Structural and electronic transport features of high quality epitaxial metastable fcc W and beta-W2N thin films compatible with spintronic multilayer nanosystems are reported in a parallel approach. The epitaxial layers have been successfully prepared in a broad range of thicknesses from a few to tens of nanometers. The scalable method of auxiliary plasma assisted substrate magnetron sputtering was used. The epitaxy relationship between the thin films and MgO (100) single-crystal substrate is highlighted by high resolution XRD investigations of the reciprocal space. Electron transport properties are discussed with respect to the striking behavior observed via resistivity over temperature cycles. The chemical stability as active buffer layers of both fcc W and beta-W2N thin films is shown in spintronic configurations, where a thin film of Fe is interposed between W or W2N layers. The reported results show that the obtained high quality W based epitaxial layers are superior template-matched buffers for epitaxial Fe layers, enabling a new class of functional spintronic heterostructures.
Although the accidental or intentional explosions produced in industrial facilities or in urban areas are events with low probability, they have a high destructive potential and potential for human injuries and/or fatalities. One of the types of such events is given by detonation of improvised explosive devices (IEDs)—dirty bombs for terrorist purposes—which may produce a high number of metallic fragments. Studying mass and spatial distributions of these fragments is useful for evaluating their lethality and destructive potential and may help to implement adequate protective measures. This work brings a closer insight into the fragment dispersion around the detonation of a steel-enclosed C4 charge with cylindrical symmetry. In this respect a specific approach involving both detonation experiments and numerical simulations performed by home-made and commercial software packages for investigation of the fragmentation process and accompanying angular scattering of the fragments was proposed. Special algorithms, which allow the estimation of the spatial distributions of fragments from the numerical analysis of perforations made by the metallic fragments generated by such IEDs on surrounding material walls, are developed. Further, numerical simulations of a similar IED device provided output parameters related to the statistical distributions of mass, kinetic energy and position of the fragments. Experimental fragmentation generated a recovered mass distribution (94 fragments of 67.5 g) that was compared with that extracted from simulation, revealing a reasonable agreement on the 0.3–1 g range. In the case of simulations, 300 fragments from a total number of 374 showed a mass ranging from 0.004 to 0.3 g. The simulations showed that the middle part of the steel case generated fragments of kinetic energy over 4 kJ and its ends generated fragments of kinetic energy under 1 kJ. Experimental fragment scattering distributions were investigated with specific home-made numerical algorithms, which, based on a set of images, analysed the correlations between spatial coordinates of perforations made by fragments on surrounding special panels and provided histograms that are discussed in relation with the fragment-induced lethality degree.
The precise control of the magnetic compensation temperature (θc) in ferrimagnetic garnets is essential for the development of cutting-edge ultrafast customizable spintronic devices. In this work we demonstrate how fine variation in stoichiometry and cation distribution in iron gadolinium garnets significanty influences θc. Two samples of Gd3Fe5O112 garnets synthesized via a new hydrothermal method and a conventional solid-state reaction, respectively, were considered. The complex study was carried out using a complex approach combining X-ray diffraction, magnetometry, and Mössbauer spectroscopy. Atomic-scale analysis revealed with unprecedent accuracy a cationic inversion between Fe3+ ang Gd3+ at octahedral and dodecahedral sites in both samples, and their chemical compositions were determined as Gd2.70Fe4.76O11.9 and Gd2.96Fe4.68O11.5, respectively. These local rearrangements have been shown to have a consistent influence on θc (290 K and 317 K, respectively) around room temperature, emphasizing the high sensitivity of exchange interactions to internal atomic order. Results clearly illustrate the strong correlation between the processing, atomic configuration and macroscopic magnetic behavior, establishing a new paradigm for the design of garnet-based materials with tunable θc. The strategy for the accurate determination of cation inversion illustrated in this work exhibits great potential in guiding material innovations for next-generation spintronics.
Expression of concern for ‘Insulin loaded iron magnetic nanoparticle–graphene oxide composites: synthesis, characterization and application for in vivo delivery of insulin’ by Kostiantyn Turcheniuk et al., RSC Adv., 2014, 4, 865–875, https://doi.org/10.1039/C3RA46307A.
