electrolyzers are attracting an increasing attention as a promising technology for the renewable electricity storage. In this work, near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) is applied for in situ monitoring of the surface state of membrane electrode assemblies with RuO2 and bimetallic Ir0.7Ru0.3O2 anodes during water splitting. We demonstrate that Ir protects Ru from the formation of an unstable hydrous Ru(IV) oxide thereby rendering bimetallic Ru-Ir oxide electrodes with higher corrosion resistance. We further show that the water splitting occurs through a surface Ru(VIII) intermediate, and, contrary to common opinion, the presence of Ir does not hinder its formation.

Effect of the nanometric scale thickness on the magnetization steps in Ca3Co2O6 thin films.

We report on the effect of the film thickness on the magnetic properties of Ca3Co2O6films with an emphasis on the magnetization steps usually observed in the M-H curves below 10 K. Films with thicknesses between 35 and 200 nm all present two magnetic transitions at about T(C1) = 22 K and T(C2) = 10 K, corresponding to a 3D long range ferrimagnetic order and the transition to the formation of a frozen spin state, respectively. The magnetization curves at 10 K exhibit the expected stepped variation. However, by decreasing the thickness below a critical value of about 60 nm, no magnetization plateau is observed when the M-H curve is recorded at 2 K. Moreover, an additional transition in the susceptibility curve is observed at 45 K. These changes can be attributed to the reduced coherence length of the propagation vector along and perpendicular to the chains, and are supported by the magnetization relaxation measurements which indicate a reduction of the relaxation time. These results are helpful for understanding the origin of the magnetization steps in the one-dimensional Ca3Co2O6 cobaltite and confront the theoretical models aimed at explaining the magnetic properties in this system.

Correlation of structural properties with energy transfer of Eu-doped ZnO thin films prepared by sol-gel process and magnetron reactive sputtering.

We investigated the structural and optical properties of Eu-doped ZnO thin films made by sol-gel technique and magnetron reactive sputtering on Si (100) substrate. The films elaborated by sol-gel process are polycrystalline while the films made by sputtering show a strongly textured growth along the c-axis. X-ray diffraction patterns and transmission electron microscopy analysis show that all samples are free of spurious phases. The presence of Eu(2+) and Eu(3+) into the ZnO matrix has been confirmed by x-ray photoemission spectroscopy. This means that a small fraction of Europium substitutes Zn(2+) as Eu(2+) into the ZnO matrix; the rest of Eu being in the trivalent state. This is probably due to the formation of Eu(2)O(3) oxide at the surface of ZnO particles. This is at the origin of the strong photoluminescence band observed at 2 eV, which is characteristic of the (5)D(0)-->(7)F(2) Eu(3+) transition. In addition the photoluminescence excitonic spectra showed efficient energy transfer from the ZnO matrix to the Eu(3+) ion, which is qualitatively similar for both films although the sputtered films have a better structural quality compared to the sol-gel process grown films.

Neutralizing monoclonal antibodies to human immunodeficiency virus type 1 do not inhibit viral transcytosis through mucosal epithelial cells.

HIV-1 transcytosis has been proposed as a potential mechanism allowing the virus to cross the epithelium during mucosal transmission. Epitopes of the HIV-1 envelope involved in this process have not been identified yet. Here, we assessed a large panel of HIV neutralizing antibodies recognizing well-characterized epitopes of the HIV-1 envelope for their ability to block HIV-1 transcytosis across a confluent epithelial monolayer. We found that all of the 13 HIV-1-specific monoclonal antibodies tested in the present study, including the three broadly neutralizing antibodies 2F5, 2G12 and IgG1b12, lacked the ability to inhibit transcytosis of cell-free and cell-associated R5- as X4-tropic HIV-1 across a tight and polarized monolayer of HEC-1 epithelial cells. In contrast, anti-gp160 polyclonal antibodies purified from serum or breast milk of HIV-1-infected individuals potently inhibited HIV-1 transcytosis. Furthermore, polymeric S-IgA exhibited similar ability to inhibit transcytosis compared to IgG despite their lower anti-gp160 specific activity. Together, these results demonstrate that the major neutralizing envelope epitopes of HIV-1 are not involved in HIV-1 transcytosis, and suggest that surface agglutination of virus particles may participate to the blocking effect observed with both polyclonal and polymeric anti-gp160 immunoglobulins.