National Institute Of Materials Physics - Romania

This work focuses on the investigation of the liquid crystalline behavior and luminescence properties of the lanthanide complexes of Eu(III), Sm(III) and Tb(III) with N-biphenyl-alkylated-4-pyridone ligands. The organic ligands having a biphenyl group attached via a long flexible spacer with either 9 or 10 carbon atoms were synthesized by the reaction between 4-hydroxypyridine and the corresponding bromide compounds. The chemical structures of the organic and lanthanide complexes were assigned based on elemental analysis, single-crystal X-ray diffraction, H-1, C-13 NMR and IR spectroscopies, and thermogravimetric analysis (TGA). The X-ray diffraction analysis of a parent compound shows that the lanthanide ions are surrounded by three monodentate pyridone ligands and three bidentate nitrate ions, giving a 9-coordinate environment. The mesogenic behavior and the type of liquid crystalline phases exhibited by the new complexes were analyzed by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM), and powder X-ray diffraction (XRD) studies. Only the lanthanide complexes with longer spacer (10) display a monotropic SmA phase, typically on a short thermal range (less than 10 degrees C). The complexes with shorter flexible chains (9) show no liquid crystalline properties with melting temperatures lower than their analogs with longer spacers. The emission spectra recorded in solid state at room temperatures show typical emission bands for each lanthanide ion employed (Eu(III), Tb(III) and Sm(III)).

Photodegradation of the aqueous solutions of acetylsalicylic acid, in the absence (ASA) and the presence of excipients (ASE), is demonstrated by the photoluminescence (PL). A shift of the PL bands from 342 and 338 nm to 358 and 361-397 nm for ASA and ASE in solid state and as aqueous solutions was reported. By exposure of the solution of ASA 0.3 M to UV light, a decrease in the PL band intensity was highlighted. This behavior was revealed for ASA in the presence of phosphate buffer (PB) having the pH equal to 6.4, 7, and 8 or by the interaction with NaOH 0.3 M. A different behavior was reported in the case of ASE. In the presence of PB, an increase in the intensity of the PL band of ASE simultaneously with a change of the ratio between the intensities of the bands at 361-364 and 394-397 nm was highlighted. The differences between PL spectra of ASA and ASE have their origin in the presence of salicylic acid (SAL). The interaction of ASE with NaOH induces a shift of the PL band at 405-407 nm. Arguments for the reaction of ASA with NaOH are shown by Raman scattering and FTIR spectroscopy.

Melt spun ribbons of Mn53Al45C2 and Mn52Al46C2 have been synthesized by rapid quenching of the melt with the purpose of monitoring the epsilon-tau phase transformation to show technologically feasible ways to increase magnetic parameters and to illustrate the viability of these alloys as the next generation of rare earth (RE)-free magnets. By differential scanning calorimetry (DSC), activation energies and temperatures of onset of the epsilon-tau phase transformation were obtained. Structural analysis was performed using X-ray diffraction (XRD) and the resulting XRD patterns were quantitatively assessed using full profile Rietveld-type analysis. Appropriate annealing was performed in order to enable the epsilon-tau phase transformation. While hcp epsilon-phase was found to be predominant in the as-cast samples, after appropriate annealing, the tetragonal tau-phase, the one that furnishes the relevant magnetic response, was found to be predominant with an abundance of about 90%. The data suggested a mechanism of hcp epsilon-phase decomposition controlled by the segregation towards the interfacial regions, having the rate of transformation governed by antiphase boundary diffusion processes. Magnetic measurements of annealed sample Mn53Al45C2, consisting of predominant tetragonal tau-phase, showed high values of magnetization and increased coercivity, consistent with an energy product of about 10 MGOe, similar with previously reported magnetization measurements, providing further insight into the realization of future class of RE-free low-cost permanent magnets.

Two novel graphene oxide-benzofuran derivatives composites were obtained through the covalent immobilization of [4-hydrazinyl-7nitrobenz-[2,1,3-d]-oxadiazole (NBDH) and respectively, N1-(7-nitrobenzo[c][1,2,5] oxadiazol-4-yl)benzene-1,2-diamine (NBD-PD), on graphene oxide. This covalent functionalization was achieved by activating the carboxylic groups on the surface of graphene oxide by the reaction with thionyl chloride followed by coupling with the amino group of benzofurazane derivatives to obtain the NBD derivatives grafted on graphene oxide. The formation of new materials was check by Raman spectroscopy, fluorescence, infrared spectroscopy and X-ray photoelectron spectroscopy, thermal analysis, scanning electron microscopy, and elemental mapping. The antimicrobial effect of the new composites was evaluated on Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa, both on planktonic and adherent biofilm populations. The cytotoxic effects of the materials on human colon cancer HCT-116 cell line and the normal human fibroblast BJ cell line were evaluated by investigating cell viability and membrane integrity. Apoptosis and colony forming ability of tumor cells were also investigated following exposure to new materials. The biological results of this study have shown that the new materials have potential in combating biofilm formation and also, the tested materials induced cytotoxicity in human colon cancer HCT-116 cell line with limited effects on normal BJ fibroblasts, suggesting their antitumor potential.