A convenient and low-cost sol–gel approach for the one-step synthesis of ZnO–P2O5–rGO nanostructures with tuned bandgap and fluorescence was investigated. The obtained hybrid nanostructures exploit the properties of zinc oxide, graphene oxide and phosphorous oxide as promising candidates for a wide range of optoelectronic applications. A predominant amorphous structure, ZnO–P2O5–rGO, containing ZnO nanorods was evidenced by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). The estimated size of the ZnO nanorods in nanostructures with P2O5 was noticed to decrease when the P2O5/ZnO ratio was increased. The presence of ZnO, P2O5 and rGO was confirmed by Fourier-transform infrared spectroscopy (FTIR) and Raman investigation. P2O5 was noticed to tune the bandgap and the fluorescence emissions of the nanostructured films, as estimated by UV–Vis–NIR and fluorescence spectroscopy, respectively. The electrical measurements performed at room temperature showed that the main influence on the film’s resistivity does not come from the 1% rGO doping but from the P2O5/ZnO ratio. It was found that a 10/90 molar ratio of P2O5/ZnO decreases the resistivity almost seven-fold compared with rGO-doped ZnO films.
Magnetic perovskite films have promising properties for use in energy-efficient spintronic devices and magnetic refrigeration. Here, an epitaxial ferromagnetic La0.67Ba0.33Mn0.95Ti0.05O3 (LBMTO-5) thin film was grown on SrTiO3(001) single crystal substrate by pulsed laser deposition. High-resolution X-ray diffraction proved the high crystallinity of the film with tetragonal symmetry. The magnetic, magnetocaloric and magnetoresistance properties at different directions of the applied magnetic field with respect to the ab plane of the film were investigated. An in-plane uni-axial magnetic anisotropy was evidenced. The LBMTO-5 epilayer exhibits a second-order ferromagnetic-paramagnetic phase transition around 234 K together with a metal–semiconductor transition close to this Curie temperature (TC). The magnetic entropy variation under 5 T induction of a magnetic field applied parallel to the film surface reaches a maximum of 17.27 mJ/cm3 K. The relative cooling power is 1400 mJ/cm3 K (53% of the reference value reported for bulk Gd) for the same applied magnetic field. Giant magnetoresistance of about 82% under 5 T is obtained at a temperature close to TC. Defined as the difference between specific resistivity obtained under 5 T with the current flowing along the magnetic easy axis and the magnetic field oriented transversally to the current, parallel and perpendicular to the sample plane, respectively, the in-plane magneto-resistance anisotropy in 5 T is about 9% near the TC.
The structural properties of VO2 thin films, grown on either LSAT or Si substrates by pulsed laser deposition (PLD), are elucidated by means of transmission electron microscopy (TEM) methods. The TEM observations confirmed the successful growth of VO2 by PLD in variable thicknesses, by optimizing the O2 partial pressure and growth temperature. The films adopt a columnar polycrystalline morphology with narrow columns, up to the film thickness height. Four VO2 polymorphs have been detected by electron diffraction and high-resolution TEM (HRTEM) analysis, with M1 being by far the most abundant phase. Post-experimental strain measurements in HRTEM images have revealed that the actual residual strain is minimized due to the columnar morphology of the VO2 grains, as well as intrinsic oxide layers in the VO2/Si epitaxy. The TEM outcomes confirmed the complementary electrical and magnetic measurements in the films, where a transition from a monoclinic M1 to a rutile VO2 R phase has been identified, influenced by the initial percentage of phases in thick VO2 films.
The manipulation of magnetic anisotropy represents the fundamental prerequisite for the application of magnetic materials. Here we present the vectorial magnetic properties of nanostructured systems and thin films of Fe and FeCo prepared on linearly trenched Mo templates with thermally controlled periodicity. The magnetic properties of the nanosystems are engineered by tuning the shape, size, thickness, and composition parameters of the thin films. Thus, we control coercivity, magnetization, orientation of the easy axis of magnetization, and the long-range magnetic order of the system in the function of the temperature. We distinguish magnetic components that emerge from the complex morpho-structural features of the undulating Fe or FeCo nanostructured films on trenched Mo templates: (i) assembly of magnetic nanowires and (ii) assembly of magnetic islands/clusters. Uniaxial anisotropy at room temperature was proven, characterized, and explained in the case of all systems. Our work contributes to the understanding of magnetic properties necessary for possible further applications of linear systems and undulated thin films.
