National Institute Of Materials Physics - Romania

Using the kp theory and configuration interaction method, we analyze the effect of heavy hole-light hole (HH-LH) mixing in CdTe quantum dots (QDs) with a single manganese (Mn) ion. We find that the hole-Mn exchange switches the coupling between two excitons whose Luttinger spinors have both HH and LH components. If the magnetic dopant is off-centered and the QD is subjected to a single pulse the system periodically bounces between bright and dark mostly HH excitons with opposite HH spins. A pump-and-probe setup allows to estimate the efficiency of this HH spin unpinning from the biexciton response. The biexciton absorption spectrum is also discussed.

Shape memory alloys are known to memorise one -or several-temperatures at which the martensite-austenite transformation was stopped before completion in the past, the memory manifesting as specific dips in subsequent calorimetric scans. Previous studies have shown that this memory can be erased by heating to higher temperatures than the ones previously recorded. In this paper, we study a distinct memory fading effect which takes place by heating to a lower temperature. This effect is reported in NiFeGa as polycrystalline ribbons, the alloy being initially studied as bulk for which the thermal memory effect was not found. If, after an initial incomplete heating up to T-1 one performs a second incomplete heating up to T-2 < T-1, a new calorimetric dip appears at T-2, as expected, while less expected was that the dip corresponding to T-1 reduces in amplitude or even vanishes ( if the arrest at T-2 is repeated). The memory fading effect is more clear for small differences T-1-T-2 and less obvious or absent for large ones. The second part of the paper employs a statistical 2D model, which associates the memorized temperatures with a depletion of certain martensite plates sizes, and also supports the memory fading effect.

The ability to elucidate the elementary steps of a chemical reaction at the atomic scale is important for the detailed understanding of the processes involved, which is key to uncover avenues for improved reaction paths. Here, we track the chemical pathway of an irreversible direct desulfurization reaction of tetracenothiophene adsorbed on the Cu(111) closed-packed surface at the submolecular level. Using the precise control of the tip position in a scanning tunneling microscope and the electric field applied across the tunnel junction, the two carbon-sulfur bonds of a thiophene unit are successively cleaved. Comparison of spatially mapped molecular states close to the Fermi level of the metallic substrate acquired at each reaction step with density functional theory calculations reveals the two elementary steps of this reaction mechanism. The first reaction step is activated by an electric field larger than 2 V nm(-1), practically in absence of tunneling electrons, opening the thiophene ring and leading to a transient intermediate. Subsequently, at the same threshold electric field and with simultaneous injection of electrons into the molecule, the exergonic detachment of the sulfur atom is triggered. Thus, a stable molecule with a bifurcated end is obtained, which is covalently bound to the metallic surface. The sulfur atom is expelled from the vicinity of the molecule.

This paper relates to a method for the preparation of lead acetate film and its use as precursor for twostep solution deposition of CH3NH3PbI3 perovskite film. For the preparation of perovskite film, lead acetate was used both in the form of trihydrate and dehydrated. The effects of lead acetate trihydrate dehydration on the structure of the resulted perovskite films were studied. The prepared perovskite films which consist of cuboid grains, show high surface coverage both on FTO and TiO2 substrates. XRD measurements have not revealed the presence of the PbI2 contaminant in perovskite film. Solvent vapor annealing method was employed to prepare perovskite film that contains lead iodide. Using impedance spectroscopy measurements, we further evaluated the influence of the prepared perovskite films on the performance of the photovoltaic devices. (C) 2017 Elsevier Ltd. All rights reserved.

Hierarchical flowers-like zinc oxide structures have been successfully obtained by a simple and fast ultrasound-assisted method performed in a ordinary ultrasonic bath using an ammonia solution and zinc acetate, in the absence of any surfactant or template. The composition, structure, crystallinity, morphology and optical properties of the materials obtained at different ultrasound irradiation times were characterized by infrared, UV-Vis and photoluminescence spectroscopy, X-ray diffraction, scanning and transmission electron microscopy investigations. It was proved that the ultrasound irradiation time manipulates both the defect content (implicit the photoluminescent properties) and morphology of the ZnO materials: shorter irradiation times leads to the synthesis of high-defected ZnO structures of flower morphology with triangular-shaped petals, while higher irradiation times favours the formation of low-defected ZnO structures with tipped rod-like petals. A plausible growth mechanism of the architectures that implies aggregation via oriented attachment followed by an Ostwald ripening is advanced based on these results. The ZnO flower-like structures present high photocatalytic activities, a total phenol mineralization being registered in the case of visible light experiments. Electron-spin resonance measurements demonstrate the generation of reactive oxygen species, namely hydroxyl radicals but also C centred radicals adducts derived most probable from the residual acetate adsorbed on ZnO surface. (C) 2016 Elsevier B.V. All rights reserved.

