National Institute Of Materials Physics - Romania

We present a detailed study regarding the bandgap dependence on diameter and composition of spherical Ge-rich GexSi1-x nanocrystals (NCs). For this, we conducted a series of atomistic density functional theory (DFT) calculations on H-passivated NCs of Ge-rich GeSi random alloys, with Ge atomic concentration varied from 50 to 100% and diameters ranging from 1 to 4 nm. As a result of the dominant confinement effect in the DFT computations, a composition invariance of the line shape of the bandgap diameter dependence was found for the entire computation range, the curves being shifted for different Ge concentrations by Delta E(eV)=0.651(1-x). The shape of the dependence of NCs bandgap on the diameter is well described by a power function 4.58/d(1.25) for 2-4 nm diameter range, while for smaller diameters, there is a tendency to limit the bandgap to a finite value. By H-passivation of the NC surface, the effect of surface states near the band edges is excluded aiming to accurately determine the NC bandgap. The number of H atoms necessary to fully passivate the spherical GexSi1-x NC surface reaches the total number atoms of the Ge+Si core for smallest NCs and still remains about 25% from total number of atoms for bigger NC diameters of 4 nm. The findings are in line with existing theoretical and experimental published data on pure Ge NCs and allow the evaluation of the GeSi NCs behavior required by desired optical sensor applications for which there is a lack of DFT simulation data in literature.

Advanced functionality in molecular electronics and spintronics is orchestrated by exact molecular arrangements at metal surfaces, but the strategies for constructing such arrangements remain limited. Here, we report the synthesis and surface hybridization of a cyclophane that comprises two pyrene groups fastened together by two ferrocene pillars. Crystallographic structure analysis revealed pyrene planes separated by similar to 352 pm and stacked in an eclipsed geometry that approximates the rare configuration of AA-stacked bilayer graphene. We deposited this cyclophane onto surfaces of Cu(111) and Co(111) at submonolayer coverage and studied the resulting hybrid entities with scanning tunnelling microscopy (STM). We found distinct characteristics of this cyclophane on each metal surface: on non-magnetic Cu(111), physisorption occurred and the two pyrene groups remained electronically coupled to each other; on ferromagnetic Co(111) nanoislands, chemisorption occurred and the two pyrene groups became electronically decoupled. Spin-polarized STM measurements revealed that the ferrocene groups had spin polarization opposite to that of the surrounding Co metal, while the pyrene stack had no spin polarization. Comparisons to the non-stacked analogue comprising only one pyrene group bolster our interpretation of the cyclophane's STM features. The design strategy presented herein can be extended to realize versatile, three-dimensional platforms in single-molecule electronics and spintronics.

Graphene oxide (GO) and N-doped graphene [(N)G] graphenes were submitted to H-2 glow discharge under different discharge regimes, in both the negative glow and positive column plasma regions. The resulted catalysts were fully characterized using several techniques such as Raman, DRIFT and XPS spectroscopy, powder X-ray diffraction, H-2 pulse chemisorption and H-2-, CO2- and NH3-TPD experiments. Density functional theory calculations were performed taking a slab model of graphene sheet with an optimized C-C bond length (1.426 angstrom) and a 16 angstrom vacuum layer between sheets. An overview of these characterizations showed that the O/C atomic ratio of GO is influenced by the plasma regime, indicating the occurrence of O removal, as also predicted by DFT calculations. In the case of (N)G, the plasma treatment also removes pyridinic N with an increase of the C/N ratio. The efficiency of the plasma modification has been checked through catalytic tests in hydroisomerization of 1-octene and hydrogenation of alpha-methyl-styrene. Contrarily to classical thermal activation requiring high temperatures, the generation of the defects by treating with plasma occurs at voltages in the range of 2 5 kV. In consequence, the hydrogenation and isomerization of alkenes resulted with high yields and good selectivities. Graphene prepared from sodium alginate from brown algae was considered as reference in these investigations.

The structure of the IrQ(ppy)(2) organometallic dual phosphorescent compound was experimentally and theoretically investigated. The Metal-to-Ligand Charge Transfer toward the phenylpiridine and quinoline ligands explains its dual phosphorescence property. The IrQ(ppy)(2) organometallic's electronic properties extend the absorption spectra toward the lower energies than Ir(ppy)(3) due to the bandgap reduction induced by the quinoline ligand. The magneto-optical measurements reveal A-terms, which are produced by splitting the triplet states and B-terms, which arise when the electronic levels are mixed in the magnetic field. The IrQ(ppy)(2) molecule's transport properties confirm an ambipolar character, consisting of a higher hole transport character induced by the phenyilpiridine ligands and a lower electron transport character induced by the quinoline ligand. (C) 2021 Elsevier B.V. All rights reserved.