Epitaxial La0.7Sr0.3MnO3 films with different thicknesses (9-90 nm) were deposited on SrTiO3 (0 0 1) substrates by pulsed laser deposition. The films have been investigated with respect to morpho-structural, magnetic, and magneto-transport properties, which have been proven to be thickness dependent. Magnetic contributions with different switching mechanisms were evidenced, depending on the perovskite film thickness. The Curie temperature increases with the film thickness. In addition, colossal magnetoresistance effects of up to 29% above room temperature were evidenced and discussed in respect to the magnetic behavior and film thickness.
Alloys possessing nominal compositions Mn53Al45C2 and Mn52Al46C2 were prepared by the melt spinning method and were subjected to complex structural, morphological and magnetic investigations. As these alloys can exhibit tetragonal L10-type and τ phase, they have good potential as rare earth (RE)—free magnets. It is, therefore, important to monitor the ε–τ phase transformation and the stability and the magnetic features of the tetragonal phase in an entire temperature interval. By using synchrotron X-ray diffraction, it has been proven that the ε–τ phase transformation occurs gradually, with the τ phase becoming predominant only after 450 °C. Moreover, this phase has been proven to be quite stable without any grain growth even at the highest temperature investigated at 800 °C. Low temperature behavior was thoroughly investigated by using a complex combination of major and minor hysteresis loops combined with the zero field cooled-field cooled magnetization protocols (ZFC-FC). Two different regimes, blocking and superparamagnetic, were documented. A spin reorientation transition was proven to occur at 55 K while a maximum magnetization observed in ZFC-FC curves proved that at about 75 K, a transition from ferro to superparamagnetic state occurs. The existence of a blocking regime below 55 K that is characteristic to nanogranular systems with superparamagnetic behavior has shown further development towards obtaining RE-free magnets.
Fe-Gd amorphous thin films of different compositions and thicknesses were analyzed with respect to their magnetic and magneto-optical behavior. By preparing samples with the same Fe/Gd elemental ratio at different thicknesses, and of various Fe/Gd ratios at constant thickness, respectively, we were able to show the influences of these two parameters on the interconnected behavior of the two magnetic sub-lattices, one of Fe and the other of Gd, which are antiferromagnetically coupled. Magneto-Optical Kerr Effect (MOKE) measurements revealed reversed hysteresis loops for sample compositions crossing the magnetic compensation point. Temperature dependent magnetization curves highlighted the variation of the overall net contribution of the two magnetic sub-lattices by changing either the Fe/Gd elemental ratio or the film thickness. 57 Fe Conversion Electron Mössbauer (CEM) spectra give additional support to the specific magnetic behavior evidenced by temperature and field dependent Superconducting Quantum Interference Device (SQUID) magnetometry.
Almost all proposed configurations and practical achievements based on superconductor/ferromagnet (S/F) heterostrucutres focus on s-wave superconductors. However, several attempts targeted also high temperature superconductors, most of them using manganite ferromagnets LaXMnO3 (X: Ca or Sr) and Y1Ba2Cu3O7−x (YBCO). Here we propose a new ferromagnetic material that can be used with YBCO for the fabrication of S/F hybrid structures. We show that a ferromagnetic order can be induced in a thin layer (∼130 nm thickness) of CaRuO3 grown by pulsed laser deposition on epitaxial YBCO film. Detailed magnetic and structural investigations show that the observations of the weak ferromagnetism are consistent with the magnetic order induced by in-plane tensile strain of about 1.7% and the easy-magnetization axis forms an angle of ∼180º with the layer plane. The value of the Curie temperature T Curie estimated using the Curie–Weiss law was 340 K. An unusual temperature dependence of the magnetic moment around the superconducting transition was observed in both field-cooled and zero-field-cooled configurations which is attributed to the paramagnetic Meissner effect.
