A Unique Mechanochemical Redox Reaction Yielding Nanostructured Double Perovskite Sr2_{2}FeMoO6_{6} With an Extraordinarily High Degree of Anti-Site Disorder

Strontium ferromolybdate, Sr(2)FeMoO(6), is an important member of the family of double perovskites with the possible technological applications in the field of spintronics and solid oxide fuel cells. Its preparation via a multi-step ceramic route or various wet chemistry-based routes is notoriously difficult. The present work demonstrates that Sr(2)FeMoO(6) can be mechanosynthesized at ambient temperature in air directly from its precursors (SrO, α-Fe, MoO(3)) in the form of nanostructured powders, without the need for solvents and/or calcination under controlled oxygen fugacity. The mechanically induced evolution of the Sr(2)FeMoO(6) phase and the far-from-equilibrium structural state of the reaction product are systematically monitored with XRD and a variety of spectroscopic techniques including Raman spectroscopy, (57)Fe Mössbauer spectroscopy, and X-ray photoelectron spectroscopy. The unique extensive oxidation of iron species (Fe(0) → Fe(3+)) with simultaneous reduction of Mo cations (Mo(6+) → Mo(5+)), occuring during the mechanosynthesis of Sr(2)FeMoO(6), is attributed to the mechanically triggered formation of tiny metallic iron nanoparticles in superparamagnetic state with a large reaction surface and a high oxidation affinity, whose steady presence in the reaction mixture of the milled educts initiates/promotes the swift redox reaction. High-resolution transmission electron microscopy observations reveal that the mechanosynthesized Sr(2)FeMoO(6), even after its moderate thermal treatment at 923 K for 30 min in air, exhibits the nanostructured nature with the average particle size of 21(4) nm. At the short-range scale, the nanostructure of the as-prepared Sr(2)FeMoO(6) is characterized by both, the strongly distorted geometry of the constituent FeO(6) octahedra and the extraordinarily high degree of anti-site disorder. The degree of anti-site disorder ASD = 0.5, derived independently from the present experimental XRD, Mössbauer, and SQUID magnetization data, corresponds to the completely random distribution of Fe(3+) and Mo(5+) cations over the sites of octahedral coordination provided by the double perovskite structure. Moreover, the fully anti-site disordered Sr(2)FeMoO(6) nanoparticles exhibit superparamagnetism with the blocking temperature T (B) = 240 K and the deteriorated effective magnetic moment μ = 0.055 μ (B) per formula unit

Perovskite Oxide Nanocrystals — Synthesis, Characterization, Functionalization, and Novel Applications

Perovskite oxide nanocrystals exhibit a wide spectrum of attractive properties such as ferroelectricity, piezoelectricity, dielectricity, ferromagnetism, magnetoresistance, and multiferroics. These properties are indispensable for applications in ferroelectric random access memories, multilayer ceramic capacitors, transducers, sensors and actuators, magnetic random access memories, and the potential new types of multiple-state memories and spintronic devices controlled by electric and magnetic fields. In the past two decades, much effort has been made to synthesize and characterize the perovskite oxide nanocrystals. Various physical and chemical deposition techniques and growth mechanisms are explored and developed to control the morphology, identical shape, uniform size, perfect crystalline structure, defects, and homogenous stoichiometry of the perovskite oxide nanocrystals. This chapter provides a comprehensive review of the state-of-the-art research activities that focus on the rational synthesis, structural characterization, functionalization, and unique applications of perovskite oxide nanocrystals in nanoelectronics. It begins with the rational synthesis of perovskite oxide nanocrystals, and then summarizes their structural characterizations. Fundamental physical properties of perovskite oxide nanocrystals are also highlighted, and a range of novel applications in nanoelectronics, information storages, and spintronics are discussed. Finally, we conclude this review with some perspectives/outlook and future researches in these fields

Ferromagnetism in Multiferroic BaTiO₃, Spinel MFe₂O₄ (M = Mn, Co, Ni, Zn) Ferrite and DMS ZnO Nanostructures

