National Institute Of Materials Physics - Romania

The formation of separate phases in crystalline materials is promoted by doping with elements with different valences and ionic radii. Control of the formation of separate phases in multiferroics is extremely important for their magnetic, ferroelectric and elastic properties, which are relevant for multifunctional applications. The ordering of dopants and incipient phase separation were studied in lead titanate-based multiferroics with the formula (Pb0.88Nd0.08)(Ti0.98-xFexMn0.02)O-3 (x = 0.00, 0.03, 0.04, 0.05) by means of a combination of Mossbauer spectroscopy, XPS, HRTEM, dielectric and anelastic spectroscopy. We found that Fe ions are substituted as Fe3+ at Ti sites and preferentially exhibit pentahedral coordination, whereas Ti ions have coexisting valences of Ti4+/Ti3+. Fe3+ ions are preferentially ordered in clusters, and there exists a transition temperature T-C1, below which phase separation occurs between a tetragonal phase T1 free of magnetic clusters and a cubic phase, and a lower transition temperature T-C2, below which the cubic phase rich in magnetic clusters is transformed into a tetragonal phase T2. The phase separation persists at the nanoscale level down to room temperature and is visible in HRTEM images as a mixing of nanodomains with different tetragonality ratios. This phase separation was observed over the whole studied concentration range of x(Fe) values. It occurs progressively with the value of x(Fe), and the transition temperature T-C2 decreases with the concentration from about 620 K (x(Fe) = 0.03) to about 600 K (x(Fe) = 0.05), while T-C1 remains nearly constant.

H2 plasma has been used to generate carbon vacancies on reduced graphene oxide to increase its catalytic activity as a hydrogenation catalyst. A relationship between the power of the plasma treatment and the exposure time with the activity of the material was observed for CvC double bond hydrogenation. The activity data in the case of 1-octene, showing skeletal isomerization besides hydrogenation, indicate that H2 plasma treatment can introduce hydrogenating and acid sites rendering a bifunctional catalyst that is reminiscent of the activity of noble metals supported on acid supports.

The reaction of manganese(II) chloride tetrahydrate with sodium azide and ONO-donor hydrazone ligand, (H2L = (E)-3-hydroxy-N'-((2)-4-hydroxy-4-phenylbut-3-en-2-ylidene)-2-naphthohydrazide), in methanol gives rise to the formation of red crystals which are stable out of the solvent. The red crystals slowly transform to brown crystals in the methanolic solution. In the last case, the rate of the transformation from red to brown crystals mainly depends on the presence of molecular oxygen and reaction temperature. Both compounds are characterized by elemental analysis, spectroscopic methods and single crystal X-ray diffraction studies. The X-ray analysis indicates that the red crystals consist of a tetranuclear Mn(II) complex molecules, [Mn-4(H0.5L)(4) (mu(1.3)-N-3)(2)(CH3OH)(4)] (1), while the brown crystals consist of dinucelar Mn(III), [Mn2L2(mu(1.1)-OCH3)(1.5)(mu(1.1)-N-3)(0.5)] (2) molecules. In complex 1 with molecules of D2 (222) point symmetry, four Mn(II) ions are connected together by four ONO-donor hydrazone ligands and two end-to-end (EE) bridging azide anions. In complex 2 two Mn(III) ions are connected together by azide or methoxy bridging groups. Magnetic susceptibility measurements on complex 1 reveal the occurrence of antiferromagnetic couplings through azide ligands and enolate oxygen atom of the ligand in which the magnetic coupling constants have been determined. (C) 2018 Elsevier Ltd. All rights reserved.

We report for the first time on the synthesis of NiO/ZnO one-dimensional (1D) nanowire (NW) based heterostructures by applying a suitable methodology of transport and condensation. The synthesis involves, firstly the growth of NiO NWs on gold (Au) catalyzed alumina substrates using the vapor-liquid-solid (VLS) mechanism and then the formation of ZnO NWs directly on the NiO NWs using the vapor-solid (VS) mechanism. Sequential evaporation-condensation over Au-seeded alumina promotes the formation of NiO NWs, driven by the VLS growth mechanism. These NiO NWs act as backbones for the condensation of epitaxial ZnO nanostructures. The detailed morphological study of these heterostructures reveals that ZnO nanowires completely cover the whole NiO nanowires completely and growing out in the form of flat leaves from the NiO nanowire branches. The diameters of the NiO NWs have been found to vary from 15 nm to 60 nm. Selected area electron diffraction data (SAED) indicate an epitaxial growth of ZnO nanowires along (101)-planes on the strongly oriented NiO nanowires along (200) crystallographic planes. Finally, NiO NW and NiO/ZnO heterostructure based conductometric gas sensing devices have been fabricated and the comparison between their sensing performances have been compared. Interestingly, NiO/ZnO NWs heterostructure based sensing devices shows superior performance compared to NiO sensors toward volatile organic compounds (VOC). (C) 2018 Elsevier B.V. All rights reserved.

Distribution of magnetic relaxation time using Mossbauer spectroscopy has been observed for CoFe2-xCrxO4 (0.1 <= x <= 0.4) annealed at lower temperature (<= 400 degrees C). The estimated cation distribution over A and B sites observed by Mossbauer spectroscopy is consistent with that obtained by the Rietveld analysis of the X-ray diffraction patterns. Saturation magnetization and magnetocrystalline anisotropy constant increase up to 20% of Cr (x = 0.2) substitution and, decrease with further increase of x. However, the coercive field as well as the Neel temperature decreases with increase in Cr3+ concentration, i.e., a crossover from the hard magnetic to soft magnetic nature by Cr substitution at the Fe site of CoFe2O4 has been observed. This behavior is attributed to the competition between strain induced magnetism and superexchange interaction between cations. (C) 2018 Elsevier B.V. All rights reserved.

