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Adsorption and incorporation of transition metals at the magnetite Fe3O4(001) surface

Bliem, Roland; Pavelec, Jiri; Gamba, Oscar; McDermott, Eamon; Wang, Zhiming; Gerhold, Stefan; Wagner, Margareta; Osiecki, Jacek LU ; Schulte, Karina LU and Schmid, Michael, et al. (2015) In Physical Review B (Condensed Matter and Materials Physics) 92(7).
Abstract
The adsorption of Ni, Co, Mn, Ti, and Zr at the (root 2 x root 2)R45 degrees-reconstructed Fe3O4(001) surface was studied by scanning tunneling microscopy, x-ray and ultraviolet photoelectron spectroscopy, low-energy electron diffraction (LEED), and density functional theory (DFT). Following deposition at room temperature, metals are either adsorbed as isolated adatoms or fill the subsurface cation vacancy sites responsible for the (root 2 x root 2)R45 degrees reconstruction. Both configurations coexist, but the ratio of adatoms to incorporated atoms depends on the metal; Ni prefers the adatom configuration, Co and Mn form adatoms and incorporated atoms in similar numbers, and Ti and Zr are almost fully incorporated. With mild annealing,... (More)
The adsorption of Ni, Co, Mn, Ti, and Zr at the (root 2 x root 2)R45 degrees-reconstructed Fe3O4(001) surface was studied by scanning tunneling microscopy, x-ray and ultraviolet photoelectron spectroscopy, low-energy electron diffraction (LEED), and density functional theory (DFT). Following deposition at room temperature, metals are either adsorbed as isolated adatoms or fill the subsurface cation vacancy sites responsible for the (root 2 x root 2)R45 degrees reconstruction. Both configurations coexist, but the ratio of adatoms to incorporated atoms depends on the metal; Ni prefers the adatom configuration, Co and Mn form adatoms and incorporated atoms in similar numbers, and Ti and Zr are almost fully incorporated. With mild annealing, all adatoms transition to the incorporated cation configuration. At high coverage, the (root 2 x root 2)R45 degrees reconstruction is lifted because all subsurface cation vacancies become occupied with metal atoms, and a (1 x 1) LEED pattern is observed. DFT+U calculations for the extreme cases, Ni and Ti, confirm the energetic preference for incorporation, with calculated oxidation states in good agreement with photoemission experiments. Because the site preference is analogous to bulk ferrite (XFe2O4) compounds, similar behavior is likely to be typical for elements forming a solid solution with Fe3O4. (Less)
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Physical Review B (Condensed Matter and Materials Physics)
volume
92
issue
7
publisher
American Physical Society
external identifiers
  • wos:000362201500004
  • scopus:84941059553
ISSN
1098-0121
DOI
10.1103/PhysRevB.92.075440
language
English
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yes
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930df5aa-6479-491a-aa6b-0f7d75f9be63 (old id 8220458)
date added to LUP
2015-11-30 07:47:23
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2017-11-12 03:37:07
@article{930df5aa-6479-491a-aa6b-0f7d75f9be63,
  abstract     = {The adsorption of Ni, Co, Mn, Ti, and Zr at the (root 2 x root 2)R45 degrees-reconstructed Fe3O4(001) surface was studied by scanning tunneling microscopy, x-ray and ultraviolet photoelectron spectroscopy, low-energy electron diffraction (LEED), and density functional theory (DFT). Following deposition at room temperature, metals are either adsorbed as isolated adatoms or fill the subsurface cation vacancy sites responsible for the (root 2 x root 2)R45 degrees reconstruction. Both configurations coexist, but the ratio of adatoms to incorporated atoms depends on the metal; Ni prefers the adatom configuration, Co and Mn form adatoms and incorporated atoms in similar numbers, and Ti and Zr are almost fully incorporated. With mild annealing, all adatoms transition to the incorporated cation configuration. At high coverage, the (root 2 x root 2)R45 degrees reconstruction is lifted because all subsurface cation vacancies become occupied with metal atoms, and a (1 x 1) LEED pattern is observed. DFT+U calculations for the extreme cases, Ni and Ti, confirm the energetic preference for incorporation, with calculated oxidation states in good agreement with photoemission experiments. Because the site preference is analogous to bulk ferrite (XFe2O4) compounds, similar behavior is likely to be typical for elements forming a solid solution with Fe3O4.},
  articleno    = {075440},
  author       = {Bliem, Roland and Pavelec, Jiri and Gamba, Oscar and McDermott, Eamon and Wang, Zhiming and Gerhold, Stefan and Wagner, Margareta and Osiecki, Jacek and Schulte, Karina and Schmid, Michael and Blaha, Peter and Diebold, Ulrike and Parkinson, Gareth S.},
  issn         = {1098-0121},
  language     = {eng},
  number       = {7},
  publisher    = {American Physical Society},
  series       = {Physical Review B (Condensed Matter and Materials Physics)},
  title        = {Adsorption and incorporation of transition metals at the magnetite Fe3O4(001) surface},
  url          = {http://dx.doi.org/10.1103/PhysRevB.92.075440},
  volume       = {92},
  year         = {2015},
}