Multiferroic magnetoelectric material has significance for new design nano-scale spintronic devices. In single-phase multiferroic BaTiO3, the magnetism occurs with doping of transition metals, TM ions, which has partially filled d-orbitals. Interestingly, the magnetic ordering is strongly related with oxygen vacancies, and thus, it is thought to be a source of ferromagnetism of TM:BaTiO3. The nanostructural MFe2O4 (M = Mn, Co, Ni, Cu, Zn, etc.) ferrite has an inverse spinel structure, for which M2+ ions in octahedral site and Fe3+ ions are equally distributed between tetrahedral and octahedral sites. These antiparallel sub-lattices (cations M2+ and Fe3+ occupy either tetrahedral or octahedral sites) are coupled with O2- ion due to superexchange interaction to form ferrimagnetic structure. Moreover, the future spintronic technologies using diluted magnetic semiconductors, DMS materials might have realized ferromagnetic origin. A simultaneous doping from TM and rare earth ions in ZnO nanoparticles could increase the antiferromagnetic ordering to achieve high-Tc ferromagnetism. The role of the oxygen vacancies as the dominant defects in doped ZnO that must involve bound magnetic polarons as the origin of ferromagnetism

Microstructure analysis of electrospun La0.8Sr0.2MnO3 nanowires using electron microscopy and electron backscatter diffraction (EBSD)

The microstructural properties of electrospun La0.8Sr0.2MnO3 (LSMO) nanofibers were investigated using electron microscopy and electron backscatter diffraction (EBSD). By means of EBSD, it is possible to measure the crystallographic orientation of the LSMO grains within an individual nanofiber. As the LSMO grains within the nanofibers are in the 10-nm range, we employ here parts of the recently developed transmission Kikuchi diffraction technique in order to enhance the Kikuchi pattern quality to enable an automated mapping of the crystallographic data. The diffraction results demonstrate that the grain orientation is not random, but there is a texture induced by the shape of the polymer nanofiber formed after the electrospinning step. Within an individual nanofiber section, the dominating grain boundaries are high-angle ones, which play an important role in the current flow through the sample (low- and high field magnetoresistance). The data obtained allow further an analysis of the grain shape aspect ratio, and elucidate the grain and grain boundary arrangement within electrospun LSMO nanofibers

Microwave Fast Sintering of Double Perovskite Ceramic Materials

The book chapter mainly deals with the microwave sintering of high quality crystals of La2MMnO6 (M = Ni or Co) ceramics. Double perovskite La2MMnO6 (M = Ni or Co) ceramics with average particle size of ~65 nm were manufactured using microwave sintering at 90°C for 10 min in N2 atmosphere for the first time. The morphology, structure, composition, and magnetic properties of the prepared compacts were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), infrared spectroscopy (IR and FTIR), and physical properties measurement system (PPMS). The corresponding dielectric property was tested in the frequency range of 1 kHz–1 MHz and in the temperature range of 300–600 K, and the ceramics exhibited a relaxation-like dielectric behavior

Study of co-precipitated nanomaterials magnetic MnxCo1-xFe2O4 (with x = 0.50 & 0.75) for Photocatalyst Application in MB degradation

The crystalline structure and magnetic properties of Mn1-xCoxFe2O4 (x = 0 & 0.25) was studied in this report. The ferrite materials were synthesized by the chemical co-precipitation method and calcinated at 1000oC for 5 hours. The obtained materials were characterized by FTIR, XRD and VSM, and for photocatalytic activity was measured by UV-Vis spectrometer. Vibration bands at tetrahedral and octahedral site were corresponded by  = 581.56 cm-1 and  = 465.83 cm-1 and 474.51 cm-1 . The obtained ferrite were confirmed by XRD as spinel structure and shown that the addition of number of Mn decreased crystallite size (D) and x-ray density (ρx), but lattice constants (a) increased. The crystallite size of samples with x = 0.50 was 34.85 nm, and x = 0.75 was 32.17 nm. The magnetic properties of nanoparticles shown that magnetization saturation (Ms)from 42.05 emu/g to 54.16 emu/g increased with the addition of number of Mn. The coercive field (Hc)decreased from 408.27 Oe to 258.37 Oe. Photocatalytic activity was observed by UV-Vis spectrometer, where percentage of MB degradation (E) increase with the addition of number on Mn from 49.08% to 69.06%, either rate constant (kapp) and half life time (t1/2).  Furthermore, ferrite material base Mn-Co-ferrite has good characteristic to applied for photocatalyst

