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Title: Transmission electron microscopy and ab initio calculations to relate interfacial intermixing and the magnetism of core/shell nanoparticles

Abstract

Significant efforts towards understanding bi-magnetic core-shell nanoparticles are underway currently as they provide a pathway towards properties unavailable with single-phased systems. Recently, we have demonstrated that the magnetism of γ-Fe2O3/CoO core-shell nanoparticles, in particular, at high temperatures, originates essentially from an interfacial doped iron-oxide layer that is formed by the migration of Co{sup 2+} from the CoO shell into the surface layers of the γ-Fe2O3 core [Skoropata et al., Phys. Rev. B 89, 024410 (2014)]. To examine directly the nature of the intermixed layer, we have used high-resolution transmission electron microscopy (HRTEM) and first-principles calculations to examine the impact of the core-shell intermixing at the atomic level. By analyzing the HRTEM images and energy dispersive spectra, the level and nature of intermixing was confirmed, mainly as doping of Co into the octahedral site vacancies of γ-Fe2O3. The average Co doping depths for different processing temperatures (150 °C and 235 °C) were 0.56 nm and 0.78 nm (determined to within 5% through simulation), respectively, establishing that the amount of core-shell intermixing can be altered purposefully with an appropriate change in synthesis conditions. Through first-principles calculations, we find that the intermixing phase of γ-Fe2O3 with Co doping is ferromagnetic, with even higher magnetization as compared tomore » that of pure γ-Fe2O3. In addition, we show that Co doping into different octahedral sites can cause different magnetizations. This was reflected in a change in overall nanoparticle magnetization, where we observed a 25% reduction in magnetization for the 235 °C versus the 150 °C sample, despite a thicker intermixed layer.« less

Authors:
; ;  [1]; ;  [2]
  1. Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan (China)
  2. Department of Physics and Astronomy, University of Manitoba, Winnipeg, Manitoba R3T 2N2 (Canada)
Publication Date:
OSTI Identifier:
22410143
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Applied Physics; Journal Volume: 117; Journal Issue: 17; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; COBALT IONS; COBALT OXIDES; COMPARATIVE EVALUATIONS; DOPED MATERIALS; FERROMAGNETIC MATERIALS; FERROMAGNETISM; IRON OXIDES; LAYERS; MAGNET CORES; MAGNETIC CORES; MAGNETISM; MAGNETIZATION; NANOPARTICLES; SURFACES; SYNTHESIS; TEMPERATURE DEPENDENCE; TRANSMISSION ELECTRON MICROSCOPY; VACANCIES

