title: Atomic structure of an ultrathin Fe-silicate film grown on a metal: a monolayer of clay?
abstract: Ultrathin Fe-doped silicate films were prepared on a Ru(0001) surface and, as a function of the Fe/Si ratio, structurally characterized by low-energy electron diffraction, X-ray photoelectron spectroscopy, infrared reflection-absorption spectroscopy, and scanning tunneling microscopy. Density functional theory (DFT) was used to identify the atomic structure. The results show that uniform substitution of Si by Fe in the silicate bilayer frame is thermodynamically unfavorable: the film segregates into a pure silicate and an Fe-silicate phase. The DFT calculations reveal that the Fe-silicate film with an Fe/Si = 1:1 ratio consists of a monolayer of [SiO4] tetrahedra on top of an iron oxide monolayer. As such, it closely resembles the structure of the clay mineral nontronite, a representative of the Fe-rich smectites. Furthermore, the DFT calculations predict formation of bridging Fe-O-Ru bonds between the Fe-silicate film and the Ru substrate accompanied by charge transfer from the metal substrate to the film, so that iron is in the oxidation state +III as in nontronite.
authors: Institute of Chemistry, Humboldt-Universität zu Berlin , Unter den Linden 6, 10099 Berlin, Germany.
authors: Radosław
authors: R
authors: Włodarczyk
authors: Joachim
authors: J
authors: Sauer
authors: Xin
authors: X
authors: Yu
authors: Jorge Anibal
authors: JA
authors: Boscoboinik
authors: Bing
authors: B
authors: Yang
authors: Shamil
authors: S
authors: Shaikhutdinov
authors: Hans-Joachim
authors: HJ
authors: Freund