Non-DMS related ferromagnetism in transition metal doped zinc oxide

We review pitfalls in recent efforts to make a conventional semiconductor, namely ZnO, ferromagnetic by means of doping with transition metal ions. Since the solubility of those elements is rather low, formation of secondary phases and the creation of defects upon low temperature processing can lead to unwanted magnetic effects. Among others, ion implantation is a method of doping, which is highly suited for the investigation of those effects. By focussing mainly on Fe, Co or Ni implanted ZnO single crystals we show that there are manifold sources for ferromagnetism in this material which can easily be confused with the formation of a ferromagnetic diluted magnetic semiconductor (DMS). We will focus on metallic as well as oxide precipitates and the difficulties of their identification.Comment: 24 pages, 22 figure

Magnetic Properties of Polycrystalline Spinel Oxides from Solid State Reaction

Spinel crystal materials of nickel, cobalt, and iron oxides have seen abundant research for their strong conductivity, ferromagnetic and ferroelectric properties, and their catalytic uses. These can be synthesized by a number of means. This project explores the use of the solid state synthesis method, which benefits from simplicity, of this family of materials, looking for interesting phase shift lines in the triangle between of varying compositions of these three metals. Nickel cobaltite and other related spinels were synthesized from two different solid state approaches and characterized using XRD and SQUID magnetometry. The range 0.5-0.6 of molar ratios of nickel to cobalt does not appear to contain any new interesting spinel structures, and varying the ratio just this small amount appears to hamper the synthesis of nickel cobalt oxide on its own

Magnetic phase diagram of nanostructured zinc ferrite as a function of inversion degree delta

Magnetic properties of spinel zinc ferrites are strongly linked to the synthesis method and the processing route since they control the microstructure of the resulting material. In this work, ZnFe_2O_4 nanoparticles were synthesized by the mechanochemical reaction of stoichiometric ZnO and alpha-Fe2O3, and single-phase ZnFe_2O_4 was obtained after 150 h of milling. The as-milled samples, with a high inversion degree, were subjected to different thermal annealings up to 600 ºC to control the inversion degree and, consequently, the magnetic properties. The as-milled samples, with a crystallite size of 11 nm and inversion degree delta = 0.57, showed ferrimagnetic behavior even above room temperature, as shown by Rietveld refinements of the X-ray diffraction pattern and superconducting quantum interference device magnetometry. The successive thermal treatments at 300, 400, 500, and 600 degrees C decrease delta from 0.15 to 0.18, affecting the magnetic properties. A magnetic phase diagram as a function of delta can be inferred from the results: for delta 0.5, a new antiferromagnetic order appeared due to the overpopulation of nonmagnetic Zn on octahedral sites that leads to equally distributed magnetic cations in octahedral and tetrahedral sites

Photoelectrochemical and theoretical investigations of spinel type ferrites (MxFe3-xO4) for water splitting: A mini-review

Solar-assisted water splitting using photoelectrochemical cells (PECs) is one of the promising pathways for the production of hydrogen for renewable energy storage. The nature of the semiconductor material is the primary factor that controls the overall energy conversion efficiency. Finding semiconductor materials with appropriate semiconducting properties (stability, efficient charge separation and transport, abundant, visible light absorption) is still a challenge for developing materials for solar water splitting. Owing to the suitable bandgap for visible light harvesting and the abundance of iron-based oxide semiconductors, they are promising candidates for PECs and have received much research attention. Spinel ferrites are subclasses of iron oxides derived from the classical magnetite (FeIIFe2 IIIO4) in which the FeII is replaced by one (some cases two) additional divalent metals. They are generally denoted as MxFe3-xO4 (M=Ca, Mg, Zn, Co, Ni, Mn, and so on) and mostly crystallize in spinel or inverse spinel structures. In this mini review, we present the current state of research in spinel ferrites as photoelectrode materials for PECs application. Strategies to improve energy conversion efficiency (nanostructuring, surface modification, and heterostructuring) will be presented. Furthermore, theoretical findings related to the electronic structure, bandgap, and magnetic properties will be presented and compared with experimental results