Citation Formats

Chi, C.-C., Hsiao, C.-H., Ouyang, Chuenhou, E-mail: houyang@mx.nthu.edu.tw, Skoropata, E., and Lierop, J. van. Transmission electron microscopy and ab initio calculations to relate interfacial intermixing and the magnetism of core/shell nanoparticles. United States: N. p., 2015. Web. doi:10.1063/1.4919044.
Chi, C.-C., Hsiao, C.-H., Ouyang, Chuenhou, E-mail: houyang@mx.nthu.edu.tw, Skoropata, E., & Lierop, J. van. Transmission electron microscopy and ab initio calculations to relate interfacial intermixing and the magnetism of core/shell nanoparticles. United States. doi:10.1063/1.4919044.
Chi, C.-C., Hsiao, C.-H., Ouyang, Chuenhou, E-mail: houyang@mx.nthu.edu.tw, Skoropata, E., and Lierop, J. van. Thu . "Transmission electron microscopy and ab initio calculations to relate interfacial intermixing and the magnetism of core/shell nanoparticles". United States. doi:10.1063/1.4919044.
@article{osti_22410143,
title = {Transmission electron microscopy and ab initio calculations to relate interfacial intermixing and the magnetism of core/shell nanoparticles},
author = {Chi, C.-C. and Hsiao, C.-H. and Ouyang, Chuenhou, E-mail: houyang@mx.nthu.edu.tw and Skoropata, E. and Lierop, J. van},
abstractNote = {Significant efforts towards understanding bi-magnetic core-shell nanoparticles are underway currently as they provide a pathway towards properties unavailable with single-phased systems. Recently, we have demonstrated that the magnetism of γ-Fe2O3/CoO core-shell nanoparticles, in particular, at high temperatures, originates essentially from an interfacial doped iron-oxide layer that is formed by the migration of Co{sup 2+} from the CoO shell into the surface layers of the γ-Fe2O3 core [Skoropata et al., Phys. Rev. B 89, 024410 (2014)]. To examine directly the nature of the intermixed layer, we have used high-resolution transmission electron microscopy (HRTEM) and first-principles calculations to examine the impact of the core-shell intermixing at the atomic level. By analyzing the HRTEM images and energy dispersive spectra, the level and nature of intermixing was confirmed, mainly as doping of Co into the octahedral site vacancies of γ-Fe2O3. The average Co doping depths for different processing temperatures (150 °C and 235 °C) were 0.56 nm and 0.78 nm (determined to within 5% through simulation), respectively, establishing that the amount of core-shell intermixing can be altered purposefully with an appropriate change in synthesis conditions. Through first-principles calculations, we find that the intermixing phase of γ-Fe2O3 with Co doping is ferromagnetic, with even higher magnetization as compared to that of pure γ-Fe2O3. In addition, we show that Co doping into different octahedral sites can cause different magnetizations. This was reflected in a change in overall nanoparticle magnetization, where we observed a 25% reduction in magnetization for the 235 °C versus the 150 °C sample, despite a thicker intermixed layer.},
doi = {10.1063/1.4919044},
journal = {Journal of Applied Physics},
number = 17,
volume = 117,
place = {United States},
year = {Thu May 07 00:00:00 EDT 2015},
month = {Thu May 07 00:00:00 EDT 2015}
}
  • We have examined the effects of core-shell intermixing on the dynamical magnetism of γ-Fe{sub 2}O{sub 3}/MnO nanoparticles. The core and shell phases were identified using x-ray diffraction, and x-ray absorption spectroscopy identified Mn ions in both octahedral and tetrahedral sites, consistent with a significant amount of substitution at the core-shell interface to form an Fe/Mn-ferrite. The dynamical response was probed by Mössbauer spectroscopy, which decouples surface and core spins, and suggested a change in the relaxation behaviour among the spin populations within γ-Fe{sub 2}O{sub 3}/MnO relative to the γ-Fe{sub 2}O{sub 3} seed particles. Interestingly, the magnetic relaxation effects at themore » atomic scale, measured via Mössbauer spectroscopy, were enhanced, indicating that the addition of an MnO shell and intermixing affected the dynamical freezing process which altered the surface magnetism of the γ-Fe{sub 2}O{sub 3} core. Our results show that both the MnO shell and the interfacial intermixed layer are important in determining the core-shell nanoparticle magnetism.« less
  • Silica-silver core-shell nanoparticles were produced using colloidal chemistry methods. Surface plasmon resonances in the silver shells were investigated using optical absorption measurements in ultraviolet-to-visible (UV-vis) spectroscopy and the effect of shell thickness on the wavelength of the resonance was noted. Further studies of the resonances were performed using electron-energy-loss spectroscopy (EELS) and energy-filtered transmission electron microscope (EFTEM) imaging. The plasmon resonance was seen in an EELS spectrum at an energy corresponding to the wavelengths measured in an UV-vis spectrophotometer, and EFTEM images confirmed that the resonance was indeed localized at the surface of the silver shell. Further features were seenmore » in the EELS spectrum and confirmed as bulk-plasmon features of silica and the carbon support film in the TEM specimen.« less
  • We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO2 and Fe49%Co49%V2%/SiO2 core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, and vanadium silicates. Magnetometry experiments havemore » shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO2-based interfacial shell.« less