Multifunctional Fe3O4@Nb2O5@Co@Re catalysts with metal loadings in the range of 2-7 wt % were prepared via a multistep process. Magnetic nanoparticles prepared by coprecipitation were covered with a niobia shell precipitated from an ammonium niobate oxalate complex in the presence of hexadecyltrimethylammonium bromide. The deposition of cobalt was performed using a deposition/precipitation procedure. Finally, rhenium has been deposited following three different routes: (i) impregnation, (ii) deposition and precipitation of rhenium chloride (ImC and PP, respectively), and (iii) impregnation with ammonium perrhenate (ImA). The characterization of these catalysts was achieved by X-ray diffraction, Raman, H-2 and NH3 temperature-programmed desorption, X-ray photoelectron spectroscopy, and transmission electron microscopy showing the influence of the preparation procedure, reduction, and Re/Co cooperation on the degree of dispersion and reduction. ImC and ImA routes led to more reduced catalysts, and the decrease in cobalt content corresponded to more reduced rhenium. An inverse relation between the acidity and the degree of reduction has been found. The screening of these catalysts in the fragmentation of the lignin confirmed the role of the structural characteristics and solvent. ImC catalysts exhibited better catalytic activity, especially for low metal loadings [2%Co@3%Re, 85% yield of LF, 15.5% yield of LR in tetrahydrofuran (THF), and 14.5% yield of insoluble LR in THF]. Although the extent was smaller, the PP catalysts allowed a more advanced fragmentation of the lignin to fragments with molecular weights between 200 and 400 Da. The catalysts were totally recovered by application of a magnetic field and recycled six times without any loss of activity or selectivity.

Two series of cyclometalated palladium(II) complexes based on Schiff bases and N-benzoylthiourea (BTU) ligands having four alkoxy groups at their periphery, with different number of carbon atoms, have been designed and prepared. The liquid crystalline behavior of these palladium(II) complexes was investigated by a combination of polarized optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction while their thermal stability was studied by thermogravimetric analysis (TGA). The palladium(II) complexes are thermally stable on a broad temperature range up to 230 degrees C showing, depending on the alkoxy chain length, either monotropic or, for longest alkyl chain, enantiotropic smectic A and C phases. The luminescent properties of palladium(II) complexes were reported. These complexes show a yellow-orange solid-state emission at room temperature with two emission maxima at lambda(max) around 580 and 650 nm, respectively, with a shoulder around 710 nm, when the samples are irradiated in the 330-380 nm range. (C) 2017 Elsevier B.V. All rights reserved.

Reduced-activation steels such as Eurofer alloys are candidates for supporting plasma facing components into kamak-like nuclear fusion reactors. In order to investigate the impact of hydrogen/deuterium insertion in their crystalline lattice, annealing treatments in hydrogen atmosphere have been applied on Eurofer slabs. The resulting samples have been analyzed with respect to local structure and atomic configuration both before and after successive annealing treatments, by X-ray diffractometry (XRD), scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS) and conversion electron Mossbauer spectroscopy (CEMS). The corroborated data point out for a bcc type structure of the non-hydrogenated alloy, with an average alloy composition approaching Fe0.9Cr0.1 along a depth of about 100 nm. EDS elemental maps do not indicate surface inhomogeneities in concentration whereas the Mossbauer spectra prove significant deviations from a homogeneous alloying. The hydrogenation increases the expulsion of the Cr atoms toward the surface layer and decreases their oxidation, with considerable influence on the surface properties of the steel. The hydrogenation treatment is therefore proposed as a potential alternative for a convenient engineering of the surface of different Fe-Cr based alloys.(C) 2017 Elsevier B.V. All rights reserved.

High performance trilayer memory capacitors with a floating gate of a single layer of Ge quantum dots (QDs) in HfO2 were fabricated using magnetron sputtering followed by rapid thermal annealing (RTA). The layer sequence of the capacitors is gate HfO2/floating gate of single layer of Ge QDs in HfO2/tunnel HfO2/p-Si wafers. Both Ge and HfO2 are nanostructured by RTA at moderate temperatures of 600-700 degrees C. By nanostructuring at 600 degrees C, the formation of a single layer of well separated Ge QDs with diameters of 2-3 nm at a density of 4-5 x 1015 m(-2) is achieved in the floating gate (intermediate layer). The Ge QDs inside the intermediate layer are arranged in a single layer and are separated from each other by HfO2 nanocrystals (NCs) about 8 nm in diameter with a tetragonal/orthorhombic structure. The Ge QDs in the single layer are located at the crossing of the HfO2 NCs boundaries. In the intermediate layer, besides Ge QDs, a part of the Ge atoms is segregated by RTA at the HfO2 NCs boundaries, while another part of the Ge atoms is present inside the HfO2 lattice stabilizing the tetragonal/orthorhombic structure. The fabricated capacitors show a memory window of 3.8. +/-. 0.5 V and a capacitance-time characteristic with 14% capacitance decay in the first 3000-4000 s followed by a very slow capacitance decrease extrapolated to 50% after 10 years. This high performance is mainly due to the floating gate of a single layer of well separated Ge QDs in HfO2, distanced from the Si substrate by the tunnel oxide layer with a precise thickness.

The electronic structure of alpha-Sn (001) thin films strained compressively in-plane was studied both experimentally and theoretically. A new topological surface state (TSS) located entirely within the gapless projected bulk bands is revealed by ab initio-based tight-binding calculations as well as directly accessed by soft x-ray angle-resolved photoemission. The topological character of this state, which is a surface resonance, is confirmed by unravelling the band inversion and by calculating the topological invariants. In agreement with experiment, electronic structure calculations show the maximum density of states in the subsurface region, while the already established TSS near the Fermi level is strongly localized at the surface. Such varied behavior is explained by the differences in orbital composition between the specific TSS and its associated bulk states, i.e., their hybridization, respectively.