National Institute Of Materials Physics - Romania

Angle-resolved photoelectron spectroscopy (ARPES) is the main experimental tool to explore electronic structure of solids resolved in the electron momentum k. Soft-X-ray ARPES (SX-ARPES), operating in a photon energy range around 1 keV, benefits from enhanced probing depth compared to the conventional VUV-range ARPES, and elemental/chemical state specificity achieved with resonant photoemission. These advantages make SX-ARPES ideally suited for buried heterostructure and impurity systems, which are at the heart of current and future electronics. These applications are illustrated here with a few pioneering results, including buried quantum-well states in semiconductor and oxide heterostructures, their bosonic coupling critically affecting electron transport, magnetic impurities in diluted magnetic semiconductors and topological materials, etc. High photon flux and detection efficiency are crucial for pushing the SX-ARPES experiment to these most photon-hungry cases.

Europium substituted bismuth ferrite powders were synthesized by the sol-gel technique. The precursor xerogel was characterized by thermal analysis. Bi1-xEuxFeO3 (x = 0-0.20) powders obtained after thermal treatment of the xerogel at 600 degrees C for 30 min were investigated by X-ray diffraction (XRD), scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Raman spectroscopy, and Mossbauer spectroscopy. Magnetic behavior at room temperature was tested using vibrating sample magnetometry. The comparative results showed that europium has a beneficial effect on the stabilization of the perovskite structure and induced a weak ferromagnetism. The particle size decreases after the introduction of Eu3+ from 167 nm for x = 0 to 51 nm for x = 0.20. Photoluminescence spectroscopy showed the enhancement of the characteristic emission peaks intensity with the increase of Eu3+ concentration.

Eu3+,Tb3+-doped Sr3Al2O6 powder phosphor was synthesized via a precursor route and subjected to a subsequent thermal treatment in reducing atmosphere. Photoluminescence and thermoluminescence properties of Sr3Al2O6:Eu3+/Eu2+,Tb3+ were investigated. The structure and morphology of oxides were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). X-ray photoelectron spectroscopy (XPS) was used for the nanocrystals surface composition analysis. X-ray diffraction patterns confirmed the formation of the cubic structure specific to Sr3Al2O6 with space group Pa3 and lattice parameter a = 15.8322 angstrom, while SEM investigations revealed equiaxial, polycrystalline particles, with sizes in the submicronic range, for both Sr3Al2O6:Eu3+,Tb3+ and Sr3Al2O6:Eu3+/Eu2+,Tb3+ samples. The photoluminescence spectra showed the typical f-f luminescence lines of the Tb(3+ )and Eu3+ - ions, accompanied by a broad Eu2+ luminescence band at 510 nm (after calcination in reducing atmosphere). The "after-glow" luminescence signal and the thermoluminescence were assigned to the recombination of close neighbor partners (electron and Eu2+ - hole centers) within the same complex of defects.

The bone remodeling research field has shifted focus towards sustainable, eco-friendly and reproducible manufacturing technologies of 3D structures. It is now accepted that a suitable internal architecture and an active interface between the 3D structure and host bone-tissue constitute the two most critical traits for a successful bone tissue engineering application. A completely reproducible synthesis set-up was recently developed for calcium phosphate (CaP) bioceramics preparation from natural highly available marble and seashells. The influence of the pressing force in the fabrication process of porous 3D scaffolds derived from such CaPs by a sacrificial porogen method using natural fibers is here investigated. The fiber-ceramic based-products underwent thermal processing, followed by surface and volume features characterization. After fibers' thermal removal, interconnected 3D channels were obtained, which could allow a suitable in vivo irrigation and implant-associated negative side-effects prevention. This method provides the prospect of tunable HA/beta-TCP content in the case of both precursors' derived-scaffolds. The morphological results revealed the internal and external pores dimensions, modulated through different pressing forces that led to a controlled total porosity, evidenced by computed tomography techniques. Further, the wettability and mechanical features supported the advance of the novel porous-ceramic-structure designs as reliable bone reconstruction alternatives.

Correlating dopant distribution to its optical response represents a complex challenge for nanomaterials science. Differentiating the "true" clustering nature from dopant pairs formed in statistical distribution complicates even more the elucidation of doping-functionality relationship. The present study associates lanthanide dopant distribution, including all significant events (enrichment, depletion and surface segregation), to its optical response in upconversion (UPC) at the ensemble and single-nanoparticle level. A small deviation from the Er nominal concentration of a few percent is able to induce clear differences in Er UPC emission color, intensity, excited-state dynamics and ultimately, UPC mechanisms, across tetragonal to monoclinic phase transformation in rationally designed Er doped ZrO2 nanoparticles. Rare evidence of a heterogeneous dopant distribution leading to the coexistence of two polymorphs in a single nanoparticle is revealed by Z- and phase contrast transmission electron microscopy (TEM). Despite their spatial proximity, Er in the two polymorphs are spectroscopically isolated, i.e. they do not communicate by energy transfer. Segregated Er, which is well imaged in TEM, is absent in UPC, while the minor phase content overlooked by X-ray diffraction and TEM is revealed by UPC. The outstanding sensitivity of combined TEM and UPC emission to subtle deviations from uniform doping in the diluted concentration regime renders such an approach relevant for various functional oxides supporting lanthanide dopants as emitters.