In this work, we investigate the photovoltaic response of Pt/0.5Ba(Zr0.2Ti0.8)O-3-0.5(Ba0.7Ca0.3)TiO3(0.5BZT-0.5BCT)/ITO structures through the insertion of a semiconductor ZnO layer at different positions. The values of short-circuit photocurrent density (J(sc)) of the Pt/ZnO/0.5BZT-0.5BCT/ITO, Pt/0.5BZT-0.5BCT/ZnO/ITO and Pt/ZnO/0.5BZT-0.5BCT/ZnO/ITO capacitors are around 5.31, 0.0034 and 0.052 mA/cm(2), respectively. The enhanced photovoltaic (PV) effect is observed when ZnO layer is inserted between Pt and the 0.5BZT-0.5BCT layer. The built-in field developed at the ZnO/ferroelectric interface in the same direction of the depolarizing field, provides a favorable electric potential for the efficient separation and transportation of photo generated e-h pairs. Furthermore, the polarization-dependent interfacial coupling effect enhances PV effect, which is confirmed by investigating the role of polarization flipping on switchable photo response. This work provides an efficient pathway in tuning the PV response in ferroelectric-based solar cells.

The thermal stress effect on the structure of phase change memory materials, namely single films and double stacked films of GeTe and SnSe, is evaluated. The crystallization temperatures of GeTe and SnSe single films are 138 degrees C and 292 degrees C, respectively. The films are amorphous before annealing and crystallize in rhombohedral and orthorhombic structures afterwards. Ge is tetrahedrally bonded and Se is bivalent after deposition. Both Ge and Se have an octahedral configuration after annealing. The double stacked structure is studied in the as-deposited state and after annealing at temperatures of 100, 210, and 350 degrees C. Pulsed laser deposition produces the crystallization of both as-deposited layers when stacked, mostly of SnSe, but also some crystalline GeTe is present. GeTe fully crystallizes after annealing at 210 degrees C, in the face-centred cubic structure. Annealing at 350 degrees C leads to the evaporation of a significant quantity of Se and to the formation of a cubic Ge0.75Sn0.25Te solid solution. Ge has an octahedral coordination, while Se is tetrahedrally bonded as a result of a combination of bivalent amorphous Se and octahedral Se from crystalline SnSe. The study shows that diffusion between layers at high annealing temperatures might suppress the memory property and determines the formation of irreversible solid solutions.

Four Ge-based organometallic (OM = C6H10 Ge2O7) polymers with similar chemical composition were used as additions for MgB2. MgB2 (OM) 0.0014 dense samples with a relative density higher than 97% were obtained by ex situ spark plasma sintering. The critical current density and the irreversibility magnetic field of the added samples are slightly improved at high magnetic fields by repagermanium (Alfa Aesar) addition when compared to the pristine reference sample. Addition of Ge-straight-chain polymer shows some improvement of the maximum volume pinning force, F-p (max). There is no significant Ge substitution in the crystal lattice of MgB2, while C substitutes for B. Pinning mechanism is mainly of a point pinning type, with the grain boundary pinning mechanism strengthening at lower temperatures and when additives are not used. A relatively high amount of carbon in the samples washes out the Ge effects on pinning-force-related parameters. The structure and morphology of the polymer additive play an important role in dispersion when mixing, impacting the quality of the superconducting properties. The nanosize dimension of the pristine MgB2 powder shows also some drawbacks in mixing and sintering.

A novel class of quaternary intermetallic alloys based on CoPt is investigated in view of their interesting magnetic properties induced by the presence of hard magnetic L1(0) phase. A Co48Pt28Ag6B18 alloy has been prepared by rapid solidification from the melt and subjected to various isothermal annealing procedures. The structure and magnetism of both as-cast and annealed samples as well as the phase evolution with temperature are investigated by means of thermal analysis, X-ray, and selected area electron diffraction, scanning and high-resolution electron microscopy, and magnetic measurements. The X-ray diffraction (XRD) analysis shows that both the as-cast alloy and the sample annealed at 400 degrees C (673 K) have a nanocrystalline structure where fcc CoPt phase predominates. Annealing at 473 degrees C promotes the formation of L1(0) phase triggered by the disorder-order phase transformation as documented in the differential scanning calorimetry results. The sample annealed at 670 degrees C (943 K) shows full formation of L1(0) CoPt as revealed by XRD. Magnetic measurements showed coercivity values ten times increased compared to the as-cast state. This confirms the full formation of L1(0) CoPt in the annealed samples. Moreover, detailed atomic resolution HREM images and SAED patterns show the occurrence of the rarely seen (003) superlattice peaks, which translated into a high ordering of the L1(0) CoPt superlattice. Such results spur more interest in finding novel classes of nanocomposite magnets based on L1(0) phase.

Data storage needs are increasing at a rapid pace across all economic sectors, so the need for new memory technologies with adequate capabilities is also high. Phase change memories (PCMs) are a leading contender in the emerging race for non-volatile memories due to their fast operation speed, high scalability, good reliability and low power consumption. However, in order to meet the present and future storage demands, PCM technologies must further increase the storage density. Here, we employ a probabilistic cellular automata approach to explore the multi-step threshold switching from the reset (off) to the set (on) state in chalcogenide stacked structures. Simulations have shown that in order to obtain multi-step switching with high contrast among different resistance states, the stacked structure needs to contain materials with a large difference among their crystallization temperatures and careful tuning of strata thicknesses. The crystallization dynamics can be controlled through the external energy pulses applied to the system, in such a way that a balance between nucleation and growth in phase change behavior can be achieved, optimized for PCMs.