The first aim of this study was to develop an ATRP process for methyl methacrylate (MMA) polymerization using Fe(CO)(5) as co-initiator. The kinetics analysis of the reaction in solution confirmed the controlled characteristic of the polymerization process. The process displays a slow initiation step and presents bimolecular termination reactions at higher molecular weights, confirmed by NMR analysis. Also, these observations are sustained by GPC, FT-IR, and XPS analyses, explaining the rather unusual dispersity values (1.4) for an ATRP reaction. The use of formic acid, which shifts the equilibrium towards Fe2+ species affording a quasi-controlled controlled polymerization process, is a key element in achieving control over the reaction. The Fe2+/Fe3+ ratio at the end of the reaction, determined by XPS analysis, suggests the possibility to generate magnetic iron oxide particles. Therefore, the synthesis strategy was adapted for use in the suspension polymerization process of MMA which permitted the production of magnetic PMMA particles through a facile one-pot approach, using only an ammonia treatment stage. The obtained PMMA particles, characterized by SEM, XPS, TEM, TGA, and XRD analyses, have porous characteristics and magnetic properties which makes them good candidates as catalyst supports, separation processes, or biomedical applications.

A series of PtCeTi-SBA-15 catalysts, with different concentrations of Pt (0.25 %, 0.5 %, 1.0 %), were synthesized. New Ti-SBA-15 material was obtained by direct synthesis and used as support in successive immobilization of Pt and Ce precursors, changing their order of addition. The characterization of the catalysts has been achieved taking an ensemble of techniques which showed preservation of the support porous structure, high dispersion of the amorphous metal oxides and Pt?, the formation of metal crystals for samples with 1wt% Pt and variation of Pt? content on surface in condition of ceria addition. The best conversion (100 %) was obtained in oxidation of hydrocarbons (CH4, C3H8 and C6H14) for the samples with 1% Pt and a significant diminish of activity was obtained for catalyst in which Ce was added on PtTi-SBA-15 sample. Differently of these, CO oxidation was totally irrespective of the catalyst composition.

We observe a strong thermally controlled magnon-mediated interlayer coupling of two ferromagnetic layers via an antiferromagnetic spacer in spin-valve type trilayers. The effect manifests itself as a coherent switching as well as collective resonant precession of the two ferromagnets, which can be controlled by varying temperature and the spacer thickness. We explain the observed behavior as due to a strong hybridization of the ferro- and antiferromagnetic magnon modes in the trilayer at temperatures just below the Neel temperature of the antiferromagnetic spacer.

The lack of order in amorphous chalcogenides offers them novel properties but also adds increased challenges in the discovery and design of advanced functional materials. The amorphous compositions in the Si-Ge-Te system are of interest for many applications such as optical data storage, optical sensors and Ovonic threshold switches. But an extended exploration of this system is still missing. In this study, magnetron co-sputtering is used for the combinatorial synthesis of thin film libraries, outside the glass formation domain. Compositional, structural and optical properties are investigated and discussed in the framework of topological constraint theory. The materials in the library are classified as stressed-rigid amorphous networks. The bandgap is heavily influenced by the Te content while the near-IR refractive index dependence on Ge concentration shows a minimum, which could be exploited in applications. A transition from a disordered to a more ordered amorphous network at 60 at% Te, is observed. The thermal stability study shows that the formed crystalline phases are dictated by the concentration of Ge and Te. New amorphous compositions in the Si-Ge-Te system were found and their properties explored, thus enabling an informed and rapid material selection and design for applications.

The structural role of V in 28Li(2)O-72SiO(2) (in mol%) lithium silicate glass doped with 0.5 mol% V2O5 was assessed using Si-29 and V-51 Nuclear Magnetic Resonance (NMR), Fourier-transform infrared (FTIR), and X-ray photoelectron (XPS) spectroscopy techniques. Despite the low amount of V2O5 used, the structural information obtained or deduced from the statistical analysis of the NMR data could explain the evolution of glass properties after V2O5 addition. The XPS results indicated that all vanadium exists in 5+ oxidation state. Both the Si-29 NMR and FTIR data point toward an increase in the polymerization of the silicate network, caused by the V2O5 acting as network former, capable to form various QVn tetrahedral units (for n = 0, 1, and 2) in the glasses. These QVn units, which are similar to phosphate units, scavenge the Li+ ions and cause the silicate network to polymerize. However, in an overall balance, the entire glass network is depolymerized due to the additional nonbridging oxygens contributed by the vanadium polyhedra. The addition of vanadium causes the network to expand and increases the ionic conductivity.

Gold nanoparticles (similar to 10 nm) were deposited on titanium dioxide nanoparticles (similar to 21 nm) and the material obtained was characterized using IR, UV-Vis, N-2 adsorption-desorption isotherm, DLS, EDS (EDX), TEM, XPS, and XRD techniques. It was found that the methylene blue dye is degraded in the presence of this material when using hydrogen peroxide as the oxidant. Tests were performed at 2, 4, 6, and 24 h, with hydrogen peroxide contents varying from 1 to 5 mg/mL. Longer exposure time and a higher content of oxidant led to the degradation of methylene blue dye at up to 90%. The material can be reused several times with no loss of activity.