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Magnetic properties of Co-doped TiO2 anatase nanopowders

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 Added by A. J. Silvestre
 Publication date 2009
  fields Physics
and research's language is English




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This letter reports on the magnetic properties of Ti1-xCoxO2 anatase phase nanopowders with different Co contents. It is shown that oxygen vacancies play a fundamental role in promoting the long-range ferromagnetic order in the material studied, in addition to the transition-metal doping. Furthermore, the results allow ruling out the premise of a strict connection between Co clustering and the ferromagnetism observed in the Co:TiO2 anatase system.



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Oxygen vacancies created in anatase TiO2 by UV photons (80 - 130 eV) provide an effective electron-doping mechanism and induce a hitherto unobserved dispersive metallic state. Angle resolved photoemission (ARPES) reveals that the quasiparticles are large polarons. These results indicate that anatase can be tuned from an insulator to a polaron gas to a weakly correlated metal as a function of doping and clarify the nature of conductivity in this material.
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.
Elucidating the carrier density at which strongly bound excitons dissociate into a plasma of uncorrelated electron-hole pairs is a central topic in the many-body physics of semiconductors. However, there is a lack of information on the high-density response of excitons absorbing in the near-to-mid ultraviolet, due to the absence of suitable experimental probes in this elusive spectral range. Here, we present a unique combination of many-body perturbation theory and state-of-the-art ultrafast broadband ultraviolet spectroscopy to unveil the interplay between the ultraviolet-absorbing two-dimensional excitons of anatase TiO$_2$ and a sea of electron-hole pairs. We discover that the critical density for the exciton Mott transition in this material is the highest ever reported in semiconductors. These results deepen our knowledge of the exciton Mott transition and pave the route toward the investigation of the exciton phase diagram in a variety of wide-gap insulators.
We develop a first-principles approach based on many-body perturbation theory to investigate the effects of the interaction between electrons and carrier plasmons on the electronic properties of highly-doped semiconductors and oxides. Through the evaluation of the electron self-energy, we account simultaneously for electron-plasmon and electron-phonon coupling in theoretical calculations of angle-resolved photoemission spectra, electron linewidths, and relaxation times. We apply this methodology to electron-doped anatase TiO2 as an illustrative example. The simulated spectra indicate that electron-plasmon coupling in TiO2 underpins the formation of satellites at energies comparable to those of polaronic spectral features. At variance with phonons, however, the energy of plasmons and their spectral fingerprints depends strongly on the carrier concentration, revealing a complex interplay between plasmon and phonon satellites. The electron-plasmon interaction accounts for approximately 40% of the total electron-boson interaction strength and it is key to improve the agreement with measured quasiparticle spectra.
The magnetic anisotropy of La0.7Sr0.3MnO3 nanopowders was measured as a function of temperature by the modified singular point detection technique. In this method singularities indicating the anisotropy field were determined analyzing ac susceptibility data. The observed relationship between temperature dependence of anisotropy constant and temperature dependence of magnetization was used to deduce the origin of magnetic anisotropy in the nanopowders. It was shown that magnetic anisotropy of La0.7Sr0.3MnO3 nanopowder is determined by two-ion (dipolar or pseudodipolar) and single-ion mechanisms.
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