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Implications and consequences of ferromagnetism universally exhibited by inorganic nanoparticles

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 Publication date 2009
  fields Physics
and research's language is English




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Occurrence of surface ferromagnetism in inorganic nanoprticles as a universal property not only explains many of the unusual magnetic features of oxidic thin films, but also suggests its possible use in creating new materials, as exemplified by multiferroic BaTiO3 nanoparticles. While the use of Mn-doped ZnO and such materials in spintronics appears doubtful, it is possible to have materials exhibiting coexistence of (bulk) superconductivity with (surface) ferromagnetism.



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It is shown that dilute niobium doping has significant effect on the ferromagnetism and microstructure of dilutely cobalt-doped anatase TiO2 films. Epitaxial films of anatase TiO2 with 3% Co, without and with 1% niobium doping were grown by pulsed-laser deposition at 875 C at different oxygen pressures. For growth at 10^{-5} Torr niobium doping suppresses the ferromagnetism, while it enhances the same in films grown at 10^{-4} Torr. High-resolution Z-contrast Scanning Transmission Electron Microscopy and Electron Energy Loss Spectroscopy show uniform surface segregation of cobalt-rich Ti_{1-x-y}Co_{x}Nb_{y}O_{2-d} phase, but without cobalt metal clusters.
We investigated the reversible ferromagnetic (FM) behavior of pure and Co doped CeO2 nanopowders. The as-sintered samples displayed an increasing paramagnetic contribution upon Co doping. Room temperature FM is obtained simply by performing thermal treatments in vacuum at temperatures as low as 500^{circ}C and it can be switched off by performing thermal treatments in oxidizing conditions. The FM contribution is enhanced as we increase the time of the thermal treatment in vacuum. Those systematic experiments establish a direct relation between ferromagnetism and oxygen vacancies and open a path for developing materials with tailored properties.
Room-temperature ferromagnetism has been observed in the nanoparticles (7 - 30 nm dia) of nonmagnetic oxides such as CeO2, Al2O3, ZnO, In2O3 and SnO2. The saturated magnetic moments in CeO_2 and Al_2O_3 nanoparticles are comparable to those observed in transition metal doped wide band semiconducting oxides. The other oxide nanoparticles show somewhat lower values of magnetization but with a clear hysteretic behavior. Conversely, the bulk samples obtained by sintering the nanoparticles at high temperatures in air or oxygen became diamagnetic. As there were no magnetic impurities present, we assume that the origin of ferromagnetism may be due to the exchange interactions between localized electron spin moments resulting from oxygen vacancies at the surfaces of nanoparticles. We suggest that ferromagnetism may be a universal characteristic of nanopartilces of metal oxides
We report on the structural properties of mixed aggregates made from rare-earth inorganic nanoparticles (radius 20 Angstroms) and polyelectrolyte-neutral block copolymers in aqueous solutions. Using scattering experiments and Monte Carlo simulations, we show that these mixed aggregates have a hierarchical core-shell microstructure. The core is made of densely packed nanoparticles and it is surrounded by a corona of neutral chains. This microstructure results from a process of controlled association and confers to the hybrid aggregates a remarkable colloidal stability.
We present a new version of the Ogre open source Python package with the capability to perform structure prediction of epitaxial inorganic interfaces by lattice and surface matching. In the lattice matching step a scan over combinations of substrate and film Miller indices is performed to identify the domain-matched interfaces with the lowest mismatch. Subsequently, surface matching is conducted by Bayesian optimization to find the optimal interfacial distance and in-plane registry between the substrate and film. For the objective function, a geometric score function is proposed, based on the overlap and empty space between atomic spheres at the interface. The score function reproduces the results of density functional theory (DFT) at a fraction of the computational cost. The optimized interfaces are pre-ranked using a score function based on the similarity of the atomic environment at the interface to the bulk environment. Final ranking of the top candidate structures is performed with DFT. Ogre streamlines DFT calculations of interface energies and electronic properties by automating the construction of interface models. The application of Ogre is demonstrated for two interfaces of interest for quantum computing and spintronics, Al/InAs and Fe/InSb.
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