Epitaxial La0.7Sr0.3MnO3 films with different thicknesses (9–90 nm) were deposited on SrTiO3 (0 0 1) substrates by pulsed laser deposition. The films have been investigated with respect to morpho-structural, magnetic, and magneto-transport properties, which have been proven to be thickness dependent. Magnetic contributions with different switching mechanisms were evidenced, depending on the perovskite film thickness. The Curie temperature increases with the film thickness. In addition, colossal magnetoresistance effects of up to 29% above room temperature were evidenced and discussed in respect to the magnetic behavior and film thickness.
Melt spun ribbons of Mn53Al45C2 and Mn52Al46C2 have been synthesized by rapid quenching of the melt with the purpose of monitoring the ε-τ 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 ε-τ 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 ε-τ phase transformation. While hcp ε-phase was found to be predominant in the as-cast samples, after appropriate annealing, the tetragonal τ-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 ε-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 τ-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.
Structural and magnetic properties of Fe oxide nanoparticles prepared by laser pyrolysis and annealed in high pressure hydrogen atmosphere were investigated. The annealing treatments were performed at 200 °C (sample A200C) and 300 °C (sample A300C). The as prepared sample, A, consists of nanoparticles with ~ 4 nm mean particle size and contains C (~ 11 at.%), Fe and O. The Fe/O ratio is between γ-Fe2O3 and Fe3O4 stoichiometric ratios. A change in the oxidation state, crystallinity and particle size is evidenced for the nanoparticles in sample A200C. The Fe oxide nanoparticles are completely reduced in sample A300C to α-Fe single phase. The blocking temperature increases from 106 K in A to 110 K in A200C and above room temperature in A300C, where strong inter-particle interactions are evidenced. Magnetic parameters, of interest for applications, have been considerably varied by the specific hydrogenation treatments, in direct connection to the induced specific changes of particle size, crystallinity and phase composition. For the A and A200C samples, a field cooling dependent unidirectional anisotropy was observed especially at low temperatures, supporting the presence of nanoparticles with core–shell-like structures. Surprisingly high MS values, almost 50% higher than for bulk metallic Fe, were evidenced in sample A300C.
ZnO nanostructures with intrinsic and extended defects were prepared by rapid decomposition of zinc-propio-nate and annealing at 400 degrees C-970 degrees C. The correlation between the structure/morphology, type of native defects (photoluminescence (PL), EPR) and ferromagnetism was investigated, together with ammonia adsorption capacity. All the samples show room temperature ferromagnetism (RTFM). Crystallite size increases while the unit cell volume, c-axis constant, microstrain and saturation magnetization relax with increasing temperature; morphology varies from aggregated nanoparticles to frameworks of well-welded crystals. 400 degrees C-800 degrees C annealed samples show a broad visible and/or a prominent violet-blue PL emission and, two narrow g = 2.0065 and g = 1.9632 EPR signals. 800 degrees C-970 degrees C annealed samples exhibit very intense green-yellow photoluminescence. The intrinsic defects in conjunction with a deformed lattice and/or pinned by grain-boundaries appear responsible for RTFM and Curie temperature exceeding 700 degrees C. Tuning the morphology, PL intensity and ferromagnetic signal by choice of annealing temperature can find applications in (gas) sensing, photonic/optoelectronic and spintronic devices.
Magnetic nanoscale materials exhibiting the L10 tetragonal phase such as FePt or ternary alloys derived from FePt show most promising magnetic properties as a novel class of rare earth free permanent magnets with high operating temperature. A granular alloy derived from binary FePt with low Pt content and the addition of Mn with the nominal composition Fe57Mn8Pt35 has been synthesized in the shape of melt-spun ribbons and subsequently annealed at 600 °C and 700 °C for promoting the formation of single phase, L10 tetragonal, hard magnetic phase. Proton-induced X-ray emission spectroscopy PIXE has been utilized for checking the compositional effect of Mn addition. Structural properties were analyzed using X-ray diffraction and diffractograms were analyzed using full profile Rietveld-type analysis with MAUD (Materials Analysis Using Diffraction) software. By using temperature-dependent synchrotron X-ray diffraction, the disorder–order phase transformation and the stability of the hard magnetic L10 phase were monitored over a large temperature range (50–800 °C). A large interval of structural stability of the L10 phase was observed and this stability was interpreted in terms of higher ordering of the L10 phase promoted by the Mn addition. It was moreover found that both crystal growth and unit cell expansion are inhibited, up to the highest temperature investigated (800 °C), proving thus that the Mn addition stabilizes the formed L10 structure further. Magnetic hysteresis loops confirmed structural data, revealing a strong coercive field for a sample wherein single phase, hard, magnetic tetragonal L10 exists. These findings open good perspectives for use as nanocomposite, rare earth free magnets, working in extreme operation conditions.