In this paper, potassium based triple cation mixed-halide perovskite films were explored in order to enhance the stability and photovoltaic performance of perovskite based solar cells. It was found that adding potassium (K+) to a double cation mixed halide perovskite (FA(0.80)MA(0.20)PbI(2.8)Cl(0.2)), structural, morphological and optoelectronic properties of perovskites are improved. The perovskite films were prepared by one-step spin coating method with and without K+ and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). The results indicate that potassium incorporation reduces significantly the yellow non-perovskite delta-phase formation and improves the perovskite film quality, thus contributing to the reduction of hysteresis, improves the stability and increases the PCE up to 12.51%. Furthermore, the doped devices exhibit reduced hysteresis and provide remarkable shelf stability by retaining more than 70% of the initial efficiency with low humidity over 850 h. (C) 2020 Elsevier B.V. All rights reserved.

The rich functionalities of transition-metal oxides and their interfaces bear an enormous technological potential. Its realization in practical devices requires, however, a significant improvement of yet relatively low electron mobility in oxide materials. Recently, a mobility boost of about 2 orders of magnitude has been demonstrated at the spinel-perovskite gamma-Al2O3/SrTiO3 interface compared to the paradigm perovskite-perovskite LaAlO3/SrTiO3 interface. We explore the fundamental physics behind this phenomenon from direct measurements of the momentum-resolved electronic structure of this interface using resonant soft-X-ray angle-resolved photoemission. We find an anomaly in orbital ordering of the mobile electrons in gamma-Al2O3/SrTiO3 which depopulates electron states in the top SrTiO3 layer. This rearrangement of the mobile electron system pushes the electron density away from the interface, which reduces its overlap with the interfacial defects and weakens the electron-phonon interaction, both effects contributing to the mobility boost. A crystal-field analysis shows that the band order alters owing to the symmetry breaking between the spinel gamma-Al2O3 and perovskite SrTiO3. Band-order engineering, exploiting the fundamental symmetry properties, emerges as another route to boost the performance of oxide devices.

Destructive quantum interference (DQI) and its effects on electron transport are studied in chemical molecules and finite physical lattices that can be described by a discrete Hamiltonian. Starting from a bipartite system whose conductance zeros are known to exist between any two points of a specially designated set, the interference set, we use the Dyson equation to develop a general algorithm for determining the zero conductance points in complex systems, which are not necessarily bipartite. We illustrate this procedure as it applies to the fulvene molecule. The stability of the conductance zeros is analyzed with respect to external perturbations.

Eu, Er, Yb-Er, and Dy-doped phosphate glasses were prepared by a wet-route processing of chemical precursors followed by melt-quenching and annealing. XRD measurements highlighted the amorphous nature of the investigated glasses. UV-Vis absorption spectra revealed peaks specific to f-f electronic transitions of the doping ions whereas FTIR and Raman spectroscopy proved the vitreous network forming role of phosphorous pentoxide. Luminescence spectra in the Vis domain, at RT, showed emission bands characteristic to the ion transitions from the excited states to the ground state. The luminescence spectra collected in the 25-160 degrees C range exhibited a decrease of the emission intensity with temperature rise. In the case of Eu and Dy-doped glasses a relatively small decrease of the emission intensity with temperature is observed by comparison with Er and, respectively, Yb-Er-doped glass where a significant change of the emission intensity is noticed, which recommends the latter as promising candidate for sensing devices.

An analysis of the field dependence of the pinning force in different, high density sintered samples of MgB2 is presented. The samples were chosen to be representative for pure MgB2, MgB2 with additives, and partially oriented massive samples. In some cases, the curves of pinning force versus magnetic field of the selected samples present peculiar profiles and application of the typical scaling procedures fails. Based on the percolation model, we show that most features of the field dependence of the critical force that generate dissipation comply with the Dew-Hughes scaling law predictions within the grain boundary pinning mechanism if a connecting factor related to the superconducting connection of the grains is used. The field dependence of the connecting function, which is dependent on the superconducting anisotropy, is the main factor that controls the boundary between dissipative and non-dissipative current transport in high magnetic field. Experimental data indicate that the connecting function is also dependent on the particular properties (e.g., the presence of slightly non-stoichiometric phases, defects, homogeneity, and others) of each sample and it has the form of a single or double peaked function in all investigated samples.

In this paper, we report studies on Al2O3/Ge/Al2O3 trilayer memory structures deposited by magnetron sputtering at room temperature on p-Si substrates coated with 3 nm SiO2. The changes of the structure, morphology and memory properties induced by rapid thermal annealing (RTA) in a broad temperature range 550-900 degrees C have been carefully investigated. High resolution transmission electron microscopy (HRTEM) revealed the existence of distinct RTA effects for different temperature ranges, in correlation with memory properties measured on Al/Al2O3/Ge/Al2O3/SiO2/p-Si/Al devices. Thus, at temperatures smaller than 650 degrees C, Ge diffuses into adjacent Al2O3, the layers remaining amorphous. The memory window increases from as-deposited samples to those annealed at 600 degrees C reaching the maximum of 5.4 V. After RTA at 700 degrees C, Ge nanocrystals (NCs) in intermediate Ge layer and Ge-rich amorphous nanoparticles in Al2O3 tunnel oxide are formed. Increasing RTA temperature to 800 and 900 degrees C, Ge NCs are no longer formed due to Ge strong diffusion. Instead, Ge-rich mixed GeAl oxide NCs of unknown crystalline structure are evidenced by HRTEM. The memory window continuously decreases with annealing temperature in the range 650-900 degrees C. The ON (OFF) charge loss of only 11% (9.8%) was found by extrapolation to 10 years.