A series of five Cu(x)CeMgAlO mixed oxides with different copper contents (x) ranging from 6 to 18 at. % with respect to cations, but with fixed 10 at. % Ce and Mg/Al atomic ratio of 3, were prepared by thermal decomposition of layered double hydroxide (LDH) precursors at 750 degrees C. The solid containing 15 at. % Cu, i.e. Cu (15)CeMgAlO, was also calcined at 550 and 650 degrees C. Powder XRD was used to characterize the crystalline structure and SEM-EDX was used to monitor the morphology and chemical composition of both as prepared and calcined materials. Additionally, the textural properties and the reducibility of the mixed oxide catalysts were studied by nitrogen adsorption/desorption and temperature programmed reduction with hydrogen (H-2-TPR) techniques, respectively. X-ray photoelectron spectroscopy (XPS) was used to determine the chemical state of the elements on the catalyst surface and the diffuse reflectance UV-vis spectroscopy, to obtain information about the stereochemistry and aggregation of copper in the Cu-containing mixed oxides. Their catalytic properties in the total oxidation of methane, used as a volatile organic compound (VOC) model molecule, were evaluated and compared with those of an industrial Pd/Al2O3 catalyst. Their catalytic behavior was explained in correlation with their physicochemical properties. Cu(15)CeMgAlO mixed oxide was shown to be the most active catalyst in this series, with a T-50 (temperature corresponding to 50% methane conversion) value of only ca. 45 degrees C higher than that of a commercial Pd/Al2O3 catalyst. This difference becomes as low as ca. 25 degrees C for the Cu(15)CeMgAlO system calcined at 550 degrees C. The influences of the contact time and of the methane concentration in the feed gas on the catalytic performances of the Cu(15)CeMgAlO catalyst have been investigated and its good stability on stream was evidenced.

Controlled deposition of g-C3N4 films, used as photoelectrodes in PEC water splitting is still considered a challenge. In this paper, nanosheets of g-C3N4 were deposited on FTO and FTO/TiO2 substrates via spray coating method. This method allows the preparation of g-C3N4 films with a better exposure of nanosheet edges to the solution and light, favoring the photocatalytic process. The morphology, chemical composition and optical properties of these films were investigated, their behavior as photoanodes in photoelectrochemical water splitting being also evaluated. The results evidenced the formation of g-C3N4 films with an enhanced visible light absorption and improved photocatalytic activity. The interaction of these films with TiO2 substrate consists in the insertion of nitrogen species in the TiO2 lattice. A significant increase in bulk donor densities value correlated with a longer lifetime of photogenerated electrons was observed for TiO2/g-C3N4 photoanode. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Mixtures of nitrogen-doped titanium dioxide (TiO2:N) with different concentrations of Ag and/or SiO2 particles (0.5, 1 and 2 wt.%) were prepared in solid state by mechanico-chemical interactions. Using UV-VIS spectroscopy, Raman scattering, photoluminescence (PL) and photoluminescence excitation (PLE), the influence of the particles on the host material is evaluated. UV-VIS spectroscopy studies indicate a TiO2:N band gap shift to the UV range with increasing concentrations of SiO2 and Ag particles. PL intensities decrease with increasing concentrations of Ag and/or SiO2 particles in the TiO2:N host matrix, which in turn could effectively restrict the electron and hole recombination. To explain these processes, the different de-excitation ways will be advanced, taking into account the energy levels diagram of TiO2:N/Ag, TiO2:N/SiO2 and TiO2:N/Ag/SiO2 systems. PLE spectra show a gradual decrease in their relative intensities after 165 min of continuous irradiation due to photosensitivity of TiO2:N. The plasmonic effect of Ag particles in the TiO2:N/Ag system is highlighted for the first time by PLE studies.

Multilayer structures comprising of SiO2/SiGe/SiO2 and containing SiGe nanoparticles were obtained by depositing SiO2 layers using reactive direct current magnetron sputtering (dcMS), whereas, Si and Ge were co-sputtered using dcMS and high-power impulse magnetron sputtering (HiPIMS). The as-grown structures subsequently underwent rapid thermal annealing (550-900 degrees C for 1 min) in N-2 ambient atmosphere. The structures were investigated using X-ray diffraction, high-resolution transmission electron microscopy together with spectral photocurrent measurements, to explore structural changes and corresponding properties. It is observed that the employment of HiPIMS facilitates the formation of SiGe nanoparticles (2.1 +/- 0.8 nm) in the as-grown structure, and that presence of such nanoparticles acts as a seed for heterogeneous nucleation, which upon annealing results in the periodically arranged columnar self-assembly of SiGe core-shell nanocrystals. An increase in photocurrent intensity by more than an order of magnitude was achieved by annealing. Furthermore, a detailed discussion is provided on strain development within the structures, the consequential interface characteristics and its effect on the photocurrent spectra.

Metal-organic frameworks (MOFs) capable of mobility and manipulation are attractive materials for potential applications in targeted drug delivery, catalysis, and small-scale machines. One way of rendering MOFs navigable is incorporating magnetically responsive nanostructures, which usually involve at least two preparation steps: the growth of the magnetic nanomaterial and its incorporation during the synthesis of the MOF crystals. Now, by using optimal combinations of salts and ligands, zeolitic imidazolate framework composite structures with ferrimagnetic behavior can be readily obtained via a one-step synthetic procedure, that is, without the incorporation of extrinsic magnetic components. The ferrimagnetism of the composite originates from binary oxides of iron and transition metals such as cobalt. This approach exhibits similarities to the natural mineralization of iron oxide species, as is observed in ores and in biomineralization.