In this study, we report on the structural, magnetic, and optical properties of Tb3+-doped CeF3 nanocrystals prepared via a polyol-assisted route, followed by calcination. X-ray diffraction analysis and electron microscopy investigations have shown the formation of a dominant Ce0.75F3 nanocrystalline phase (of about 99%), with a relatively uniform distribution of nanocrystals about 15 nm in size. Magnetization curves showed typical paramagnetic properties related to the presence of Ce3+ and Tb3+ ions. The magnetic susceptibility showed a weak inflexion at about 150 K, assigned to the cerium ions’ crystal field splitting. Under UV light excitation of the Ce3+ ions, we observed Tb3+ green luminescence with a quantum yield of about 20%.
With the aim of demonstrating phase coexistence of two magnetic phases in an intermediate annealing regime and obtaining highly coercive FePt nanocomposite magnets, two alloys of slightly off-equiatomic composition of a binary Fe-Pt system were prepared by dynamic rotation switching and ball milling. The alloys, with a composition Fe53Pt47 and Fe55Pt45, were subsequently annealed at 400 °C and 550 °C and structurally and magnetically characterized by means of X-ray diffraction, 57Fe Mössbauer spectrometry and Superconducting Quantum Interference Device (SQUID) magnetometry measurements. Gradual disorder–order phase transformation and temperature-dependent evolution of the phase structure were monitored using X-ray diffraction of synchrotron radiation. It was shown that for annealing temperatures as low as 400 °C, a predominant, highly ordered L10 phase is formed in both alloys, coexisting with a cubic L12 soft magnetic FePt phase. The coexistence of the two phases is evidenced through all the investigating techniques that we employed. SQUID magnetometry hysteresis loops of samples annealed at 400 °C exhibit inflection points that witness the coexistence of the soft and hard magnetic phases and high values of coercivity and remanence are obtained. For the samples annealed at 500 °C, the hysteresis loops are continuous, without inflection points, witnessing complete exchange coupling of the hard and soft magnetic phases and further enhancement of the coercive field. Maximum energy products comparable with values of current permanent magnets are found for both samples for annealing temperatures as low as 500 °C. These findings demonstrate an interesting method to obtain rare earth-free permanent nanocomposite magnets with hard–soft exchange-coupled magnetic phases.
Among the rare-earth-free systems that are currently investigated in search for novel permanent magnet solutions for various applications, with special emphasis on the magnets required to operate in extreme conditions, the FePt binary system, where the tetragonal hard magnetic L10 phase can be formed by suitable microstructure processing via annealing, has been extensively studied. A variation of this system, the ternary FeMnPt system, has been also recently shown to exhibit good permanent magnet behavior due to the suitable formation of the L10 phase. In addition to be likely to form the L10 phase as its parent binary system, the ternary FeMnPt benefits from the reduced costs due to the reduced amount of Pt and may exhibit particular magnetic structure due to the influence of the antiferromagnetic Mn. In the present work, we have employed a mixed sputtering technique, based on the use of both elemental and compound target for developing L10 FeMnPt thin films with specific structural features that triggers better magnetic performances in terms of coercivity and maximum energy products. The as-obtained films have been thermally annealed and characterized by means of transmission electron microscopy, X-ray diffraction, Mossbauer spectroscopy, magneto-optic Kerr effect (MOKE) and SQUID magnetometry. The aim is to correlate the Mn induced microstructural and lattice changes with the magnetic properties and to optimize the microstructure for an early formation of the ordered L10 phase and increased coercivity compared to the as-prepared, structurally disordered, face centred cubic initial state of the films.